JP2021075641A - Rubber composition for tire tread, and pneumatic tire - Google Patents

Abstract

To provide a rubber composition for a tire tread which is excellent in processability, gives a cured product having excellent tensile breaking strength, and exhibits excellent rolling performance when formed into a tire, and to provide a pneumatic tire using the rubber composition for a tire tread.SOLUTION: The rubber composition for a tire tread contains: a conjugated diene rubber containing 30 mass% or more of a specific conjugated diene rubber produced by a conjugated diene rubber production method comprising specific steps; silica; a silane coupling agent; and a nonionic surfactant containing a polypropyleneoxy block and a polyethyleneoxy block. The content of the silica is 30 pts.mass or more based on 100 pts.mass of the conjugated diene rubber. The content of the silane coupling agent is 3-30 mass% based on the content of the silica. The content of the nonionic surfactant is 0.1-15 mass% based on the content of the silica.SELECTED DRAWING: Figure 1

Description

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

In recent years, from the viewpoint of fuel efficiency of vehicles, improvement of tire rolling performance (low rolling resistance) has been required. On the other hand, there is known a method of improving the rolling performance of a tire by blending silica with a rubber component constituting the tire to reduce the hysteresis loss (tan δ).
However, since silica has a low affinity with the rubber component and has high cohesiveness between the silicas, even if silica is simply mixed with the rubber component, the silica is not dispersed and the effect of improving the rolling performance is sufficiently obtained. There was a problem that it could not be done.

Under such circumstances, for example, claim 1 of Patent Document 1 describes a rubber composition for a tire tread containing a conjugated diene-based rubber produced by a method for producing a conjugated diene-based rubber including steps A, B, and C in this order. The thing is disclosed. Patent Document 1 describes that the rubber composition for tire tread exhibits excellent rolling performance and the like when made into a tire.

On the other hand, Patent Document 2 describes a tread portion, a pair of sidewall portions, a pair of bead portions, a carcass composed of at least one carcass ply extending in a tread shape between bead cores in each bead portion, and a tread. In an agricultural pneumatic tire provided with a tread rubber arranged outside in the radial direction of the carcass, an ionic surfactant having one or more oxyalkylene groups in the molecule and an ionic surfactant on the surface layer of the tread rubber. Pneumatic tires for agriculture are described, characterized in that a surface rubber containing at least one of the ether-type nonionic surfactants of polyoxyethylene is arranged.
It is described that the nonionic surfactant is at least one selected from the compounds represented by the following formula (I).
R ⁸ O (R ⁷ O) _n H (I)
[In formula (I), R ⁸ represents an alkyl or alkenyl group having 1 to 15 carbon atoms, and the alkyl group and alkenyl group may be linear, branched or cyclic; R ⁷ is , An alkylene group having 2 to 4 carbon atoms; a means an average number of added moles, which is 11 to 30. ]

Japanese Unexamined Patent Publication No. 2016-47887 Japanese Unexamined Patent Publication No. 2014-181262

Recently, due to environmental problems and resource problems, further improvement in tire rolling performance is required. Further, from the viewpoint of manufacturing efficiency, further improvement (reduction of viscosity) is required in the processability of the rubber composition used for the tire.

Under such circumstances, the present inventors prepared a rubber composition for a tire tread with reference to Patent Documents 1 and 2, and examined workability and rolling performance when made into a tire. Given the ever-increasing demands, it became clear that further improvements would be desirable.
Further, it has been clarified that when the rubber composition contains a nonionic surfactant, it is desirable to further improve the tensile breaking strength and the like of the cured product obtained from the rubber composition as described above.

Therefore, in view of the above circumstances, the present invention provides a rubber composition for tire tread, which is excellent in workability, tensile breaking strength of the obtained cured product, and rolling performance when made into a tire, and the rubber for tire tread. It is an object of the present invention to provide a pneumatic tire using the composition.

As a result of diligent studies on the above problems, the present inventors have made a specific nonionic surfactant with respect to a rubber composition containing a conjugated diene rubber containing a specific conjugated diene rubber, silica and a silane coupling agent. We have found that the above problems can be solved by blending an agent, and have arrived at the present invention.
That is, the present inventors have found that the above problems can be solved by the following configuration.

[1] Conjugated diene rubber containing 30% by mass or more of specific conjugated diene rubber,
With silica
Silane coupling agent and
Contains polypropylene oxyblock and nonionic surfactants including polyethylene oxyblock,
The content of the silica is 30 parts by mass or more with respect to 100 parts by mass of the conjugated diene rubber.
The content of the silane coupling agent is 3 to 30% by mass with respect to the content of the silica.
The content of the nonionic surfactant is 0.1 to 15% by mass with respect to the content of the silica.
In the first step, the specific conjugated diene-based rubber polymerizes a monomer containing a conjugated diene compound in an inert solvent using a polymerization initiator to obtain a conjugated diene-based polymer chain having an active terminal. The polyorganosiloxane represented by the general formula (1) described later is added to the conjugated diene polymer chain having the active terminal in the polyorganosiloxane with respect to 1 mol of the polymerization initiator used in the first step. The second step of adding and reacting the siloxane structure (-Si-O-) of the above in a ratio of 1 mol or more in terms of the number of repeating units, and the conjugated diene system obtained by reacting the polyorganosiloxane obtained in the second step. A rubber composition for tire tread, which is a conjugated diene rubber produced by a method for producing a conjugated diene rubber, which comprises a third step of reacting a polymer chain with a compound represented by the general formula (2) described later. ..
[2] The rubber composition for tire tread according to [1], wherein the nonionic surfactant has a hydroxy group at all terminals of the nonionic surfactant.
[3] The rubber composition for tire tread according to [1] or [2], wherein the nonionic surfactant contains a compound represented by the formula (X) described later.
[4] The rubber composition for tire tread according to any one of [1] to [3], wherein the CTAB adsorption specific surface area of the silica is 115 to 300 m ^{2 / g.}
[5] The specific conjugated diene rubber is
A polymer block (A) containing 80 to 100% by mass of an isoprene monomer unit and 0 to 20% by mass of an aromatic vinyl monomer unit, and
It has a structure in which a polymer block (B) containing 50 to 100% by mass of a 1,3-butadiene monomer unit and 0 to 50% by mass of an aromatic vinyl monomer unit is continuously formed [1]. ] To [4]. Rubber composition for tire tread.
[6] A pneumatic tire including a tire tread portion manufactured by using the rubber composition for tire tread according to any one of [1] to [5].

As shown below, according to the present invention, a rubber composition for a tire tread having excellent workability, tensile breaking strength of the obtained cured product, and rolling performance when made into a tire, and the above-mentioned rubber for a tire tread. Pneumatic tires using the composition can be provided.

It is a partial cross-sectional schematic diagram of an example of embodiment of the pneumatic tire of this invention.

The rubber composition for a tire tread of the present invention will be described below.
The numerical range represented by using "~" in the present specification means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.
In the present specification, the method for producing each component is not particularly limited. For example, conventionally known ones can be mentioned.
In the present specification, unless otherwise specified, each component may use a substance corresponding to the component individually or in combination of two or more kinds. When a component contains two or more substances, the content of the component means the total content of the two or more substances.
In the present specification, the effect of the present invention may be more excellent if at least one of workability, tensile breaking strength and rolling performance is more excellent.

[Rubber composition for tire tread]
The rubber composition for a tire tread of the present invention (hereinafter, also referred to as "composition of the present invention") comprises a conjugated diene rubber containing a specific conjugated diene rubber, silica, a silane coupling agent, and a specific structure. Contains a nonionic surfactant having. The content of the silica is 30 parts by mass or more with respect to 100 parts by mass of the conjugated diene rubber. The content of the silane coupling agent is 3 to 30% by mass with respect to the content of the silica. The content of the nonionic surfactant is 0.1 to 15% by mass with respect to the content of the silica.
Since the composition of the present invention has such a structure, it is considered that the above-mentioned effects can be obtained. The reason is not clear, but it is thought to be as follows.

Since the specific conjugated diene rubber contained in the composition of the present invention has a polyorganosiloxane structure having a structure similar to that of silica, it is considered that the polyorganosiloxane structure has an affinity with silica and prevents silica from agglomerating. In addition, since the specific conjugated diene rubber also has a structure derived from a nitrogen atom-containing silane such as aminosilane, it is considered that this promotes silanization between the silane coupling agent and silica and further suppresses silica aggregation. ..

In addition, the composition of the present invention contains a polypropylene oxyblock and a nonionic surfactant containing a polyethylene oxyblock. Since the nonionic surfactant has the polypropylene oxyblock, the polypropylene oxyblock is easily entangled with the conjugated diene rubber containing the specific conjugated diene rubber, so that the polyethylene oxyblock is introduced into the conjugated diene rubber. It is thought that.
Further, since the oxygen atoms in the polypropylene oxyblock and the polyethylene oxyblock can interact with the hydroxyl groups on the surface of the silica, it is considered that the polypropylene oxyblock and the polyethylene oxyblock can contribute to the suppression of aggregation between the silicas.
For the above reasons, in the composition of the present invention, by using the nonionic surfactant with respect to the specific conjugated diene rubber and the conjugated diene rubber containing silica, the silica is dispersed in the conjugated diene rubber. The properties are extremely high, and it is considered that the composition of the present invention exhibits excellent processability. Further, it is considered that the dispersibility of silica is extremely high also in the tire obtained from the composition of the present invention, and the effects of silica (rolling performance and tensile breaking strength) are sufficiently exhibited.
However, the above mechanism is an estimation, and even if it is other than the mechanism, it is within the scope of the present invention if the requirements of the present invention are satisfied.

Hereinafter, each component contained in the composition of the present invention will be described.

[1] Conjugated Diene Rubber The conjugated diene rubber contained in the composition of the present invention contains 30% by mass or more of the specific conjugated diene rubber.
First, a specific conjugated diene-based rubber will be described.

[Specific conjugated diene rubber]
The specific conjugated diene-based rubber contained in the composition of the present invention is a conjugated diene-based rubber produced by a method for producing a conjugated diene-based rubber comprising the following steps 1 to 3.
(1) First step (1) First step (2) First step of polymerizing a monomer containing a conjugated diene compound in an inert solvent using a polymerization initiator to obtain a conjugated diene polymer chain having an active terminal. 2 steps The polyorganosiloxane represented by the general formula (1) described later is added to the conjugated diene polymer chain having an active end with respect to 1 mol of the polymerization initiator used in the first step. 2nd step (3) 3rd step of adding and reacting at a ratio of 1 mol or more in terms of the number of repeating units of the siloxane structure (-Si-O-) in the 3rd step The polyorganosiloxane obtained in the above 2nd step is reacted. The third step of reacting the conjugated diene polymer chain with the compound represented by the general formula (2) described later

First, the reason for specifying the specific conjugated diene rubber by the manufacturing method as described above will be described.
As described above, in the third step, the compound represented by the general formula (2) described later is reacted with the conjugated diene-based polymer chain obtained by reacting the polyorganosiloxane obtained in the second step. Here, A ¹ in the compound represented by the general formula (2) has binds to react with the reactive residues formed by the reaction of a conjugated diene polymer chain polyorganosiloxane having active terminal. However, as described later, the reaction residue generated by the reaction between the conjugated diene polymer chain having an active terminal and polyorganosiloxane can have various structures, and therefore is represented by the general formula (2) as the reaction residue. The structure of a compound after it has reacted is extremely complex, and it is technically impossible to analyze the structure, or the cost and time required to perform the task of identifying the structure are significantly excessive. Needs. Therefore, it is a so-called "impossible / impractical situation" to describe a specific conjugated diene rubber as "a conjugated diene rubber manufactured by a method for producing a conjugated diene rubber comprising the first to third steps". Exists.

Hereinafter, each step will be described.

[First step]
The first step is a step of polymerizing a monomer containing a conjugated diene compound in an inert solvent using a polymerization initiator to obtain a conjugated diene-based polymer chain having an active terminal.
First, each component and the like used in the first step will be described.

<Conjugated diene compound>
The conjugated diene compound used as a monomer in order to obtain a conjugated diene polymer chain having an active terminal in the first step is not particularly limited, but is limited to 1,3-butadiene, isoprene, and 2,3-dimethyl-. 1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadien, Examples thereof include 3-butyl-1,3-octadien. Among these, 1,3-butadiene and isoprene are preferable because the effect of the present invention is more excellent. These conjugated diene compounds may be used alone or in combination of two or more.

<Aromatic vinyl compound>
Further, in the first step, an aromatic vinyl compound may be used together with the conjugated diene compound as the monomer used for the polymerization. Aromatic vinyl compounds used as monomers include styrene, methylstyrene, ethylstyrene, t-butylstyrene, α-methylstyrene, α-methyl-p-methylstyrene, chlorostyrene, bromostyrene, methoxystyrene, and dimethylamino. Examples thereof include methylstyrene, dimethylaminoethylstyrene, diethylaminomethylstyrene, diethylaminoethylstyrene, cyanoethylstyrene, vinylnaphthalene and the like. Among these, styrene is preferable because the effect of the present invention is more excellent.

The conjugated diene-based polymer chain having an active terminal obtained in the first step preferably contains 50 to 100% by mass of a conjugated diene monomer unit for the reason that the effect of the present invention is more excellent, and is 52 to 95% by mass. It is more preferable to contain%, and it is preferable to contain 0 to 50% by mass of the aromatic vinyl monomer unit, and more preferably 5 to 48% by mass.

<Other copolymerizable compounds>
Further, in the first step, a compound copolymerizable with the conjugated diene compound (other copolymerizable compound) other than the aromatic vinyl compound may be used together with the conjugated diene compound. Examples of the compound copolymerizable with such a conjugated diene compound include a chain olefin compound such as ethylene, propylene and 1-butene; a cyclic olefin compound such as cyclopentene and 2-norbornene; 1,5-hexadien and 1,6- Non-conjugated diene compounds such as heptadiene, 1,7-octadien, dicyclopentadiene, 5-ethylidene-2-norbornene; (meth) methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and the like ( Examples include (meth) acrylic acid esters; other (meth) acrylic acid derivatives such as (meth) acrylonitrile, (meth) acrylamide; and the like. For the reason that the effect of the present invention is more excellent, the compound copolymerizable with these conjugated diene compounds has 10 as a monomer unit in the conjugated diene polymer chain having an active terminal obtained in the first step. It is preferably mass% or less, and more preferably 5 mass% or less.

<Inactive solvent>
The inert solvent used for the polymerization is usually used in solution polymerization and is not particularly limited as long as it does not inhibit the polymerization reaction. Specific examples of the inert solvent include chain aliphatic hydrocarbons such as butane, pentane, hexane and heptane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; And so on. These inert solvents may be used alone or in combination of two or more. The amount of the inert solvent used is not particularly limited, but the monomer concentration is, for example, 1 to 50% by mass, and is preferably 10 to 40% by mass for the reason that the effect of the present invention is more excellent. The quantity.

<Polymerization initiator>
The polymerization initiator used for the polymerization is not particularly limited as long as it can polymerize a monomer containing a conjugated diene compound to give a conjugated diene-based polymer chain having an active terminal. Specific examples thereof include a polymerization initiator using an organic alkali metal compound, an organic alkaline earth metal compound, a lanthanum series metal compound, or the like as a main catalyst. Examples of the organic alkali metal compound include organic monolithium compounds such as n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium and stillbenlithium; dilithiomethane, 1,4-dilithiobutane, 1, Organic polyvalent lithium compounds such as 4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene, 1,3,5-tris (lithiomethyl) benzene; organic sodium compounds such as sodium naphthalene; organic such as potassium naphthalene Potassium compounds; and the like. Examples of the organic alkaline earth metal compound include di-n-butylmagnesium, di-n-hexylmagnesium, diethoxycalcium, calcium distearate, dit-butoxystrontium, diethoxybarium, and diisopropoxy. Examples thereof include barium, diethyl mercaptobarium, dit-butoxybarium, diphenoxybarium, diethylaminobarium, barium distearate, and diketyl barium. Examples of the polymerization initiator using a lanthanum-series metal compound as a main catalyst include lantern-series metals such as lanthanum, cerium, placeodim, neodym, samarium, and gadrinium, and lanthanum-series metals composed of carboxylic acids and phosphorus-containing organic acids. Examples thereof include a polymerization initiator composed of an alkylaluminum compound, an organoaluminum hydride compound, an organoaluminum halide compound and other co-catalysts having the salt of the above as a main catalyst. Among these polymerization initiators, an organic monolithium compound and an organic polyvalent lithium compound are preferably used, an organic monolithium compound is more preferably used, and n-butyllithium is particularly preferable, because the effect of the present invention is more excellent. It is preferably used.
The organic alkali metal compound is previously reacted with a secondary amine compound such as dibutylamine, dihexylamine, dibenzylamine, pyrrolidine, piperidine, hexamethyleneimine, and heptamethyleneimine to obtain an organic alkali metal amide compound. You may use it. These polymerization initiators may be used alone or in combination of two or more.

Examples of the organic alkali metal amide compound include those obtained by reacting an organic alkali metal compound with a secondary amine compound, and among them, for the reason that the effect of the present invention is more excellent, the following general formula (3) is used. The compound represented can be preferably used.

In the general formula (3), M ¹ represents an alkali metal atom, and R ¹¹ and R ¹² are independently alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, amino group protective groups, or hydrolysis. R ¹¹ and R ¹² may be bonded to each other to form a ring structure together with the nitrogen atom to which they are bonded, and when the ring structure is formed, they are bonded to each other. In addition to the nitrogen atoms to be bonded, a ring structure may be formed with heteroatoms other than the nitrogen atoms to which they are bonded.

The alkyl group is not particularly limited, but an alkyl group having 1 to 20 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable, for the reason that the effect of the present invention is more excellent. Examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and n-. Examples thereof include a xyl group, an n-heptyl group, an n-octyl group and an n-decyl group.

The cycloalkyl group is not particularly limited, but a cycloalkyl group having 3 to 20 carbon atoms is preferable, and a cycloalkyl group having 3 to 12 carbon atoms is more preferable, for the reason that the effect of the present invention is more excellent. Examples of such a cycloalkyl group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclododecyl group and the like.

The aryl group is not particularly limited, but an aryl group having 6 to 12 carbon atoms is preferable, and an aryl group having 6 to 10 carbon atoms is more preferable, for the reason that the effect of the present invention is more excellent. Examples of such an aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group and the like.

The aralkyl group is not particularly limited, but an aralkyl group having 7 to 13 carbon atoms is preferable, and an aralkyl group having 7 to 9 carbon atoms is more preferable, for the reason that the effect of the present invention is more excellent. Examples of such an aralkyl group include a benzyl group and a phenethyl group.

The protecting group for the amino group is not particularly limited as long as it is a group that acts as a protecting group for the amino group, and examples thereof include an alkylsilyl group. Examples of such an alkylsilyl group include a trimethylsilyl group, a triethylsilyl group, a triphenylsilyl group, a methyldiphenylsilyl group, an ethylmethylphenylsilyl group, a tert-butyldimethylsilyl group and the like.
When R ¹¹ and / or R ¹² are amino group protecting groups, at one end of the polymer chain forming the obtained conjugated diene rubber by removing the amino group protecting group, ^{A structure in which R 13} and / or R ¹⁴ in the general formula (5) described later is a hydrogen atom can be introduced.

The group capable of hydrolyzing to generate a hydroxyl group is not particularly limited, and may be a group that produces a hydroxyl group by hydrolysis in the presence of an acid or the like. For example, an alkoxyalkyl group or an epoxy group. Examples include groups containing.
Examples of the alkoxyalkyl group include a methoxymethyl group, an ethoxymethyl group, an ethoxyethyl group, a propoxymethyl group, a butoxymethyl group, a butoxyethyl group, a propoxyethyl group and the like.
Examples of the group containing an epoxy group include a group represented by the following general formula (4).
−Z ¹ −Z ² −E ¹ (4)
In the general formula (4), Z ¹ is an alkylene group or an alkylarylene group having 1 to 10 carbon atoms, Z ² is a methylene group, a sulfur atom or an oxygen atom, and E ¹ is a glycidyl group.

Further, R ¹¹ and R ¹² may be bonded to each other to form a ring structure together with the nitrogen atom to which they are bonded. In this case, R ¹¹ and R ^{12 are formed by the nitrogen atom bonded to the ring structure.} Specific examples of the structure to be formed include an azetidine ring (R ¹¹ and R ¹² are propylene groups), a pyrrolidine ring (R ¹¹ and R ¹² are butylene groups), and a piperidine ring (R ¹¹ and R ¹² are pentylene groups). , hexamethyleneimine ring ^{(R 11} and ^{R 12,} hexylene group) and the like.
When R ¹¹ and R ¹² are bonded to each other to form a ring structure together with the nitrogen atom to which they are bonded, the ring structure is preferably a 4- to 8-membered ring structure.

Further, in the general formula (3), M ¹ is an alkali metal atom, and examples of such an alkali metal atom include a lithium atom, a sodium atom, and a potassium atom. Among these, from the viewpoint of polymerization activity. , Lithium atom is preferred.

When a compound represented by the general formula (3) is used as the polymerization initiator in the first step, the amine structure forming the organic alkali metal amide compound remains in a state of being bonded to the polymerization initiation terminal of the polymer chain. Will be done. Therefore, when a compound represented by the general formula (3) is used as the polymerization initiator, a structure represented by the following general formula (5) is formed at one end of the polymer chain forming the obtained conjugated diene rubber. Is introduced.

In the general formula (5), R ¹³ and R ¹⁴ can independently generate a hydroxyl group by hydrogen atom, alkyl group, cycloalkyl group, aryl group, aralkyl group, amino group protective group, or hydrolysis. Representing a group, R ¹³ and R ¹⁴ may be bonded to each other to form a ring structure with the nitrogen atom to which they are bonded, and in the case of forming the ring structure, in addition to the nitrogen atom to which they are bonded. , They may form a ring structure together with a hetero atom other than the nitrogen atom to which they are bonded.

Examples of the alkyl group, cycloalkyl group, aryl group, aralkyl group, amino group protective group, or group capable of hydrolyzing to generate a hydroxyl group as R ¹³ and R ^{14 are R 11} and R ^{12 in the general formula (3).} Also, when R ¹³ and R ¹⁴ are bonded to each other to form a ring structure together with the nitrogen atom to which they are bonded, R ^{11 and R 12} in the general formula (3) can be mentioned. Can be the same.
The ^{hydrogen atoms that can become R 13} and R ¹⁴ are introduced when the protecting group of the amino group is removed.

When an organic alkali metal amide compound is used as the polymerization initiator, the obtained specific conjugated diene rubber has an amine structure at one end and a specific structure derived from the modifier at the other end. Can be. As a result, the effect of the present invention becomes more excellent due to the effect of such an amine structure.

The method of adding the organic alkali metal amide compound as the polymerization initiator to the polymerization system is not particularly limited, and the organic alkali metal compound is reacted with the secondary amine compound in advance to obtain the organic alkali metal amide compound. , This can be mixed with a monomer containing a conjugated diene compound to allow the polymerization reaction to proceed. Alternatively, the organic alkali metal compound and the secondary amine compound are separately added to the polymerization system, and these are mixed with a monomer containing a conjugated diene compound to generate an organic alkali metal amide compound in the polymerization system. Therefore, a method of advancing the polymerization reaction may be adopted. The reaction conditions such as the reaction temperature are not particularly limited, and may be, for example, according to the target polymerization reaction conditions.

The amount of the secondary amine compound used may be determined according to the amount of the desired polymerization initiator added, but is usually 0.01 to 1.5 mmol, preferably 0.1 per 1 mmol of the organic alkali metal compound. It is in the range of ~ 1.2 mmol, more preferably 0.5 ~ 1.0 mmol.

The amount of the polymerization initiator used may be determined according to the molecular weight of the target conjugated diene-based polymer chain, but is usually 1 to 50 mmol, preferably 1.5 to 20 mmol, or more, per 1000 g of the monomer. It is preferably in the range of 2 to 15 mmol.

<Polymerization temperature, etc.>
The polymerization temperature is usually −80 to + 150 ° C., preferably 0 to 100 ° C., more preferably 30 to 90 ° C. for the reason that the effect of the present invention is more excellent. As the polymerization mode, any mode such as batch type or continuous type can be adopted, but when the conjugated diene compound and the aromatic vinyl compound are copolymerized, the conjugated diene monomer unit and the aromatic vinyl monomer are used. The batch formula is preferable because it is easy to control the randomness of the combination with the unit.

<Polar compound>
When polymerizing a monomer containing a conjugated diene compound, a polar compound is added to an inert organic solvent in order to adjust the vinyl bond content in the conjugated diene monomer unit in the obtained conjugated diene polymer chain. Is preferable. Examples of the polar compound include ether compounds such as dibutyl ether, tetrahydrofuran and 2,2-di (tetrahydrofuryl) propane; tertiary amines such as tetramethylethylenediamine; alkali metal alkoxides; phosphine compounds; and the like. Among these, ether compounds and tertiary amines are preferable, tertiary amines are more preferable, and tetramethylethylenediamine is particularly preferable, for the reason that the effect of the present invention is more excellent. These polar compounds may be used alone or in combination of two or more. The amount of the polar compound to be used may be determined according to the target vinyl bond content, preferably 0.001 to 100 mol, more preferably 0.01 to 10 mol, based on 1 mol of the polymerization initiator. is there. When the amount of the polar compound used is in this range, the vinyl bond content in the conjugated diene monomer unit can be easily adjusted, and problems due to deactivation of the polymerization initiator are unlikely to occur.

<Vinyl bond content>
The vinyl bond content in the conjugated diene monomer unit in the conjugated diene polymer chain having an active terminal obtained in the first step is preferably 1 to 90% by mass because the effect of the present invention is more excellent. It is more preferably 3 to 80% by mass, and particularly preferably 5 to 70% by mass.

<Molecular weight>
The weight average molecular weight (Mw) of the conjugated diene polymer chain having an active terminal obtained in the first step is not particularly limited, but is measured by polystyrene-equivalent gel permeation chromatography for the reason that the effect of the present invention is more excellent. As the value to be obtained, 100,000 to 1,000,000 is preferable, 150,000 to 700,000 is more preferable, and 150,000 to 500,000 is particularly preferable.

Further, the molecular weight distribution represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the conjugated diene polymer chain having an active terminal obtained in the first step is also particularly limited. Although not, it is preferably 1.0 to 3.0, more preferably 1.0 to 2.5. When the molecular weight distribution (Mw / Mn) of the conjugated diene polymer chain having an active terminal is within the above range, the production of a specific conjugated diene rubber becomes easy.

<Preferable aspect>
The first step is preferably the following step because the effect of the present invention is more excellent.
That is, isoprene, or a monomer containing isoprene and an aromatic vinyl compound, is polymerized with a polymerization initiator in an inert solvent, and isoprene monomer unit 80 to 100% by mass and aromatic vinyl monomer unit 0. Step A to form a polymer block (A) having an active end containing ~ 20% by mass, and
The polymer block (A) having the active terminal is mixed with 1,3-butadiene, or a monomer containing 1,3-butadiene and an aromatic vinyl compound to continue the polymerization reaction, and 1,3 A polymer block (B) having an active terminal containing 50 to 100% by mass of a butadiene monomer unit and 0 to 50% by mass of an aromatic vinyl monomer unit is formed in succession with the polymer block (A). It is preferable that the step B of obtaining a conjugated diene polymer chain having an active terminal is provided.

By adopting such a step, the conjugated diene-based polymer chain having an active terminal obtained in the first step can be obtained in an isoprene monomer unit of 80 to 100% by mass and an aromatic vinyl monomer unit of 0 to 20% by mass. The polymer block (A) containing% and the polymer block (B) containing 1,3-butadiene monomer unit 50 to 100% by mass and aromatic vinyl monomer unit 0 to 50% by mass are continuous. (Hereinafter, also referred to as “PI block”) can be included. In this case, the obtained specific conjugated diene rubber also has a PI block.
Hereinafter, such an embodiment will be described.

(Step A)
The polymer block (A) formed in the step A may contain 80 to 100% by mass of an isoprene monomer unit and 0 to 20% by mass of an aromatic vinyl monomer unit in the polymer block (A). However, for the reason that the effect of the present invention is more excellent, it is preferable that the isoprene monomer unit contains 85 to 95% by mass and the aromatic vinyl monomer unit 5 to 15% by mass, and the isoprene monomer unit 89. More preferably, it contains ~ 95% by mass and 5-11% by mass of the aromatic vinyl monomer unit.

As the aromatic vinyl compound used to form the aromatic vinyl monomer unit contained in the polymer block (A), the same aromatic vinyl compound as described above can be used, and the effect of the present invention can be obtained. Of these, styrene is preferred for better reasons. In addition, these aromatic vinyl compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

The polymer block (A) is preferably composed of only the isoprene monomer unit, or the isoprene monomer unit and the aromatic vinyl monomer unit, for the reason that the effect of the present invention is more excellent, but it is desirable. Therefore, in addition to the isoprene monomer unit, or the isoprene monomer unit and the aromatic vinyl monomer unit, other monomer units may be contained. Other compounds used to compose other monomeric units include 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, 1,3. -Conjugated diene compounds other than isoprene such as pentadiene and 1,3-hexadiene; α, β-unsaturated nitriles such as acrylonitrile and methacrylonitrile; unsaturated carboxylic acids such as acrylic acid, methacryl test, and maleic anhydride. Or acid anhydrides; unsaturated carboxylic acid esters such as methyl methacrylate, ethyl acrylate, and butyl acrylate; 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, dicyclopentadiene, and 5 -Etidene-2-Non-conjugated diene such as norbornen; etc. Among these, 1,3-butadiene is preferable because the effect of the present invention is more excellent. These other monomers can be used alone or in combination of two or more. The content ratio of the other monomer units in the polymer block (A) is preferably 20% by mass or less, more preferably 10% by mass or less, for the reason that the effect of the present invention is more excellent. , 6% by mass or less is more preferable.

In the present invention, the polymer block (A) in the conjugated diene-based polymer chain is obtained by polymerizing a monomer containing isoprene or an isoprene and an aromatic vinyl compound in an inert solvent with a polymerization initiator. It is formed. The polymer block (A) formed has an active terminal.

As the inert solvent used for polymerizing isoprene or a monomer containing isoprene and an aromatic vinyl compound in order to form the polymer block (A), the same inert solvent as described above may be used. it can. The amount of the inert solvent used is such that the monomer concentration is preferably 1 to 80% by mass, more preferably 10 to 50% by mass, for the reason that the effect of the present invention is more excellent. ..

As the polymerization initiator used for forming the polymer block (A), isoprene or a monomer containing isoprene and an aromatic vinyl compound may be polymerized to give a polymer chain having an active terminal. If it can be done, it is not particularly limited. As a specific example thereof, the same polymerization initiator as described above can be used.

The amount of the polymerization initiator used may be determined according to the target molecular weight, but isoprene or 100 g of a monomer containing isoprene or an aromatic vinyl compound is preferable because the effect of the present invention is more excellent. Is in the range of 4 to 250 mmol, more preferably 6 to 200 mmol, and particularly preferably 10 to 70 mmol.

The polymerization temperature when polymerizing isoprene or a monomer containing isoprene and an aromatic vinyl compound is preferably −80 to + 150 ° C., more preferably 0 to 100 ° C., because the effect of the present invention is more excellent. More preferably, it is in the range of 20 to 90 ° C. As the polymerization mode, any mode such as a batch type or a continuous type can be adopted. Further, as the bonding mode, various bonding modes such as a block shape, a tapered shape, and a random shape can be used.

Further, for the reason that the effect of the present invention is more excellent, in order to adjust the vinyl bond content in the isoprene monomer unit in the polymer block (A), a polar compound may be added to the inert solvent during the polymerization. preferable. As the polar compound, the same polar compound as described above can be used. The amount of the polar compound used may be determined according to the target vinyl bond content, and is preferably 0.01 to 30 mol, more preferably 0.05 to 10 mol, with respect to 1 mol of the polymerization initiator. When the amount of the polar compound used is within the above range, the vinyl bond content in the isoprene monomer unit can be easily adjusted, and problems due to deactivation of the polymerization initiator are unlikely to occur. Further, by increasing the amount of the polar compound used within the above range, the vinyl bond content in the isoprene monomer unit can be increased.

The vinyl bond content in the isoprene monomer unit in the polymer block (A) is preferably 5 to 90% by mass, more preferably 5 to 80% by mass, for the reason that the effect of the present invention is more excellent. In the present specification, the vinyl bond content in the isoprene monomer unit has an isoprene monomer unit having a 1,2-structure and a 3,4-structure in the isoprene monomer unit. It shall refer to the ratio of the total amount of isoprene monomer units.

The weight average molecular weight (Mw) of the polymer block (A) is preferably 500 to 15,000 as a polystyrene-equivalent value measured by gel permeation chromatography because the effect of the present invention is more excellent. It is more preferably 1000 to 12,000, and particularly preferably 1,500 to 10,000.

Further, the molecular weight distribution represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer block (A) is 1.0 because the effect of the present invention is more excellent. It is preferably ~ 1.5, and more preferably 1.0 to 1.3. When the value (Mw / Mn) of the molecular weight distribution of the polymer block (A) is within the above range, the conjugated diene rubber can be more easily produced.

(Step B)
The polymer block (B) in the conjugated diene-based polymer chain formed in step B is 50 to 100% by mass of 1,3-butadiene monomer unit and a single amount of aromatic vinyl in the polymer block (B). It may contain 0 to 50% by mass of body units, but for the reason that the effect of the present invention is more excellent, 1,3-butadiene monomer units 52 to 95% by mass and aromatic vinyl monomer units 5 to 5 by mass. It preferably contains 48% by mass. When the content ratio of the 1,3-butadiene monomer unit and the aromatic vinyl monomer unit is within the above range, the production of the conjugated diene rubber becomes easier.

As the aromatic vinyl compound used to form the aromatic vinyl monomer unit contained in the polymer block (B), the same aromatic vinyl compounds as those described above can be used. Styrene is preferred because of the greater effect of the invention.

The polymer block (B) is composed of only 1,3-butadiene monomer units, or 1,3-butadiene monomer units and aromatic vinyl monomer units for the reason that the effect of the present invention is more excellent. However, as long as the essential properties in the present invention are not impaired, 1,3-butadiene monomer units, or 1,3-butadiene monomer units and aromatic vinyl monomers are optionally used. In addition to the units, other monomeric units may be included. As the other monomer used to form the other monomer unit, the same compound as the compound exemplified in the above-mentioned polymer block (A) (excluding 1,3-butadiene) is used. be able to. Further, in the polymer block (B), isoprene can be used as another monomer. The content ratio of the other monomer units in the polymer block (B) is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 35% by mass or less. preferable.

The polymer block (B) in the conjugated diene-based polymer chain contains the above-mentioned polymer block (A) having an active terminal and 1,3-butadiene, or 1,3-butadiene and an aromatic vinyl compound. By mixing the polymer and the polymer and continuing the polymerization reaction, it is formed in succession with the polymer block (A). The polymer block (B) formed has an active terminal. On the other hand, the active terminal disappears from the polymer block (A).

The inertness used to polymerize the polymer block (A) with a monomer containing 1,3-butadiene, or 1,3-butadiene and an aromatic vinyl compound to form the polymer block (B). The solvent is not particularly limited, and the same solvent as the above-mentioned inert solvent can be used.

The amount of the polymer block (A) having an active terminal used in forming the polymer block (B) may be determined according to the target molecular weight, but for the reason that the effect of the present invention is more excellent, it may be determined. Per 100 g of monomer containing 1,3-butadiene, or 1,3-butadiene and aromatic vinyl compounds, preferably 0.1 to 5 mmol, more preferably 0.15 to 2 mmol, even more preferably 0.2. It is in the range of ~ 1.5 mmol.

The method for mixing the polymer block (A) with 1,3-butadiene, or a monomer containing 1,3-butadiene and an aromatic vinyl compound is not particularly limited, and 1,3-butadiene, or 1,3 A polymer block (A) having an active end may be added to a solution of a monomer containing −butadiene and an aromatic vinyl compound, or 1,3 may be added to a solution of the polymer block (A) having an active end. -Butadiene, or monomers containing 1,3-butadiene and aromatic vinyl compounds may be added. From the viewpoint of controlling polymerization, a method of adding the polymer block (A) having an active terminal to a solution of 1,3-butadiene or a monomer containing 1,3-butadiene and an aromatic vinyl compound is preferable.

The polymerization temperature when polymerizing a monomer containing 1,3-butadiene or a monomer containing 1,3-butadiene and an aromatic vinyl compound is preferably −80 to + 150 ° C., because the effect of the present invention is more excellent. It is preferably in the range of 0 to 100 ° C, more preferably 20 to 90 ° C. As the polymerization mode, any mode such as a batch type or a continuous type can be adopted. When the polymer block (B) is a copolymer chain, the batch type is preferable because it is easy to control the randomness of the bond.

When the polymer block (B) is a copolymer chain, the bonding mode of each monomer can be, for example, various bonding modes such as a block shape, a tapered shape, and a random shape. Among these, the random shape is preferable because the effect of the present invention is more excellent. When the bonding mode of 1,3-butadiene and the aromatic vinyl compound is randomized, the total amount of 1,3-butadiene and the aromatic vinyl compound in the polymerization system is due to the superior effect of the present invention. 1,3-butadiene or 1,3-butadiene and the aromatic vinyl compound are continuously or intermittently supplied into the polymerization system for polymerization so that the ratio of the aromatic vinyl compound to the amount does not become too high. Is preferable.

Further, for the reason that the effect of the present invention is more excellent, in order to adjust the vinyl bond content in the 1,3-butadiene monomer unit in the polymer block (B), a single amount of isoprene in the polymer block (A). As in the case of adjusting the vinyl bond content in the body unit, it is preferable to add a polar compound to the inert solvent during the polymerization. However, when preparing the polymer block (A), an amount of polar compound sufficient to adjust the vinyl bond content in the 1,3-butadiene monomer unit in the polymer block (B) was added to the inert solvent. If is added, it is not necessary to add a new polar compound. As the polar compound used for adjusting the vinyl bond content, the same polar compound as described above can be used. The amount of the polar compound used may be determined according to the target vinyl bond content, and the polymerization initiation used in the initial polymerization reaction (polymerization reaction for forming the first polymer block (A)) may be started. It may be adjusted in the range of preferably 0.01 to 100 mol, more preferably 0.1 to 30 mol, with respect to 1 mol of the agent. When the amount of the polar compound used is in this range, the vinyl bond content in the 1,3-butadiene monomer unit can be easily adjusted, and problems due to deactivation of the polymerization initiator are unlikely to occur.

The vinyl bond content in the 1,3-butadiene monomer unit in the polymer block (B) is preferably 1 to 90% by mass, more preferably 3 to 80% by mass because the effect of the present invention is more excellent. , Particularly preferably 5 to 70% by mass.

In this way, a conjugated diene-based polymer chain having an active terminal having a polymer block (A) and a polymer block (B) can be obtained. From the viewpoint of productivity, the conjugated diene-based polymer chain having an active end is composed of a polymer block (A) and a polymer block (B), and the end of the polymer block (B) is the active end. It is preferable, but it may have a plurality of polymer blocks (A) or may have other polymer blocks. For example, a conjugated diene-based polymer chain having an active terminal such as polymer block (A) -polymer block (B) -polymer block (A) can be mentioned. In this case, an active terminal is formed at the end of the polymer block (A) formed following the polymer block (B). When the polymer block (A) is formed on the active terminal side of the conjugated diene-based polymer chain, the amount of isoprene used is determined by the initial polymerization reaction (first polymer block) because the effect of the present invention is more excellent. It is preferably 10 to 100 mol, more preferably 15 to 70 mol, and 20 to 35 mol with respect to 1 mol of the polymerization initiator used in (polymerization reaction for forming (A)). Is particularly preferred.

Mass ratio of polymer block (A) to polymer block (B) in a conjugated diene-based polymer chain having an active terminal (when a plurality of polymer blocks (A) and polymer blocks (B) are present, each of them (Mass ratio based on the total mass of) is 0.001 to 0 in (mass of polymer block (A)) / (mass of polymer block (B)) because the effect of the present invention is more excellent. It is preferably 0.1, more preferably 0.003 to 0.07, and particularly preferably 0.005 to 0.05.

With the total monomer unit of the isoprene monomer unit and the 1,3-butadiene monomer unit in the conjugated diene polymer chain having the polymer block (A) and the polymer block (B) and having an active terminal. , The content ratio with the aromatic vinyl monomer unit is the isoprene monomer unit and the 1,3-butadiene monomer in the conjugated diene polymer chain having an active terminal because the effect of the present invention is more excellent. The total monomer unit is preferably 50 to 100% by mass and the aromatic vinyl monomer unit is preferably 0 to 50% by mass, and the total unit amount of the isoprene monomer unit and the 1,3-butadiene monomer unit. More preferably, the body unit is 52 to 95% by mass, and the aromatic vinyl monomer unit is 5 to 48% by mass. Further, vinyl bonds in the isoprene monomer unit and the 1,3-butadiene monomer unit in the conjugated diene-based polymer chain having the polymer block (A) and the polymer block (B) and having an active terminal. The content is preferably in the same range as the vinyl bond content in the 1,3-butadiene monomer unit in the polymer block (B) described above, for the reason that the effect of the present invention is more excellent.

[Second step]
In the second step, the polymerization initiator 1 in which the polyorganosiloxane represented by the following general formula (1) was used in the conjugated diene polymer chain having the active terminal obtained in the first step in the first step. This is a step of adding and reacting the siloxane structure (-Si-O-) in the polyorganosiloxane at a ratio of 1 mol or more in terms of the number of repeating units to the molars.

In the general formula (1), R ^{1 to} R ⁸ are alkyl groups having 1 to 6 carbon atoms or aryl groups having 6 to 12 carbon atoms, and these may be the same or different from each other. X ¹ and X ⁴ are composed of an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a group having 4 to 12 carbon atoms containing an epoxy group. Any group selected from the group, which may be the same or different from each other. X ² is an alkoxy group having 1 to 5 carbon atoms or a group having 4 to 12 carbon atoms containing an epoxy group, and a plurality of X ² may be the same as or different from each other. X ³ is a group containing 2 to 20 repeating units of alkylene glycol, and ^{when there are a plurality of X 3} , they may be the same or different from each other. m is an integer of 3 to 200, n is an integer of 0 to 200, k is an integer of 0 to 200, and m + n + k is 3 or more.

In the polyorganosiloxane represented by the general formula (1), examples of the alkyl group having 1 to 6 carbon atoms which can constitute ^{R 1 to} R ⁸ , X ¹ and X ^{4 in the general formula (1) are methyl.} Examples thereof include a group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group and a cyclohexyl group. Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group and a methylphenyl group. Among these, a methyl group and an ethyl group are preferable from the viewpoint of easiness of producing the polyorganosiloxane itself.

Further, in the polyorganosiloxane represented by the general formula (1), examples of the alkoxy group having 1 to 5 carbon atoms that can constitute ^{X 1} , X ² and X ^{4 include a methoxy group, an ethoxy group, and a propoxy group.} Examples thereof include an isopropoxy group and a butoxy group. Among these, a methoxy group and an ethoxy group are preferable from the viewpoint of easiness of producing the polyorganosiloxane itself.

Further, in the polyorganosiloxane represented by the general formula (1), examples of the group having 4 to 12 carbon atoms containing an epoxy group capable of forming ^{X 1} , X ² and X ^{4 include the following general formula (6).} ) Can be mentioned.
-Z ^3- Z ^4- E ² (6)
In the general formula (6), Z ³ is an alkylene group or an alkylarylene group having 1 to 10 carbon atoms, Z ⁴ is a methylene group, a sulfur atom or an oxygen atom, and E ² is a carbon having an epoxy group. It is a hydrocarbon group of several 2 to 10.

The group represented by the general formula (6), because the effects of the present invention is more excellent, it is preferable that Z ⁴ is an oxygen atom, Z ⁴ is an oxygen atom, and, E ² is glycidyl group Some are more preferable, and Z ³ is an alkylene group having 1 to ^{3 carbon atoms, Z 4} is an oxygen atom, and E ² is a glycidyl group.

Further, in the polyorganosiloxane represented by the general formula (1), X ¹ and X ⁴ are groups having 4 to 12 carbon atoms containing an epoxy group for the reason that the effect of the present invention is more excellent than the above. , Or an alkyl group having 1 to 6 carbon atoms is preferable. As the X ^2, among the above, because the effect of the present invention is more excellent group having 4 to 12 carbon atoms containing an epoxy group is preferable. Further, for the reason that the effect of the present invention is more excellent ^{, it is more preferable that X 1} and X ⁴ are alkyl groups having 1 to 6 carbon atoms and X ² is a group having 4 to 12 carbon atoms containing an epoxy group. ..

Further, in the polyorganosiloxane represented by the general formula (1), ^{as a group containing a repeating unit of X 3} , that is, 2 to 20 alkylene glycols, the following general formula ( The group represented by 7) is preferable.

In the general formula (7), t is an integer of 2 to 20, X ⁵ is an alkylene group or an alkylarylene group having 2 to 10 carbon atoms, R ¹⁵ is a hydrogen atom or a methyl group, and X ⁶ is a carbon. It is an alkoxy group or an aryloxy group having a number of 1 to 10. Among these, it is preferable that t is an integer of 2 to 8, X ⁵ is an alkylene group having 3 carbon atoms, R ¹⁵ is a hydrogen atom, and X ⁶ is a methoxy group. In the general formula (7), * is a coupling position.

In the polyorganosiloxane represented by the general formula (1), m is an integer of 3 to 200, preferably an integer of 20 to 150, and more preferably an integer of 30 to 120. When m is 3 or more, the coupling rate of the obtained conjugated diene rubber is high, and as a result, the effect of the present invention is more excellent. Further, when m is 200 or less, the polyorganosiloxane itself represented by the general formula (1) can be more easily produced, its viscosity does not become too high, and it becomes easier to handle.

Further, in the polyorganosiloxane represented by the general formula (1), n is an integer of 0 to 200, preferably an integer of 0 to 150, and more preferably an integer of 0 to 120. k is an integer from 0 to 200, preferably an integer from 0 to 150, and more preferably an integer from 0 to 130.
The total number of m, n and k is 3 or more, preferably 3 to 400, more preferably 20 to 300, and particularly preferably 30 to 250. When the total number of m, n and k is 3 or more, the reaction between the polyorganosiloxane represented by the general formula (1) and the conjugated diene polymer chain having an active terminal is likely to proceed, and further, m, When the total number of n and k is 400 or less, the polyorganosiloxane itself represented by the general formula (1) can be easily produced, its viscosity does not become too high, and it is easy to handle.

The amount of polyorganosiloxane used in the second step is the number of repeating units of the siloxane structure (-Si-O-) in the polyorganosiloxane with respect to 1 mol of the polymerization initiator used for polymerization in the first step described above. It is preferably 1 to 2.5 mol, more preferably 1.1 to 2 mol, for the reason that the effect of the present invention is more excellent.

By setting the amount of polyorganosiloxane used to 1 mol or more in terms of the number of repeating units of the siloxane structure (-Si-O-) with respect to 1 mol of the polymerization initiator, the active terminal obtained in the first step can be obtained. Of the active ends of the conjugated diene-based polymer chain having, substantially all the active ends can be reacted with polyorganosiloxane, which is preferable. That is, the alkyl metal group as the active terminal of the conjugated diene polymer chain having the active terminal obtained in the first step, that is, −R ⁻ M ⁺ (R is a hydrocarbon group forming the polymer chain terminal). , M can be in a state in which a group represented by an alkali metal atom, an alkaline earth metal atom, or a lanthanum series metal atom) does not substantially remain.

As a result, when the compound represented by the general formula (2) is reacted in the third step described later, the compound represented by the general formula (2) is the active terminal obtained by the first step. It is possible to substantially suppress the direct reaction with the active end of the conjugated diene-based polymer chain having. As a result, with respect to the reaction residue generated by reacting the compound represented by the general formula (2) with the conjugated diene polymer chain and the polyorganosiloxane represented by the general formula (1). It can be reacted appropriately. As a result, a modified structure of the compound represented by the general formula (2) is appropriately introduced into the conjugated diene-based polymer chain via the structure derived from the polyorganosiloxane represented by the general formula (1). It is possible to realize the effect of introducing such a modified structure, that is, excellent tensile breaking strength and rolling performance. In addition, it is considered that the workability will be improved. Wet performance is also expected to improve.

The method for reacting the polyorganosiloxane with the conjugated diene polymer chain having an active terminal is not particularly limited, and examples thereof include a method of mixing these in a solvent in which each of them can be dissolved. As the solvent used at this time, those exemplified as the inert solvent used in the first step described above can be used. Further, in this case, a method of adding polyorganosiloxane to the polymerization solution used for the polymerization for obtaining the conjugated diene-based polymer chain having an active terminal is convenient and preferable. In this case, the polyorganosiloxane is preferably dissolved in an inert solvent and added to the polymerization system, and the solution concentration is preferably in the range of 1 to 50% by mass. The reaction temperature is not particularly limited, but is usually 0 to 120 ° C., and the reaction time is also not particularly limited, but is usually 1 minute to 1 hour.

The timing of adding the polyorganosiloxane to the solution containing the conjugated diene polymer chain having an active end is not particularly limited, but the polymerization reaction is not completed and the conjugated diene polymer chain having an active end is contained. The state in which the solution to be prepared also contains a monomer, more specifically, the solution containing a conjugated diene-based polymer chain having an active terminal is a single amount of 100 ppm or more, more preferably 300 to 50,000 ppm. It is desirable to add the polyorganosiloxane to this solution with the body contained. By adding the polyorganosiloxane in this way, it is possible to suppress side reactions between the conjugated diene polymer chain having an active terminal and impurities contained in the polymerization system, and to control the reaction satisfactorily. It becomes.

In the second step, polyorganosiloxane as a modifier is reacted with the active terminal of the conjugated diene-based polymer chain having the active terminal obtained in the first step described above, but the conjugated diene-based weight The active end of the coalesced chain will react with the silicon atom in the siloxane structure. Alternatively, a portion of the active end of the conjugated diene polymer chain, in alkoxy group, or epoxy group in the side chain of the polyorganosiloxane (general formula (1), an alkoxy group or an epoxy to form an X ² contained as an essential It will react with the group etc.). Then, according to the second step, a modified structure with siloxane is introduced into the conjugated diene-based polymer chain by such a reaction.

Specifically, the active end of the conjugated diene polymer chain reacts with the silicon atom in the siloxane structure, so that the conjugated diene polymer chain is formed by the silicon atom in the siloxane structure and the conjugated diene polymer chain. A new bond is formed between the active end and the modified structure by siloxane is introduced at the end of the conjugated diene polymer chain, and the oxygen atom in the siloxane structure and the active end of the conjugated diene polymer chain are introduced. ^{A group represented by −O−} M ⁺ (M is an alkali metal atom, an alkaline earth metal atom, or a lanthanum series metal atom) as these reaction residues with the metal atom forming the above. Is considered to be formed.

Alternatively, the active end of the conjugated diene polymer chain reacts with the epoxy group of the side chain of the polyorganosiloxane to open the epoxy group, and the carbon atom of the portion where the epoxy group is opened and the conjugated diene weight. A new bond is formed with the active end of the coalesced chain, a siloxane structure is introduced at the end of the conjugated diene polymer chain, and the oxygen atom in the epoxy group and the activity of the conjugated diene polymer chain are active. It is considered that a group represented by ^−O− M ⁺ is formed as these reaction residues with the metal atom forming the terminal. Alternatively, the active end of the conjugated diene polymer chain reacts with the alkoxy group of the side chain of the polyorganosiloxane to eliminate the alkoxy group, and the conjugated diene polymer chain is conjugated with the silicon atom in the siloxane structure. A new bond is formed with the active end of the diene-based polymer chain, and a siloxane structure is introduced at the end of the conjugated diene-based polymer chain.

In particular, in the second step, the amount of polyorganosiloxane used is 1 mol or more in terms of the number of repeating units of the siloxane structure (-Si-O-) with respect to 1 mol of the polymerization initiator. Among the conjugated diene-based polymer chains having active terminals obtained in the first step, a modified structure with siloxane can be introduced into almost all the conjugated diene-based polymer chains. Therefore, the alkyl metal group as the active terminal of the conjugated diene-based polymer chain having the active terminal obtained in the first step, that is, -R ^- M ⁺ , can be brought into a state in which almost all of them do not remain. Instead, a group represented by ^−O− M ⁺ as a reaction residue will be formed. However, in the present invention, if it is a very small amount (for example, 5% by mass or less), it may contain a conjugated diene polymer chain having an unmodified active terminal that has not been modified with siloxane (for example, 5% by mass or less). That is, if the amount is very small, the alkyl metal group as the active terminal of the conjugated diene polymer chain having the active terminal obtained in the first step, that is, the one in which −R ⁻ M ⁺ remains is contained. Often), it does not rule out such cases.

In the second step, the effect of the present invention is not impaired in the state before the polyorganosiloxane represented by the general formula (1) is reacted with the conjugated diene polymer chain having an active terminal. , Even if a part of the active end of the conjugated diene polymer chain having an active end is added to the polymerization system with a coupling agent or a denaturing agent usually used conventionally to perform coupling or denaturation. Good.

[Third step]
The third step is a step of reacting the conjugated diene polymer chain obtained by reacting the polyorganosiloxane obtained in the second step with a compound represented by the following general formula (2).

In the general formula (2), R ⁹ is a hydrocarbyl group, and A ¹ is a group capable of reacting with a reaction residue generated by a reaction between a conjugated diene polymer chain having an active terminal and a polyorganosiloxane. , A ² is a group containing a nitrogen atom, p is an integer of 0 to 2, q is an integer of 1 to 3, r is an integer of 1 to 3, and p + q + r = 4.

According to the present invention, in the above-mentioned second step, substantially of the alkyl metal group as the active terminal of the conjugated diene polymer chain having the active terminal obtained in the first step, that is, −R ⁻ M ^+. a state so as not to remain any, instead of this, by reaction with a polyorganosiloxane represented by the general formula (1), -O as a reaction residue ^- as having a group represented by M ⁺ Therefore, according to the third step of the present invention, the compound represented by the general formula (2) has a group (−O ⁻ M ^{+) represented by −O−} M ^{+ as such a reaction residue.} It can be appropriately reacted with (including those in which the represented group is hydrolyzed and converted into a hydroxyl group).

That is, according to the present invention, the compound represented by the general formula (2) ^{reacts with the group represented by −R−} M ⁺ , so that the compound represented by the general formula (2) is directly applied to the conjugated diene polymer chain by the general formula. It is possible to appropriately suppress the introduction of the modified structure by the compound represented by (2), whereby the conjugated diene-based polymer chain becomes the polyorganosiloxane represented by the general formula (1). The modified structure of the compound represented by the general formula (2) can be appropriately introduced through the derived structure. As a result, excellent tensile breaking strength and rolling performance can be realized. In addition, it is considered that the workability will be improved. Wet performance is also expected to improve.

However, the conjugated diene polymer chain obtained by reacting the polyorganosiloxane used in the third step may be one that has undergone the second step described above, and is a conjugated diene polymer having a modified structure with siloxane introduced therein. In addition to the chains, if the amount is very small (for example, 5% by mass or less), a conjugated diene polymer chain having an unmodified active terminal into which a siloxane-modified structure has not been introduced may remain (for example, 5% by mass or less). That is, if the amount is very small, the alkyl metal group as the active terminal of the conjugated diene polymer chain having the active terminal obtained in the first step, that is, the one in which −R ⁻ M ⁺ remains is contained. ^{In addition, a part of −O−} M ⁺ as a reaction residue formed as a result of introducing a modified structure with siloxane was hydrolyzed and converted into a hydroxyl group. May be good.

In the compound represented by the general formula (2), R ⁹ in the general formula (2) is a hydrocarbyl group, and examples thereof include an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group and an aralkyl group. , An alkyl group having 1 to 6 carbon atoms is preferable because the effect of the present invention is more excellent. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group and the like, and among these, the effect of the present invention is more effective. For excellent reasons, a methyl group and an ethyl group are more preferable.

In the compound represented by the general formula (2), A ¹ in the general formula (2) is a reaction residue (typically) generated by the reaction of a conjugated diene polymer chain having an active terminal with polyorganosiloxane. is, ^-O - a group capable of reacting with group) represented by ^{M +,} it is preferable -OR 10 ^{(R 10} is a group represented by hydrogen or a hydrocarbyl group). Examples of the hydrocarbyl group that can constitute R ¹⁰ include an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group and the like, and from the viewpoint of reactivity with the above reaction residue, the number of carbon atoms is 1 to 1. It is preferably an alkyl group of 6. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group and the like, and among these, the effect of the present invention is more effective. For excellent reasons, a methyl group and an ethyl group are more preferable.

In the compound represented by the general formula (2), A ² in the general formula (2) is a group containing a nitrogen atom, and is not particularly limited as long as it is a group containing a nitrogen atom, but has a nitrogen atom. It is preferably an organic group, for example, 3-aminopropyl group, 4-aminobutyl group, 3- (2-aminoethylamino) propyl group, 2-dimethylaminoethyl group, 3-dimethylaminopropyl group, 3-. Diethylaminopropyl group, 3-dipropylaminopropyl group, 3-dibutylaminopropyl group, 3-phenylmethylaminopropyl group, 3- (4-methylpiperazinyl) propyl group, N, N-bis (trimethylsilyl) aminopropyl Examples include groups, N, N-bis (triethylsilyl) aminopropyl groups, N, N', N'-tris (trimethylsilyl) -N- (2-aminoethyl) -3-aminopropyl groups and the like. Among these, for the reason that the effect of the present invention is more excellent, primary amino groups having an active hydrogen atom such as 3-aminopropyl group, 4-aminobutyl group, 3- (2-aminoethylamino) propyl group and / Or a group containing a secondary amino group having an active hydrogen atom is preferable. The "active hydrogen atom" refers to a hydrogen atom bonded to an atom other than a carbon atom, and preferably has a lower binding energy than the carbon-hydrogen bond of a polymethylene chain.
^{A 2} in the general formula (2) is mentioned as one of preferred embodiments in which it does not contain a group containing an oxygen atom.

In the compound represented by the general formula (2), p is an integer of 0 to 2, q is an integer of 1 to 3, r is an integer of 1 to 3, and p + q + r = 4. From the viewpoint of reactivity between the conjugated diene polymer chain having an active terminal and the reaction residue generated by the reaction with polyorganosiloxane, p is preferably an integer of 0 to 1, and q is an integer of 2 to 3. Yes, r is an integer of 1-2, more preferably p = 0, q = 3, r = 1. ^{When p is 2, the groups represented by R 9} contained in one molecule of the compound represented by the general formula (2) may be the same or different from each other. It may be. Similarly, when q is 2 or 3, a group represented by the general formula A ¹ which contains multiple compounds per molecule represented by (2) may be the same, together ^{It may be different, and when r is 2 or 3, the groups represented by A 2} contained in one molecule of the compound represented by the general formula (2) are the same. It may be different from each other.

Specific examples of the compound represented by the general formula (2) are not particularly limited, but for example, A ² in the general formula (2) is a primary amino group having an active hydrogen atom and / or an active hydrogen atom. As a compound which is a group containing a secondary amino group, 3-aminopropyldimethylmethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyldimethylethoxysilane, 3-aminopropyl methyl diethoxy silane, as a ^2, such as 3-aminopropyltriethoxysilane, 3-amino compound having a propyl group; 4-aminobutyl dimethylmethoxysilane, 4-aminobutyl methyl dimethoxy silane, 4-aminobutyl trimethoxysilane 4-amino-butyldimethyl silane, 4-aminobutyl methyl diethoxy silane, 4 compounds having a 4-aminobutyl group as a ^2, such as aminobutyl triethoxysilane; 3- (2-aminoethylamino) propyl dimethyl Methoxysilane, 3- (2-aminoethylamino) propylmethyldimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino) propyldimethylethoxysilane, 3- (2-) aminoethylamino) propyl methyl diethoxy silane, as a ^2, such as 3- (2-aminoethylamino) propyltriethoxysilane, compounds having a 3- (2-aminoethylamino) propyl group; and the like.

Further, as a compound in which A ² in the general formula (2) is a group other than a primary amino group having an active hydrogen atom and / or a group containing a secondary amino group having an active hydrogen atom, 3-dimethylamino. Propyltrimethoxysilane, 3-dimethylaminopropylmethyldimethoxysilane, 3-dimethylaminopropyldimethylmethoxysilane, 3-dimethylaminopropyltriethoxysilane, 3-dimethylaminopropylmethyldiethoxysilane, 3-dimethylaminopropyldimethylethoxysilane Such as A ² , a compound having a 3-dimethylaminopropyl group; 3-diethylaminopropyltrimethoxysilane, 3-diethylaminopropylmethyldimethoxysilane, 3-diethylaminopropyldimethylmethoxysilane, 3-diethylaminopropyltriethoxysilane, 3- diethylaminopropyl methyl diethoxy silane, 3 as a ^2, such as diethylaminopropyl dimethyl silane, a compound having a 3-diethylamino-propyl; 3-dipropyl-aminopropyltrimethoxysilane, 3-dipropyl-aminopropyl methyl dimethoxy silane, 3 - dipropyl aminopropyldimethylmethoxysilane, 3-dipropyl-aminopropyltriethoxysilane, 3-dipropyl-aminopropyl methyl diethoxy silane, as a ^2, such as 3-dipropylamino-aminopropyldimethylethoxysilane, 3-dipropylamino Compounds with propyl groups; 3-dibutylaminopropyltrimethoxysilane, 3-dibutylaminopropylmethyldimethoxysilane, 3-dibutylaminopropyldimethylmethoxysilane, 3-dibutylaminopropyltriethoxysilane, 3-dibutylaminopropylmethyldiethoxy silane, 3 as a ^2, such as dibutyl-aminopropyldimethylethoxysilane, 3-compound having dibutyl aminopropyl group; 3-phenyl-methyl aminopropyl trimethoxy silane, 3-phenylmethyl-aminopropyl methyl dimethoxysilane, 3-phenylmethyl aminopropyldimethylmethoxysilane, 3-phenylmethyl-aminopropyltriethoxysilane, 3-phenylmethyl-aminopropyl methyl diethoxy silane, as a ^2, such as 3-phenylmethyl-aminopropyldimethylethoxysilane, 3-phenylmethyl-aminopropyl group Compounds; 3- (4-Methylpiperadi) Nyl) propyltrimethoxysilane, 3- (4-methylpiperazinyl) propylmethyldimethoxysilane, 3- (4-methylpiperazinyl) propyldimethylmethoxysilane, 3- (4-methylpiperazinyl) propyltriethoxy silane, 3- (4-methylpiperazinyl) propyl methyl diethoxy silane, 3- (4-methylpiperazinyl) as ^{a 2,} such as dimethyl silane, 3- (4-methylpiperazinyl) propyl Compounds with;

N, N-bis (trimethylsilyl) aminopropyltrimethoxysilane, N, N-bis (trimethylsilyl) aminopropyltriethoxysilane, N, N-bis (trimethylsilyl) aminopropylmethyldimethoxysilane, N, N-bis (trimethylsilyl) as ^{a 2,} such as amino propyl methyl diethoxy silane, N, compounds with N- bis (trimethylsilyl) aminopropyl groups; N, N- bis (triethylsilyl) aminopropyltrimethoxysilane, N, N- bis (trimethylsilyl) aminopropyltriethoxysilane, N, N- bis (triethylsilyl) aminopropylmethyldimethoxysilane, N, as a ^2, such as N- bis (triethylsilyl) aminopropyl methyl diethoxy silane, N, N- bis (triethylsilyl ) Compounds with aminopropyl groups; N, N', N'-tris (trimethylsilyl) -N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N, N', N'-tris (trimethylsilyl) -N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N, N', N'-tris (trimethylsilyl) -N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N, N ', as ^{a 2,} such as N'- tris (trimethylsilyl) -N- (2-aminoethyl) -3-aminopropyl methyl diethoxy silane, N, N', N'- tris (trimethylsilyl) -N- ( 2-Aminoethyl) -3-aminopropyl group-bearing compounds; and the like.
Of these, compounds represented by the general formula (2), from the viewpoint of obtaining superior effects of the present invention (especially low rolling resistance), having a group containing a secondary amino group having an active hydrogen atom as A ² preferably compound is, more preferably a compound having a group containing a secondary amino group having a primary amino group and an active hydrogen atom having an active hydrogen atom as a ^2, 3- (2-aminoethyl Compounds having an amino) propyl group are more preferred.

The amount of the compound represented by the general formula (2) is not particularly limited, but is preferably 0.1 with respect to 1 mol of the polymerization initiator used in the first step because the effect of the present invention is more excellent. It is ~ 5 mol, more preferably 0.2-2 mol, still more preferably 0.4 ~ 1.5 mol.

The timing for adding the compound represented by the general formula (2) to the solution containing the conjugated diene polymer chain is after the addition of the polyorganosiloxane represented by the general formula (1) in the second step described above. If so, there is no particular limitation. For example, as in the second step described above, the polymerization reaction is not completed, and the solution containing the conjugated diene-based polymer chain also contains the monomer, more specifically, the conjugated diene. The compound represented by the general formula (2) is added to this solution in a state where the solution containing the system polymer chain contains 100 ppm or more, more preferably 300 to 50,000 ppm of monomer. Can be done. By adding the compound represented by the general formula (2) in this way, side reactions between the conjugated diene polymer chain and impurities contained in the polymerization system are suppressed, and the reaction is satisfactorily controlled. It becomes possible. Alternatively, by adding an alcohol such as water or methanol to the solution containing the conjugated diene polymer chain before or after adding the compound represented by the general formula (2), the solution can be used. A modification reaction in a state where the group represented by ^−O− M ⁺ as a reaction residue formed by the reaction with the polyorganosiloxane represented by the general formula (1) is hydrolyzed and converted into a hydroxyl group. May be done. When the compound represented by the general formula (2) is added to the solution containing the conjugated diene polymer chain, the compound represented by the general formula (2) may be added after being dissolved in the inert solvent. However, it may be added directly without being dissolved in the inert solvent. The reaction temperature and reaction time are the same as in the first step.

Then, after reacting the compound represented by the general formula (2), if necessary, a known polymerization inhibitor or the like is added to inactivate the reaction system, and then, if desired, a phenol-based stabilizer. , Anti-aging agents such as phosphorus-based stabilizers and sulfur-based stabilizers, crumbing agents, and anti-scale agents are added to the reaction solution, and then the polymerization solvent is separated from the reaction solution by direct drying or steam stripping. Then, the conjugated diene-based rubber is collected. Before separating the polymerization solvent from the reaction solution, a spreading oil may be mixed with the polymerization solution and the conjugated diene rubber may be recovered as the oil spreading rubber.

Examples of the spreading oil used when recovering the conjugated diene-based rubber as an oil-extended rubber include paraffin-based, aromatic-based and naphthen-based petroleum-based softeners, plant-based softeners, and fatty acids. When a petroleum-based softener is used, the content of polycyclic aromatics extracted by the method of IP346 (inspection method of THE INSTITUTE PETROLEUM in the United Kingdom) is preferably less than 3%. When the spreading oil is used, the amount used is preferably 5 to 100 parts by mass, more preferably 10 to 60 parts by mass, and further preferably 20 to 50 parts by mass with respect to 100 parts by mass of the conjugated diene rubber. ..

As described above, in the specific conjugated diene-based rubber, the polyorganosiloxane represented by the general formula (1) as a modifier in the above-mentioned second step is used with respect to 1 mol of the polymerization initiator used in the first step. Then, the siloxane structure (-Si-O-) in the polyorganosiloxane is added at a ratio of 1 mol or more in terms of the number of repeating units to carry out the reaction, and then, in the above-mentioned third step, it is generally used as a modifier. It is obtained by carrying out the reaction using the compound represented by the formula (2). Therefore, the specific conjugated diene rubber includes one in which a modified structure by siloxane and a modified structure by a compound represented by the general formula (2) are introduced at the end of the polymer chain. , The polymer chain terminal may include one in which only a modified structure with siloxane is introduced. Further, as long as the effect of the present invention is not impaired, for example, only a modified structure by a compound represented by the general formula (2) is introduced at the end of the polymer chain, or any modified structure is introduced. It may contain something that does not exist. In particular, in the present invention, from the viewpoint of more appropriately realizing the effects of the present invention, a modified structure with siloxane and a modified structure with a compound represented by the general formula (2) are introduced at the end of the polymer chain. The ratio is preferably 10% by mass or more, and more preferably 20% by mass or more. The upper limit is not particularly limited.

<Monomer unit content>
The specific conjugated diene-based rubber is a conjugated diene monomer unit constituting the specific conjugated diene-based rubber and an aromatic vinyl monomer unit that can be used as needed because the effect of the present invention is more excellent. Of the total, those containing 50 to 100% by mass of the conjugated diene monomer unit are preferable, those containing 52 to 95% by mass are more preferable, and those containing 0 to 50% by mass of the aromatic vinyl monomer unit are preferable. preferable.

<Vinyl bond content>
The vinyl bond content in the conjugated diene monomer unit in the specific conjugated diene rubber is preferably 1 to 90% by mass, more preferably 3 to 80% by mass, and particularly preferably 3 to 80% by mass because the effect of the present invention is more excellent. It is 5 to 70% by mass.

[Coupling rate]
The coupling ratio of the specific conjugated diene rubber is not particularly limited, but is preferably 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 40% by mass or more because the effect of the present invention is more excellent. It is preferably 80% by mass or less, more preferably 75% by mass or less, and particularly preferably 70% by mass or less. The coupling ratio is determined by reacting with a polyorganosiloxane represented by the general formula (1), a compound represented by the general formula (2), and a coupling agent or other modifier used as necessary. It is the mass fraction of the polymer molecule having a molecular weight of 1.8 times or more the peak top molecular weight of the conjugated diene polymer chain having the previous active end with respect to the total amount of the finally obtained conjugated diene rubber. The molecular weight at this time shall be determined as a polystyrene-equivalent molecular weight by gel permeation chromatography.

[Molecular weight]
The weight average molecular weight (Mw) of the specific conjugated diene rubber is a value measured by gel permeation chromatography in terms of polystyrene, preferably 100,000 to 3,000,000, and more preferably 150,000 to 2. 000,000, particularly preferably 200,000 to 1,500,000. By setting the weight average molecular weight of the conjugated diene rubber within the above range, silica can be easily blended into the conjugated diene rubber, the processability of the rubber composition can be further improved, and the effects of the present invention can be further improved. Will be better.

The molecular weight distribution represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the specific conjugated diene rubber is 1.1 to 1 and 3 because the effect of the present invention is more excellent. It is preferably 0, more preferably 1.2 to 2.5, and particularly preferably 1.2 to 2.2.

〔viscosity〕
The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the specific conjugated diene rubber is preferably 20 to 100, more preferably 30 to 90, and particularly preferably 35 to 80, because the effect of the present invention is more excellent. .. When the conjugated diene rubber is an oil-extended rubber, it is preferable that the Mooney viscosity of the oil-extended rubber is in the above range.

〔Content〕
As described above, the content of the specific conjugated diene rubber in the conjugated diene rubber (including the specific conjugated diene rubber) (including the specific conjugated diene rubber) is 30% by mass or more.
The upper limit of the content of the specific conjugated diene rubber in the conjugated diene rubber is not particularly limited and is 100% by mass. The content of the specific conjugated diene rubber in the conjugated diene rubber is preferably 50% by mass or more, more preferably 60 to 90% by mass, and 60 by mass, for the reason that the effect of the present invention is more excellent. It is more preferably ~ 85% by mass.

[Other rubber components]
The conjugated diene-based rubber may further contain a rubber component (other rubber component) other than the specific conjugated diene-based rubber.
Examples of such other rubber components include conjugated diene rubbers (y) other than the specific conjugated diene rubbers.
Examples of the conjugated diene rubber (y) include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), a copolymer of aromatic vinyl and conjugated diene, and acrylonitrile-butadiene copolymer rubber (Acrylonitrile-butadiene copolymer rubber). NBR), butyl rubber (IIR), halogenated butyl rubber (Br-IIR, Cl-IIR), chloroprene rubber (CR) and the like. Among them, butadiene rubber (BR), which is a copolymer of aromatic vinyl and conjugated diene, is preferable because the effect of the present invention is more excellent.

The content of the other rubber component (conjugated diene rubber (y)) in the conjugated diene rubber is not particularly limited, but is preferably 0 to 50% by mass for the reason that the effect of the present invention is more excellent. It is more preferably 10 to 40% by mass, further preferably 15 to 40% by mass.

(Weight average molecular weight of conjugated diene rubber (y))
The weight average molecular weight of the conjugated diene rubber (y) is not particularly limited, but is preferably 100,000 to 1,500,000, preferably 600,000 to 1,300,000 from the viewpoint of handling. Is more preferable. The weight average molecular weight (Mw) of the conjugated diene rubber (y) shall be measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent in terms of standard polystyrene.

(Glass transition temperature of conjugated diene rubber (y))
The Tg (glass transition temperature) of the conjugated diene rubber (y) is not particularly limited, but is preferably −10 ° C. or lower for the reason that the effect of the present invention is more excellent.
The glass transition temperature of each conjugated diene rubber (y) was measured at a heating rate of 10 ° C./min using a differential scanning calorimeter (DSC) and calculated by the midpoint method.

[2] Silica The silica contained in the composition of the present invention is not particularly limited. As the silica, for example, any conventionally known silica blended in a rubber composition for applications such as tires can be used.
Examples of the silica include wet silica, dry silica, fumed silica, and diatomaceous earth.

(CTAB adsorption specific surface area of silica)
The CTAB (cetyltrimethylammonium bromide) adsorption specific surface area of the silica is preferably 115 to 300 m ² / g, more preferably ^{140 to 250 m 2 / g, for the reason that the effect of the present invention is more excellent.} It is more preferably 180 to 230 m ^{2 / g.}

In the present specification, the CTAB adsorption specific surface area of silica is a value obtained by measuring the amount of CTAB adsorbed on the silica surface according to JIS K6217-3: 2001 "Part 3: How to obtain the specific surface area-CTAB adsorption method". is there.

<Silica content>
In the present invention, the content of the silica is 30 parts by mass or more with respect to 100 parts by mass of the conjugated diene rubber.
The "100 parts by mass of the conjugated diene rubber" which is the standard of the content of the silica means "100 parts by mass of the conjugated diene rubber containing 30% by mass or more of the specific conjugated diene rubber".
The content of the silica is preferably 50 to 200 parts by mass and more preferably 70 to 150 parts by mass with respect to 100 parts by mass of the conjugated diene rubber because the effect of the present invention is more excellent. preferable.

[3] Silane Coupling Agent The silane coupling agent contained in the composition of the present invention is not particularly limited as long as it is a silane compound having a hydrolyzable group and an organic functional group.
The hydrolyzable group is not particularly limited, and examples thereof include an alkoxy group, a phenoxy group, a carboxyl group, and an alkenyloxy group. Of these, an alkoxy group is preferable because the effect of the present invention is more excellent. When the hydrolyzable group is an alkoxy group, the number of carbon atoms of the alkoxy group is preferably 1 to 16 and more preferably 1 to 4 for the reason that the effect of the present invention is more excellent. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group and the like.

The organic functional group is not particularly limited, but is preferably a group capable of forming a chemical bond with an organic compound, for example, an epoxy group, a vinyl group, an acryloyl group, a methacryloyl group, an amino group, a sulfide group, a mercapto group, or a block. Examples thereof include a mercapto group (protected mercapto group) (for example, an octanoylthio group), and among them, a sulfide group (particularly, a disulfide group and a tetrasulfide group), a mercapto group, and a blocked mercapto group for the reason that the effect of the present invention is more excellent. Is preferable.

Specific examples of the above silane coupling agent include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) disulfide, and 3-trimethoxy. Cyrilpropyl-N, N-dimethylthiocarbamoyl-tetrasulfide, trimethoxysilylpropyl-mercaptobenzothiazole tetrasulfide, triethoxysilylpropyl-methacrylate-monosulfide, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyl-tetrasulfide Silane coupling agent having a sulfide group such as;
Mercaptosilanes such as mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane;
Examples thereof include compounds represented by the following general formula (S) such as 3-octanoylthio-1-propyltriethoxysilane.
(C _n H _{2n + 1} O) _3- Si-C _m H _2m- S-CO-C _k H _{2k + 1} General formula (S)
In the general formula (S), n represents an integer of 1 to 3, m represents an integer of 1 to 5 (preferably an integer of 2 to 4), and k represents an integer of 1 to 15 (preferably 5 to 5). (An integer of 10).
As the silane coupling agent, one of these may be used alone, or two or more thereof may be used in combination.

The silane coupling agent is preferably a silane coupling agent having a sulfide group or a compound represented by the above general formula (S) because the effect of the present invention is more excellent.

<Content of silane coupling agent>
In the composition of the present invention, the content of the silane coupling agent is 3 to 30% by mass with respect to the content of silica described above. Among them, 5 to 20% by mass is preferable for the reason that the effect of the present invention is more excellent.

Further, in the composition of the present invention, the content of the silane coupling agent is 1 to 30 parts by mass with respect to 100 parts by mass of the above-mentioned conjugated diene rubber because the effect of the present invention is more excellent. It is preferably 2 to 20 parts by mass, more preferably 4 to 9 parts by mass.

[4] Nonionic Surfactant The nonionic surfactant contained in the composition of the present invention is a compound containing polypropylene oxyblock (PPOB) and polyethylene oxyblock (PEOB).
In the nonionic surfactant, it is considered that polypropylene oxyblock (PPOB) can function as a relatively hydrophobic group and polyethylene oxyblock (PEOB) can function as a relatively hydrophilic group.
The composition of the present invention is excellent in processability, tensile breaking strength, and rolling performance by containing the above nonionic surfactant.
In the present invention, polypropylene oxyblock (PPOB) refers to a block polymer whose repeating unit is a propylene oxy group.
Polyethylene oxyblock (PEOB) refers to a block polymer whose repeating unit is an ethyleneoxy group.
The nonionic surfactant may be a block copolymer having at least one PPOB and one PEOB in one molecule.

In the nonionic surfactant, the sequences of PPOB and PEOB are not particularly limited. For example, the diblock of PPOB-PEOB; triblocks such as PPOB-PEOB-PPOB, PEOB-PPOB-PEOB can be mentioned.
The PPOB and PEOB sequences are preferably triblock, and more preferably PPOB-PEOB-PPOB, from the viewpoint that the effects of the present invention are more excellent.

The nonionic surfactant is preferably linear as one of the preferred embodiments.

The degree of polymerization of one PPPOB contained in the nonionic surfactant is not particularly limited (as long as the number of repeating units of the propyleneoxy group is 2 or more). The same applies to PEOB.
The higher the proportion of PPOB in the nonionic surfactant, the higher the affinity with the diene rubber tends to be.

The nonionic surfactant preferably has a hydroxy group, more preferably a plurality of hydroxy groups per molecule, and two hydroxy groups per molecule, from the viewpoint that the effect of the present invention is more excellent. It is more preferable to have a group.

From the viewpoint that the effect of the present invention is more excellent, the nonionic surfactant preferably has a hydroxy group at the end of the nonionic surfactant, and has all the terminals of the nonionic surfactant. It is more preferable to have a hydroxy group.
One of the preferred embodiments of the nonionic surfactant is that it is linear and has one hydroxy group at each end thereof.

式（Ｘ）中、ａ、ｂ、ｃはそれぞれ独立に２以上である。 Examples of the nonionic surfactant include a compound represented by the following formula (X) or a compound represented by the following formula (I).

In formula (X), a, b, and c are 2 or more independently.

式（Ｉ）中、ａ、ｂ、ｃはそれぞれ独立に２以上である。

In formula (I), a, b, and c are 2 or more independently.

<A, b, c>
In the present invention, b and a + c in the formula (X) or the formula (I) ^{can be analyzed by NMR (nuclear magnetic resonance) (for example, 1} H-NMR). For example, deuterated chloroform or heavy DMSO can be used as the solvent in the above analysis.

In the formula (X), the above b means the average value of the number of repeating units of the ethyleneoxy group. Further, a + c means the average value of the total number of repeating units of the propyleneoxy group. The above a and c may be 1/2 of the average value of the total number of repeating units of the propyleneoxy group.
In the formula (X), the above a to c can be independently set to 2 or more.

In the formula (I), the above b means the average value of the number of repeating units of the propyleneoxy group. Further, a + c means the average value of the total number of repeating units of ethyleneoxy groups. The above a and c may be 1/2 of the average value of the total number of repeating units of ethyleneoxy groups.
In the formula (I), the above a to c can be independently set to 2 or more.

In the formula (I), b is preferably 100 or less, more preferably 10 to 90, still more preferably 50 to 85, from the viewpoint of being superior to the effect of the present invention.
In the formula (I), a + c is preferably 100 or less, more preferably 4 to 65, still more preferably 5 to 55, particularly preferably 5 to 40, and most preferably 5 to 40, from the viewpoint of being superior to the effect of the present invention. It is 10 to 40.

The nonionic surfactant preferably contains a compound represented by the above formula (X) from the viewpoint that the effect of the present invention is more excellent.

The compound represented by the above formula (X) as the nonionic surfactant has block B in which the repeating unit is an ethyleneoxy group and the number of repeating units is b in the center as the main chain, and block B of the above block B. Both linear blocks having a block A having a repeating unit of a propyleneoxy group and a repeating unit number of a and a block C having a repeating unit of a propyleneoxy group and a repeating unit number of c on both sides. It is a polymer and has hydroxy groups at both ends.

<A + c>
The total (a + c) of a and c shown in the formula (X) can be, for example, 100 or less, the effect of the present invention (particularly workability and / or rolling performance) is more excellent, and the conjugated diene rubber From the viewpoint of excellent affinity with and dispersibility of silica, it is preferably 55 to 95, more preferably 65 to 85, and even more preferably 70 to 85.

<B>
The b represented by the formula (X) can be, for example, 100 or less, the effect of the present invention (particularly workability and / or rolling performance) is more excellent, the dispersibility of silica is excellent, and the compound with the conjugated diene rubber From the viewpoint of excellent balance between affinity and dispersibility of silica, it is preferably 5 to 45, more preferably 15 to 35, and even more preferably 15 to 30.

The compound represented by the above formula (X) as the nonionic surfactant preferably has b of 5 to 45 and a + c of 55 to 95 from the viewpoint of more excellent effect of the present invention. , B is 15 to 35, a + c is more preferably 65 to 85, b is 15 to 30, and a + c is more preferably 70 to 85.

As a method for producing the nonionic surfactant, for example, a conventionally known method can be used. Specifically, for example, the nonionic surfactant can be obtained by sequentially reacting 1 mol of water with propylene oxide or ethylene oxide in an appropriate amount using an alkaline catalyst such as sodium hydroxide. it can.

<Content of nonionic surfactant>
In the present invention, the content of the nonionic surfactant is 0.1 to 15% by mass with respect to the content of the silica.
When the content of the nonionic surfactant is in the above range, the composition of the present invention is excellent in processability, rolling performance, and tensile strength at break.

The content of the nonionic surfactant is more excellent in the effect of the present invention, is excellent in affinity with the conjugated diene rubber containing the specific conjugated diene rubber in a predetermined amount, and is excellent in silica dispersibility. From this viewpoint, it is preferably 0.5 to 15% by mass, more preferably 1 to 15% by mass, and further preferably 3 to 15% by mass with respect to the content of the silica.

[5] Optional component (glycerin partial fatty acid ester)
The composition of the present invention preferably contains a glycerin partial fatty acid ester together with the nonionic surfactant described above. Since the glycerin partial fatty acid ester improves the dispersibility of the nonionic surfactant, as a result, the dispersibility of silica is further enhanced, and the above-mentioned effect of the present invention becomes more excellent. In the present invention, the partial fatty acid ester refers to a compound in which some hydroxyl groups of a polyhydric alcohol are esterified with a fatty acid. Glycerin partial fatty acid esters include glycerin monofatty acid esters and / or glycerin difatty acid esters.

-Fatty acid Examples of the fatty acid of the glycerin partial fatty acid ester include monovalent carboxylic acid.
Specifically, for example, acetic acid, propionic acid, butanoic acid, pentanoic acid, isopentanoic acid, caproic acid (hexanoic acid), heptanic acid, caproic acid (octanoic acid), nonanoic acid, capric acid (decanoic acid), lauric acid ( Saturated fatty acids such as undecanoic acid), myristic acid (tetradecanoic acid), palmitic acid (hexadecanoic acid), stearic acid (octadecanoic acid), arachidic acid (eicosanoic acid), behenic acid (docosic acid), tetracosanoic acid, hexacosanoic acid; olein Unsaturated fatty acids such as acids, linoleic acid, linolenic acid, ellaidic acid and erucic acid; hydroxy fatty acids such as ricinoleic acid and hydroxystearic acid can be mentioned.

-Carbon number The fatty acid is preferably a saturated fatty acid having 14 to 24 carbon atoms, more preferably 16 to 22 carbon atoms, and most preferably stearic acid from the viewpoint of silica dispersibility. One type of fatty acid may be used alone or two or more types may be used in combination, but when there are two or more types of fatty acids, one of them is preferably stearic acid. The number of carbon atoms means the number of all carbon atoms that the saturated fatty acid has per molecule.

The glycerin partial fatty acid ester preferably contains a glycerin monofatty acid ester from the viewpoint of silica dispersibility.
When the glycerin partial fatty acid ester is a mixture of the glycerin monofatty acid ester and the glycerin difatty acid ester, the content of the glycerin monofatty acid ester in the total amount of the glycerin partial fatty acid ester is preferably at least 50% by mass.

-The nonionic surfactant / glycerin partial fatty acid ester When the composition of the present invention further contains the glycerin partial fatty acid ester, the effect of the present invention is more excellent, and the specific conjugated diene rubber is contained in a predetermined amount. From the viewpoint of excellent affinity with conjugated diene rubber and excellent dispersibility of silica, the ratio of the content of the above-mentioned nonionic surfactant to the content of the glycerin partial fatty acid ester (the above-mentioned nonionic surfactant). The agent / glycerin partial fatty acid ester) is preferably 0.01 to 10 in mass ratio, more preferably 0.1 to 1.0, and further preferably 0.2 to 0.5. preferable.

-Content of glycerin partial fatty acid ester Further, when the composition of the present invention further contains glycerin partial fatty acid ester, the content of glycerin partial fatty acid ester is determined by the above-mentioned specific conjugated diene rubber for the same reason as above. It is preferably 0.1 to 10 parts by mass, and more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the conjugated diene rubber contained in the above amount.

-Total content of the nonionic surfactant and the glycerin partial fatty acid ester When the composition of the present invention further contains the glycerin partial fatty acid ester, the nonionic surfactant and the glycerin partial fatty acid ester described above are further contained. For the same reason as described above, the total content of the above is preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the conjugated diene rubber containing the specific conjugated diene rubber in a predetermined amount. ..
One type of glycerin partial fatty acid ester may be used alone, or two or more types may be used in combination.

(Fatty acid metal salt)
The composition of the present invention preferably contains a fatty acid metal salt together with the above-mentioned nonionic surfactant. Since the fatty acid metal salt improves the dispersibility of the nonionic surfactant, as a result, the dispersibility of silica is further enhanced, and the above-mentioned effect of the present invention becomes more excellent.

The fatty acid metal salt is a salt of a fatty acid and a metal.
Examples of the fatty acid of the fatty acid metal salt include the same fatty acids as those of the glycerin partial fatty acid ester.
From the viewpoint of silica dispersibility, the fatty acid is preferably a saturated fatty acid having 8 to 24 carbon atoms, more preferably a saturated fatty acid having 10 to 22 carbon atoms, further preferably a saturated fatty acid having 16 to 22 carbon atoms, and stearic acid. Most preferred. One type of fatty acid may be used alone, or two or more types may be used in combination. The number of carbon atoms means the number of all carbon atoms that the saturated fatty acid has per molecule.

-Metal of fatty acid metal salt Examples of the metal of the fatty acid metal salt include alkali metals, alkaline earth metals, transition metals (metals of groups 3 to 11), aluminum, germanium, tin, antimony and the like.
Among them, the metal of the fatty acid metal salt is preferably an alkali metal (lithium, potassium, sodium, etc.) or an alkaline earth metal (berylium, magnesium, calcium, strontium, barium, etc.) from the viewpoint of silica dispersibility, and is alkaline. Earth metals are more preferred, magnesium is even more preferred.

Specific examples of preferable fatty acid metal salts include potassium stearate, zinc stearate, magnesium stearate, magnesium oleate, magnesium palmitate, magnesium myristate, magnesium laurate, magnesium linoleate, magnesium behenate and the like.

-Nonionic Surfactant / Fatty Acid Metal Salt When the composition of the present invention further contains a fatty acid metal salt, the effect of the present invention is more excellent, and the conjugated diene containing the specific conjugated diene rubber in a predetermined amount. From the viewpoint of excellent affinity with system rubber and excellent dispersibility of silica, the ratio of the content of the above-mentioned nonionic surfactant to the content of the fatty acid metal salt (the above-mentioned nonionic surfactant / The fatty acid metal salt) is preferably 0.01 to 10 by mass, more preferably 0.1 to 1.0, and even more preferably 0.2 to 0.5.

-Content of fatty acid metal salt Further, when the composition of the present invention further contains a fatty acid metal salt, the content of the fatty acid metal salt is the above-mentioned specific conjugated diene rubber in a predetermined amount for the same reason as described above. It is preferably 0.1 to 10 parts by mass, and more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the above-mentioned conjugated diene rubber containing.

-Total content of the above-mentioned nonionic surfactant and fatty acid metal salt Further, when the composition of the present invention further contains the fatty acid metal salt, the total content of the above-mentioned nonionic surfactant and fatty acid metal salt is contained. For the same reason as described above, the amount is preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the conjugated diene-based rubber containing the specific conjugated diene-based rubber in a predetermined amount.
One type of fatty acid metal salt may be used alone, or two or more types may be used in combination.

The composition of the present invention preferably contains both a glycerin partial acid ester and a fatty acid metal salt together with the above-mentioned nonionic surfactant for the reason that the above-mentioned effect of the present invention is further excellent.

(Other additives)
If necessary, the composition of the present invention may further contain additives as long as the effects and purposes are not impaired.
Examples of the additive include a filler other than silica (for example, carbon black), zinc oxide (zinc oxide), stearic acid, an antiaging agent, a silane compound other than the silane coupling agent, a processing aid, and an oil ( For example, various additives commonly used in rubber compositions such as process oils, aroma oils), liquid polymers, terpene resins, thermosetting resins, vulcanizing agents (eg sulfur), vulcanization accelerators, etc. Be done.

[Carbon black]
The composition of the present invention preferably further contains carbon black for the reason that the effect of the present invention is more excellent.
The carbon black is not particularly limited, and for example, various grades such as SAF-HS, SAF, ISAF-HS, ISAF, ISAF-LS, IISAF-HS, HAF-HS, HAF, HAF-LS, FEF, GPF, SRF and the like. Can be used.
The nitrogen adsorption specific surface area (N ₂ SA) of the carbon black is not particularly limited, but is preferably 50 to ²⁰⁰ m 2 / g, ^{preferably 70 to 150 m 2} / g, for the reason that the effect of the present invention is more excellent. Is more preferable.
Here, the nitrogen adsorption specific surface area (N ₂ SA) is the amount of nitrogen adsorbed on the carbon black surface according to JIS K6217-2: 2001 "Part 2: How to obtain the specific surface area-Nitrogen adsorption method-Single point method". It is a measured value.

In the composition of the present invention, the content of carbon black is not particularly limited, but for the reason that the effect of the present invention is more excellent, the content of the specific conjugated diene rubber is contained in a predetermined amount with respect to 100 parts by mass of the conjugated diene rubber. The amount is preferably 1 to 100 parts by mass, and more preferably 2 to 10 parts by mass.

[Specific alkyltriethoxysilane]
The composition of the present invention further contains alkyltriethoxysilane represented by the following general formula (I) (hereinafter, also referred to as "specific alkyltriethoxysilane") for the reason that the effect of the present invention is more excellent. preferable. The silane coupling agent does not contain the specific alkyltriethoxysilane.

In the above general formula (I), R ¹ represents an alkyl group having 7 to 20 carbon atoms. Et represents an ethyl group.
Specific examples of the alkyl group having 7 to 20 carbon atoms include a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group and a dodecyl group. Of these, an octyl group and a nonyl group are preferable because the effect of the present invention is more excellent.

In the composition of the present invention, the content of the specific alkyltriethoxysilane is not particularly limited, but for the reason that the effect of the present invention is more excellent, 2.0 to 10.0% by mass with respect to the above-mentioned silica content. Is preferable.

(Manufacturing method of rubber composition for tire tread)
The method for producing the composition of the present invention is not particularly limited, and as a specific example thereof, each of the above-mentioned components is kneaded using a known method or apparatus (for example, Banbury mixer, kneader, roll, etc.). The method etc. can be mentioned. When the composition of the present invention contains sulfur or a vulcanization accelerator, components other than sulfur and the vulcanization accelerator are first mixed at a high temperature (preferably 100 to 160 ° C.), cooled, and then sulfur or It is preferable to mix the vulcanization accelerator.
In addition, the composition of the present invention can be vulcanized or crosslinked under conventionally known vulcanization or crosslinking conditions.

[Pneumatic tires]
The pneumatic tire of the present invention is a pneumatic tire manufactured by using the composition of the present invention described above. Among them, it is preferable that the tire is a pneumatic tire in which the composition of the present invention is used (arranged) for the tire tread (cap tread).

FIG. 1 shows a schematic partial cross-sectional view of an example of an embodiment of the pneumatic tire of the present invention, but the pneumatic tire of the present invention is not limited to the embodiment shown in FIG.

In FIG. 1, reference numeral 1 represents a bead portion, reference numeral 2 represents a sidewall portion, and reference numeral 3 represents a tire tread portion.
Further, a carcass layer 4 in which a fiber cord is embedded is mounted between the pair of left and right bead portions 1, and the end portion of the carcass layer 4 is placed around the bead core 5 and the bead filler 6 from the inside to the outside of the tire. It is folded back and rolled up.
Further, in the tire tread portion 3, a belt layer 7 is arranged on the outside of the carcass layer 4 over one circumference of the tire.
Further, in the bead portion 1, the rim cushion 8 is arranged at a portion in contact with the rim.
The tire tread portion 3 is formed by the composition of the present invention described above.

The pneumatic tire of the present invention can be manufactured, for example, according to a conventionally known method. Further, as the gas to be filled in the pneumatic tire, an inert gas such as nitrogen, argon or helium can be used in addition to normal or adjusted oxygen partial pressure.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

[Manufacturing of specific conjugated diene rubber]
The specific conjugated diene rubber 1 was produced as follows.
Here, the specific conjugated diene rubber 1 is a conjugated diene rubber produced by the method for producing a conjugated diene rubber including the above-mentioned steps 1 to 3, and corresponds to the above-mentioned specific conjugated diene rubber. Further, the specific conjugated diene rubber 1 includes the above-mentioned steps A and B in the first step, and has a PI block.

<Specific conjugated diene rubber 1>
To a nitrogen-substituted 800 ml ampoule bottle, 74.3 g of cyclohexane and 0.48 mmol of tetramethylethylenediamine were added, and 4.76 mmol of n-butyllithium (tetramethylethylenediamine as a polar compound with respect to 1 mol of n-butyllithium) was added. The amount of the above is 0.10 mol) was added. Then, 17.3 g of isoprene and 1.3 g of styrene were slowly added and reacted in an ampoule bottle at 50 ° C. for 120 minutes to obtain a polymer block (A) having an active terminal. The weight average molecular weight (Mw) of this polymer block (A) is 6,500, the molecular weight distribution (Mw / Mn) is 1.12, the styrene monomer unit content is 7.0% by mass, and the isoprene monomer unit. The content was 93.0% by mass, and the vinyl bond content was 7.5% by mass.

After charging 4000 g of cyclohexane, 3.57 mmol of tetramethylethylenediamine, 252 g of 1,3-butadiene, and 348 g of styrene in an autoclave with a stirrer under a nitrogen atmosphere, the polymer block (A) having the active terminal obtained above was charged. Was added and polymerization was started at 50 ° C. (the amount of tetramethylethylenediamine as a polar compound present in the reaction system was 0.85 mol with respect to 1 mol of n-butyllithium used). After 15 minutes from the start of the polymerization, 338 g of 1,3-butadiene and 62 g of styrene were continuously added over 60 minutes. The maximum temperature during the polymerization reaction was 70 ° C. After the completion of continuous addition, the polymerization reaction was continued for another 15 minutes, and after confirming that the polymerization conversion rate was in the range of 95% to 100%, 40 polyorganosiloxane represented by the following formula (11) was added. In the state of a xylene solution having a mass% concentration, 1.51 g (1.1 times the molar amount of n-butyllithium used in terms of the number of repeating units of the siloxane structure (-Si-O-) in the polyorganosiloxane) (Amount corresponding to) was added and reacted for 30 minutes. Then, 4.76 mmol of 3- (2-aminoethylamino) propyltrimethoxysilane (equivalent to 1.0 times the molar amount of n-butyllithium used) was added and reacted for 10 minutes. Then, as a polymerization inhibitor, methanol corresponding to twice the molar amount of n-butyllithium used was added to obtain a solution containing a conjugated diene rubber. To this solution, 0.15 part of Irganox 1520L (manufactured by BASF) as an anti-aging agent was added to 100 parts of conjugated diene rubber, the solvent was removed by steam stripping, and the temperature was 60 ° C. for 24 hours. Vacuum drying was performed to obtain a solid conjugated diene rubber. The obtained conjugated diene-based rubber is designated as the specific conjugated diene-based rubber 1. The weight average molecular weight (Mw) of the specific conjugated diene rubber 1 is 570,000, the coupling rate is 45.0%, the styrene monomer unit content is 41.1% by mass, and the vinyl bond content is 33.5% by mass. %Met.

In the above formula (11), X ¹ , X ⁴ , R ^{1 to} R ³ and R ^{5 to} R ⁸ are methyl groups. In the above formula (11), m is 80 and k is 120. In the above formula (11), X ² is a group represented by the following formula (12) (where * represents a bonding position).

<Manufacturing of rubber composition for tire tread>
The components shown in Table 1 below were blended in the proportions (parts by mass) shown in the same table.
Specifically, first, among the components shown in the same table, the components excluding sulfur and the vulcanization accelerator were mixed for 5 minutes using a 1.7 liter sealed Banbury mixer. The temperature at the time of release was 152 ° C., and the mixture was cooled to room temperature to obtain a masterbatch. Further, sulfur and a vulcanization accelerator were added to the obtained master batch, and these were mixed for 3 minutes using the above-mentioned Banbury mixer and released at 110 ° C. to obtain a rubber composition for tire tread.
When the rubber component is an oil-extended product, the mass portion represents the net amount of rubber (the amount excluding oil).

<Making a vulcanized rubber sheet>
Each tire tread rubber composition (unvulcanized) obtained as described above is press-vulcanized at 160 ° C. for 20 minutes in a mold to vulcanize a rubber sheet (length 15 cm x width 15 cm x thickness 0.2 cm). ) Was prepared.

<Evaluation>
The rubber composition for each tire tread or each vulcanized rubber sheet obtained as described above was evaluated as follows.

(Workability)
_{-Measurement of Mooney Viscosity The Mooney viscosity (ML 1 + 4} ) at 100 ° C. was measured for each tire tread rubber composition obtained as described above according to JIS K6300-1: 2013.
-Evaluation result of Mooney viscosity The evaluation result of Mooney viscosity is shown in the "Workability" column of Table 1 as an index with the Mooney viscosity of the standard example as 100.
-Evaluation criteria for workability The smaller the index of Mooney viscosity, the lower the viscosity and the better the workability.

(Tensile breaking strength)
-Tensile test A dumbbell-shaped No. 3 test piece was punched out from each vulcanized rubber sheet prepared as described above in accordance with JIS K6251: 2010. Using each of the above test pieces, a tensile test was conducted under the conditions of room temperature (23 ° C.) and a tensile speed of 500 mm / min, and the tensile breaking strength of each test piece was measured.
-Evaluation result of tensile breaking strength The obtained tensile breaking strength result is shown in the "Tensile breaking strength" column of Table 1 as an index with the value of the standard example as 100.
-Evaluation Criteria for Tensile Breaking Strength In the present invention, if the result (index) of the tensile breaking strength is 100 or more, the tensile breaking strength is considered to be excellent.
The larger the index of "tensile breaking strength", the higher the tensile breaking strength. The higher the tensile breaking strength, the better the wear resistance when the tire is made, which is preferable.

(Rolling performance)
-Measurement of tan δ (60 ° C.) According to JIS K6394: 2007, using a viscoelastic spectrometer (manufactured by Toyo Seiki Seisakusho Co., Ltd.), conditions of stretch deformation strain rate of 10% ± 2%, frequency of 20 Hz, and temperature of 60 ° C. Then, the tan δ (60 ° C.) of each vulcanized rubber sheet prepared as described above was measured.
-Evaluation result of tan δ (60 ° C.) The evaluation result of tan δ (60 ° C.) is shown in the “Rolling performance” column of Table 1 as an index with tan δ (60 ° C.) as 100 as an index.
-Evaluation criteria for tan δ (60 ° C) The smaller the index of tan δ (60 ° C), the better the rolling performance (low rolling resistance). The smaller the index, the better the rolling performance.

The details of each component shown in Table 1 are as follows.
-Specific conjugated diene rubber 1: Specific conjugated diene rubber manufactured as described above 1

-Conjugated diene rubber 1: butadiene rubber. Nippon Zeon Corporation Nipol BR 1220. Glass transition temperature: -106 ° C. The conjugated diene rubber 1 corresponds to the conjugated diene rubber (y).

-Silica: Zeosil 1165MP manufactured by Solvay. CTAB adsorption specific surface area 152 m ² / g

-Carbon black: Seest KH N339 (N ₂ SA93m ² / g, manufactured by Tokai Carbon Co., Ltd.)

・ Stearic acid: Industrial stearic acid N manufactured by Chiba Fatty Acid Co., Ltd.
・ Zinc white: Zinc oxide 3 types manufactured by Shodo Chemical Co., Ltd. ・ Anti-aging agent: 6PPD (manufactured by Flexis)

-Silane coupling agent: Si69 (bis (3-triethoxysilylpropyl) tetrasulfide, manufactured by Evonik Degussa)

・ Oil (TDAE): Extract No. 4 S, manufactured by Shell Lubricants Japan

-Nonionic surfactant 1: A compound represented by the following formula (X), in which b is 20, a + c is 80, and a and c are 2 or more, respectively (nonionic surfactant). ).

-Nonionic surfactant 2: A compound represented by the following formula (X), in which b is 40, a + c is 60, and a and c are 2 or more, respectively (nonionic surfactant). ).

式（Ｉ）中、ｂは８０であり、ａ＋ｃは２０であり、ａ、ｃがそれぞれ２以上である。 -Nonionic surfactant 3 (reverse structure): A compound represented by the following formula (I).

In formula (I), b is 80, a + c is 20, and a and c are 2 or more, respectively.

-Nonionic Surfactant 4 (Random Type) (Comparison): Trade Name Adeka Polyether PR-3007, manufactured by ADEKA Corporation. A linear polyoxyethylene oxypropylene random copolymer having hydroxy groups at both ends. The nonionic surfactant 4 is not a copolymer having a polyoxyethylene block and a polyoxypropylene block.
-Nonionic surfactant 5 (PPO only) (comparison): Trade name ADEKApolyether P-2000, manufactured by ADEKA. A linear polyoxypropylene glycol having hydroxy groups at both ends. The nonionic surfactant 5 does not have a polyethylene oxyblock.

-Vulcanization accelerator 1 (CZ): Noxera CZ-G manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.
-Vulcanization accelerator 2 (DPG): Noxeller D manufactured by Ouchi Shinko Chemical Industry Co., Ltd.
・ Sulfur: Oil-treated sulfur manufactured by Hosoi Chemical Co., Ltd.

As is clear from the results shown in Table 1, the compositions of the present invention exhibited excellent workability, tensile breaking strength and rolling performance.

On the other hand, Comparative Example 1 which does not contain the above nonionic surfactant and instead contains a nonionic surfactant of a random copolymer of propylene oxide and ethylene oxide does not sufficiently improve the rolling performance. Yes, the tensile breaking strength was lower than that of the standard example.
Comparative Example 2 containing the nonionic surfactant which does not contain the nonionic surfactant and instead contains the nonionic surfactant whose skeleton is only PPO has insufficient improvement in processability and rolling performance, and is more than the standard example. The tensile breaking strength was also low.
Comparative Example 3 in which the content of the silane coupling agent was higher than the predetermined range had a lower tensile breaking strength than the standard example.
In Comparative Example 4 in which the content of the silane coupling agent was less than the predetermined range, the improvement in workability was insufficient, the tensile breaking strength was lower than that in the standard example, and the rolling performance was poor.
Comparative Example 5, which contained the nonionic surfactant but whose content exceeded 15% by mass with respect to the silica content, had insufficient tensile breaking strength as compared with the standard example.

1 bead part 2 sidewall part 3 tire tread part 4 carcass layer 5 bead core 6 bead filler 7 belt layer 8 rim cushion

Claims (6)

Conjugated diene rubber containing 30% by mass or more of specific conjugated diene rubber,
With silica
Silane coupling agent and
Contains polypropylene oxyblock and nonionic surfactants including polyethylene oxyblock,
The silica content is 30 parts by mass or more with respect to 100 parts by mass of the conjugated diene rubber.
The content of the silane coupling agent is 3 to 30% by mass with respect to the content of the silica.
The content of the nonionic surfactant is 0.1 to 15% by mass with respect to the content of the silica.
In the first step, the specific conjugated diene-based rubber polymerizes a monomer containing a conjugated diene compound in an inert solvent using a polymerization initiator to obtain a conjugated diene-based polymer chain having an active terminal. The polyorganosiloxane represented by the following general formula (1) is added to the conjugated diene polymer chain having the active terminal with respect to 1 mol of the polymerization initiator used in the first step, in the polyorganosiloxane. The second step of adding and reacting the siloxane structure (-Si-O-) at a ratio of 1 mol or more in terms of the number of repeating units, and the conjugated diene-based weight obtained by reacting the polyorganosiloxane obtained in the second step. A rubber composition for tire tread, which is a conjugated diene-based rubber produced by a method for producing a conjugated diene-based rubber, which comprises a third step of reacting a coalesced chain with a compound represented by the following general formula (2).

In the general formula (1), R ^{1 to} R ⁸ are alkyl groups having 1 to 6 carbon atoms or aryl groups having 6 to 12 carbon atoms, and these may be the same or different from each other.
In the general formula (1), X ¹ and X ⁴ contain an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and an epoxy group. Any group selected from the group consisting of 4-12 groups, which may be the same or different from each other.
Formula (1), X ² is a group having 4 to 12 carbon atoms containing alkoxy group or an epoxy group, of 1 to 5 carbon atoms, X ² there are a plurality of even different and the same as each other May be.
In the general formula (1), X ³ is a group containing repeating units of 2 to 20 alkylene glycols, and ^{when there are a plurality of X 3} , they may be the same or different from each other.
In the general formula (1), m is an integer of 3 to 200, n is an integer of 0 to 200, k is an integer of 0 to 200, and m + n + k is 3 or more.

In the general formula (2), R ⁹ is a hydrocarbyl group.
In the general formula (2), A ¹ is a group capable of reacting with a reaction residue generated by a reaction between a conjugated diene polymer chain having an active terminal and polyorganosiloxane.
In the general formula (2), A ² is a group containing a nitrogen atom.
In the general formula (2), p is an integer of 0 to 2, q is an integer of 1 to 3, r is an integer of 1 to 3, and p + q + r = 4. The rubber composition for a tire tread according to claim 1, wherein the nonionic surfactant has a hydroxy group at all terminals of the nonionic surfactant. The rubber composition for a tire tread according to claim 1 or 2, wherein the nonionic surfactant contains a compound represented by the following formula (X).

In formula (X), a, b, and c are 2 or more independently. The rubber composition for a tire tread according to any one of claims 1 to 3, wherein the silica has a CTAB adsorption specific surface area of 115 to 300 m ^{2 / g.} The specific conjugated diene rubber
A polymer block (A) containing 80 to 100% by mass of an isoprene monomer unit and 0 to 20% by mass of an aromatic vinyl monomer unit, and
The claim has a structure in which a polymer block (B) containing 50 to 100% by mass of a 1,3-butadiene monomer unit and 0 to 50% by mass of an aromatic vinyl monomer unit is formed in succession. A rubber composition for a tire tread according to any one of 1 to 4. A pneumatic tire comprising a tire tread portion manufactured by using the rubber composition for tire tread according to any one of claims 1 to 5.

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