KR20210124053A - Conjugated diene polymer, method for producing conjugated diene polymer, conjugated diene polymer composition, and rubber composition - Google Patents

Abstract

The present invention obtains a conjugated diene polymer having excellent tensile strength, wear resistance, and low hysteresis loss when being a vulcanizate. The conjugated diene polymer has 7 or more of a branched degree (Bn) by a GPC-light scattering measuring method using a viscometer, and 45 x 10^4 or more and 500 x 10^4 or less of a weight average molecular weight. In the conjugated diene polymer, a content of an aromatic vinyl monomer unit is 30 to 45 mass% and a content (mass%) value of the aromatic vinyl monomer unit is more than a vinyl binding amount (mol%) in the conjugated diene monomer unit.

Description

A conjugated diene-based polymer, a method for producing a conjugated diene-based polymer, a conjugated diene-based polymer composition, and a rubber composition TECHNICAL FIELD

The present invention relates to a conjugated diene-based polymer, a method for producing a conjugated diene-based polymer, a conjugated diene-based polymer composition, and a rubber composition.

BACKGROUND ART Conventionally, there has been an increasing demand for fuel economy reduction in automobiles, and improvement of rubber materials used for automobile tires, particularly tire treads in contact with the road surface, has been demanded.

In recent years, due to an increase in the demand for fuel efficiency regulation for automobiles, automobiles tend to be lightweight due to resinization of the members and the like, and also for tires, the demand for thinner tire members is increasing from the viewpoint of weight reduction.

In order to reduce the weight of the tire, in particular, it is necessary to reduce the thickness of the tread portion in contact with the road surface having a high ratio of rubber material, and in the tread portion, there is a demand for a rubber material superior in tensile strength even more than before.

Further, in order to reduce energy loss due to the tire during running, a rubber material used for a tire tread is required to have a low rolling resistance, that is, a material having low hysteresis loss properties.

On the other hand, from the viewpoint of safety, it is required to have sufficient wear resistance for practical use.

Examples of the rubber material satisfying the above requirements include a rubber composition comprising a rubbery polymer having a predetermined structure and a reinforcing filler such as carbon black or silica.

That is, by introducing a functional group having affinity or reactivity with silica into the molecular terminal portion of the rubber-like polymer with high mobility, the dispersibility of silica in the rubber composition is improved, and furthermore, the rubber-like polymer is bonded to silica particles. The mobility of the molecular terminal portion of the polymer is reduced, so that the reduction of hysteresis loss, the improvement of abrasion resistance, and the breaking strength are attained.

For example, Patent Documents 1 to 3 propose a rubber composition of a modified conjugated diene polymer obtained by reacting an amino group-containing alkoxysilane with an active terminal of a conjugated diene polymer and silica.

Japanese Patent Laid-Open No. 2005-290355 Japanese Patent Laid-Open No. 11-189616 Japanese Patent Laid-Open No. 2003-171418

However, in the conventionally proposed rubber composition, silica has a hydrophilic surface with respect to carbon black having a hydrophobic surface. There is a problem in that the dispersibility is poor. Therefore, the rubber composition containing silica needs to contain a silane modifier or the like separately in order to impart a bond between the silica and the conjugated diene polymer and to improve dispersibility in the rubber composition.

In addition, when a functional group with high reactivity with silica is introduced into the molecular terminal of the conjugated diene-based polymer, the reaction with silica particles proceeds during the kneading process, resulting in an increase in the viscosity of the rubber composition, making it difficult to open, Alternatively, when forming a sheet after kneading, there is a problem in that the workability tends to deteriorate, such as surface roughness or sheet peeling easily.

In addition, the conventionally proposed rubber composition containing silica as described above has a problem that the balance between tensile strength, abrasion resistance and low hysteresis loss is insufficient when the rubber composition is made into a vulcanized product.

Then, in this invention, it aims at providing the conjugated diene polymer from which the rubber composition excellent in tensile strength, abrasion resistance, and low hysteresis loss property in the case of a vulcanization|vulcanization substance is obtained.

As a result of intensive research and examination to solve the problems of the prior art, the present inventors have found that the branching degree (Bn) is at least a specific numerical value, the weight average molecular weight is in a specific numerical range, and the content of the aromatic vinyl monomer unit is in a specific numerical range. , Tensile strength when the conjugated diene-based copolymer in which the relationship between the content (mass %) of the aromatic vinyl monomer unit and the value of the vinyl bond amount (mol%) in the conjugated diene monomer unit is set as a vulcanized product , abrasion resistance and low hysteresis loss properties were found to be excellent, and the present invention was completed.

That is, the present invention is as follows.

〔One〕

The branching degree (Bn) by GPC-light scattering method with a viscosity detector is 7 or more,

It is a conjugated diene-based polymer having a weight average molecular weight of 45 × 10 ⁴ or more and 500 × 10 ^{4 or less,}

content of the aromatic vinyl monomer unit in the said conjugated diene polymer is 30-45 mass %,

A conjugated diene-based polymer wherein the content (mass%) of the aromatic vinyl monomer unit is larger than the value of the vinyl bond amount (mol%) in the conjugated diene monomer unit.

〔2〕

The conjugated diene-based polymer according to [1], wherein the conjugated diene-based polymer has a rate of modification measured by column adsorption GPC of 60% by mass or more.

[3]

The conjugated diene polymer according to [1] or [2], which contains a nitrogen atom and a silicon atom.

〔4〕

The conjugated diene-based polymer has a three-branched or more star-shaped polymer structure,

In the branched chain of at least one star structure, a portion derived from a vinyl monomer containing an alkoxysilyl group or a halosilyl group, and a portion derived from a vinyl monomer containing an alkoxysilyl group or a halosilyl group, further having a main chain branching structure of

The conjugated diene-based polymer according to any one of [1] to [3].

[5]

The conjugated diene polymer according to the above [4], wherein the vinyl monomer containing an alkoxysilyl group or a halosilyl group is a compound represented by the following formula (1) or (2).

(In Formula (1), R<^1> represents a hydrogen atom, a C1-C20 alkyl group, or a C6-C20 aryl group, and may have a branched structure in the part.

R ² to R ³ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and may have a branched structure in a part thereof.

In the case of two or more, R ¹ to R ³ are each independent.

X ¹ represents an independent halogen atom.

m represents the integer of 0-2, n represents the integer of 0-3, l represents the integer of 0-3. (m+n+1) represents 3.)

(In formula (2), R ² to R ⁵ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and may have a branched structure in a part thereof. ² to R ⁵ are each independent.

X ² to X ^{3 each} represent an independent halogen atom.

m represents the integer of 0-2, n represents the integer of 0-3, l represents the integer of 0-3. (m+n+1) represents 3.

a represents the integer of 0-2, b represents the integer of 0-3, c represents the integer of 0-3. (a+b+c) represents 3.)

[6]

The conjugated diene polymer according to [5], wherein in the formula (1), R ¹ is a hydrogen atom and m=0, which has a monomer unit based on the compound represented by the formula (1).

[7]

The conjugated diene polymer according to [5], wherein in the formula (2), m = 0 and b = 0, which has a monomer unit based on the compound represented by the formula (2).

〔8〕

In the ^{above [5] having a monomer unit based on the compound represented by the formula (1), wherein R 1} is a hydrogen atom, m=0, l=0, and n=3 in the formula (1) The disclosed conjugated diene-based polymer.

[9]

In the formula (2), m=0, l=0, n=3, a=0, b=0, and c=3, a monomer based on the compound represented by the formula (2). The conjugated diene-based polymer according to [5], which has a unit.

[10]

A method for producing the conjugated diene-based polymer according to any one of [1] to [9], the method comprising:

Using an organolithium compound as a polymerization initiator, polymerizing at least a conjugated diene compound and an aromatic vinyl compound in a solvent containing a polar compound, adding a branching agent to obtain a conjugated diene-based polymer having a main chain branched structure; A method for producing a conjugated diene-based polymer.

[11]

The method for producing the conjugated diene-based polymer according to the above [10], further comprising a step of reacting the conjugated diene-based polymer having a branched main chain structure with a coupling agent.

[12]

100 parts by mass of the conjugated diene-based polymer according to any one of [1] to [9];

1 to 60 parts by mass of a rubber softener

Containing, a conjugated diene-based polymer composition.

[13]

A rubber composition comprising a rubber component and 5.0 parts by mass or more and 150 parts by mass or less of a filler with respect to 100 parts by mass of the rubber component,

The rubber composition, wherein the rubber component contains 10 parts by mass or more of the conjugated diene-based polymer according to any one of [1] to [9], based on 100 parts by mass of the total amount of the rubber component.

ADVANTAGE OF THE INVENTION According to this invention, the conjugated diene polymer excellent in tensile strength, abrasion resistance, and low hysteresis loss property when it is set as a vulcanized|vulcanized material can be obtained.

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

In addition, the following this embodiment is an illustration for demonstrating this invention, and this invention is not limited to the following embodiment. The present invention can be implemented with appropriate modifications within the scope of the gist.

[Conjugated diene-based polymer]

The conjugated diene-based polymer of the present embodiment,

The branching degree (Bn) by GPC-light scattering method with a viscosity detector is 7 or more,

It is a conjugated diene polymer having a weight average molecular weight of 45×10 ⁴ or more and 500×10 ⁴ or less, wherein the content of the aromatic vinyl monomer unit in the conjugated diene polymer is 30 to 45 mass%, and the content of the aromatic vinyl monomer unit (mass%) ) is a conjugated diene-based polymer that is larger than the value of the amount of vinyl bonds (mol%) in the conjugated diene monomer unit.

As described above, the branching degree (Bn), the weight average molecular weight, the content of the aromatic vinyl monomer unit, and the “value of the content of the aromatic vinyl monomer unit” and “the value of the amount of vinyl bonds in the conjugated diene monomer unit” determine the size relationship. As a result, a conjugated diene-based polymer having excellent workability when set as a vulcanized product and excellent in tensile strength and abrasion resistance when set as a vulcanized product can be obtained.

(branch map (Bn))

The conjugated diene-based polymer of the present embodiment has a degree of branching (Bn) (hereinafter simply referred to as a degree of branching (Bn) by GPC-light scattering method with a viscosity detector from the viewpoint of workability, abrasion resistance, and breaking strength. .) is 7 or greater.

The branching degree (Bn) of 7 or more means that the conjugated diene-based polymer of the present embodiment has substantially 7 or more side chain polymer chains with respect to the longest polymer main chain.

The degree of branching (Bn) of the conjugated diene-based polymer was determined by using the shrinkage factor (g') measured by GPC-light scattering method with a viscosity detector, g'=6Bn/{(Bn+1)(Bn+2)} is defined as

In general, a branched polymer tends to have a smaller molecular size when compared with a straight-chain polymer having the same absolute molecular weight.

The shrinkage factor (g') is an index of the ratio of the size occupied by the molecule to the linear polymer, which is supposed to have the same absolute molecular weight. That is, as the degree of branching of the polymer increases, the shrinkage factor (g') tends to decrease.

Conforms to a relational expression of 3.883M ^0.771 - In the conjugated diene-based polymer according to one embodiment of the invention with respect to shrinkage factor, when using the intrinsic viscosity of a size indicator of the molecule, the polymer, the intrinsic viscosity [η] = a straight-chain do. In the above formula, M is an absolute molecular weight.

However, the shrinkage factor indicates the rate of molecular size reduction and does not accurately indicate the branching structure of the polymer.

Then, the branching degree (Bn) of the conjugated diene polymer is calculated using the value of the shrinkage factor (g') at each absolute molecular weight of the conjugated diene polymer. The calculated "branching degree (Bn)" accurately indicates the number of polymers directly or indirectly bonded to each other with respect to the longest main chain structure.

The calculated degree of branching (Bn) is an index indicating the branching structure of the conjugated diene-based polymer. For example, in the case of a general four-branched star polymer (in the central part, four polymer chains are connected), two arms of the polymer chain are bonded to the longest highly branched main chain structure, so the degree of branching (Bn) is 2 evaluated.

In the case of an 8-branched star polymer, six arms of the polymer chain are bonded to the longest highly branched main chain structure, so the degree of branching (Bn) is evaluated as 6.

The conjugated diene-based polymer of the present embodiment has a branching degree (Bn) of 7 or more. In this case, 7 arms of the polymer chain are bonded to the longest highly branched main chain structure, and the same as the 9-branched star polymer structure. It means that it is a conjugated diene-type polymer which has a branch.

Here, a "branch" is formed by direct or indirect bonding of another polymer with respect to one polymer. In addition, the "branching degree (Bn)" is the number of polymers directly or indirectly bonded to each other with respect to the longest main chain structure.

When the branching degree (Bn) is 7 or more, the conjugated diene-based polymer of the present embodiment is very excellent in workability when used as a vulcanized product, and is excellent in abrasion resistance and breaking strength when set as a vulcanized product.

In general, when the absolute molecular weight of the conjugated diene-based polymer increases, the processability tends to deteriorate, and when the absolute molecular weight of the conjugated diene-based polymer having a linear polymer structure is increased, the viscosity when used as a vulcanized product increases significantly. As a result, the workability is significantly deteriorated.

Therefore, even if a large number of functional groups are introduced into the conjugated diene polymer to improve affinity and/or reactivity with silica to be blended as a filler, the silica cannot be sufficiently dispersed in the conjugated diene polymer in the kneading step. . As a result, the function of the introduced functional group is not exhibited, and there is a tendency that the effect of improving the low hysteresis loss property by introducing the functional group, which would have been expected originally, does not tend to be exhibited.

On the other hand, in the conjugated diene-based polymer of the present embodiment, by specifying a branching degree (Bn) of 7 or more, the increase in viscosity at the time of setting it as a vulcanized substance accompanying an increase in absolute molecular weight is significantly suppressed. For example, in the kneading step, it is sufficiently mixed with silica and the like, and it becomes possible to disperse the silica around the conjugated diene-based polymer. As a result, for example, in a conjugated diene-based polymer, by setting the molecular weight to be large, the abrasion resistance and tensile strength can be improved, and silica is dispersed around the polymer by sufficient kneading, so that the functional group acts and/or reacts. This makes it possible to obtain a rubber composition having a practically sufficient low hysteresis loss property.

The absolute molecular weight of the conjugated diene-based polymer can be measured by the method described in Examples described later.

The branching degree (Bn) of the conjugated diene-based polymer of the present embodiment is 7 or more, preferably 8 or more, and more preferably 9 or more. A conjugated diene-based polymer having a branching degree (Bn) within this range tends to be excellent in workability when used as a vulcanized product.

The upper limit of the branching degree (Bn) of the conjugated diene polymer is not particularly limited and may be equal to or greater than the detection limit, but is preferably 84 or less, more preferably 80 or less, still more preferably 64 or less, and further More preferably, it is 57 or less.

The conjugated diene polymer of this embodiment tends to be excellent in abrasion resistance when it is set as a vulcanized|vulcanized material because the branching degree (Bn) is 84 or less.

The degree of branching of the conjugated diene-based polymer of the present embodiment can be controlled by adjusting the addition amount of the branching agent, and by adjusting the combination of the addition amount of the branching agent and the addition amount of the terminal coupling agent, or the modifier having a nitrogen atom-containing group. , 7 or more can be controlled.

Specifically, control of the degree of branching includes the number of functional groups of the branching agent, the amount of addition of the branching agent, the timing of addition of the branching agent, and the functional number of the coupling agent or the modifying agent containing a nitrogen atom, the coupling agent or the modifying agent containing a nitrogen atom. It can be controlled by adjusting the addition amount. More specifically, it describes in the manufacturing method of the conjugated diene type polymer described later.

(monomer)

The conjugated diene polymer of this embodiment contains a conjugated diene compound and an aromatic vinyl compound as a compound which forms a monomeric unit.

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

Among these, 1, 3- butadiene and isoprene are preferable from a viewpoint of the easiness of industrial availability.

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

Moreover, although it is not limited to the following as an aromatic vinyl compound, For example, styrene, p-methylstyrene, (alpha)-methylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene, and diphenylethylene are mentioned.

Among these, the viewpoint of industrial availability to styrene is preferable.

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

(Coupling agent)

The conjugated diene-based polymer of the present embodiment may be subjected to a coupling reaction using a reactive compound (hereinafter, also referred to as a coupling agent) with respect to the active terminal of the conjugated diene-based polymer obtained in the polymerization step.

The coupling agent used in the coupling reaction step may have any structure as long as it is a bifunctional or more reactive compound. Preferably, a bifunctional or more reactive compound having a silicon atom is preferable.

More specifically, it describes in the manufacturing method of the conjugated diene type polymer described later.

By using the reactive compound which has a silicon atom for a coupling agent, the conjugated diene type polymer of this embodiment becomes a thing which has a silicon atom.

It is preferable that the conjugated diene polymer of this embodiment contains a nitrogen atom.

The conjugated diene-based polymer containing a nitrogen atom is, for example, subjected to a coupling reaction using a modifier having a nitrogen atom-containing group described below, and an organic monolithium compound having a substituted amino group as the polymerization initiator. and the like.

(content of nitrogen atoms)

It is preferable that content of the nitrogen atom of the conjugated diene type polymer of this embodiment is 5 mass ppm or more with respect to the total amount of the said conjugated diene type polymer. The nitrogen atom content (hereinafter, sometimes referred to as "nitrogen content") is a nitrogen-containing functional group of the conjugated diene-based polymer, for example, a nitrogen-containing functional group at the start terminal, in the main chain, and at the terminal end. is the total amount of nitrogen atoms in

The nitrogen content of the conjugated diene polymer is more preferably 8 mass ppm or more, still more preferably 10 mass ppm or more, and still more preferably 13 mass ppm or more with respect to the total amount of the conjugated diene polymer.

By setting it as the above-mentioned content, when the conjugated diene-type polymer of this embodiment is made into a vulcanization material, there exists a tendency excellent in the balance of low hysteresis loss property and wet skid resistance.

In addition, in the polymerization step of the conjugated diene-based polymer of the present embodiment, when an organomonolithium compound having a substituted amino group is used as the polymerization initiator, from the viewpoint of suppressing the chain transfer reaction during polymerization, the conjugated diene-based polymer is It is preferable that nitrogen content is 150 mass ppm or less, It is more preferable that it is 100 mass ppm or less, It is still more preferable that it is 80 mass ppm or less.

The nitrogen content can be measured by an oxidative combustion-chemiluminescence method (JIS-2609: crude oil and crude oil products-nitrogen content test method). More specifically, it can be measured by the method described in Examples to be described later.

(A modifier having a nitrogen atom-containing group)

The conjugated diene-based polymer of the present embodiment is a reactive compound having a nitrogen atom-containing group with respect to the active terminal of the conjugated diene-based polymer obtained through the polymerization step and further branching step (hereinafter referred to as “modifier having a nitrogen atom-containing group”). It is preferable that it is a conjugated diene-type polymer obtained by performing a coupling reaction by this.

In particular, it is more preferable that a coupling agent having a nitrogen atom-containing group and a functional group having a bifunctional or higher function is reacted at the end of polymerization.

The conjugated diene-based polymer coupled using a modifier having a nitrogen atom-containing group has good dispersibility of silica, good processability, and is a vulcanized material when a rubber composition containing a filler such as silica is blended. When this is done, the balance between low hysteresis loss and wet skid resistance tends to improve dramatically.

More specifically, it describes in the manufacturing method of the conjugated diene type polymer described later.

The modifier having a nitrogen atom-containing group is not limited to the following, but for example, an isocyanate compound, an isothiocyanate compound, an isocyanuric acid derivative, a nitrogen group-containing carbonyl compound, a nitrogen group-containing vinyl compound, and a nitrogen group-containing agent. An epoxy compound etc. are mentioned.

The modifier having a nitrogen atom-containing group preferably has a nitrogen atom-containing functional group, and the nitrogen atom-containing functional group is preferably an amine compound having no active hydrogen, for example, a tertiary amine compound, the active hydrogen and a protective amine compound substituted with a protecting group, an imine compound represented by the general formula -N=C, and an alkoxysilane compound bonded to the nitrogen atom-containing group.

More specifically, it describes in the manufacturing method of the conjugated diene type polymer described later.

(Modification rate of conjugated diene-based polymer)

It is preferable that the modified rate measured by the column adsorption GPC method of the conjugated diene type polymer of this embodiment is 60 mass % or more.

In this specification, "modification rate" shows the mass ratio of the conjugated diene type polymer which has a nitrogen atom containing functional group with respect to the total amount of a conjugated diene type polymer.

For example, when a modifier having a nitrogen atom-containing group is reacted with the terminal end of the polymer, the conjugated diene polymer having a nitrogen atom-containing functional group by the modifier having a nitrogen atom-containing group, relative to the total amount of the conjugated diene polymer A mass ratio is expressed as a denaturation rate.

On the other hand, even when the polymer is branched by a branching agent containing a nitrogen atom, the resulting conjugated diene-based polymer has a nitrogen atom-containing functional group, so this branched polymer is also counted when calculating the modification rate.

That is, in this specification, the mass ratio of the total of the polymer which was subjected to a coupling reaction with a modifier having a nitrogen atom-containing functional group and/or a polymer branched by a branching agent having a nitrogen atom-containing functional group is the “modification rate”.

When the conjugated diene polymer of the present embodiment is modified with a modifier having a nitrogen atom-containing group at least at one end, workability is improved when a rubber composition containing a filler or the like is obtained, and the rubber composition is converted into a vulcanized product. There is a tendency for a dramatic improvement effect of low hysteresis loss properties to be obtained while maintaining the abrasion resistance and breaking strength.

The conjugated diene-based polymer of the present embodiment has a denaturation rate measured by column adsorption GPC with respect to the total amount of the conjugated diene-based polymer from the viewpoint of workability, abrasion resistance, breaking strength, and a balance between low hysteresis loss and wet skid resistance (hereinafter , also simply described as "modification rate") is preferably 60 mass % or more.

The said modification rate becomes like this. Preferably it is 70 mass % or more, More preferably, it is 75 mass % or more, More preferably, it is 80 mass % or more.

Although the upper limit of the said modification rate is not specifically limited, For example, it is 98 mass %. When the denaturation rate is within the above range, the dispersibility of silica in a vulcanized product is improved, and the low hysteresis loss property is excellent.

A denaturation rate can be measured by the chromatography which can isolate|separate the functional group-containing modified|denatured component and a non-denatured component.

As a method using this chromatography, a column for gel permeation chromatography with a polar substance such as silica adsorbing a specific functional group as a filler is used, and an internal standard of a non-adsorbed component is used for comparison and quantitation (column adsorption). GPC method).

More specifically, the rate of denaturation is the difference between a chromatogram measured by a polystyrene gel column and a chromatogram measured by a silica column for a sample and a sample solution containing a low molecular weight internal standard polystyrene, adsorption to a silica column obtained by measuring the amount.

More specifically, the denaturation rate can be measured by the method described in the Example.

In the conjugated diene-based polymer of the present embodiment, the modification rate can be controlled by adjusting the addition amount and reaction method of the modifying agent, the addition amount of the branching agent and the reaction method, and thereby can be controlled to 60% by mass or more. .

For example, as a polymerization initiator, a method of polymerization using an organolithium compound having at least one nitrogen atom in a molecule to be described later, a method of copolymerizing a monomer having at least one nitrogen atom in a molecule, and at least one nitrogen in a molecule The modification rate can be controlled by appropriately combining a method of using a branching agent having an atom and a method of using a modifying agent having a structural formula described later and adjusting polymerization conditions and reaction conditions.

(Branched structure of conjugated diene-based polymer)

The conjugated diene-based polymer of the present embodiment is a conjugated diene-based polymer having a three-branched or more star-shaped polymer structure from the viewpoint of a balance between workability and abrasion resistance, and an alkoxysilyl group or a halosilyl group in at least one branched chain of the star structure It is preferable that it is a conjugated diene-based polymer having a portion derived from a vinyl-based monomer that contains, and a portion derived from a vinyl-based monomer containing an alkoxysilyl group or a halosilyl group, further having a branched main chain structure.

The portion derived from the vinyl monomer containing the alkoxysilyl group or the halosilyl group is a portion containing silylbenzene in the conjugated diene-based polymer. When the vinyl monomer as the branching agent reacts with the polymer chain, OH of the alkoxysilyl group included in the branching agent or halogen of the halosilyl group becomes a leaving group, and the polymer active terminal is substituted, thereby bonding. In addition, the vinyl structure of the said vinyl monomer produces|generates a branched structure by superposing|polymerizing as a conjugated diene. Thereby, since the structure which the polymer chain couple|bonded with the silicon of silylbenzene is produced|generated, this structure is called a part derived from a vinylic monomer. When the vinyl-based monomer has a plurality of leaving groups, a plurality of polymer chains may be bonded to silicon of silylbenzene. Of course, the silylbenzene to which the plurality of polymer chains are bonded is also a part derived from the vinyl-based monomer.

The "star polymer structure" as used herein refers to a structure in which a plurality of polymer chains (arms) are bonded from one central branch point.

In addition, one central branching point here has the substituent containing the atom derived from a coupling agent, or the nitrogen atom derived from a modifier|denaturant.

The "main chain branched structure" as used herein refers to a structure in which a branching point is formed at a portion in which the polymer chain is derived from a vinyl monomer containing an alkoxysilyl group or a halosilyl group, and a polymer chain (arm) extends from the branching point. say

In particular, in a main chain branched structure containing a vinyl monomer containing an alkoxysilyl group or a ^{halosilyl group, when the signal is detected by 29} Si-NMR, it is in the range of -45 ppm to -65 ppm, and more limitedly, -50 ppm to -60 ppm. A peak derived from the branched main chain structure is detected in the range of .

In the conjugated diene-based polymer of the present embodiment, from the viewpoint of improving the degree of branching (Bn), the main chain branching point constituted by a portion derived from a vinyl monomer containing an alkoxysilyl group or a halosilyl group is preferably two branching points or more. , The branched structure derived from the star polymer structure formed by the coupling agent in the reaction step performed after the polymerization and branching steps is preferably 3 or more branches, more preferably 4 or more branches, and still more preferably 8 branches or more. The portion derived from the vinyl-based monomer refers to a structure including silylbenzene, as described above.

In addition, the degree of branching (Bn) increases in either case of modification with a coupling agent forming a star structure or when a branching agent is introduced into the polymer. The contribution to (Bn) is large.

In the design of the polymer, the degree of branching (Bn) can be controlled by selection of a coupling agent, selection of a type of branching agent, or setting of an addition amount, but by taking the contribution rate into consideration, control of the degree of branching (Bn) is easy.

(main chain branch structure)

In the conjugated diene-based polymer of the present embodiment, the main chain branching structure is preferably at least the second branching point at the branching point in the portion derived from the vinyl monomer containing an alkoxysilyl group or a halosilyl group, and more preferably at least the third branch point. and more preferably at least the fourth branch point.

In addition, the branching point forming the main chain branching structure preferably has at least two or more polymer chains, more preferably has three or more polymer chains that are not main chains, and more preferably has 4 polymer chains that are not main chains. have more than one dog

(Star-shaped polymer structure)

The conjugated diene-based polymer of the present embodiment preferably has a star-shaped polymer structure, and branches derived from the star-shaped polymer structure are preferably 3 or more branches, more preferably 4 or more branches, still more preferably 6 or more branches, It is still more preferable that it is 8 or more branches.

The conjugated diene-based polymer of the present embodiment is a conjugated diene-based polymer having a three-branched or more star-shaped polymer structure, and a portion derived from a vinyl-based monomer containing an alkoxysilyl group or a halosilyl group in at least one branched chain of a star-shaped structure. A preferred embodiment is a conjugated diene polymer having a further branched main chain structure in the portion derived from the vinyl monomer containing the alkoxysilyl group or the halosilyl group. Regarding the method for obtaining a conjugated diene-based polymer having such a structure, the "star polymer structure" can be formed by adjusting the number of functional groups of the coupling agent and the amount of the coupling agent added, and the "main chain branched structure" is a branching agent It can control by adjusting the number of functional groups, the addition amount of a branching agent, and the timing of addition of a branching agent.

As a specific manufacturing method, polymerization is performed using an organolithium compound as a polymerization initiator, a branching agent that additionally imparts a specific branching point is added during or after polymerization, and a modifier that imparts a specific branching rate after continuing polymerization A method of denaturation using

A means for controlling such polymerization conditions is described in the production method in Examples to be described later.

(Detailed structure of the main chain branching structure)

The conjugated diene-based polymer of the present embodiment is a monomer unit in which the moiety derived from the vinyl monomer containing the above-described alkoxysilyl group or halosilyl group is based on a compound represented by the following formula (1) or (2), It is preferable to have the branching point of the polymer chain by the monomeric unit based on the compound represented by following formula (1) or (2). The conjugated diene-based polymer of the present embodiment is more preferably a conjugated diene-based polymer obtained using a coupling agent, and more preferably a modified conjugated diene-based polymer in which at least one end of the conjugated diene-based polymer is modified with a nitrogen atom-containing group. desirable.

(In Formula (1), R<^1> represents a hydrogen atom, a C1-C20 alkyl group, or a C6-C20 aryl group, and may have a branched structure in the part.

R ² to R ³ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and may have a branched structure in a part thereof.

In the case of two or more, R ¹ to R ³ are each independent.

X ¹ represents an independent halogen atom.

m represents the integer of 0-2, n represents the integer of 0-3, l represents the integer of 0-3. (m+n+1) represents 3.)

(In formula (2), R ² to R ⁵ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and may have a branched structure in a part thereof.

In the case of ^two or more ^{R 2 to R 5} , each is independent.

X ² to X ^{3 each} represent an independent halogen atom.

m represents the integer of 0-2, n represents the integer of 0-3, l represents the integer of 0-3.

(m+n+1) represents 3.

a represents the integer of 0-2, b represents the integer of 0-3, c represents the integer of 0-3. (a+b+c) represents 3.)

The conjugated diene-based polymer of the present embodiment is a conjugated diene-based polymer having a monomer unit based on the compound represented by the formula (1), wherein ^{R 1 is a hydrogen atom and m=0 in the above formula (1).} It is preferable to be Thereby, the branching index is improved, and the effect of improvement of abrasion resistance and workability is acquired.

Further, the conjugated diene-based polymer of the present embodiment is a conjugated diene-based polymer having a monomer unit based on a compound represented by the formula (2) wherein m=0 and b=0 in the formula (2). it is preferable Thereby, the effect of improvement of abrasion resistance and workability is acquired.

Further, the conjugated diene-based polymer of the present embodiment is, in the formula (2), m=0, l=0, n=3, a=0, b=0, and c=3, the formula (2) It is preferable that it is a conjugated diene polymer which has a monomeric unit based on the compound represented by ). Thereby, the effect of improvement of abrasion resistance and workability is acquired.

In the conjugated diene polymer of the present embodiment, in the formula (1), R ¹ is a hydrogen atom, m=0, l=0, and n=3, a compound represented by the formula (1). It is more preferable that it is a conjugated diene-type polymer which has a monomer unit based on . Thereby, the denaturation rate and branching degree are improved, and the effect of improvement of fuel economy performance, abrasion resistance, and workability is acquired.

(branching agent)

In the conjugated diene polymer of this embodiment, it is preferable to use the branching agent represented by following formula (1) or Formula (2) as a branching agent when constructing a main chain branched structure.

The moiety derived from a vinyl monomer containing an alkoxysilyl group or a halosilyl group is a monomer unit based on a compound represented by the following formula (1) or (2), and the conjugated diene-based polymer of the present embodiment is It is preferable that it is a structure which has the branch point of the polymer chain by the monomeric unit based on the compound represented by Formula (1) or (2).

(In Formula (1), R<^1> represents a hydrogen atom, a C1-C20 alkyl group, or a C6-C20 aryl group, and may have a branched structure in the part.

R ² to R ³ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and may have a branched structure in a part thereof.

In the case of two or more, R ¹ to R ³ are each independent.

X ¹ represents an independent halogen atom.

m represents the integer of 0-2, n represents the integer of 0-3, l represents the integer of 0-3. (m+n+1) represents 3.)

(In formula (2), R ² to R ⁵ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and may have a branched structure in a part thereof.

In the case of ^two or more ^{R 2 to R 5} , each is independent.

X ² to X ^{3 each} represent an independent halogen atom.

m represents the integer of 0-2, n represents the integer of 0-3, l represents the integer of 0-3.

(m+n+1) represents 3.

a represents the integer of 0-2, b represents the integer of 0-3, c represents the integer of 0-3. (a+b+c) represents 3.)

In the present embodiment, the branching agent used when constructing the main chain branching structure of the conjugated diene polymer is, from the viewpoint of continuity of polymerization and improvement of the degree of branching, preferably R ¹ in Formula (1) is a hydrogen atom, , it is preferably a compound of m=0.

In addition, in this embodiment, the branching agent used when constructing the main chain branched structure of the conjugated diene polymer is a compound of m=0 and b=0 in Formula (2) from a viewpoint of a branching degree improvement. It is preferable to be

In addition, the R ¹ from the viewpoint of improvement of In, conjugated diene-based branching agent to be used when building the main chain branching structure of the polymer, the continuity of the polymerization, modification ratio and branching to this embodiment, equation (1) It is a hydrogen atom, m=0, l=0, and it is more preferable that it is a compound of n=3.

In addition, in this embodiment, the branching agent used when constructing the main chain branched structure of the conjugated diene polymer is, from a viewpoint of a modification rate and the improvement of a branching degree, in said Formula (2), m=0, l= Preference is given to compounds in which 0, n=3, a=0, b=0, c=3.

Although not limited to the following as a branching agent represented by said Formula (1), For example, trimethoxy (4-vinylphenyl) silane, triethoxy (4-vinylphenyl) silane, tripropoxy (4 -Vinylphenyl)silane, tributoxy(4-vinylphenyl)silane, triisopropoxy(4-vinylphenyl)silane, trimethoxy(3-vinylphenyl)silane, triethoxy(3-vinylphenyl)silane , tripropoxy (3-vinylphenyl) silane, tributoxy (3-vinylphenyl) silane, triisopropoxy (3-vinylphenyl) silane, trimethoxy (2-vinylphenyl) silane, triethoxy ( 2-vinylphenyl)silane, tripropoxy(2-vinylphenyl)silane, tributoxy(2-vinylphenyl)silane, triisopropoxy(2-vinylphenyl)silane, dimethoxymethyl (4-vinylphenyl) Silane, diethoxymethyl (4-vinylphenyl) silane, dipropoxymethyl (4-vinylphenyl) silane, dibutoxymethyl (4-vinylphenyl) silane, diisopropoxymethyl (4-vinylphenyl) silane, dime Toxymethyl (3-vinylphenyl) silane, diethoxymethyl (3-vinylphenyl) silane, dipropoxymethyl (3-vinylphenyl) silane, dibutoxymethyl (3-vinylphenyl) silane, diisopropoxymethyl ( 3-vinylphenyl)silane, dimethoxymethyl (2-vinylphenyl)silane, diethoxymethyl (2-vinylphenyl)silane, dipropoxymethyl (2-vinylphenyl)silane, dibutoxymethyl (2-vinylphenyl) silane and diisopropoxymethyl (2-vinylphenyl) silane.

Further, examples of the branching agent represented by the formula (1) include dimethylmethoxy(4-vinylphenyl)silane, dimethylethoxy(4-vinylphenyl)silane, and dimethylpropoxy(4-vinylphenyl)silane. , dimethylbutoxy(4-vinylphenyl)silane, dimethylisopropoxy(4-vinylphenyl)silane, dimethylmethoxy(3-vinylphenyl)silane, dimethylethoxy(3-vinylphenyl)silane, dimethylpropoxy( 3-vinylphenyl)silane, dimethylbutoxy(3-vinylphenyl)silane, dimethylisopropoxy(3-vinylphenyl)silane, dimethylmethoxy(2-vinylphenyl)silane, dimethylethoxy(2-vinylphenyl) Silane, dimethylpropoxy(2-vinylphenyl)silane, dimethylbutoxy(2-vinylphenyl)silane, dimethylisopropoxy(2-vinylphenyl)silane, trimethoxy(4-isopropenylphenyl)silane, tri Ethoxy (4-isopropenylphenyl) silane, tripropoxy (4-isopropenylphenyl) silane, tributoxy (4-isopropenylphenyl) silane, triisopropoxy (4-isopropenylphenyl) Silane, trimethoxy (3-isopropenylphenyl) silane, triethoxy (3-isopropenylphenyl) silane, tripropoxy (3-isopropenylphenyl) silane, tributoxy (3-isopropenyl) Phenyl) silane, triisopropoxy (3-isopropenylphenyl) silane, trimethoxy (2-isopropenylphenyl) silane, triethoxy (2-isopropenylphenyl) silane, tripropoxy (2- Isopropenylphenyl)silane, tributoxy(2-isopropenylphenyl)silane, triisopropoxy(2-isopropenylphenyl)silane, dimethoxymethyl (4-isopropenylphenyl)silane, diethoxymethyl (4-isopropenylphenyl)silane, dipropoxymethyl (4-isopropenylphenyl)silane, dibutoxymethyl (4-isopropenylphenyl)silane, diisopropoxymethyl (4-isopropenylphenyl) Silane, dimethoxymethyl (3-isopropenylphenyl) silane, diethoxymethyl (3-isopropenylphenyl) silane, dipropoxymethyl (3-isopropenylphenyl) silane, dibutoxymethyl (3-isopro Phenylphenyl) silane, diisopropoxymethyl (3-isopropenylphenyl) silane, dimethoxymethyl (2-isopropenylphenyl) silane, diethoxymethyl (2-isopropenylphenyl) silane, dipropoxymethyl (2-isopropenylphenyl)silane, dibutoxymethyl (2-isopropenylphenyl)silane, diisopropoxymethyl (2-isopropenylphenyl)silane, dimethylmethoxy (4-isopropene) Nylphenyl)silane, dimethylethoxy(4-isopropenylphenyl)silane, dimethylpropoxy(4-isopropenylphenyl)silane, dimethylbutoxy(4-isopropenylphenyl)silane, dimethylisopropoxy(4 -Isopropenylphenyl)silane, dimethylmethoxy(3-isopropenylphenyl)silane, dimethylethoxy(3-isopropenylphenyl)silane, dimethylpropoxy(3-isopropenylphenyl)silane, dimethylbutoxy (3-isopropenylphenyl)silane, dimethylisopropoxy(3-isopropenylphenyl)silane, dimethylmethoxy(2-isopropenylphenyl)silane, dimethylethoxy(2-isopropenylphenyl)silane, Dimethylpropoxy(2-isopropenylphenyl)silane, dimethylbutoxy(2-isopropenylphenyl)silane, dimethylisopropoxy(2-isopropenylphenyl)silane, trichloro(4-vinylphenyl)silane, Trichloro(3-vinylphenyl)silane, trichloro(2-vinylphenyl)silane, tribromo(4-vinylphenyl)silane, tribromo(3-vinylphenyl)silane, tribromo(2-vinylphenyl)silane ) silane, dichloromethyl (4-vinylphenyl) silane, dichloromethyl (3-vinylphenyl) silane, dichloromethyl (2-vinylphenyl) silane, dibromomethyl (4-vinylphenyl) silane, dibromomethyl ( 3-vinylphenyl)silane, dibromomethyl(2-vinylphenyl)silane, dimethylchloro(4-vinylphenyl)silane, dimethylchloro(3-vinylphenyl)silane, dimethylchloro(2-vinylphenyl)silane, dimethyl and bromo(4-vinylphenyl)silane, dimethylbromo(3-vinylphenyl)silane, and dimethylbromo(2-vinylphenyl)silane.

Among these, trimethoxy(4-vinylphenyl)silane, triethoxy(4-vinylphenyl)silane, tripropoxy(4-vinylphenyl)silane, tributoxy(4-vinylphenyl)silane, triiso Propoxy (4-vinylphenyl) silane, trimethoxy (3-vinylphenyl) silane, triethoxy (3-vinylphenyl) silane, tripropoxy (3-vinylphenyl) silane, tributoxy (3-vinyl) Phenyl) silane, triisopropoxy (3-vinylphenyl) silane, and trichloro (4-vinylphenyl) silane are preferable, and trimethoxy (4-vinylphenyl) silane, triethoxy (4-vinylphenyl) silane , tripropoxy(4-vinylphenyl)silane, tributoxy(4-vinylphenyl)silane, and triisopropoxy(4-vinylphenyl)silane are more preferable.

Although not limited to the following as a branching agent represented by said Formula (2), For example, 1, 1-bis (4-trimethoxysilyl phenyl) ethylene, 1, 1-bis (4-triethoxy) Silylphenyl)ethylene, 1,1-bis(4-tripropoxysilylphenyl)ethylene, 1,1-bis(4-tripentoxysilylphenyl)ethylene, 1,1-bis(4-triisopropoxysilyl) Phenyl)ethylene, 1,1-bis(3-trimethoxysilylphenyl)ethylene, 1,1-bis(3-triethoxysilylphenyl)ethylene, 1,1-bis(3-tripropoxysilylphenyl) Ethylene, 1,1-bis(3-tripentoxysilylphenyl)ethylene, 1,1-bis(3-triisopropoxysilylphenyl)ethylene, 1,1-bis(2-trimethoxysilylphenyl)ethylene , 1,1-bis(2-triethoxysilylphenyl)ethylene, 1,1-bis(3-tripropoxysilylphenyl)ethylene, 1,1-bis(2-tripentoxysilylphenyl)ethylene, 1 ,1-bis(2-triisopropoxysilylphenyl)ethylene, 1,1-bis(4-(dimethylmethoxysilyl)phenyl)ethylene, 1,1-bis(4-(diethylmethoxysilyl)phenyl) ) Ethylene, 1,1-bis (4- (dipropylmethoxysilyl) phenyl) ethylene, 1,1-bis (4- (dimethylethoxysilyl) phenyl) ethylene, 1,1-bis (4- (di ethylethoxysilyl)phenyl)ethylene and 1,1-bis(4-(dipropylethoxysilyl)phenyl)ethylene.

Among these, 1,1-bis(4-trimethoxysilylphenyl)ethylene, 1,1-bis(4-triethoxysilylphenyl)ethylene, 1,1-bis(4-tripropoxysilylphenyl) Ethylene, 1,1-bis(4-tripentoxysilylphenyl)ethylene and 1,1-bis(4-triisopropoxysilylphenyl)ethylene are preferable, and 1,1-bis(4-trimethoxysilyl) Phenyl) ethylene is more preferable.

(weight average molecular weight)

The weight average molecular weight of the conjugated diene copolymer of the present embodiment is 45×10 ⁴ or more and 500×10 ⁴ or less, preferably 50×10 ⁴ or more, and more preferably 60×10 ⁴ or more. Further, the above weight average molecular weight is preferably 450 × 10 ⁴ or less, more preferably 400 × 10 ⁴ or less, more preferably 350 × 10 ⁴ or less.

When the weight average molecular weight is 45×10 ⁴ or more, it is excellent in abrasion resistance when it is set as a vulcanized product. In addition, when the weight average molecular weight is 500×10 ⁴ or less, the workability and dispersibility of the filler in the case of a vulcanized product are excellent, and practically sufficient breaking properties are obtained.

The weight average molecular weight of a conjugated diene polymer can be measured by the method as described in the Example mentioned later.

The weight average molecular weight of the conjugated diene-based polymer of the present embodiment can be controlled within the above numerical range by adjusting the addition amount of the polymerization monomer, polymerization temperature, polymerization time, and the like.

(absolute molecular weight)

The absolute molecular weight is measured by a GPC-light scattering method with a viscosity detector.

In general, a polymer having a branched structure tends to have a smaller molecular size when compared with a straight-chain polymer having the same molecular weight. Therefore, the molecular weight of the polymer is sieved, and the molecular weight of the polymer having a branched structure is too small in the polystyrene equivalent molecular weight obtained by gel permeation chromatography (hereinafter also referred to as "GPC"), which is a relative comparison with a standard polystyrene sample. tends to be overestimated.

On the other hand, according to the light scattering method, since the molecular weight (absolute molecular weight) is measured by directly observing the size of the molecule, it is not affected by the interaction with the polymer structure or the column filler, and the branched structure of the conjugated diene-based polymer, etc. It tends to be able to accurately measure molecular weight without being affected by the polymer structure.

The absolute molecular weight of the conjugated diene-based polymer of the present embodiment ^{is preferably 70 × 10 4} to 100 × 10 ⁵ from the viewpoint of tensile strength and abrasion resistance, more preferably 80 × 10 ⁴ to 500 × 10 ⁴ , It is more preferably 90×10 ⁴ to 350×10 ^{4 .}

The absolute molecular weight of the conjugated diene-based polymer can be controlled within the above numerical range by adjusting the addition amount of the polymerization initiator, the polymerization temperature, the polymerization time, the addition amount of the branching agent, and the like.

(Content of aromatic vinyl monomer unit)

The conjugated diene-type polymer of this embodiment may be the polymer of a conjugated diene compound, an aromatic vinyl compound, and a branching agent, and a copolymer of monomers other than these may be sufficient as it.

For example, when the conjugated diene monomer is butadiene or isoprene, and this and a branching agent containing a vinyl aromatic moiety are polymerized, the polymer chain is so-called polybutadiene or polyisoprene, and the branched moiety contains a structure derived from vinyl aromatics. become a polymer. By having such a structure, the linearity per one polymer chain improves, and the improvement of the crosslinking density after vulcanization becomes possible, and the effect of the improvement of abrasion resistance is exhibited. Therefore, the conjugated diene-type polymer of this embodiment is suitable for uses, such as a tire, resin modification, the interior and exterior of an automobile, a vibration-proof rubber, and footwear.

A copolymer of a conjugated diene compound, an aromatic vinyl compound, and a branching agent is suitable when the conjugated diene-based polymer is provided for use in the tread of tires. From such a viewpoint, in the conjugated diene-based polymer of the present embodiment, the content of the aromatic vinyl monomer unit is 30 to 45 mass%, and from the viewpoint of abrasion resistance and tensile strength, 32 mass% or more is preferable, and 34 mass% It is more preferable that it is more than it, and it is still more preferable that it is 36 mass % or more.

Moreover, from a fuel-efficient viewpoint, it is preferable that it is 43 mass % or less, and it is more preferable that it is 41 mass % or less.

The content of the aromatic vinyl monomer unit in the conjugated diene polymer can be controlled within the above numerical range by adjusting the amount of the aromatic vinyl monomer added in the polymerization step.

In the conjugated diene-based polymer of the present embodiment, the value of the content (mass %) of the aromatic vinyl monomer unit in the conjugated diene-based polymer is larger than the value of the amount of vinyl bonds (mol%) in the conjugated diene monomer unit. .

From this viewpoint, it is preferable that the value of the vinyl bond amount is small. As a method of reducing the value of the vinyl bond amount (mol%), it is effective to add a branching agent during polymerization of the conjugated diene-based polymer and perform the polymerization step while maintaining the randomization performance. Thereby, the value of content (mass %) of an aromatic vinyl monomeric unit is controllable to a thing larger than the amount of vinyl bonds (mol%) in a conjugated diene monomeric unit.

By reducing the value of the amount of vinyl bonds in the conjugated diene monomer unit, the molecular chain length of the conjugated diene compound can be lengthened, and when it is set as a vulcanized product, the tensile strength tends to be excellent.

The amount of vinyl bonds in the conjugated diene monomer unit is preferably 45 mol% or less, more preferably 40 mol% or less, still more preferably 35 mol% or less, and still more preferably 30 mol% or less.

Here, content (mass %) of an aromatic vinyl monomeric unit in the conjugated diene polymer of this embodiment can be measured by the ultraviolet absorption of a phenyl group, From this, content (mass %) of a conjugated diene monomeric unit can also be calculated|required. Specifically, it measures according to the method described in the Example mentioned later.

When the content (mass%) of the aromatic vinyl monomer unit is larger than the value of the amount of vinyl bonds (mol%) in the conjugated diene monomer unit, the vulcanized product tends to have excellent tensile strength and abrasion resistance.

Here, when the modified diene-based polymer is a copolymer of butadiene and styrene, the amount of vinyl bonds in the butadiene bonding unit (1,2-bonds) according to the Hampton method (RRHampton, Analytical Chemistry, 21, 923 (1949)). quantity) can be obtained. Specifically, it can measure by the method described in the Example mentioned later.

When the conjugated diene-based polymer of the present embodiment is a conjugated diene-aromatic vinyl copolymer, it is preferable that the number of blocks in which 30 or more aromatic vinyl units are chained is small or absent. More specifically, when the copolymer is a butadiene-styrene copolymer, the copolymer is decomposed by the method of Kolthoff (the method described in IMKOLTHOFF, et al., J. Polym. Sci. 1, 429 (1946)), In a known method for analyzing the amount of polystyrene insoluble in methanol, the block in which 30 or more aromatic vinyl units are chained 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-based polymer of the present embodiment is a conjugated diene-aromatic vinyl copolymer, from the viewpoint of improving fuel economy performance, it is preferable that the ratio in which the aromatic vinyl unit exists alone is higher.

Specifically, when the copolymer is a butadiene-styrene copolymer, the copolymer is decomposed by ozone decomposition known as the method of Tanaka et al. (Polymer, 22, 1721 (1981)), and the styrene chain is decomposed by GPC. When distribution is analyzed, it is preferable that the amount of isolated styrene is 40 mass % or more with respect to the total amount of combined styrene, and it is preferable that the chain styrene structure of 8 or more chains of styrene is 5.0 mass % or less.

In this case, the obtained vulcanized rubber has excellent performance with particularly low hysteresis loss.

[Method for Producing Conjugated Diene-Based Polymer]

The manufacturing method of the conjugated diene polymer of this embodiment is the above-mentioned weight average molecular weight, branching degree (Bn) is 7 or more, content of an aromatic vinyl monomeric unit is 30-45 mass %, Content of an aromatic vinyl monomeric unit (mass %) is larger than the value of the amount of vinyl bonds (mol%) in the conjugated diene monomer unit is a production method for obtaining a conjugated diene-based polymer, using an organolithium compound as a polymerization initiator, comprising a polar compound It has the process of adding a branching agent while superposing|polymerizing at least a conjugated diene compound and an aromatic vinyl compound in a solvent, and obtaining the conjugated diene type polymer which has a main chain branched structure.

The method for producing the conjugated diene-based polymer of the present embodiment uses an organolithium compound as a polymerization initiator, polymerizes at least a conjugated diene compound and an aromatic vinyl compound, and uses at least any of the aforementioned various branching agents to form a main chain branching structure. It is preferable to have a polymerization and branching step of obtaining a conjugated diene polymer having .

(Polymerization and Branching Process)

The polymerization and branching step in the method for producing the conjugated diene-based polymer of the present embodiment, for example, by using an organolithium compound as a polymerization initiator, polymerizing at least a conjugated diene compound and an aromatic vinyl compound, and adding a branching agent. , a step of obtaining a conjugated diene-based polymer having a branched main chain structure.

In a polymerization process, it is preferable to superpose|polymerize by the growth reaction by a living anionic polymerization reaction, and by this, the conjugated diene type polymer which has an active terminal can be obtained. After that, even in the branching step using a branching agent, main chain branching can be appropriately controlled, and by performing the coupling step, there is a tendency that a conjugated diene polymer having a high modification rate can be obtained.

<Polymerization Initiator>

As a polymerization initiator, it is preferable to use an organolithium compound and to use an organomonolithium compound at least.

Examples of the organomonolithium compound include, but are not limited to, low molecular weight compounds and solubilized organomonolithium compounds.

Further, examples of the organomonolithium compound include compounds having a carbon-lithium bond, a compound having a nitrogen-lithium bond, and a compound having a tin-lithium bond in the bonding mode between the organic group and the lithium. have.

The amount of the organic monolithium compound used as the polymerization initiator is preferably determined by the target conjugated diene polymer.

The usage-amount of monomers, such as a conjugated diene compound, with respect to the usage-amount of a polymerization initiator relates to the polymerization degree of the conjugated diene type polymer made into the objective. That is, it tends to relate to a number average molecular weight and/or a weight average molecular weight.

Therefore, in order to increase the molecular weight of the conjugated diene-based polymer, the amount of the polymerization initiator may be adjusted in a direction to decrease, and in order to decrease the molecular weight, the amount of the polymerization initiator may be adjusted in a direction to increase.

From the viewpoint of being used as one method of introducing a nitrogen atom into the conjugated diene-based polymer, the organomonolithium compound is preferably an organomonolithium compound having a substituted amino group, for example, an alkyllithium compound having a substituted amino group. , or dialkylaminolithium.

In this case, a conjugated diene-based polymer having a nitrogen atom having an amino group at the polymerization initiating terminal is obtained. When the conjugated diene-based polymer obtained in the polymerization step has a nitrogen atom containing an amino group at the polymerization initiating terminal, a chain transfer reaction tends to occur when anionic polymerization proceeds, and a coupling agent or modifier for the active terminal after polymerization is completed. Therefore, it is difficult to obtain a sufficient reaction amount and the absolute molecular weight tends to be small. Therefore, from the viewpoint of tensile strength and abrasion resistance when the conjugated diene-based copolymer of the present embodiment is used as a vulcanized product, it is preferable to select a polymerization temperature that can control the chain transfer reaction and to perform polymerization.

The substituted amino group is an amino group having no active hydrogen or a structure in which active hydrogen is protected.

Examples of the alkyllithium compound having an amino group having no active hydrogen include, but are not limited to, 3-dimethylaminopropyllithium, 3-diethylaminopropyllithium, 4-(methylpropylamino)butyllithium, and 4-hexamethyleneiminobutyllithium is mentioned.

Although not limited to the following as an alkyllithium compound which has the amino group of the structure which protected the active hydrogen, For example, 3-bistrimethylsilylaminopropyl lithium and 4-trimethylsilyl methylamino butyl lithium are mentioned.

Examples of dialkylaminolithium include, but are not limited to, lithium dimethylamide, lithium diethylamide, lithium dipropylamide, lithium dibutylamide, lithium di-n-hexylamide, lithium diheptylamide, lithium Diisopropylamide, lithium dioctylamide, lithium-di-2-ethylhexylamide, lithium didecylamide, lithium ethylpropylamide, lithium ethylbutylamide, lithium ethylbenzylamide, lithium methylphenethylamide, lithium hexamethylene Mead, lithium pyrrolidide, lithium piperidide, lithium heptamethyleneimide, lithium morpholide, 1-lithioazacyclooctane, 6-lithio-1,3,3-trimethyl-6-azabicyclo[3.2 .1]octane, and 1-lithio-1,2,3,6-tetrahydropyridine.

The organomonolithium compound having these substituted amino groups is prepared by reacting a small amount of a polymerizable monomer, for example, a monomer such as 1,3-butadiene, isoprene, or styrene, and solubilizing it in n-hexane or cyclohexane. can also be used as

The organomonolithium compound is preferably an alkyllithium compound from the viewpoints of industrial availability and easy control of polymerization reaction. In this case, a conjugated diene-based polymer having an alkyl group at the polymerization initiating 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 stilbenelithium. have.

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

These organomonolithium 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 said other organometallic compound, an alkaline-earth metal compound, another alkali metal compound, and another organometallic compound are mentioned, for example.

Although it is not limited to the following as an alkaline-earth metal compound, For example, an organomagnesium compound, an organocalcium compound, and an organostrontium compound are mentioned. Moreover, the compound of the alkoxide of an alkaline-earth metal, a sulfonate, a carbonate, and an amide is also mentioned.

Examples of the organomagnesium compound include dibutylmagnesium and ethylbutylmagnesium. As another organometallic compound, an organoaluminum compound is mentioned, for example.

Polymerization process WHEREIN: Although it is not limited to the following as a polymerization reaction mode, For example, the polymerization reaction mode of a batch type (it is also called "batch type") and a continuous type is mentioned.

In continuous mode, one or two or more connected reactors may be used. The continuous reactor is, for example, a tank equipped with a stirrer or a tubular one. In the continuous mode, preferably, a monomer, an inert solvent, and a polymerization initiator are continuously fed to the reactor to obtain a polymer solution containing a polymer in the reactor, and the polymer solution is continuously discharged.

As the batch-type reactor, for example, a tank-type reactor equipped with a stirrer is used. In the batch mode, preferably, a monomer, an inert solvent, and a polymerization initiator are fed, and if necessary, the monomer is added continuously or intermittently during polymerization to obtain a polymer solution containing the polymer in the reactor, and the polymerization is terminated. Afterwards, the polymer solution is discharged.

In the method for producing the conjugated diene-based polymer of the present embodiment, in order to obtain a conjugated diene-based polymer having an active terminal at a high ratio, the continuous method is preferable, in which the polymer can be continuously discharged and subjected to the next reaction in a short time. .

It is preferable to superpose|polymerize in an inert solvent, and, as for the polymerization process of a conjugated diene type polymer, the solvent which is compatible with the said conjugated diene type polymer is more preferable.

As a preferable solvent, hydrocarbon solvents, such as a saturated hydrocarbon and an aromatic hydrocarbon, are mentioned, for example. Specific examples of the hydrocarbon-based 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.

By treating impurities such as allenes and acetylenes with an organometallic compound before being subjected to polymerization, a conjugated diene polymer having a high concentration of active ends tends to be obtained, and a modified conjugated diene polymer having a high modification rate is obtained. It is preferable because it tends to

<Polar compound (polar substance)>

In the polymerization step, at least a conjugated diene compound and an aromatic vinyl compound are polymerized in a solvent containing a polar compound (sometimes referred to as a polar substance in this specification) using the organolithium compound described above as a polymerization initiator. , a branching agent is added to obtain a conjugated diene-based polymer having a branched main chain structure.

By adding the polar compound to the solvent, the aromatic vinyl compound can be randomly copolymerized with the conjugated diene compound, and also tends to function effectively as a vinylating agent for controlling the microstructure of the conjugated diene moiety.

Moreover, in the polymerization of a conjugated diene compound, a polar compound tends to be effective also in the acceleration|stimulation of a polymerization reaction, etc. Therefore, when industrially producing a conjugated diene-based polymer, it is common to add a certain amount of a polar compound to improve productivity.

In addition, in terms other than production efficiency, if the addition amount of the polar compound is reduced, the polymerization time is too long and the ratio of the active end of the polymer deactivated on the way increases, so that the ratio of low molecular weight components increases, or the coupling rate at the end of polymerization and / Or the bad effect that a denaturation rate cannot be raised, or it may generate|occur|produce. Conventionally, polymer designs have been used to branch a polymer chain by reacting a polyfunctional coupling agent containing nitrogen or the like at the end of polymerization. I can't do it according to the settings either. That is, since the vinylating agent also has the role of a polymerization accelerator, it was difficult to independently control the amount of vinyl bonds and the degree of branching and/or the rate of modification.

On the other hand, as in the production method of the present embodiment, by branching the polymer chain with a branching agent, the formation of a branched structure does not depend only on the coupling reaction of the active end of the polymer. It is possible to manufacture a polymer with a high degree of branching even if the addition amount of the agent is reduced. Therefore, while controlling the weight average molecular weight to 45×10 ⁴ or more and 500×10 ⁴ or less, the content of the aromatic vinyl monomer unit in the conjugated diene-based polymer is in the range of 30 to 45 mass%, and the degree of branching (Bn) is 7 As mentioned above, the value of content (mass %) of an aromatic vinyl monomeric unit is larger than the value of the value of the amount of vinyl bonds (mol%) in a conjugated diene monomeric unit, and manufacture of a conjugated diene type polymer is also industrially possible.

Although not limited to the following as a polar compound, For example, 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 quinuclidine; alkali metal alkoxide compounds such as potassium-tert-amylate, potassium-tert-butyrate, sodium-tert-butyrate, and sodium amylate; Phosphine compounds, such as triphenylphosphine, etc. can be used.

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

Many polar compounds have an effective randomizing effect in the copolymerization of a conjugated diene compound and an aromatic vinyl compound at the same time, and there exists a tendency which can be used as a control agent for distribution adjustment of an aromatic vinyl monomer unit, or a styrene block amount.

The amount of the polar compound used is correlated with the polymer active end amount, and the polymer active end amount depends on the amount of the polymerization initiator.

0.01 mol or more and 1 mol or less are preferable with respect to 1 mol of polymerization initiator, and, as for the usage-amount of a polar compound, 0.1 mol or more and 0.8 mol or less are preferable.

By setting it as below the said upper limit, in the conjugated diene polymer of this embodiment, content (mass %) of an aromatic vinyl monomeric unit is 30-45 mass %, and the value of content (mass %) of an aromatic vinyl monomer unit is conjugated. A conjugated diene-based polymer larger than the value of the amount of vinyl bonds (mol%) in the diene monomer unit is obtained. Moreover, by setting it as more than a lower limit, it is easy to hold|maintain an active end of a polymer, a polymerization reaction is accelerated|stimulated and the coupling rate of the terminal improves. The content of the aromatic vinyl monomer unit in the conjugated diene polymer is set to be 30 mass % or more from the viewpoint of abrasion resistance and tensile strength, preferably 32 mass % or more, more preferably 34 mass % or more, more preferably 36 mass % or more desirable.

As a method of randomizing the conjugated diene compound and the aromatic vinyl compound, for example, as described in Japanese Patent Laid-Open No. 59-140211, a copolymerization reaction is initiated with the whole amount of styrene and a part of 1,3-butadiene, , a method in which the remaining 1,3-butadiene is intermittently added during the copolymerization reaction may be used.

<Addition of branching agent>

In the method for producing the conjugated diene polymer of the present embodiment, a branching agent is added while polymerizing the conjugated diene compound and the aromatic vinyl compound as described above to obtain a conjugated diene polymer having a branched main chain structure.

The addition amount of the branching agent is not particularly limited and can be selected depending on the purpose, etc., It is preferably 0.03 mol or more and 0.5 mol or less, more preferably 0.05 mol or more and 0.4 mol or less, and 0.01 mol or more and 0.25 mol or less with respect to 1 mol of polymerization initiator. more preferably.

The branching agent can be used in an appropriate amount according to the number of branching points of the main chain branching structure of the conjugated diene moiety of the target conjugated diene-based polymer.

In addition, by adding a branching agent during polymerization of the conjugated diene-based polymer, the active end of the conjugated diene-based polymer can be reduced from the amount of the polymerization initiator added, and the active end of the polymer is maintained by the polar compound at least promoting the reaction at the initial stage of polymerization. do. Thereby, it is possible to obtain a conjugated diene-based polymer in which the content (mass%) of the aromatic vinyl monomer unit is larger than the value of the vinyl bond amount (mol%) of the conjugated diene monomer unit, and the coupling rate or the modification rate is A high conjugated diene polymer can be obtained, and furthermore, the branching degree (Bn) of the conjugated diene polymer can be 7 or more.

When the branching agent is not added, the randomization ability of the aromatic vinyl compound and the conjugated diene compound becomes small even when the amount of the polar compound to be added to achieve a predetermined microstructure ratio is selected, and the content of the above-described aromatic vinyl monomer unit is 30 to 45 In the mass % conjugated diene-based polymer, the polymerization terminal tends to be an aromatic vinyl monomer unit. In such a state, it tends to be difficult to obtain a conjugated diene-based polymer having a high coupling rate or modification rate, and it tends to be difficult to set the branching degree (Bn) to 7 or more.

The present inventors, as mentioned above, in the conjugated diene-type polymer whose content of an aromatic vinyl monomer unit is 30-45 (mass %) WHEREIN: As a result of changing the addition amount of a polar compound and studying, the vinyl bond amount of a conjugated diene monomer unit It was discovered that there was a tendency for the tensile strength and abrasion resistance to be excellent, so that there were few (mol%).

In particular, when compared with the conjugated diene polymer of the same glass transition temperature, the content (mass %) of the aromatic vinyl monomer unit is greater than the value of the vinyl bond amount (mol %) of the conjugated diene monomer unit. and excellent wear resistance.

In the process of designing and manufacturing a normal conjugated diene-based polymer, the content of the aromatic vinyl monomer unit is set by mass and the amount of vinyl bonds is set in mol%, so it is arithmetic to compare these absolute values Although it is difficult to think that there is, as a result of repeated experiments by varying the addition amount of the polar compound in the polymerization step, the value of (mass %) of the aromatic vinyl monomer unit and the vinyl bond amount (mol %) of the conjugated diene monomer unit was compared, and when the value of content of an aromatic vinyl monomeric unit was large, it discovered that the tensile strength and abrasion resistance of the polymer of this embodiment were high.

The timing of adding the branching agent is not particularly limited and can be selected depending on the purpose, etc., but from the viewpoint of improving the absolute molecular weight of the conjugated diene-based polymer and improving the modification rate, the timing after the polymerization initiator is added is the timing of the raw material conversion rate of 20% or more. It is preferable, and it is more preferable that it is 40 % or more, It is more preferable that it is 50 % or more, It is still more preferable that it is 65 % or more, It is still more preferable that it is 75 % or more.

By setting it as the said range, even when there is little amount of a polar compound, the conjugated diene type polymer of a high modification rate is obtained.

In addition, after adding a branching agent, a desired monomer may be added by lot, and a polymerization process may be continued after branching, and the content described above may be repeated.

The monomer to be added is not particularly limited, but from the viewpoint of improving the modification rate of the conjugated diene polymer, the total amount of the conjugated diene monomer used in the polymerization step, for example, 5% or more of the total amount of butadiene is preferable, and 10% or more More preferably, it is more preferable that it is 15 % or more, It is still more preferable that it is 20 % or more, It is still more preferable that it is 25 % or more.

When the amount of the monomer to be added is within the above range, the molecular weight between the branching point by the branching agent and the branching point by the coupling agent becomes long, and it tends to take a molecular structure with high linearity.

By setting it as a molecular structure with high linearity, entanglement between molecular chains of a conjugated diene polymer increases when it is set as a vulcanizate, and there exists a tendency for a rubber composition excellent in abrasion resistance, handling stability, and breaking strength to be obtained.

The polymerization temperature in the polymerization step is preferably a temperature at which living anionic polymerization proceeds, more preferably 0°C or higher, and still more preferably 120°C or lower from the viewpoint of productivity. By being in such a range, there exists a tendency that the reaction amount of the modifier with respect to the active terminal after completion|finish of polymerization can fully be ensured. More preferably, it is 50 degreeC or more and 100 degrees C or less.

Moreover, it is preferable that it is 60 degreeC or more from a viewpoint of fully completing the polymerization reaction of the aromatic vinyl monomer in the conjugated diene polymer of this embodiment, and controlling content of an aromatic vinyl monomer unit to 30-45 mass %, and it is 65 degreeC or more. It is more preferable, and it is still more preferable that it is 70 degreeC or more.

In the manufacturing method of the conjugated diene polymer of this embodiment, the addition amount of the branching agent in the branching process of forming a main chain branched structure is as above-mentioned.

The branching agent is a branching point of the main chain branching structure of the conjugated diene portion of the conjugated diene-based polymer, and may be used in an appropriate amount depending on the desired number of branching points.

(Coupling process)

In the manufacturing method of the conjugated diene type polymer of this embodiment, it is preferable to have the coupling process of coupling the conjugated diene type polymer obtained through the polymerization and branching process mentioned above with a coupling agent.

As the coupling step, for example, a reactive compound having a bifunctional or higher function with respect to the active terminal of the conjugated diene polymer (hereinafter also referred to as a “coupling agent”) is used, or a modifier having a nitrogen atom-containing group is used. The coupling process performed is preferable.

In the coupling step, for example, a coupling reaction can be carried out with a coupling agent or a modifier having a nitrogen atom-containing group with respect to one end of the active terminal of the conjugated diene-based polymer to obtain a conjugated diene-based polymer.

<Coupling agent>

When the manufacturing method of the conjugated diene polymer of this embodiment has a coupling process, A coupling agent is although it does not specifically limit, As long as it is a bifunctional or more than reactive compound, what kind of structure can be used suitably, and it can use the bifunctional thing which has a nitrogen atom. The above reactive compounds are more preferable.

<A modifier having a nitrogen atom-containing group>

The modifier having a nitrogen atom-containing group is not limited to the following, but for example, an isocyanate compound, an isothiocyanate compound, an isocyanuric acid derivative, a carbonyl compound having a nitrogen atom-containing group, and a vinyl compound having a nitrogen atom-containing group. , and an epoxy compound having a nitrogen atom-containing group.

In the modifier having a nitrogen atom-containing group, the nitrogen atom-containing group is preferably an amine compound having no active hydrogen, and as the modifier having a nitrogen atom-containing group, for example, a tertiary amine compound, the active hydrogen and a protective amine compound substituted with a protecting group, an imine compound represented by the general formula -N=C, and an alkoxysilane compound bonded to the nitrogen atom-containing group.

Although not limited to the following as an isocyanate compound which is a modifier which has a nitrogen atom containing group, For example, 2, 4- tolylene diisocyanate, 2, 6-tolylene diisocyanate, diphenylmethane diisocyanate, Polymeric type diphenyl Methane diisocyanate (C-MDI), phenyl isocyanate, isophorone diisocyanate, hexamethylene diisocyanate, butyl isocyanate, 1,3,5-benzene triisocyanate, etc. are mentioned.

Although not limited to the following as an isocyanuric acid derivative which is a modifier which has a nitrogen atom containing group, For example, 1,3,5-tris(3-trimethoxysilylpropyl)isocyanurate, 1,3, 5-tris(3-triethoxysilylpropyl)isocyanurate, 1,3,5-tri(oxiran-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-trione etc. are mentioned.

Examples of the carbonyl compound as a denaturant having a nitrogen atom-containing group include, but are not limited to, 1,3-dimethyl-2-imidazolidinone and 1-methyl-3-ethyl-2-imidazolidinone. , 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-pyridyl ketone, methyl-4-pyridyl ketone, propyl-2-pyridyl ketone, Di-4-pyridyl ketone, 2-benzoylpyridine, N,N,N',N'-tetramethylurea, N,N-dimethyl-N',N'-diphenylurea, N,N-diethylcarin methyl bamate, N,N-diethylacetamide, N,N-dimethyl-N',N'-dimethylaminoacetamide, N,N-dimethylpicolinic acid amide, N,N-dimethylisonicotinic acid amide, etc. can

Although not limited to the following as a vinyl compound which is a modifier which has a nitrogen atom containing group, For example, N,N- dimethyl acrylamide, N,N- dimethylmethacrylamide, N-methylmaleimide, N-methylphthal Mead, 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-dimethylaminophenyl)ethylene etc. are mentioned.

Although not limited to the following as an epoxy compound which is a modifier which has a nitrogen atom containing group, For example, the epoxy group containing hydrocarbon compound couple|bonded with the amino group is mentioned, Furthermore, you may have the epoxy group couple|bonded with the ether group. Although not limited to the following as such an epoxy compound, For example, the epoxy compound represented by General formula (i) is mentioned.

In the formula (i), R ⁷ is a divalent hydrocarbon group, a polar group having oxygen such as ether, epoxy, ketone, and ketone, a polar group having sulfur such as thioether or thioketone, a tertiary amino group, already It is a divalent organic group which has at least 1 sort(s) of polar group chosen from the group which consists of polar groups which have nitrogen, such as a no group.

The divalent 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 C1-C20 divalent hydrocarbon group. 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 the formula (i), R ⁸ and R ⁶ represent a hydrogen atom, a monovalent alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and R ⁸ and R ⁶ may be the same as or different from each other.

R ⁹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a structure of the following formula (ii).

R ⁸ and R ⁶ may have a cyclic structure bonded to each other.

Moreover, when R<^9> is a monovalent|monohydric hydrocarbon group, the cyclic structure couple|bonded with ^{R<8> may be sufficient.} However, the N and R ⁸ is bonded to the R ⁹ only when the direct bond, R ⁹ may be either a hydrogen atom.

In said formula (i), o is an integer of 1 or more.

In said formula (ii), R<^1> , R<^2> is respectively defined similarly to ^R<7> , R<^8> of said formula (i). R ¹ , R ² may be the same as or different from ^{R 7} and R ^{8 , respectively.}

As an epoxy compound which is a modifier which has a nitrogen atom containing group, Especially preferably, it is a compound which has one or more diglycidylamino groups and one or more glycidoxy groups in a molecule|numerator.

Although it is not limited to the following as an epoxy compound used as a modifier which has a nitrogen atom containing group, For example, N,N- diglycidyl-4-glycidoxyaniline, 1-N,N- diglycidyl Aminomethyl-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-diglycidylaniline, 4,4'-diglycidyl-dibenzylmethylamine, N, N-diglycidylaniline, N,N-diglycidylorthotoluidine, N,N-diglycidylaminomethylcyclohexane, etc. are mentioned. Among these, N,N-diglycidyl-4-glycidoxyaniline and 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane are mentioned as especially preferable.

Although not limited to the following as an alkoxysilane compound which is a modifier which has a nitrogen atom containing group, For example, 3-dimethylaminopropyl trimethoxysilane, 3-dimethylamino propylmethyl dimethoxysilane, 3-diethylamino propyl tri Ethoxysilane, 3-morpholinopropyltrimethoxysilane, 3-piperidinopropyltriethoxysilane, 3-hexamethyleneiminopropylmethyldiethoxysilane, 3-(4-methyl-1-piperazino ) propyltrimethoxysilane, 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 -Trimethoxysilylpropyl)-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-silacyclo Octane, 2,2-dimethoxy-8-(N,N-diethylamino)methyl-1,6-dioxa-2-silacyclooctane, etc. are mentioned.

As a protective amine compound capable of forming a primary or secondary amine as a modifier having a nitrogen atom-containing group, the compound having an unsaturated bond and a protective amine in its molecule is not limited to the following, but for example, 4,4'-vinylidenebis[N,N-bis(trimethylsilyl)aniline], 4,4'-vinylidenebis[N,N-bis(triethylsilyl)aniline], 4,4'-vinylidene bis[N,N-bis(t-butyldimethylsilyl)aniline], 4,4'-vinylidenebis[N-methyl-N-(trimethylsilyl)aniline], 4,4'-vinylidenebis[N- ethyl-N-(trimethylsilyl)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(trimethylsilyl)aminophenyl]-1-[4-N,N-dimethylaminophenyl]ethylene; and the like.

As a protective amine compound which is a modifier having a nitrogen atom-containing group and capable of forming primary or secondary amine, the compound having an alkoxysilane and a protective amine in the molecule 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)propyl Methyldiethoxysilane, 3-(3-trimethylsilyl-1-hexahydropyrimidinyl)propyltrimethoxysilane, 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-trimethoxy Silylbutyl)-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, N-(1,3-dimethylbutylidene)-3-methyl(dimethoxysilyl)-1-propanamine, N-(1,3-dimethylbutylidene)-3-methyl ( diethoxysilyl)-1-propanamine, N-(1-methylethylidene)-3-(triethoxysilyl)-1-propanamine, N-(1-methylethylidene)-3-(tri Methoxysilyl)-1-propanamine, N-(1-methylethylidene)-3-methyl(dimethoxysilyl)-1-propanamine, N-(1-methylethylidene)-3-methyl ( diethoxysilyl)-1-propanamine, N-ethylidene-3-(triethoxysilyl)-1-propanamine, N-ethylidene-3-(trimethoxysilyl)-1-propanamine, N- Ethylene-3-methyl (dimethoxysilyl) -1-propanamine, N-ethylidene-3-methyl (diethoxysilyl) -1-propanamine is mentioned.

Further, as a protective amine compound capable of forming a primary or secondary amine as a modifier having a nitrogen atom-containing group, as a compound having an alkoxysilane and a protective amine in the molecule, N-(1-methylpropylidene) -3-(triethoxysilyl)-1-propanamine, N-(1-methylpropylidene)-3-(trimethoxysilyl)-1-propanamine, N-(1-methylpropylidene)-3 -Methyl (dimethoxysilyl) -1-propanamine, N- (1-methylpropylidene) -3-methyl (diethoxysilyl) -1-propanamine, N-benzylidene-3-methyl (dimethoxysilyl) Propan-1-amine, N-benzylidene-3-methyl(diethoxysilyl)propan-1-amine, N-4-methylbenzylidene-3-(triethoxysilyl)propan-1-amine, N-4 -Methylbenzylidene-3-(trimethoxysilyl)propan-1-amine, N-4-methylbenzylidene-3-methyl(dimethoxysilyl)propan-1-amine, N-4-methylbenzylidene-3 -Methyl (diethoxysilyl) propan-1-amine, N-naphthylidene-3- (triethoxysilyl) propan-1-amine, N-naphthylidene-3- (trimethoxysilyl) propane-1 -amine, N-naphthylidene-3-methyl (dimethoxysilyl) propan-1-amine, -1,1- (1,4-phenylene) bis (N- (3-methyl (dimethoxysilyl) propyl ) methanamine), 1,1- (1,4-phenylene) bis (N- (3-methyl (diethoxysilyl) propyl) methanamine), 2-ethoxy-2-methyl-1- (benzylidene) aminoethyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-(methylisobutylideneaminoethyl)-1-aza-2-silacyclopentane, and the like.

Particularly preferred examples of the alkoxysilane compound as a modifier having a nitrogen atom-containing group include, but are not limited to, tris(3-trimethoxysilylpropyl)amine, tris(3-triethoxysilylpropyl)amine, Tris(3-tripropoxysilylpropyl)amine, bis(3-trimethoxysilylpropyl)-[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]amine, 3- (4-methylpiperazin-1-yl)propyltrimethoxysilane, 3-(4-methylpiperazin-1-yl)propyltriethoxysilane, tetrakis(3-trimethoxysilylpropyl)-1, 3-propanediamine, tris(3-trimethoxysilylpropyl)-[3-(1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane)propyl]-1,3-propanediamine; Tris(3-trimethoxysilylpropyl)-[3-(1-methoxy-2-methyl-1-sila-2-azacyclopentane)propyl]-1,3-propanediamine, bis(3-trie Toxysilylpropyl)-[3-(2,2-diethoxy-1-aza-2-silacyclopentane)propyl]-[3-(1-ethoxy-2-trimethylsilyl-1-sila-2-aza) Cyclopentane)propyl]-1,3-propanediamine, tetrakis(3-trimethoxysilylpropyl)-1,3-bisaminomethylcyclohexane, tris(3-trimethoxysilylpropyl)-[3-( 2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-1,3-bisaminomethylcyclohexane.

Further, particularly preferred examples of the alkoxysilane compound as a modifier having a nitrogen atom-containing group include tetrakis(3-trimethoxysilylpropyl)-1,6-hexamethylenediamine and pentakis(3-trimethoxysilylpropyl)-di Ethylenetriamine, tris(3-trimethoxysilylpropyl)-methyl-1,3-propanediamine, tetrakis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]silane , bis(3-trimethoxysilylpropyl)-bis[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, 3-tris[2-(2,2-dimethoxy-1-aza-2-silacyclopentane) )ethoxy]silyl-1-trimethoxysilylpropane, 1-[3-(1-methoxy-2-trimethylsilyl-1-sila-2-azacyclopentane)propyl]-3,4,5-tris (3-trimethoxysilylpropyl)-cyclohexane, 1-[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-3,4,5-tris(3-tri Methoxysilylpropyl)-cyclohexane, 3,4,5-tris(3-trimethoxysilylpropyl)-cyclohexyl-[3-(2,2-dimethoxy-1-aza-2-silacyclopentane) Propyl]ether, (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, tris[3-(2,2-dimethoxy-1) -aza-2-silacyclopentane)propyl]phosphate, N-(1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propanamine, N-(1,3-dimethylbutylidene) den)-3-(trimethoxysilyl)-1-propanamine, N-benzylidene-3-(triethoxysilyl)propan-1-amine, N-benzylidene-3-(trimethoxysilyl)propane -1-amine, 1,1-(1,4-phenylene)bis(N-(3(triethoxysilyl)propyl)methanamine), 1,1-(1,4-phenylene)bis(N -(3(trimethoxy Silyl) propyl) methanamine), 2-methoxy-2-methyl-1- (benzylideneaminoethyl) -1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1- (4- methoxybenzylideneaminoethyl)-1-aza-2-silacyclopentane.

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

(Preferred structure of conjugated diene-based polymer)

It is preferable that the conjugated diene polymer of this embodiment contains the structure derived from the compound which has a nitrogen atom containing group represented by either of following general formula (i) or (A)-(E).

In the formula (i), R ⁷ is a divalent hydrocarbon group, a polar group having oxygen such as ether, epoxy, ketone, and ketone, a polar group having sulfur such as thioether or thioketone, a tertiary amino group, already It is a divalent organic group which has at least 1 sort(s) of polar group chosen from the group which consists of polar groups which have nitrogen, such as a no group.

The divalent 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 C1-C20 divalent hydrocarbon group. 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 the formula (i), R ⁸ and R ⁶ represent a hydrogen atom or a monovalent alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R ^{8 and R 6} may be the same as or different from each other. .

R ⁹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a structure of the following formula (ii).

R ⁸ and R ⁶ may have a cyclic structure bonded to each other.

Moreover, when R<^9> is a monovalent|monohydric hydrocarbon group, the cyclic structure couple|bonded with ^{R<8> may be sufficient.} However, the N and R ⁸ is bonded to the R ⁹ only when the direct bond, R ⁹ may be either a hydrogen atom. In formula (i), o is an integer of 1 or more.

In said formula (ii), R<^1> , R<^2> is respectively defined similarly to ^R<7> , R<^8> of said formula (i). R ¹ , R ² may be the same as or different from ^{R 7} and R ^{8 , respectively.}

(In formula (A), R ¹² to R ¹⁵ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, R ¹⁶ represents an alkylene group having 1 to 10 carbon atoms, R ¹⁷ represents a C1-C20 alkylene group.

q represents the integer of 1 or 2, r represents the integer of 2 or 3, and (q+r) represents the integer of 4 or more. In the case of two or more, R ¹² to R ¹⁵ are each independent.)

(In formula (B), R ¹⁸ to R ²³ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ²⁴ to R ²⁶ are each independently, each independently having 1 to 20 carbon atoms represents an alkylene group.

s, t, and u each independently represent the integer of 1-3, and (s+t+u) represents the integer of 4 or more. In the case of two or more, R ¹⁸ to R ²³ are each independent.)

(In the formula (C), R ²⁷ to R ²⁹ each independently represent a single bond or an alkylene group having 1 to 20 carbon atoms, and R ³⁰ to R ³³ and R ³⁵ are each independently independently from 1 to 20 carbon atoms. represents an alkyl group, R ³⁴ and R ³⁷ each independently represent an alkylene group ^{having 1 to 20 carbon atoms, and R 36} represents an alkyl group having 1 to 20 carbon atoms or a trialkylsilyl group.

w represents the integer of 1-3, and x represents 1 or 2.

In the case of two or more R ²⁷ to R ³⁷ , w and k, respectively, each is independent and may be the same or different.

i represents the integer of 0-6, j represents the integer of 0-6, k represents the integer of 0-6, (i+j+k) is the integer of 4-10.

A represents a hydrocarbon group having 1 to 20 carbon atoms, or an organic group having at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a silicon atom, a sulfur atom, and a phosphorus atom, and having no active hydrogen. )

(In formula (D), R ³⁶ represents an alkylene group having 1 to 20 carbon atoms, and R ³⁷ , R ³⁹ , and R ⁴⁰ are each independently an alkyl group having 1 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms. group, R ³⁸ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and z represents an integer of 1 to 3.)

^{R 41} to R ⁴⁴ in the formula (E) each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ⁴⁵ to R ⁴⁷ are each independently an alkyl group having 1 to 20 carbon atoms. Represents a rengi.

m and n represent the integers of 1-3, and may be same or different.

In the case of two or more, R ⁴¹ to R ⁴⁷ are each independent.

The modifier having a nitrogen atom-containing group represented by the formula (A) is not limited to the following, for example, 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-trimethoxy Silylbutyl)-1-aza-2-silacyclohexane, 2,2-dimethoxy-1-(5-trimethoxysilylpentyl)-1-aza-2-silacycloheptane, 2,2-dimethoxy- 1-(3-dimethoxymethylsilylpropyl)-1-aza-2-silacyclopentane, 2,2-diethoxy-1-(3-diethoxyethylsilylpropyl)-1-aza-2-silacyclopentane , 2-Methoxy-2-methyl-1-(3-trimethoxysilylpropyl)-1-aza-2-silacyclopentane, 2-ethoxy,2-ethyl-1-(3-triethoxysilyl Propyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-(3-dimethoxymethylsilylpropyl)-1-aza-2-silacyclopentane, and 2-ethoxy- 2-ethyl-1-(3-diethoxyethylsilylpropyl)-1-aza-2-silacyclopentane.

Among these, it is preferable that q represents 2 and r represents 3 from the viewpoint of reactivity and interaction with the functional group of the modifier having a nitrogen atom-containing group and inorganic filler such as silica, and from the viewpoint of processability. Specifically, 2,2-dimethoxy-1-(3-trimethoxysilylpropyl)-1-aza-2-silacyclopentane, and 2,2-diethoxy-1-(3-triethoxysilyl) propyl)-1-aza-2-silacyclopentane is preferred.

The reaction temperature, reaction time, etc., when the modifier having a nitrogen atom-containing group represented by the formula (A) is reacted with the active end of the polymer is not particularly limited, but reacts at 0°C or more and 120°C or less for 30 seconds or more It is preferable to do

The total number of moles of alkoxy groups bonded to silyl groups in the compound of the modifier having a nitrogen atom-containing group represented by the formula (A) is 0.6 times or more and 3.0 times or less the number of moles added to the alkali metal compound and/or alkaline earth metal compound of the polymerization initiator. It is preferable that it is a range which becomes 0.8 times or more and 2.5 times or less, and it is more preferable that it is a range used as 0.8 times or more and 2.0 times or less. From the viewpoint of obtaining a sufficient denaturation rate and molecular weight and branched structure of the obtained conjugated diene polymer, it is preferable to set it to 0.6 times or more, and it is preferable to obtain a branched polymer component by coupling the polymer ends to improve processability. , It is preferable to set it as 3.0 times or less from a viewpoint of a modifier cost.

More specifically, the number of moles of the polymerization initiator is preferably 3.0 moles or more, and more preferably 4.0 times moles or more with respect to the number of moles of the modifier.

Examples of the modifier having a nitrogen atom-containing group represented by the formula (B) include, but are not limited to, tris(3-trimethoxysilylpropyl)amine and tris(3-methyldimethoxysilylpropyl)amine. , tris(3-triethoxysilylpropyl)amine, tris(3-methyldiethoxysilylpropyl)amine, tris(trimethoxysilylmethyl)amine, tris(2-trimethoxysilylethyl)amine, and tris( 4-trimethoxysilylbutyl)amine is mentioned.

Among these, it is preferable that all of s, t, and u represent 3 from the viewpoint of the reactivity and interaction of the functional group of the modifier and the inorganic filler such as silica, and the viewpoint of workability. Preferred specific examples include tris(3-trimethoxysilylpropyl)amine and tris(3-triethoxysilylpropyl)amine.

The reaction temperature, reaction time, etc., when the modifier having a nitrogen atom-containing group represented by the formula (B) is reacted with the active end of the polymer is not particularly limited, but reacts at 0°C or more and 120°C or less for 30 seconds or more It is preferable to do

The total number of moles of alkoxy groups bonded to silyl groups in the compound of the modifier represented by the formula (B) is preferably in the range of 0.6 times or more and 3.0 times or less of the moles of lithium constituting the polymerization initiator, and 0.8 times or more. It is more preferable that it is the range used as 2.5 times or less, and it is still more preferable that it is the range used as 0.8 times or more and 2.0 times or less. In the conjugated diene-based polymer, from the viewpoint of obtaining a sufficient modification rate, molecular weight and branched structure, it is preferable to set it to 0.6 times or more, and in addition to that it is preferable to obtain a branched polymer component by coupling polymer ends to improve processability. , It is preferable to set it as 3.0 times or less from a viewpoint of a modifier cost.

Preferably the mole number of a more specific polymerization initiator is 4.0 times mole or more with respect to the mole number of a modifier, More preferably, it is 5.0 times mole or more.

In the formula (C), A is preferably represented by any of the following general formulas (II) to (V).

(In formula (II), B ¹ represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms, and a represents an integer of 1 to 10. B ¹ in the presence of two or more is each independent.)

(In the formula (III), B ² represents a single bond or a hydrocarbon group ^{having 1 to 20 carbon atoms, B 3} represents an alkyl group having 1 to 20 carbon atoms, and a represents an integer of 1 to 10. There are a plurality of each. B ² and B ^{3 in this case} are each independent.)

(In formula (IV), B ⁴ represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms, and a represents an integer of 1 to 10. B ⁴ in the presence of two or more is each independent.)

(In formula (V), B ⁵ represents a single bond or a hydrocarbon group having 1 to 20 carbon atoms, and a represents an integer of 1 to 10. B ⁵ in the presence of two or more is each independent.)

In the formula (C), the modifier having a nitrogen atom-containing group in the case where A is represented by the formula (II) is not limited to the following, for example, 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-sila) Cyclopentane)propyl]amine, tetrakis(3-trimethoxysilylpropyl)-1,3-propanediamine, tris(3-trimethoxysilylpropyl)-[3-(2,2-dimethoxy-1- Aza-2-silacyclopentane)propyl]-1,3-propanediamine, bis(3-trimethoxysilylpropyl)-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-trimethoxysilylpropyl)-[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-triethoxysilylpropyl)-1,3-propanediamine, tris(3-trie Toxysilylpropyl)-[3-(2,2-diethoxy-1-aza-2-silacyclopentane)propyl]-1,3-propanediamine, bis(3-triethoxysilylpropyl)-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-triethoxysilyl propyl)-[3-(1-ethoxy-2-trimethylsilyl-1-sila-2-azacyclopentane)propyl]-1,3-propanediamine.

Moreover, in said Formula (C), as a modifier which has a nitrogen-atom containing group in the case where A is represented by Formula (II), it is 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-Bisaminomethylcyclohexane, tris(3-trimethoxysilylpropyl)-[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-1,3-bis Aminomethylcyclohexane, 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-dimethoxy-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-propane Diamine, tris(3-triethoxysilylpropyl)-[3-(2,2-diethoxy-1-aza-2-silacyclopentane)propyl]-1,3-bisaminomethylcyclohexane, bis(3 -triethoxysilylpropyl)-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)propyl]-(3-triethoxysilylpropyl)-[3-(1-ethoxy-2-trimethylsilyl-1-sila-2-aza) Cyclopentane)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, and penta kiss(3-trimethoxysilylpropyl)-diethylenetriamine.

In the formula (C), the modifier having a nitrogen atom-containing group in the case where A is represented by the formula (III) 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-propane Diamine, bis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-(3-trimethoxysilylpropyl)-methyl-1,3-propanediamine, tris(3- Triethoxysilylpropyl)-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), and N ¹ -(3-(bis(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 (C), the modifier having a nitrogen atom-containing group in the case where A is represented by the formula (IV) 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-trimethoxysilylpropyl)-[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, and bis(3-trimethoxy silylpropyl)-bis[3-(1-methoxy-2-methyl-1-sila-2-azacyclopentane)propyl]silane.

In the formula (C), the modifier having a nitrogen atom-containing group in the case where A is represented by the formula (V) is not limited to the following, for example, 3-tris[2-(2,2-dime). Toxy-1-aza-2-silacyclopentane)ethoxy]silyl-1-(2,2-dimethoxy-1-aza-2-silacyclopentane)propane, and 3-tris[2-(2,2) -dimethoxy-1-aza-2-silacyclopentane)ethoxy]silyl-1-trimethoxysilylpropane.

In the formula (C), A is preferably represented by a formula (II) or a formula (III), and k represents 0.

Such a modifier having a nitrogen atom-containing group tends to be readily available, and tends to have better abrasion resistance and low hysteresis loss performance when a conjugated diene-based polymer is used as a vulcanized product. Examples of the modifier having a nitrogen atom-containing group include, but are not limited to, bis(3-trimethoxysilylpropyl)-[3-(2,2-dimethoxy-1-aza-2-silacyclo). Pentane)propyl]amine, tris(3-trimethoxysilylpropyl)amine, tris(3-triethoxysilylpropyl)amine, tris(3-trimethoxysilylpropyl)-[3-(2,2-dimethy oxy-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, and bis[3-(2,2-dimethoxy-1-aza-2-silacyclopentane)propyl]-(3-trismethoxysilylpropyl )-methyl-1,3-propanediamine.

In the formula (C), A is more preferably represented by formula (II) or formula (III), k represents 0, and in formula (II) or formula (III), a is, An integer of 2 to 10 is represented.

Thereby, there exists a tendency for it to become more excellent in abrasion resistance and low hysteresis loss performance at the time of vulcanization|vulcanization.

Examples of the modifier having a nitrogen atom-containing group 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, and N ¹ -(3 -(bis(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 is mentioned.

The addition amount of the compound represented by the formula (C) as the modifier having a nitrogen atom-containing group can be adjusted so that the modifier reacts so as to have a desired stoichiometric ratio with the moles of lithium constituting the polymerization initiator, thereby The desired star-like hyperbranching structure tends to be achieved.

The number of moles of lithium constituting the specific polymerization initiator is preferably 5.0 moles or more, more preferably 6.0 moles or more with respect to the number of moles of the modifier.

In this case, in Formula (C), it is preferable that it is an integer of 5-10, and, as for the number of functional groups ((w-1)xi+xxj+k) of a modifier, it is more preferable that it is an integer of 6-10.

The modifier having a nitrogen atom-containing group represented by the formula (D) is not limited to the following, for example, N-(1,3-dimethylbutylidene)-3-(triethoxysilyl)-1 -propanamine, N-(1,3-dimethylbutylidene)-3-(trimethoxysilyl)-1-propanamine, N-(1,3-dimethylbutylidene)-3-methyl(dimethoxy Silyl)-1-propanamine, N-(1,3-dimethylbutylidene)-3-methyl(diethoxysilyl)-1-propanamine, N-(1-methylethylidene)-3-(tri Ethoxysilyl)-1-propanamine, N-(1-methylethylidene)-3-(trimethoxysilyl)-1-propanamine, N-(1-methylethylidene)-3-methyl ( Dimethoxysilyl)-1-propanamine, N-(1-methylethylidene)-3-methyl(diethoxysilyl)-1-propanamine, N-ethylidene-3-(triethoxysilyl)-1 -Propanamine, N-ethylidene-3-(trimethoxysilyl)-1-propanamine, N-ethylidene-3-methyl(dimethoxysilyl)-1-propanamine, N-ethylidene-3-methyl (diethoxysilyl)-1-propanamine, N-(1-methylpropylidene)-3-(triethoxysilyl)-1-propanamine, N-(1-methylpropylidene)-3-(trimethyl Toxysilyl)-1-propanamine, N-(1-methylpropylidene)-3-methyl(dimethoxysilyl)-1-propanamine, N-(1-methylpropylidene)-3-methyl(diethoxysilyl )-1-propanamine, N-benzylidene-3-(triethoxysilyl)propan-1-amine, N-benzylidene-3-(trimethoxysilyl)propan-1-amine, N-benzylidene- 3-methyl(dimethoxysilyl)propan-1-amine, N-benzylidene-3-methyl(diethoxysilyl)propan-1-amine, N-4-methylbenzylidene-3-(triethoxysilyl)propane -1-amine, N-4-methylbenzylidene-3-(trimethoxysilyl)propan-1-amine, N-4-methylbenzylidene-3-methyl(dimethoxysilyl)propan-1-amine, N -4-methylbenzylidene-3-methyl(diethoxysilyl)propan-1-amine, N-naphthylidene-3-(triethoxysilyl)propan-1-amine, N-naphthylidene-3-( trimethoxysilyl)propan-1-amine, N-naphthylidene-3-methyl(dimethoxysilyl)propan-1-amine, and the like, and 1,1-(1,4-phenylene)bis( N-(3(triethoxysilyl)propyl)methanamine), 1,1-(1,4-phenylene) bis(N-(3(trimethoxysilyl)propyl)methanamine), 1,1-(1,4-phenylene)bis(N-(3-methyl(dimethoxysilyl)propyl)methanamine), 1 ,1-(1,4-phenylene)bis(N-(3-methyl(diethoxysilyl)propyl)methanamine), 2-methoxy-2-methyl-1-(benzylideneaminoethyl)-1- Aza-2-silacyclopentane, 2-methoxy-2-methyl-1-(p-methoxybenzylideneaminoethyl)-1-aza-2-silacyclopentane, 2-ethoxy-2-methyl-1 -(benzylideneaminoethyl)-1-aza-2-silacyclopentane, 2-methoxy-2-methyl-1-(methylisobutylideneaminoethyl)-1-aza-2-silacyclopentane; have.

The reaction temperature, reaction time, etc. when the modifier having a nitrogen atom-containing group represented by the formula (D) is reacted with the active end of the polymer is not particularly limited, but reacts at 0°C or more and 120°C or less for 30 seconds or more It is preferable to do

It is preferable that the total number of moles of alkoxy groups bonded to silyl groups in the compound of the modifier represented by the formula (D) is 0.2 times or more and 2.0 times or less of the moles of lithium constituting the polymerization initiator, 0.3 times or more. It is more preferable that it is the range used as 1.5 times or less. It is preferable to set it as 0.3 times or more from a viewpoint of obtaining sufficient denaturation rate and molecular weight in a conjugated diene polymer, and it is preferable to set it as 2.0 times or less from a viewpoint of a modifier cost.

More specifically, the number of moles of the polymerization initiator is preferably 0.5 moles or more, more preferably 1.0 times moles or more with respect to the number of moles of the modifier.

The modifier having a nitrogen atom-containing group represented by the formula (E) is not limited to the following, for example, N-(3-(1H-imidazol-1-yl)propyl)-3-(trie Toxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine, N-(3-(1H-imidazol-1-yl)propyl)-3-(trimethoxysilyl)- N-(3-(trimethoxysilyl)propyl)propan-1-amine, N-(3-(1H-imidazol-1-yl)propyl)-3-(ethyldiethoxysilyl)-N-(3 -(ethyldiethoxysilyl)propyl)propan-1-amine, N-(3-(1H-imidazol-1-yl)propyl)-3-(methyldimethoxysilyl)-N-(3-(methyldimethyl Toxysilyl)propyl)propan-1-amine, N-(3-(1H-imidazol-1-yl)propyl)-3-(diethylethoxysilyl)-N-(3-(diethylethoxysilyl) )propyl)propan-1-amine, N-(3-(1H-imidazol-1-yl)propyl)-3-(dimethylmethoxysilyl)-N-(3-(dimethylmethoxysilyl)propyl)propane -1-amines are mentioned.

The reaction temperature, reaction time, etc. when the modifier having a nitrogen atom-containing group represented by the formula (E) is reacted with the active end of the polymer is not particularly limited, but reacts at 0°C or more and 120°C or less for 30 seconds or more It is preferable to do

The total number of moles of alkoxy groups bonded to silyl groups in the compound of the modifier represented by the formula (E) is preferably in the range of 0.2 times or more and 2.0 times or less of the moles of lithium constituting the polymerization initiator, 0.3 times or more. It is more preferable that it is the range used as 1.5 times or less. It is preferable to set it as 0.3 times or more from a viewpoint of obtaining sufficient denaturation rate and molecular weight in a conjugated diene polymer, and it is preferable to set it as 2.0 times or less from a viewpoint of a modifier cost.

In the conjugated diene-based polymer of the present embodiment, the ratio of the nitrogen atom-containing polymer in the conjugated diene-based polymer is expressed by a modification rate.

The modification rate is preferably 60 mass% or more, more preferably 65 mass% or more, still more preferably 70 mass% or more, still more preferably 75 mass% or more, still more preferably 80 mass% or more, Especially preferably, it is 82 mass % or more.

When the modification rate is 60% by mass or more, the vulcanized product tends to be excellent in workability, and the vulcanized product tends to be more excellent in abrasion resistance and low hysteresis loss performance.

In this embodiment, after a coupling process or before a coupling process, you may perform the condensation reaction process made to carry out a condensation reaction in presence of a condensation accelerator.

The conjugated diene polymer of the present embodiment may hydrogenate the conjugated diene moiety.

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

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

Although it does not specifically limit as a catalyst, For example, Heterogeneous catalysts, such as a catalyst which supported the noble metal on the porous inorganic substance; Homogeneous catalysts, such as a catalyst made to solubilize salts, such as nickel and cobalt, and reacted with organic aluminum etc., and a catalyst using metallocenes, such as titanocene, are mentioned. Among these, a titanocene catalyst is preferable from a viewpoint of being able to select mild hydrogenation conditions.

In addition, hydrogenation of an aromatic group can be performed by using the 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 a metal such as Ni, Pt, Pd, and Ru is supported on carbon, silica, alumina, diatomaceous earth, or the like, (2) A so-called Ziegler type hydrogenation catalyst using an organic acid salt such as Ni, Co, Fe, Cr, or a transition metal salt such as acetylacetone salt, and a reducing agent such as organoaluminum; (3) an organometallic such as Ti, Ru, Rh, Zr So-called organometallic complexes, such as a compound, etc. are mentioned. In addition, although it does not specifically limit as a hydrogenation catalyst, For example, Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication Hei 1 The well-known hydrogenation catalysts described in Unexamined-Japanese-Patent No. -37970, Unexamined-Japanese-Patent No. 1-53851, Unexamined-Japanese-Patent No. 2-9041, and Unexamined-Japanese-Patent No. 8-109219 are also mentioned. As a preferable hydrogenation catalyst, the reaction mixture of a titanocene compound and a reducing organometallic compound is mentioned.

In the manufacturing method of the conjugated diene type polymer of this embodiment, you may add a deactivator, a neutralizing agent, etc. to a polymer solution after a coupling process as needed.

Although it does not restrict to the following as a deactivator, 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 versatic acid (a carboxylic acid mixture having 9 to 11 carbon atoms and having 10 carbon atoms as the center); The aqueous solution of an inorganic acid and carbon dioxide gas are mentioned.

In the manufacturing method of the conjugated diene polymer of this embodiment, it is preferable to add the stabilizer for rubber|gum from a viewpoint of preventing the formation of gel after polymerization, and a viewpoint of improving stability at the time of processing.

As a stabilizer for rubber, it is not limited to the following, Although a well-known thing can be used, For example, 2,6-di-tert-butyl-4-hydroxytoluene (it is also described as "BHT" hereafter), n -Oxidation of octadecyl-3-(4'-hydroxy-3',5'-di-tert-butylphenol)propionate, 2-methyl-4,6-bis[(octylthio)methyl]phenol, etc. An inhibitor is preferred.

[Conjugated diene-based polymer composition]

In order to further improve the productivity of the conjugated diene polymer of the present embodiment and workability when a rubber composition containing a filler, etc. is prepared, a conjugated diene polymer composition to which a softener for rubber is added as necessary can be obtained.

Although it does not specifically limit as a rubber softener, For example, extender oil, liquid rubber, resin, etc. are mentioned.

The method of adding the rubber softener to the conjugated diene-based polymer is not limited to the following, but the rubber softener is added to the conjugated diene-based polymer solution and mixed to obtain a polymer solution containing the rubber softener. method is preferred.

Preferred extender oils include, for example, aroma oil, naphthenic oil, and paraffin oil. Among these, the aromatic replacement oil whose polycyclic aromatic (PCA) component by IP346 method is 3 mass % or less is preferable from a viewpoint of environmental safety, and oil bleed prevention and a viewpoint of a wet grip characteristic. As an aroma substitute oil, in addition to TDAE (Treated Distillate Aromatic Extracts), MES (Mild Extraction Solvate), etc. shown in Kautschuk Gummi Kunststoffe 52 (12) 799 (1999), RAE (Residual Aromatic Extracts) is mentioned.

Although it is not limited to the following as a preferable liquid rubber, For example, liquid polybutadiene, liquid styrene-butadiene rubber, etc. are mentioned.

As an effect of adding liquid rubber, in addition to improving workability when a rubber composition containing a conjugated diene polymer and a filler, etc. is prepared, the glass transition temperature of the rubber composition can be shifted to the low temperature side, It tends to improve abrasion resistance, low hysteresis loss property, and low temperature characteristics when it is set as a vulcanizate.

Preferred resins as the rubber softener include, but are not limited to, aromatic petroleum resins, coumarone-indene resins, terpene resins, rosin derivatives (including tung oil resin), tall oil, and derivatives of tall oil. , rosin ester resins, natural and synthetic terpene resins, aliphatic hydrocarbon resins, aromatic hydrocarbon resins, mixed aliphatic/aromatic hydrocarbon resins, coumarin-indene resins, phenolic resins, p-tert-butylphenol-acetylene resins, phenol-formaldehyde resins , xylene-formaldehyde resin, mono-olefin oligomer, di-olefin oligomer, hydrogenated aromatic hydrocarbon resin, cyclic aliphatic hydrocarbon resin, hydrogenated hydrocarbon resin, hydrocarbon resin, hydrogenated copper oil resin, hydrogenated oil resin, monofunctional or polyfunctional with hydrogenated oil resin Ester of a functional alcohol, etc. are mentioned. These resins may be used by 1 type, and may use 2 or more types together. When hydrogenating, all unsaturated groups may be hydrogenated, and some may remain.

As an effect of adding the resin as a softener for rubber, in addition to improving workability when a rubber composition containing a conjugated diene-based polymer and a filler, etc. is prepared, the breaking strength when a vulcanized product is improved. tends to

In the conjugated diene-based polymer composition of the present embodiment, the amount of the extender oil, liquid rubber, or resin added as the rubber softener is not particularly limited, but 1 part by mass per 100 parts by mass of the conjugated diene-based polymer of the present embodiment. It shall be 60 mass parts or less, Preferably they are 5 mass parts or more and 50 mass parts or less, More preferably, they are 10 mass parts or more and 37.5 mass parts or less.

When the softener for rubber is added within the above range, the workability when a rubber composition containing a conjugated diene polymer and a filler is blended becomes good, and the fracture strength and abrasion resistance in the case of a vulcanized product tend to be good.

(Desolvation process)

As described above, a method for obtaining a conjugated diene-based polymer composition from adding a rubber softener (eg, extender oil) to a conjugated diene-based polymer solution and mixing to obtain a polymer solution containing a rubber softener includes: A known method can be used. For example, after separating the solvent by steam stripping or the like, the polymer is separated by filtration, and further dehydrated and dried to obtain a polymer, a method of concentrating in a flushing tank and devolatilizing with a vent extruder or the like, a drum dryer A method of devolatilization directly is mentioned.

[Rubber composition]

The rubber composition of this embodiment contains a rubber component and 5.0 mass parts or more and 150 mass parts or less of a filler with respect to 100 mass parts of said rubber components.

In addition, from the viewpoint of improving fuel economy performance, workability, and abrasion resistance, the rubber component contains 10 parts by mass of the above-described conjugated diene-based polymer or the above-described conjugated diene-based polymer composition with respect to the total amount (100 parts by mass) of the rubber component. include more than

(Silica-based inorganic filler)

It is preferable that the said filler contains a silica-type inorganic filler.

The rubber composition of this embodiment, by dispersing the silica-based inorganic filler, tends to be more excellent in workability when used as a vulcanized product, and tends to be excellent in low hysteresis loss, tensile strength, and abrasion resistance when used as a vulcanized product. have.

When the rubber composition of this embodiment is used for a vulcanized rubber use, such as an automobile part, such as a tire and vibration-proof rubber|gum, and shoes, it is especially preferable to contain a silica-type inorganic filler.

(rubbery polymer)

The rubber composition of the present embodiment comprises a rubbery polymer other than the above-described conjugated diene-based polymer of the present embodiment (hereinafter simply referred to as “other rubbery polymer”) with the above-described conjugated diene-based polymer of the present embodiment; Can be used in combination.

Although not limited to the following as said other rubbery polymer, For example, a conjugated diene type polymer or its hydrogenated substance, a random copolymer of a conjugated diene type compound and a vinyl aromatic compound, or its hydrogenated substance, a conjugated diene type compound, and A block copolymer of a vinyl aromatic compound or its hydrogenated substance, a non-diene type polymer, and a natural rubber are mentioned.

Specifically, butadiene rubber or its hydrogenated product, isoprene rubber or its hydrogenated product, styrene-butadiene rubber or its hydrogenated product, styrene-butadiene block copolymer or its hydrogenated product, styrene-isoprene block copolymer or its hydrogenated product, etc. A styrenic elastomer, an acrylonitrile-butadiene rubber, or its hydrogenated substance is mentioned.

Examples of the non-diene-based polymer include, but are not limited to, ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-butene-diene rubber, ethylene-butene rubber, ethylene-hexene rubber, and ethylene-octene rubber. Olefin elastomers, such as butyl rubber, brominated butyl rubber, acrylic rubber, fluororubber, silicone rubber, chlorinated polyethylene rubber, epichlorohydrin rubber, α,β-unsaturated nitrile-acrylic acid ester-conjugated diene copolymer rubber, urethane rubber, and polysulfurized rubber.

Although it is not limited to the following as a natural rubber, For example, RSS3-5 which are smoke sheets, SMR, and an epoxidized natural rubber are mentioned.

The various other rubber-like polymers mentioned above may be modified rubbers to which a functional group having a polarity, such as a hydroxyl group or an amino group, is provided. When used for tires, butadiene rubber, isoprene rubber, styrene-butadiene rubber, natural rubber, and butyl rubber are preferably used.

It is preferable that they are 2000 or more and 2000000 or less from a viewpoint of the balance of performance and a process characteristic, and, as for the weight average molecular weight of the said other rubber-like polymer, it is more preferable that they are 5000 or more and 1500000 or less. Moreover, as another rubbery polymer, a low molecular-weight rubbery polymer, so-called liquid rubber, can also be used.

Other rubbery polymers may be used individually by 1 type, and may use 2 or more types together.

In the case where the rubber composition of the present embodiment is a rubber composition containing the conjugated diene polymer of the present embodiment and another rubbery polymer, the content ratio of the above-mentioned conjugated diene polymer to the other rubbery polymer (mass ratio) is 10/90 or more and 100/0 or less, preferably 20/80 or more and 90/10 or less, and 30/70 or more 80/20 as (the above-mentioned conjugated diene polymer/other rubbery polymer) The following are more preferable.

Therefore, a rubber component contains 10 mass parts or more and 100 mass parts or less of the conjugated diene polymer of this embodiment mentioned above with respect to the total amount (100 mass parts) of the said rubber component, Preferably 20 mass parts or more and 90 mass parts. Partial or less is included, More preferably, 30 mass parts or more and 80 mass parts or less are included.

When the content ratio of (conjugated diene polymer/other rubbery polymer described above) is within the above range, the vulcanized product is excellent in tensile strength, abrasion resistance, and low hysteresis loss properties.

(filler)

Although it is not limited to the following as a filler contained in the rubber composition of this embodiment, For example, carbon black, a metal oxide, and a metal hydroxide other than the silica-type inorganic filler mentioned above are mentioned. Among these, silica-based inorganic fillers are preferable.

A filler may be used individually by 1 type, and may use 2 or more types together.

Content of the filler in the rubber composition of this embodiment is 5.0 mass parts or more and 150 mass parts with respect to 100 mass parts of rubber components containing the above-mentioned conjugated diene polymer, 20 mass parts or more and 100 mass parts or less are preferable, 30 More than 90 parts by mass is more preferable.

In the rubber composition of this embodiment, the content of the filler is 5.0 parts by mass or more with respect to 100 parts by mass of the rubber component from the viewpoint of expressing the effect of adding the filler, the filler is sufficiently dispersed, and the processability and mechanical strength of the composition From a viewpoint of making it a practically sufficient thing, it is 150 mass parts or less with respect to 100 mass parts of rubber components.

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

Specific examples of the silica-based inorganic filler include, but are not limited to, inorganic fibrous substances such as silica, clay, talc, mica, diatomaceous earth, wollastonite, montmorillonite, zeolite, and glass fiber.

Moreover, the mixture of the silica-type inorganic filler which made the surface hydrophobic, the silica-type inorganic filler, and inorganic fillers other than the silica type is also mentioned.

Among these, from viewpoints, such as intensity|strength and abrasion resistance, a silica and glass fiber are preferable, and a silica is more preferable.

Examples of the silica include fumed silica, wet silica, and synthetic silicate silica. Among these silicas, from the viewpoint of the effect of improving the tensile strength, wet silica is preferable.

From the viewpoint of obtaining practically good abrasion resistance and breaking strength in the rubber composition of the present embodiment, the silica-based inorganic filler preferably has a nitrogen adsorption specific surface area obtained by the BET adsorption method of 100 m 2 /g or more and 300 m 2 /g or less. and more preferably 170 m 2 /g or more and 250 m 2 /g or less. In addition, if necessary, a silica-based inorganic filler with a relatively small specific surface area (eg, a specific surface area of less than 200 m 2 /g) and a silica-based inorganic filler with a relatively large specific surface area (eg, 200 m 2 /g or more) can be used in combination. In particular, when a silica-based inorganic filler having a relatively large specific surface area (eg, 200 m 2 /g or more) is used, the rubber composition containing the conjugated diene-based polymer of the present embodiment described above is The dispersibility is improved, and it is particularly effective in improving the abrasion resistance, and there is a tendency that good breaking strength and low hysteresis loss properties can be highly balanced.

As for content of the silica-type inorganic filler in the rubber composition of this embodiment, 5.0 mass parts or more and 150 mass parts are preferable with respect to 100 mass parts of rubber components containing the conjugated diene type polymer of this embodiment mentioned above, 20 mass parts or more 100 A mass part or less is more preferable. In the rubber composition of this embodiment, the content of the silica-based inorganic filler is preferably 5.0 parts by mass or more with respect to 100 parts by mass of the rubber component from the viewpoint of expressing the effect of adding the silica-based inorganic filler, and the silica-based inorganic filler is It is preferable that it is 150 mass parts or less with respect to 100 mass parts of rubber components from a viewpoint of fully disperse|distributing and making the workability and mechanical strength of a rubber composition a practically sufficient thing.

The rubber composition of the present embodiment may contain carbon black. Examples of carbon black include, but are not limited to the following, carbon black of each class such as SRF, FEF, HAF, ISAF, and SAF. Among these, carbon black having a nitrogen adsorption specific surface area of 50 m 2 /g or more and a dibutyl phthalate (DBP) oil absorption of 80 mL/100 g or less is preferable.

The rubber composition of this embodiment WHEREIN: As for content of carbon black, 0.5 mass part or more and 100 mass parts or less are preferable with respect to 100 mass parts of rubber components containing the conjugated diene-type polymer of this embodiment, 3.0 mass parts or more 100 More preferably not more than 5.0 parts by mass and not more than 50 parts by mass. In the rubber composition of the present embodiment, the carbon black content is 0.5 parts by mass or more with respect to 100 parts by mass of the rubber component from the viewpoint of expressing the performance required for applications such as tires, such as dry grip performance and conductivity. It is preferable, and it is preferable to set it as 100 mass parts or less with respect to 100 mass parts of rubber components from a dispersible viewpoint.

(metal oxide, metal hydroxide)

The rubber composition of the present embodiment may contain a metal oxide or a metal hydroxide other than the silica-based inorganic filler and carbon black.

The metal oxide refers to solid particles having the chemical formula MxOy (M represents a metal atom, and x and y each independently represent an integer of 1 to 6) as a main component of a structural unit.

Examples of the metal oxide include, but are not limited to, alumina, titanium oxide, magnesium oxide, and zinc oxide.

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

(Silane coupling agent)

The rubber composition of the present embodiment may contain a silane coupling agent. The silane coupling agent has a function of making the interaction between the rubber component and the inorganic filler intimate. In particular, when a silica-based inorganic filler is used as the inorganic filler, the silane coupling agent has a group having affinity or binding property to each of the rubber component and the silica-based inorganic filler, and the sulfur-bonded moiety and the alkoxysilyl group or silanol group are 1 The compound which has in a molecule|numerator is preferable. Although not limited to the following as such a compound, For example, bis-[3-(triethoxysilyl)-propyl]-tetrasulfide, bis-[3-(triethoxysilyl)-propyl]-disulfide , bis-[2-(triethoxysilyl)-ethyl]-tetrasulfide.

In the rubber composition of this embodiment, the content of the silane coupling agent is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 0.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the above-mentioned inorganic filler, 1.0 mass part or more and 15 mass parts or less are more preferable. There exists a tendency which can make the said addition effect by a silane coupling agent more remarkable that content of a silane coupling agent is the said range.

(Softener for rubber)

From the viewpoint of improving the workability of the rubber composition of the present embodiment, a softening agent for rubber may be added in a step separate from the softening agent for rubber added to the above-described conjugated diene-based polymer of the present embodiment.

The amount of the softener for rubber to be added is, based on 100 parts by mass of the rubber component containing the above-mentioned conjugated diene-based polymer, the amount including the softening agent for rubber contained in the above-mentioned conjugated diene-based polymer or other rubbery polymer, and the rubber composition It is expressed as the total amount of the rubber softener added when making

As the softener for rubber, mineral oil or a liquid or low molecular weight synthetic softener is suitable.

A softener for mineral oil-based rubber called process oil or extender oil, which is used to soften rubber, increase its use, and improve processability, is a mixture of aromatic rings, naphthenic rings, and paraffin chains, and the number of carbon atoms in the paraffin chain is all carbon. What occupies 50% or more of the carbon atoms is called a paraffinic system, a naphthenic system in which the number of naphthenic ring carbon atoms occupies 30% or more and 45% or less of the total carbon is called a naphthenic system, and a naphthenic system in which the aromatic carbon number exceeds 30% of the total carbon is called an aromatic system. When the conjugated diene-based polymer of the present embodiment is a copolymer of a conjugated diene compound and a vinyl aromatic compound, the rubber softener to be used is preferably one having an appropriate aromatic content because it tends to have good affinity with the copolymer.

In the rubber composition of the present embodiment, the content of the softener for rubber is preferably 0 parts by mass or more and 100 parts by mass or less, more preferably 10 parts by mass or more and 90 parts by mass or less, and 30 parts by mass with respect to 100 parts by mass of the rubber component. Part 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 rubber components, there exists a tendency for suppressing bleed-out and suppressing the stickiness of the rubber composition surface.

[Method for producing rubber composition]

The rubber composition of the present embodiment includes a rubber component containing the conjugated diene polymer of the present embodiment and another rubbery polymer, a silica-based inorganic filler, carbon black or other filler, a silane coupling agent, a rubber softener, and the like. It can be manufactured by mixing an additive. Although not limited to the following as these mixing methods, For example, melt-kneading method using general mixers, such as an open roll, a Banbury mixer, a kneader, a single screw extruder, a twin screw extruder, a multi screw extruder, each component After dissolution mixing, the method of heating and removing a solvent is mentioned. Among these, the melt-kneading method by a roll, a Banbury mixer, a kneader, and an extruder is preferable from a viewpoint of productivity and favorable kneading|mixing property. In addition, any of a method of kneading a rubber component, a filler, a silane coupling agent, and an additive at once or a method of mixing the rubber component with a plurality of times is applicable.

The rubber composition of the present embodiment may be a vulcanized composition subjected to a vulcanization treatment with a vulcanizing agent. Although not limited to the following as a vulcanizing agent, For example, radical generators, such as an organic peroxide and an azo compound, an oxime compound, a nitroso compound, a polyamine compound, sulfur, and a sulfur compound are mentioned. The sulfur compounds include sulfur monochloride, sulfur dichloride, disulfide compounds, high molecular weight polysulfur compounds, and the like.

The rubber composition of this embodiment WHEREIN: 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 vulcanizing agent, 0.1 mass part or more and 15 mass parts or less are more preferable. As the vulcanization method, a conventionally known method can be applied, and the vulcanization temperature is preferably 120°C or more and 200°C or less, and more preferably 140°C or more and 180°C or less.

In the case of vulcanization, you may use a vulcanization accelerator as needed. As the vulcanization accelerator, a conventionally known material can be used, and although it is not limited to the following, for example, sulfenamide-based, guanidine-based, thiuram-based, aldehyde-amine-based, aldehyde-ammonia-based, thiazole-based, thiourea and dithiocarbamate-based vulcanization accelerators.

In addition, in the case of vulcanization, you may use a vulcanization auxiliary|assistant as needed. Examples of the vulcanization aid include, but are not limited to, zinc oxide and stearic acid. 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.

Various additives such as softeners and fillers other than those described above, heat-resistant stabilizers, antistatic agents, weather-resisting stabilizers, anti-aging agents, colorants, lubricants, etc. may be used. As other softeners, a well-known softening agent can be used. Although not limited to the following as another filler, For example, calcium carbonate, magnesium carbonate, aluminum sulfate, and barium sulfate are mentioned. As the heat-resistant stabilizer, antistatic agent, weather-resistant stabilizer, anti-aging agent, colorant, and lubricant, each known material can be used.

〔tire〕

The rubber composition of this embodiment is suitably used as a rubber composition for tires.

Examples of the rubber composition for tires include, but are not limited to, various tires such as fuel economy tires, all-season tires, high-performance tires, and studless tires: Tire parts such as tread, carcass, sidewall, and bead part is available for use in In particular, since the rubber composition for tires is excellent in abrasion resistance, tensile strength, and low hysteresis loss when it is made into a vulcanized product, it is suitably used for treads of fuel economy tires and high performance tires.

[Example]

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

Various physical properties in Examples and Comparative Examples were measured by the methods shown below.

In the following, the conjugated diene-based polymer before the coupling reaction is described as “conjugated diene-based polymer before coupling reaction” and the coupled conjugated diene-based polymer is described as “coupling conjugated diene-based polymer”. It may be described as "conjugated diene polymer".

(Physical property 1) Molecular weight

Measurement condition 1:

Using a GPC measuring device (trade name "HLC-8320GPC" manufactured by Tosoh Corporation) in which the conjugated diene polymer or coupling conjugated diene polymer before the coupling reaction was used as a sample and three columns using polystyrene gel as a filler were connected. , RI detector (trade name "HLC8020" manufactured by Tosoh Corporation) to measure the chromatogram, and based on the calibration curve obtained using standard polystyrene, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw) /Mn) was found.

As the eluent, 5 mmol/L of triethylamine-containing THF (tetrahydrofuran) was used. The column was used by connecting three trade names "TSKgel SuperMultiporeHZ-H" manufactured by Tosoh Corporation, and connecting the trade name "TSKguardcolumn SuperMP(HZ)-H" manufactured by Tosoh Corporation as a guard column in the preceding stage.

10 mg of the measurement sample was dissolved in 10 mL of THF to prepare a measurement solution, 10 µL of the measurement solution was poured into a GPC measuring apparatus, and the measurement was performed under the conditions of an oven temperature of 40°C and a THF flow rate of 0.35 mL/min.

Among the various samples measured under the measurement condition 1, the sample having a molecular weight distribution (Mw/Mn) of less than 1.6 was measured again under the measurement condition 2 below.

It measured under the measurement condition 1, and about the sample whose molecular weight distribution value was 1.6 or more, it measured under the measurement condition 1, and the measured value was employ|adopted.

Measurement condition 2:

The conjugated diene polymer or coupling conjugated diene polymer before the coupling reaction was used as a sample, and the chromatogram was measured using a GPC measuring device in which three columns using polystyrene gel as a filler were connected, and standard polystyrene was used. Based on the calibration curve, the weight average molecular weight (Mw) and the number average molecular weight (Mn) were calculated|required.

As the eluent, 5 mmol/L of triethylamine-containing THF was used. As the column, a guard column: "TSKguardcolumn SuperH-H" manufactured by Tosoh Corporation, and a column: "TSKgel SuperH5000", "TSKgel SuperH6000", and "TSKgel SuperH7000" manufactured by Tosoh Corporation were used.

An RI detector (trade name "HLC8020" manufactured by Tosoh Corporation) was used under the conditions of an oven temperature of 40°C and a THF flow rate of 0.6 mL/min. 10 mg of the sample for a measurement was melt|dissolved in 20 mL of THF, it was set as the measurement solution, 20 microliters of the measurement solutions were inject|poured into the GPC measuring apparatus, and it measured.

It measured under the measurement condition 1, and about the sample whose molecular weight distribution value was less than 1.6, it measured under the measurement condition 2, and the measured value was employ|adopted.

(Physical Properties 2) Polymer Mooney Viscosity

Using the conjugated diene polymer or coupling conjugated diene polymer before the coupling reaction as a sample, using a Mooney viscometer (trade name "VR1132" manufactured by Uejima Seisakusho Co., Ltd.), in accordance with ISO289, using an L-type rotor Mooney viscosity was measured.

The measurement temperature was made into 110 degreeC when making the conjugated diene-type polymer before a coupling reaction a sample, and when using a coupling-conjugated diene-type polymer as a sample, it was 120 degreeC.

First, the sample was preheated at the test temperature for 1 minute, the rotor was rotated at 2 rpm, and the torque after 4 minutes was measured to obtain the Mooney viscosity (ML ₍₁₊₄₎ ).

(Physical property 3) Branching degree (Bn)

The degree of branching (Bn) of the conjugated diene-based polymer was measured by a GPC-light scattering method with a viscosity detector as follows.

Light scattering using a gel permeation chromatography (GPC) measuring apparatus (trade name "GPCmax VE-2001" manufactured by Malvern) in which a coupling conjugated diene-based polymer was used as a sample and three columns using polystyrene-based gel as a filler were connected. A detector, an RI detector, and a viscosity detector (trade name "TDA305" manufactured by Malvern) were used for measurement using three detectors connected in sequence, and based on standard polystyrene, the absolute molecular weight was determined from the results of the light scattering detector and the RI detector, the RI detector and the Intrinsic viscosity was calculated|required from the result of a viscosity detector.

A linear polymer, the intrinsic viscosity [η] = - use as according to 3.883M ^0.771, yielding a shrinkage factor (g ') as the intrinsic viscosity ratio corresponding to the molecular weight. In addition, in formula, M represents an absolute molecular weight.

Then, the degree of branching (Bn) defined as g'=6Bn/{(Bn+1)(Bn+2)} was calculated using the obtained shrinkage factor (g').

As the eluent, 5 mmol/L of triethylamine-containing tetrahydrofuran (hereinafter also referred to as “THF”) was used.

The column was used by connecting the brand names "TSKgel G4000HXL", "TSKgel G5000HXL" and "TSKgel G6000HXL" manufactured by Tosoh Corporation.

20 mg of the measurement sample was dissolved in 10 mL of THF to prepare a measurement solution, 100 µL of the measurement solution was poured into a GPC measuring apparatus, and the measurement was performed under the conditions of an oven temperature of 40°C and a THF flow rate of 1 mL/min.

(Physical properties 4) Modification rate

The rate of modification of the conjugated diene-based polymer was measured by column adsorption GPC method as follows.

Measurement was performed by applying the property of adsorbing the modified basic polymer component to a GPC column using silica gel as a filler using a coupling conjugated diene-based polymer as a sample.

The amount of adsorption to the silica column is measured from the difference between the chromatogram measured by the polystyrene column and the chromatogram measured by the silica column for a sample solution containing the sample and the low molecular weight internal standard polystyrene, and the denaturation rate is calculated. did.

Specifically, it is as showing below. In addition, the measurement condition 1 of the above (physical property 1), the following measurement condition 3 for the sample whose molecular weight distribution value was 1.6 or more, and the measurement condition 4 below for the sample whose molecular weight distribution value was less than 1.6 measured.

<Preparation of sample solution>:

10 mg of sample and 5 mg of standard polystyrene were dissolved in 20 mL of THF to prepare a sample solution.

GPC measurement conditions using a polystyrene column:

Measurement condition 3:

Using the trade name "HLC-8320GPC" manufactured by Tosoh Corporation, 5 mmol/L of triethylamine-containing THF was used as the eluent, 10 µL of the sample solution was injected into the apparatus, and the column oven temperature was 40° C., and the THF flow rate was 0.35 mL/min. Under the conditions, chromatograms were obtained using an RI detector. The column was used by connecting three trade names "TSKgel SuperMultiporeHZ-H" manufactured by Tosoh Corporation, and connecting the trade name "TSKguardcolumn SuperMP(HZ)-H" manufactured by Tosoh Corporation as a guard column in the preceding stage.

Measurement condition 4:

5 mmol/L of triethylamine-containing THF was used as the eluent, and 20 µL of the sample solution was injected into the apparatus for measurement. As the column, a guard column: "TSKguardcolumn SuperH-H" manufactured by Tosoh Corporation, and a column: "TSKgel SuperH5000", "TSKgel SuperH6000", and "TSKgel SuperH7000" manufactured by Tosoh Corporation were used. It measured using the RI detector (HLC8020 by Tosoh Corporation) under the conditions of a column oven temperature of 40 degreeC, and a THF flow rate of 0.6 mL/min, and obtained the chromatogram.

GPC measurement conditions using a silica-based column:

Using the trade name "HLC-8320GPC" manufactured by Tosoh Corporation, using THF as the eluent, 50 μL of the sample solution was injected into the apparatus, and the RI detector was used at a column oven temperature of 40° C. and a THF flow rate of 0.5 ml/min. A chromatogram was obtained. The column was used by connecting trade names "Zorbax PSM-1000S", "PSM-300S", and "PSM-60S", and connecting and using the trade name "DIOL 4.6 x 12.5 mm 5micron" as a guard column in the front end.

To calculate the rate of denaturation:

The total peak area of the chromatogram using the polystyrene column is 100, the peak area of the sample is P1, the peak area of the standard polystyrene is P2, and the total of the peak area of the chromatogram using the silica column is 100, and the sample The peak area of P3 and the peak area of standard polystyrene were set as P4, and the denaturation rate (%) was calculated|required from the following formula.

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

(However, P1+P2=P3+P4=100)

(Physical property 5) Amount of bound styrene

A coupling conjugated diene-based polymer containing no softener for rubber was used as a sample, and 100 mg of the sample was prepared as a 100 mL solution in chloroform and dissolved to obtain a measurement sample.

The amount of bound styrene (mass %) with respect to 100 mass % of the coupling conjugated diene polymer which is a sample was measured based on the absorption amount of the ultraviolet absorption wavelength (254 nm vicinity) by the phenyl group of styrene (measuring apparatus: Shimadzu Corporation make. of the spectrophotometer "UV-2450").

(Physical property 6) Microstructure of butadiene moiety (1,2-vinyl bond amount)

A coupling conjugated diene-based polymer containing no softener for rubber was used as a sample, and 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 1000 cm -1} , and the absorbance at a predetermined wavenumber was measured by Hampton's method (RRHampton, Analytical Chemistry ₂₁ , the method described in 923 (1949)). According to the formula, the microstructure of the butadiene moiety, ie, the amount of 1,2-vinyl bonds (mol%), was calculated (measurement device: Fourier transform infrared spectrophotometer "FT-IR230" manufactured by Bunko, Japan).

(Physical property 7) Molecular weight (absolute molecular weight) by GPC-light scattering method measurement

Using a coupling conjugated diene-based polymer as a sample and using a GPC-light scattering measuring device in which three columns with polystyrene gel as a filler are connected, the chromatogram is measured, and the weight average molecular weight is based on the solution viscosity and the light scattering method. (Mw-i) was calculated|required (it is also called "absolute molecular weight".).

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

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

Under the conditions of an oven temperature of 40 degreeC and a THF flow volume of 1.0 mL/min, the GPC-light scattering measuring apparatus (trade name "Viscotek TDAmax" manufactured by Malvern Corporation) was used. 10 mg of the sample for a measurement was melt|dissolved in 20 mL of THF, it was set as the measurement solution, 200 microliters of the measurement solutions were injected into the GPC measuring apparatus, and it measured.

(Physical property 8) Glass transition temperature (Tg)

When the coupling conjugated diene-based polymer is a dielectric product, using a differential scanning calorimeter “DSC3200S” manufactured by Mac Sciences Co., Ltd. in accordance with ISO22768:2006 using the coupling conjugated diene-based polymer after extracting the extender oil as a sample, A DSC curve was recorded while the temperature was raised from -100°C to 20°C/min under a flow of 50 mL/min of helium, and the peak top (Inflection point) of the DSC differential curve was taken as the glass transition temperature.

(Physical properties 9) Nitrogen content

When the coupling conjugated diene-based polymer is a dielectric product, using the coupling conjugated diene-based polymer after extracting the extender oil as a sample, a trace amount in accordance with JIS-2609: Crude oil and petroleum products-nitrogen content test method and chemiluminescence method Nitrogen content was calculated|required using the all-nitrogen analyzer ("TN-2100H" by Mitsubishi Chemical Analytech).

[Production of Conjugated Diene Polymer]

(Example 1) Coupling conjugated diene-based polymer (A1)

The internal volume is 10L, the ratio (L/D) of the inner height (L) to the diameter (D) is 4.0, having an inlet at the bottom and an outlet at the top, having a stirrer, a tank reactor equipped with a stirrer, and a jacket for temperature control Two tank pressure vessels were connected as polymerization reactors.

The previously dehydrated 1,3-butadiene was mixed at 17.7 g/min, styrene at 10.9 g/min, and cyclohexane at 175.2 g/min. In a static mixer provided in the middle of the pipe for supplying this mixed solution to the inlet of the reactor, n-butyllithium for inert treatment of residual impurities was added and mixed at 0.103 mmol/min, and then continuously supplied to the bottom of the reactor. In addition, 2,2-bis(2-oxolanyl)propane as a polar material at a rate of 0.064 mmol/min and n-butyllithium as a polymerization initiator at a rate of 0.134 mmol/min were vigorously mixed with a stirrer. First, it was supplied to the bottom of the reactor, and the internal temperature of the reactor was maintained at 77°C.

The polymer solution was continuously withdrawn from the top of the reactor in the first stage, continuously fed to the bottom of the reactor in the second stage to continue the reaction at 82° C., and further fed to the static mixer from the top of the second stage. When the polymerization is sufficiently stable, while copolymerizing 1,3-butadiene and styrene, trimethoxy(4-vinylphenyl)silane as a branching agent is added from the bottom of the second reactor at a rate of 0.007 mmol/min, and the main chain A polymerization reaction and branching reaction were performed to obtain a conjugated diene-based polymer having a branched structure. In addition, when the polymerization reaction and branching reaction are stable, a small amount of the conjugated diene-based polymer solution before addition of the coupling agent is extracted, and after adding an antioxidant (BHT) so that it becomes 0.2 g per 100 g of the polymer, the solvent is removed, and various molecular weights (physical properties) 1) and Mooney viscosity (physical property 2) were measured. The physical properties are shown in Table 1.

Next, 0.043 mmol/N-benzylidene-3-(triethoxysilyl)propan-1-amine (abbreviated as "a" in the table) was added to the polymer solution flowing out from the outlet of the reactor as a coupling agent. Add continuously at a rate of minutes, mix using a static mixer, and react by coupling. At this time, the time until the coupling agent is added to the polymer solution discharged from the outlet of the reactor is 4.8 minutes, the temperature is 68°C, and the difference between the temperature in the polymerization step and the temperature until the coupling agent is added is 2°C it was After the coupling reaction, a small amount of the conjugated diene-based polymer solution is extracted, an antioxidant (BHT) is added so that 0.2 g per 100 g of the polymer, the solvent is removed, the amount of bound styrene (physical property 5), and the microstructure of the butadiene moiety ( 1,2-Vinyl bonding amount: Physical property 6) was measured.

The measurement results are shown in Table 1.

Next, to the polymer solution subjected to the coupling reaction, an antioxidant (BHT) was continuously added at a rate of 0.055 g/min (n-hexane solution) to 0.2 g per 100 g of the polymer, and the coupling reaction was terminated. Simultaneously with the antioxidant, SRAE oil (JOMO Process NC140 manufactured by JX Nikko Nisseki Energy Co., Ltd.) was continuously added to 25.0 g with respect to 100 g of the polymer as a softener for rubber, followed by mixing with a static mixer. The solvent is removed by steam stripping, and has a four-branched structure derived from a branching agent (hereinafter also referred to as "branching agent structure (1)") which is a compound represented by the following formula (1) in a part of the main chain, and a coupling agent A coupling conjugated diene-based polymer (A1) having an derived three-branched star polymer structure was obtained. Table 1 shows the physical properties of A1. In addition, for the polymer before the addition of the branching agent, the polymer after the addition of the branching agent, and the polymer in each step after the addition of the coupling agent, the molecular weight by GPC measurement and the degree of branching by GPC measurement with a viscometer are compared by comparison of the coupling conjugate. The structure of the diene-based polymer was identified. Hereinafter, the structure of each sample was similarly identified.

(In Formula (1), R<^1> represents a hydrogen atom, a C1-C20 alkyl group, or a C6-C20 aryl group, and may have a branched structure in the part.

R ² to R ³ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and may have a branched structure in a part thereof.

In the case of two or more, R ¹ to R ³ are each independent.

X ¹ represents an independent halogen atom.

m represents the integer of 0-2, n represents the integer of 0-3, l represents the integer of 0-3. (m+n+1) represents 3.)

(Example 2) Coupling conjugated diene-based polymer (A2)

A coupling diene copolymer (A2) was obtained in the same manner as in Example 1 except that the polar substance 2,2-bis(2-oxolanyl)propane was used at 0.055 mmol/min. Table 1 shows the physical properties of A2.

(Example 3) Coupling conjugated diene-based polymer (A3)

0.152 mmol/min of n-butyllithium as a polymerization initiator, 0.070 mmol/min of 2,2-bis(2-oxolanyl)propane, 0.008 mmol/min of trimethoxy(4-vinylphenyl)silane as a branching agent, The coupling agent is N-benzylidene-3-(triethoxysilyl)propan-1-amine to tetrakis(3-trimethoxysilylpropyl-1,3-propanediamine (abbreviated as “b” in the table). A coupling conjugated diene copolymer (A3) was obtained in the same manner as in Example 1, except that the amount of the coupling agent added was 0.015 mmol/min.

(Example 4) Coupling conjugated diene-based polymer (A4)

The coupling agent was changed from N-benzylidene-3-(triethoxysilyl)propan-1-amine to tetraethoxysilane (abbreviated as “c” in the table), and the amount of the coupling agent added was 0.018 mmol/min. Except having set it as Example 1, it carried out similarly to Example 1, and obtained the coupling conjugated diene copolymer (A4). Table 1 shows the physical properties of A4.

(Example 5) Coupling conjugated diene-based polymer (A5)

Coupling was carried out in the same manner as in Example 1 except that 1,3-butadiene was 15.8 g/min, styrene was 12.8 g/min, and 2,2-bis(2-oxolanyl)propane was 0.070 mmol/min. A conjugated diene copolymer (A5) was obtained. Table 1 shows the physical properties of A5.

(Example 6) Coupling conjugated diene-based polymer (A6)

1,3-butadiene was 20.0 g/min, styrene was 8.6 g/min, 2,2-bis(2-oxolanyl)propane was 0.058 mmol/min, and the rubber softener was SRAE oil 37.5 per 100 g of polymer. Except having set it as g, it carried out similarly to Example 1, and obtained the coupling conjugated diene copolymer (A6). Table 1 shows the physical properties of A6.

(Example 7) Coupling conjugated diene-based polymer (A7)

0.103 mmol/min of n-butyllithium as a polymerization initiator, 0.045 mmol of 2,2-bis(2-oxolanyl)propane, 0.005 mmol/min of trimethoxy(4-vinylphenyl)silane as a branching agent, couple Except having set the addition amount of a ring agent to 0.033 mmol/min, it carried out similarly to Example 1, and obtained the coupling conjugated diene copolymer (A7). Table 2 shows the physical properties of A7.

(Example 8) Coupling conjugated diene-based polymer (A8)

0.188 mmol/min of n-butyllithium as a polymerization initiator, 0.089 mmol/min of 2,2-bis(2-oxolanyl)propane, and 0.009 mmol/min of trimethoxy(4-vinylphenyl)silane as a branching agent , A coupling conjugated diene copolymer (A8) was obtained in the same manner as in Example 1 except that the addition amount of the coupling agent was 0.060 mmol/min. Table 2 shows the physical properties of A8.

(Example 9) Coupling conjugated diene-based polymer (A9)

0.152 mmol/min of n-butyllithium as a polymerization initiator, 0.016 mmol/min of 2,2-bis(2-oxolanyl)propane, and 0.008 mmol/min of trimethoxy(4-vinylphenyl)silane as a branching agent , The coupling agent is abbreviated as "b" in the table from N-benzylidene-3-(triethoxysilyl)propan-1-amine to tetrakis(3-trimethoxysilylpropyl-1,3-propanediamine (in the table). ) to obtain a coupling conjugated diene copolymer (A9) in the same manner as in Example 1, except that the amount of the coupling agent added was 0.015 mmol/min.

(Example 10) Coupling conjugated diene-based polymer (A10)

The polymerization initiator was a lithium amide prepared in advance, and a mixed solution of piperidinolithium (also referred to as “1-lithopiperidine”) and n-butyllithium (the molar ratio of the mixed solution was 0.75:0.25). Except this, it carried out similarly to Example 8, and obtained the coupling diene copolymer (A10). Table 2 shows the physical properties of A10.

(Example 11) Coupling conjugated diene-based polymer (A11)

For the coupling agent, the amount of N-benzylidene-3-(triethoxysilyl)propan-1-amine added is 0.0130 mmol/min, and the amount of tetrakis(3-trimethoxysilylpropyl-1,3-propanediamine added is 0.0075). A coupling diene copolymer (A11) was obtained in the same manner as in Example 1, except that the mixed solution (abbreviated as "a/b" in the table) was prepared in advance so as to obtain a rate of mmol/min. are shown in Table 2.

(Example 12) Coupling conjugated diene-based polymer (A12)

As in Example 11, except that the coupling agent was changed from N-benzylidene-3-(triethoxysilyl)propan-1-amine to 3-(4-methylpiperazin-1-yl)propyltrimethoxysilane , a mixed solution with tetrakis(3-trimethoxysilylpropyl-1,3-propanediamine (abbreviated as "d/b" in the table) was prepared, and other conditions were the same as in Example 1, A ring diene copolymer (A12) was obtained, and the physical properties of A12 are shown in Table 2.

(Comparative Example 1) Coupling conjugated diene-based polymer (B1)

The internal volume is 10L, the ratio (L/D) of the inner height (L) to the diameter (D) is 4.0, having an inlet at the bottom and an outlet at the top, having a stirrer, a tank reactor equipped with a stirrer, and a jacket for temperature control Two tank pressure vessels were connected as polymerization reactors.

1,3-butadiene, which had been previously dehydrated, was mixed under the conditions of 18.6 g/min, styrene at 10.0 g/min, and cyclohexane at 175.2 g/min to obtain a mixed solution.

In a static mixer provided in the middle of a pipe for supplying this mixed solution to the inlet of the reactor, n-butyllithium for inert treatment of residual impurities was added and mixed at 0.103 mmol/min, and then continuously supplied to the bottom of the reactor. In addition, 2,2-bis(2-oxolanyl)propane as a polar material at a rate of 0.072 mmol/min and n-butyllithium as a polymerization initiator at a rate of 0.134 mmol/min were vigorously mixed with a stirrer. First, it was supplied to the bottom of the reactor, and the internal temperature of the reactor was maintained at 77°C.

The polymer solution was continuously withdrawn from the top of the reactor in the first stage, continuously fed to the bottom of the reactor in the second stage, the reaction was continued at 82° C., and further fed to the static mixer from the top of the second stage. A small amount of the conjugated diene-based polymer solution before addition of the coupling agent was taken out, and antioxidant (BHT) was added so as to be 0.2 g per 100 g of the polymer, and then the solvent was removed, and Mooney viscosity and various molecular weights at 110° C. were measured. Physical properties are shown in Table 3.

Then, to the polymer solution flowing out from the outlet of the reactor, as a coupling agent, N-benzylidene-3-(triethoxysilyl)propan-1-amine was continuously added at a rate of 0.043 mmol/min, and the static mixer was stirred was used for mixing and coupling reaction. At this time, the time until the coupling agent is added to the polymer solution discharged from the outlet of the reactor is 4.8 minutes, the temperature is 68°C, and the difference between the temperature in the polymerization step and the temperature until the coupling agent is added is 2°C it was After the coupling reaction, a small amount of the conjugated diene-based polymer solution is extracted, an antioxidant (BHT) is added so that 0.2 g per 100 g of the polymer, the solvent is removed, the amount of bound styrene (physical property 5), and the microstructure of the butadiene moiety ( 1,2-Vinyl bonding amount: Physical property 6) was measured. The measurement results are shown in Table 3.

Next, to the polymer solution subjected to the coupling reaction, an antioxidant (BHT) was continuously added at a rate of 0.055 g/min (n-hexane solution) to 0.2 g per 100 g of the polymer, and the coupling reaction was terminated. Simultaneously with the antioxidant, SRAE oil (JOMO Process NC140 manufactured by JX Nikko Nisseki Energy Co., Ltd.) was continuously added to 25.0 g with respect to 100 g of the polymer as a softener for rubber, followed by mixing with a static mixer. The solvent was removed by steam stripping to obtain a coupling conjugated diene-based polymer (B1). The physical properties of B1 are shown in Table 3. About the polymer in each process after addition of a coupling agent, the structure of the coupling-conjugated diene polymer was identified by the comparison of the molecular weight by GPC measurement, and the branching degree by GPC measurement with a viscometer.

(Comparative Example 2) Coupling conjugated diene-based polymer (B2)

1,3-butadiene at 17.7 g/min, styrene at 10.9 g/min, n-butyllithium as a polymerization initiator at 0.152 mmol/min, 2,2-bis(2-oxolanyl)propane at 0.070 mmol/min and no branching agent was added. In addition, the coupling agent is N-benzylidene-3-(triethoxysilyl)propan-1-amine to tetrakis(3-trimethoxysilylpropyl-1,3-propanediamine (abbreviated as "b" in the table) .) to obtain a coupling conjugated diene copolymer (B2) in the same manner as in Comparative Example 1, except that the addition amount of the coupling agent was 0.015 mmol/min. Table 3 shows the physical properties of B2.

(Comparative Example 3) Coupling conjugated diene-based polymer (B3)

The polymerization initiator was 0.152 mmol/min of n-butyllithium and 0.093 mmol/min of 2,2-bis(2-oxolanyl)propane, and no branching agent was added. In addition, the coupling agent is N-benzylidene-3-(triethoxysilyl)propan-1-amine to tetrakis(3-trimethoxysilylpropyl-1,3-propanediamine (abbreviated as "b" in the table) A coupling conjugated diene copolymer (B3) was obtained in the same manner as in Comparative Example 1, except that the amount of the coupling agent added was 0.015 mmol/min.

(Comparative Example 4) Coupling conjugated diene-based polymer (B4)

1,3-butadiene at 14.3 g/min, styrene at 14.3 g/min, n-butyllithium as a polymerization initiator at 0.152 mmol/min, 2,2-bis(2-oxolanyl)propane at 0.103 mmol/min. and trimethoxy(4-vinylphenyl)silane as a branching agent at 0.008 mmol/min, and a coupling agent as tetrakis(3- The coupling conjugate was changed to trimethoxysilylpropyl-1,3-propanediamine (abbreviated as "b" in the table), except that the addition amount of the coupling agent was 0.015 mmol/min. A diene copolymer (B4) was obtained, and the physical properties of B4 are shown in Table 3.

(Comparative Example 5) Coupling conjugated diene-based polymer (B5)

Coupling was carried out in the same manner as in Comparative Example 4 except that 1,3-butadiene was 21.4 g/min, styrene was 7.2 g/min, and 2,2-bis(2-oxolanyl)propane was 0.042 mmol/min. A conjugated diene copolymer (B5) was obtained. The physical properties of B5 are shown in Table 3.

(Examples 13 to 24, and Comparative Examples 6 to 10)

Samples A1 to A12 and B1 to B5 shown in Tables 1 to 3 were used as raw rubber, and rubber compositions containing each raw rubber were obtained according to the formulations shown below.

Coupling conjugated diene polymer (A1 to A12, and B1 to B5: 100 parts by mass (excluding oil)

Silica 1 (trade name "Ultrasil7000GR" manufactured by Evonik Degussa, nitrogen adsorption specific surface area 170 m ² /g): 75.0 parts by mass

Carbon black (trade name "Sist KH(N339)" manufactured by Tokai Carbon Corporation): 5.0 parts by mass

Silane coupling agent (trade name "Si75" manufactured by Evonik Degus Corporation, bis(triethoxysilylpropyl)disulfide): 6.0 parts by mass

S-RAE oil (trade name "Process NC140" manufactured by JX Nikko Nisseki Energy Corporation): 37.5 parts by mass

(Including the amount previously added as a softener for rubber contained in Samples A1 to A12 and B1 to B5)

Zincization: 2.5 parts by mass

Stearic acid: 2.0 parts by mass

Anti-aging agent (N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine): 2.0 parts by mass

Sulfur: 1.7 parts by mass

Vulcanization accelerator 1 (N-cyclohexyl-2-benzothiazyl sulfinamide): 1.7 parts by mass

Vulcanization accelerator 2 (diphenylguanidine): 2.0 parts by mass

The above materials were kneaded by the following method to obtain a rubber composition. Using a sealed kneader (content 0.3L) equipped with a temperature control device, as the first stage kneading, under the conditions of a filling rate of 65% and a rotor rotation speed of 30 to 50 rpm, raw rubber (Samples A1 to A12, B1 to B5) ), filler (silica 1, silica 2, carbon black), silane coupling agent, process oil, zinc oxide, and stearic acid were kneaded. At this time, the temperature of the hermetic mixer was controlled, and the discharge temperature was 155 to 160° C. to obtain each rubber composition (formulation).

Then, as a second stage of kneading, the blend obtained above was cooled to room temperature, an antiaging agent was added, and kneaded again in order to improve the dispersion of silica. Again in this case, the discharge temperature of the formulation was adjusted to 155 to 160° C. by temperature control of the mixer. After cooling, as kneading in the third stage, sulfur and vulcanization accelerators 1 and 2 were added and kneaded with an open roll set at 70°C. Thereafter, it was molded and vulcanized by a vulcanization press at 160°C for 20 minutes. The rubber composition before vulcanization and the rubber composition after vulcanization were evaluated. Specifically, it evaluated by the following method. The results are shown in Tables 4 to 6.

(Evaluation 1) Tensile strength

According to the tensile test method of JIS K6251, the tensile strength was measured, and the result of Comparative Example 6 was indexed as 100. It shows that tensile strength and tensile elongation are favorable, so that an index|index is large.

(Evaluation 2) Wear resistance

Using an Akron abrasion tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd.), in accordance with JIS K6264-2, the amount of wear at a load of 44.4 N and 1000 rotations was measured, and the result of Comparative Example 6 was indexed as 100. It shows that abrasion resistance is so good that an index|index is large.

(Evaluation 3) Fuel economy

Viscoelasticity parameters were measured in torsion mode using the viscoelasticity tester "ARES" manufactured by Rheometrics Scientific. For each measurement value, the result for the rubber composition of Comparative Example 6 was indexed as 100. The tan δ measured at 0°C at a frequency of 10 Hz and a strain of 1% was used as an index of wet grip properties. It shows that wet grip property is so good that an index|exponent is large. In addition, tan δ measured at 50°C at a frequency of 10 Hz and a strain of 3% was used as an index of fuel economy (RR performance). It shows that fuel economy saving property is so good that an index|index is large.

As shown in Tables 4 to 6, Examples 13 to 24 using the coupling conjugated diene-based polymers (A1 to A12) of Examples 1 to 12 used the coupling conjugated diene-based polymers of Comparative Examples 1 to 5. In comparison with Comparative Examples 6 to 10, it was confirmed that the vulcanized material was excellent in the balance of tensile strength, abrasion resistance, and low hysteresis loss properties.

The rubber composition according to the present invention has industrial applicability in fields such as tire treads, automobile interior and exterior products, vibration-proof rubber, belts, shoes, foams, and various industrial products.

Claims (13)

The branching degree (Bn) by GPC-light scattering method with a viscosity detector is 7 or more,
It is a conjugated diene-based polymer having a weight average molecular weight of 45 × 10 ⁴ or more and 500 × 10 ^{4 or less,}
content of the aromatic vinyl monomer unit in the said conjugated diene polymer is 30-45 mass %,
The value of content (mass %) of an aromatic vinyl monomeric unit is larger than the value of the amount of vinyl bonds (mol%) in a conjugated diene monomeric unit,
Conjugated diene-based polymer. According to claim 1, wherein the rate of denaturation of the conjugated diene-based polymer measured by column adsorption GPC method,
Conjugated diene-type polymer of 60 mass % or more. The conjugated diene-based polymer according to claim 1 or 2, which contains a nitrogen atom and a silicon atom. The method according to claim 1 or 2, wherein the conjugated diene-based polymer has a three-branched or more star-shaped polymer structure,
In the branched chain of at least one star structure, a portion derived from a vinyl monomer containing an alkoxysilyl group or a halosilyl group, and a portion derived from a vinyl monomer containing an alkoxysilyl group or a halosilyl group, further having a main chain branching structure of
Conjugated diene-based polymer. The method according to claim 4, wherein the vinyl-based monomer comprising an alkoxysilyl group or a halosilyl group,
A compound represented by the following formula (1) or (2),
Conjugated diene-based polymer.

(In Formula (1), R<^1> represents a hydrogen atom, a C1-C20 alkyl group, or a C6-C20 aryl group, and may have a branched structure in the part.
R ² to R ³ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and may have a branched structure in a part thereof.
In the case of two or more, R ¹ to R ³ are each independent.
X ¹ represents an independent halogen atom.
m represents the integer of 0-2, n represents the integer of 0-3, l represents the integer of 0-3. (m+n+1) represents 3.)
(In formula (2), R ² to R ⁵ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and may have a branched structure in a part thereof. ² to R ⁵ are each independent.
X ² to X ^{3 each} represent an independent halogen atom.
m represents the integer of 0-2, n represents the integer of 0-3, l represents the integer of 0-3. (m+n+1) represents 3.
a represents the integer of 0-2, b represents the integer of 0-3, c represents the integer of 0-3. (a+b+c) represents 3.) The conjugated diene polymer having a monomer unit based on the compound represented by the formula (1) according to claim 5, wherein in the formula (1), R ^{1 is a hydrogen atom and m=0.} The conjugated diene polymer having a monomer unit based on the compound represented by the formula (2) according to claim 5, wherein in the formula (2), m=0 and b=0. A monomer unit based on the compound represented by the formula (1) according to claim 5, wherein in the formula (1), R ¹ is a hydrogen atom, m=0, l=0, and n=3; A conjugated diene-based polymer having The formula (2) according to claim 5, wherein m=0, l=0, n=3, a=0, b=0, and c=3 in the formula (2). A conjugated diene-based polymer having a monomer unit based on the compound used. A method for producing the conjugated diene-based polymer according to claim 1 or 2,
Using an organolithium compound as a polymerization initiator, polymerizing at least a conjugated diene compound and an aromatic vinyl compound in a solvent containing a polar compound, adding a branching agent to obtain a conjugated diene-based polymer having a main chain branched structure; A method for producing a conjugated diene-based polymer. The method for producing a conjugated diene-based polymer according to claim 10, further comprising a step of reacting a coupling agent with the conjugated diene-based polymer having the branched main chain structure. 100 parts by mass of the conjugated diene-based polymer according to claim 1 or 2;
1 to 60 parts by mass of a rubber softener
Containing, a conjugated diene-based polymer composition. A rubber composition comprising a rubber component and 5.0 parts by mass or more and 150 parts by mass or less of a filler with respect to 100 parts by mass of the rubber component,
The said rubber component contains 10 mass parts or more of the conjugated diene type polymer of Claim 1 or 2 with respect to 100 mass parts of total amounts of the said rubber component, The rubber composition.