JP2016216694A - Manufacturing method of modified conjugated diene polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a modified conjugated diene copolymer composition excellent in balance of processability, rolling resistance, wet skid resistance, tensile property and abrasion resistance.SOLUTION: The invention relates to a manufacturing method of a modified conjugated diene copolymer composition including a mixing process of mixing a predetermined amount of (A) a rubber component containing a both terminal modified conjugated diene polymer (Component (A)), (B) a silica inorganic filler (Component (B)), (C) a silane coupling agent (Component (C)), (D) a vulcanization accelerator aid and/or an aging inhibitor (Component (D)), where the mixing process includes a process [1]: a process for mixing the Component (A), the Component (B), the Component (C) and the Component (D) at same time or a process [2]: a process for mixing the Component (A) and the Component (D) to prepare a first mixture and then mixing the first mixture, the Component (B) and the Component (C).SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a modified conjugated diene polymer composition.

  In recent years, with the emphasis on resource saving and environmental measures, the level of demand for automobile tires with excellent fuel efficiency is increasing. As a method of manufacturing tires with excellent fuel efficiency, as a material that constitutes the tread that is the contact surface with the road surface in order to reduce the rolling resistance, it is possible to suppress the energy loss of the tire and bridge that has excellent rolling resistance characteristics It is known to use rubber materials that can form rubber. Further, in view of the growing demand for low fuel consumption for tires, a technique for improving the rolling resistance characteristics of the rubber material constituting the base tread has been studied. As a method for improving the rolling resistance characteristics of a tire, for example, a technique for improving wet skid resistance and rolling resistance characteristics by adding silica to a rubber composition is known.

  For example, in Patent Document 1, in a vulcanizable rubber composition containing a rubber polymer, a vulcanizing agent, a filler, and a coupling agent, the filler includes silica, and the coupling agent includes: A rubber composition is described which is at least bifunctional capable of reacting with the silica and the rubber polymer.

  In Patent Document 2, a nitrogen atom and / or a silicon atom is added to the active terminal of a copolymer obtained by polymerizing a monomer component containing a conjugated diene compound and a silicon-containing vinyl compound using a specific polymerization initiator. A conjugated diene polymer obtained by reacting a compound to be contained and silica, and in 100% by mass of the rubber component, the content of the conjugated diene polymer is 90% by mass or less, and the rubber component is 100% by mass. The rubber composition whose content of the said silica is 5-40 mass parts with respect to a part is described.

  Patent Document 3 discloses a nitrogen atom and / or silicon at the active terminal of a copolymer obtained by polymerizing a monomer component containing a conjugated diene compound and a silicon-containing vinyl compound using a specific polymerization initiator. A conjugated diene polymer obtained by reacting an atom-containing compound and silica, wherein the content of the conjugated diene polymer is 25 to 50% by mass, and the silica with respect to 100 parts by mass of the rubber component The rubber composition whose content is 40-80 mass parts is described.

Japanese Patent No. 3933207 JP 2013-108035 A Specification JP 2013-108042 A Specification

  However, in the production of the rubber composition described in Patent Documents 1 to 3, the silica tends to aggregate particles due to the hydrogen bond of the silanol group which is a functional group on the surface, and the silica dispersibility in the rubber is reduced. In order to increase the kneading time, it is necessary to lengthen the kneading time. However, if the kneading time is lengthened, there is a problem that the rubber molecular chain is broken and physical properties such as tensile properties are lowered. Moreover, there exists a problem that a compound viscosity increases by aggregation of silica particles and a workability is deteriorated.

  In order to eliminate the problem of agglomeration of silica particles by blending silica into these rubber compositions, the present inventors have, for example, a filler such as silica together with a rubber component containing a styrene-butadiene copolymer, And a coupling agent in a kneading machine, and then kneading. In the next stage, a processing agent and a protective agent such as an oil, an activator, and an anti-aging agent are blended and kneaded, thereby rolling resistance of the rubber composition. It has been found that characteristics, wet skid resistance, and wear resistance tend to be improved. However, the rubber composition is insufficient in breaking strength and processability, and there is room for further improvement.

  On the other hand, the inventors of the present application are active terminals of a copolymer obtained by polymerizing a monomer component containing a conjugated diene compound and a silicon-containing vinyl compound using a specific polymerization initiator having a nitrogen atom in the molecule. Further, it has been found that a both-end modified conjugated diene polymer obtained by reacting a compound containing a nitrogen atom and / or a silicon atom tends to have an excellent balance of rolling resistance characteristics, fracture strength, and workability. . However, when the both-end modified conjugated diene polymer and silica are kneaded, there is a problem of aggregation of the silica particles described above.

  Further, even when the above blending method is used for kneading the both-end-modified conjugated diene polymer and silica, a balance including workability, rolling resistance characteristics, wet skid resistance, fracture strength, and wear resistance. It was found that there was room for improvement.

  In view of the above problems, the present invention is a method for producing a modified conjugated diene polymer composition using a both-end-modified conjugated diene polymer and silica, which has processability, rolling resistance characteristics, wet skid resistance, tension It aims at providing the manufacturing method from which the modified | denatured conjugated diene polymer composition excellent in the balance of a characteristic and abrasion resistance is obtained.

  As a result of intensive studies to solve the above problems, the present inventor has completed the present invention. The present invention is as follows.

1. (A) 100 parts by mass of a rubber component (component (A)) containing a both-end-modified conjugated diene polymer;
(B) Silica-based inorganic filler (component (B)) 30 to 300 parts by mass;
(C) 0.03-90 parts by mass of a silane coupling agent (component (C)),
(D) a vulcanization acceleration aid and / or an anti-aging agent (component (D)),
A method for producing a modified conjugated diene polymer composition comprising a kneading step of kneading
The kneading step includes
Step [a]: Step of kneading component (A), component (B), component (C), and component (D) at the same time, or step [b]: Mixing component (A) and component (D) A method for producing a modified conjugated diene polymer composition, comprising a step of kneading the first kneaded product, component (B) and component (C) after kneading to produce a first kneaded product.

2. The terminal-modified conjugated diene polymer is
An active terminal of a conjugated diene polymer polymerized using a polymerization initiator (a1) containing a compound represented by the following general formula (1) or (2) and an organolithium compound;
A nitrogen atom-containing compound (a2);
2. The method for producing a modified conjugated diene polymer composition according to 1 above, which is a both-end modified conjugated diene polymer obtained by reacting a bisphenol.

（一般式（１）中、Ｒ¹及びＲ²は、各々独立して、炭素数１〜１２のアルキル基、炭素数３〜１４のシクロアルキル基、及び炭素数６〜２０のアラルキル基からなる群より選択されるいずれかを表す。Ｒ¹及びＲ²は、結合して隣接した窒素原子とともに環状構造を形成していてもよく、その場合、Ｒ¹及びＲ²は、合計の炭素数が５〜１２の炭化水素基を表し、不飽和結合を有していても、分岐構造を有していてもよい。）

(In General Formula (1), R ¹ and R ² each independently comprise an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aralkyl group having 6 to 20 carbon atoms. R ¹ and R ² may be bonded to form a cyclic structure with the adjacent nitrogen atom, in which case R ¹ and R ² have a total number of carbon atoms It represents 5-12 hydrocarbon groups and may have an unsaturated bond or a branched structure.)

（一般式（２）中、Ｒ¹及びＲ²は、前記一般式（１）中のＲ¹及びＲ²と同様であり、Ｒ³は、炭素数１〜２０のアルキレン基、又は下記式（３）〜（５）からなる群より選ばれるいずれかを表し、前記Ｒ³が炭素数１〜２０のアルキレン基である場合は、Ｘは、Ｃｌ、Ｂｒ、及びＩからなる群より選ばれるいずれかを表し、前記Ｒ³が下記式（３）〜（５）からなる群より選ばれるいずれかである場合は、Ｘは水素原子を表す。）

(In the general formula (2), R ¹ and R ² are the same as R ¹ and R ² in the general formula (1) in, R ³ is an alkylene group having 1 to 20 carbon atoms, or the following formula ( 3) to any one selected from the group consisting of (5), and when R ³ is an alkylene group having 1 to 20 carbon atoms, X is any selected from the group consisting of Cl, Br and I In the case where R ³ is any one selected from the group consisting of the following formulas (3) to (5), X represents a hydrogen atom.)

3. The manufacturing method of the modified conjugated diene polymer composition of said 1 or 2 whose said nitrogen atom containing compound (a2) is a compound represented by following General formula (6).

（一般式（６）中、Ｒ⁴〜Ｒ⁷は、各々独立して、炭素数１〜２０のアルキル基又は炭素数６〜２０のアリール基を表し、Ｒ⁸は炭素数３〜１０のアルキレン基を表し、Ｒ⁹は炭素数１〜２０のアルキレン基を表し、ｍは１又は２の整数であり、ｎは２又は３の整数である。）

(In General Formula (6), R ^{4 to} R ⁷ each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ⁸ is an alkylene having 3 to 10 carbon atoms. R ⁹ represents an alkylene group having 1 to 20 carbon atoms, m is an integer of 1 or 2, and n is an integer of 2 or 3.)

4). (E) Any of the above 1-3, comprising a step of kneading carbon black in an amount of 0.5 to 100 parts by mass with respect to 100 parts by mass of the rubber component containing the (A) both-end-modified conjugated diene polymer. A method for producing the modified conjugated diene polymer composition described in 1.

5. 5. The method for producing a modified conjugated diene polymer composition as described in 4 above, which comprises a step of kneading the component (B), the component (C) and the (E) carbon black at the same time.

  According to the present invention, a modified conjugated diene polymer composition having an excellent balance of workability, rolling resistance characteristics, wet skid resistance, tensile characteristics, and wear resistance can be obtained.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. In addition, this invention is not restrict | limited to the following embodiment, A various deformation | transformation can be implemented within the range of the summary.

  The production method of the modified conjugated diene polymer composition of the present embodiment includes (A) 100 parts by mass of a rubber component (component (A)) containing both terminal-modified conjugated diene polymers, and (B) silica-based inorganic filler. 30-300 parts by weight of agent (component (B)), (C) 0.03-90 parts by weight of silane coupling agent (component (C)), (D) vulcanization accelerator and / or anti-aging agent (Component (D)) and a method for producing a modified conjugated diene-based polymer composition, wherein the kneading step comprises step [A]: component (A), component Step (B), component (C) and component (D) are simultaneously kneaded, or step [b]: Component (A) and component (D) are kneaded to produce a first kneaded product. Then, the process of kneading said 1st kneaded material, a component (B), and a component (C) is included.

  First, each component used for manufacture of the modified conjugated diene polymer composition of the present embodiment will be described.

<(A) Rubber Component Containing Both End-Modified Conjugated Diene Polymer>
In the method for producing a modified conjugated diene polymer composition of this embodiment, (A) a rubber component (component (A)) containing a both-end modified conjugated diene polymer is used. In the present specification, the “both terminal-modified conjugated diene polymer” is a conjugated diene polymer in which both the polymerization initiation terminal and the polymerization termination terminal are modified. In the present specification, (A) the rubber component containing the both-end-modified conjugated diene polymer may be simply referred to as “component (A)”.

Both terminal-modified conjugated diene polymers are preferably
An active terminal of a conjugated diene polymer polymerized using a polymerization initiator (a1) containing a compound represented by the following general formula (1) or (2) and an organolithium compound;
It can be set as the both terminal modified conjugated diene polymer obtained by making a nitrogen atom containing compound (a2) react.

<Polymerization initiator (a1)>
The polymerization initiator (a1) preferably contains a compound represented by the following general formula (1) or general formula (2) and an organic lithium compound.

一般式（１）中、Ｒ¹及びＲ²は、各々独立して、炭素数１〜１２のアルキル基、炭素数３〜１４のシクロアルキル基、及び炭素数６〜２０のアラルキル基からなる群より選択されるいずれかを表す。

In the general formula (1), R ¹ and R ² are each independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and the group consisting of aralkyl group having 6 to 20 carbon atoms Represents one selected from

In general formula (1), R ¹ and R ² are not limited to the following, but for example, each independently methyl, ethyl, propyl, butyl, octyl, cyclopropyl, cyclohexyl, 3-phenyl Examples include groups such as -1-propyl, isobutyl, decyl, heptyl, and phenyl.

  Examples of the compound represented by the general formula (1) include, but are not limited to, dimethylamine, diethylamine, dibutylamine, dipropylamine, diheptylamine, dihexylamine, dioctylamine, di- Examples include 2-ethylhexylamine, didecylamine, ethylpropylamine, ethylbutylamine, ethylbenzylamine, and methylphenethylamine.

  From the viewpoint of reducing rolling resistance and reducing unpleasant odor of the resulting modified conjugated diene polymer composition, the compound represented by the general formula (1) is preferably dibutylamine or dihexylamine, more preferably. Is dibutylamine.

In the general formula (1), R ¹ and R ² may be bonded to form a cyclic structure with the adjacent nitrogen atom. In that case, R ¹ and R ^{2 each} have 5 to 12 carbon atoms in total. And may have an unsaturated bond or a branched structure.

In the general formula (1), when R ¹ and R ² are bonded to form a cyclic structure with the adjacent nitrogen atom, the compound represented by the general formula (1) is not limited to the following. Examples thereof include piperidine, hexamethyleneimine, azacyclooctane, 1,3,3-trimethyl-6-azabicyclo (3.2.1) octane, 1,2,3,6-tetrahydropyridine and the like.

In the general formula (1), when R ¹ and R ² are bonded to form a cyclic structure with an adjacent nitrogen atom, the rolling resistance of the resulting modified conjugated diene polymer is reduced, and the unpleasant odor is reduced. From the viewpoint, the compound represented by the general formula (1) is preferably piperidine, hexamethyleneimine, azacyclooctane, or 1,3,3-trimethyl-6-azabicyclo (3.2.1) octane. Piperidine or hexamethyleneimine is preferred.

一般式（２）中、Ｒ¹及びＲ²は、上記一般式（１）中のＲ¹及びＲ²と同様であり、Ｒ³は、炭素数１〜２０のアルキレン基、又は下記式（３）〜（５）からなる群より選ばれるいずれかを表し、上記Ｒ³が炭素数１〜２０のアルキレン基である場合は、Ｘは、Ｃｌ、Ｂｒ、及びＩからなる群より選ばれるいずれかを表し、上記Ｒ³が下記式（３）〜（５）からなる群より選ばれるいずれかである場合は、Ｘは水素原子を表す。

In the general formula (2), R ¹ and R ² are the same as R ¹ and R ² in general formula (1), R ³ is an alkylene group having 1 to 20 carbon atoms, or the following formula (3 ) To (5), and when R ³ is an alkylene group having 1 to 20 carbon atoms, X is any one selected from the group consisting of Cl, Br, and I. And R ³ is any one selected from the group consisting of the following formulas (3) to (5), X represents a hydrogen atom.

In the general formula (2), when R ³ is an alkylene group having 1 to 20 carbon atoms, from the viewpoint of reactivity and interaction with an inorganic filler such as carbon black and silica, , R ³ preferably has 2 to 16 carbon atoms, more preferably 3 to 10 carbon atoms.

In the general formula (2), when R ³ is an alkylene group having 1 to 20 carbon atoms, the compound represented by the general formula (2) is not limited to the following. Chloro-dimethylpropan-1-amine, 3-chloro-diethylpropan-1-amine, 3-chloro-dibutylpropan-1-amine, 3-chloro-dipropylpropan-1-amine, 3-chloro-diheptylpropane -1-amine, 3-chloro-dihexylpropan-1-amine, 3-chloropropyl-ethylhexane-1-amine, 3-chloro-didecylpropan-1-amine, 3-chloro-ethylpropane-1- Amine, 3-chloro-ethylbutan-1-amine, 3-chloro-ethylpropan-1-amine, benzyl-3-chloro-ethylpropan-1-amine, 3-c Ro-ethylphenethylpropan-1-amine, 3-chloro-methylphenethylpropan-1-amine, 1- (3-chloropropyl) piperidine, 1- (3-chloropropyl) hexamethyleneimine, 1- (3-chloro Propyl) azacyclooctane, 6- (3-chloropropyl) -1,3,3-trimethyl-6-azabicyclo (3.2.1) octane, 1- (3-chloropropyl) -1,2,3 6-tetrahydropyridine, 1- (3-bromopropyl) hexamethyleneimine, 1- (3-iodopropyl) hexamethyleneimine, 1- (3-chlorobutyl) hexamethyleneimine, 1- (3-chloropentyl) hexamethylene Imine, 1- (3-chlorohexyl) hexamethyleneimine, 1- (3-chlorodecyl) hexamethyleneimine, etc. Is mentioned.

In the general formula (2), when R ³ is an alkylene group having 1 to 20 carbon atoms, the compound represented by the general formula (2) includes reactivity with inorganic fillers such as carbon black and silica, and From the viewpoint of interaction, 3-chloro-dibutylpropan-1-amine, 1- (3-chloropropyl) piperidine, or 1- (3-chloropropyl) hexamethyleneimine is preferable, and 1- (3 -Chloropropyl) piperidine, 1- (3-chloropropyl) hexamethyleneimine.

In the general formula (2), when R ³ is any one selected from the group consisting of the above formulas (3) to (5), the compound represented by the general formula (2) is limited to the following. For example, N, N-dimethyl-2-butenyl-1-amine, N, N-diethyl-2-butenyl-1-amine, N, N-dibutyl-2-butenyl-1-amine, N , N-dipropyl-2-butenyl-1-amine, N, N-diheptyl-2-butenyl-1-amine, N, N-dihexyl-2-butenyl-1-amine, N, N-dioctyl 2-butenyl-1-amine, N, N- (di-2-ethylhexyl) -2-butenyl-1-amine, N, N-didecyl-2-butenyl-1-amine, N, N-ethyl Propyl-2-butenyl-1-amine, N, N-ethylbutyl-2-bute 1-amine, N, N-ethylbenzyl-2-butenyl-1-amine, N, N-methylphenethyl-2-butenyl-1-amine, N, N-dimethyl-2-methyl-2-butenyl- 1-amine, N, N-diethyl-2-methyl-2-butenyl-1-amine, N, N-dibutyl-2-methyl-2-butenyl-1-amine, N, N-dipropyl-2-methyl- 2-butenyl-1-amine, (N, N-diheptyl-2-methyl-2-butenyl-1-amine, N, N-dihexyl-2-methyl-2-butenyl-1-amine, N , N-dimethyl-3-methyl-2-butenyl-1-amine, N, N-diethyl-3-methyl-2-butenyl-1-amine, N, N-dibutyl-3-methyl-2-butenyl-1 -Amine, N, N-dipropyl-3-methyl-2- Butenyl-1-amine, N, N-diheptyl-3-methyl-2-butenyl-1-amine, N, N-dihexyl-3-methyl-2-butenyl-1-amine, 1- (2 -Butenyl) piperidine, 1- (2-butenyl) hexamethyleneimine, 1- (2-butenyl) azacyclooctane, 6- (2-butenyl) 1,3,3-trimethyl-6-azabicyclo (3.2. 1) Octane, 1- (2-butenyl) -1,2,3,6-tetrahydropyridine, (2-methyl-2-butenyl) hexamethyleneimine, (3-methyl-2-butenyl) hexamethyleneimine, etc. Can be mentioned.

In the general formula (2), when R ³ is any one selected from the above formulas (3) to (5), the compound represented by the general formula (2) is a modified conjugated diene polymer obtained. From the viewpoint of reducing rolling resistance, N, N-dibutyl-2-butenyl-1-amine, 1- (2-butenyl) piperidine, or 1- (2-butenyl) hexamethyleneimine is preferable, and more preferably 1 -(2-butenyl) piperidine, or 1- (2-butenyl) hexamethyleneimine.

  The organolithium compound contained in the polymerization initiator (a1) is not limited to the following, and examples thereof include n-butyllithium, sec-butyllithium, tert-butyllithium, n-propyllithium, and iso-propyl. Lithium etc. are mentioned.

  The polymerization initiator (a1) is represented by the following general formula (7) or (8), in which the compound represented by the general formula (1) or (2) reacts with the organic lithium compound before the polymerization reaction. It is preferable that it is a compound. In addition, in the polymerization initiator (a1), the compound represented by the general formula (1) or (2) other than the compound represented by the general formula (7) or (8) and the organolithium compound are not yet present. Reaction components may be included.

In General Formula (7), R ¹ and R ² are each independently a group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aralkyl group having 6 to 20 carbon atoms. Represents one selected from

In the general formula (7), R ¹ and R ² are not limited to the following, but for example, each independently, methyl, ethyl, propyl, butyl, octyl, cyclopropyl, cyclohexyl, 3-phenyl- Examples include groups such as 1-propyl, isobutyl, decyl, heptyl, and phenyl.

The compound represented by the general formula (7) is not limited to the following, but for example, dimethylaminolithium, diethylaminolithium, dibutylaminolithium, dipropylaminolithium, diheptylaminolithium, and dihexyl. Aminolithium, dioctylaminolithium, di-2-ethylhexylaminolithium, didecylaminolithium, ethylpropylaminolithium, ethylbutylaminolithium, ethylbenzylaminolithium, methylphenethylaminolithium, and the above R ¹ and R ^If the condition of ² is satisfied, these analogs are included.

  From the viewpoint of solubility of the polymerization initiator in a solvent and reduction in rolling resistance of the resulting conjugated diene polymer, the compound represented by the general formula (7) is dibutylaminolithium or dihexylaminolithium. Dibutylamino lithium is more preferable.

In General Formula (7), R ¹ and R ² may be bonded to form a cyclic structure with the adjacent nitrogen atom, and in this case, R ¹ and R ² have 5 to 12 carbon atoms in total. And may have an unsaturated bond or a branched structure.

In the general formula (7), when R ¹ and R ² are bonded to form a cyclic structure with the adjacent nitrogen atom, the compound represented by the general formula (7) is not limited to the following. For example, piperidinolithium, hexamethyleneiminolithium, lithium azacyclooctane, lithium-1,3,3-trimethyl-6-azabicyclo (3.2.1) octane, 1,2,3,6- Examples thereof include tetrahydropyridinolithium and the like, and the like are included as long as the conditions of R ¹ and R ² are satisfied.

In the general formula (7), when R ¹ and R ² are bonded to form a cyclic structure with the adjacent nitrogen atom, the solubility of the polymerization initiator in the solvent and the resulting modified conjugated diene polymer are uncomfortable. From the viewpoint of reducing odor, the compound represented by the general formula (7) includes piperidinolithium, hexamethyleneiminolithium, lithium azacyclooctane, or lithium-1,3,3-trimethyl-6-azabicyclo ( 3.2.1) Octane is preferred, more preferably piperidinolithium or hexamethyleneiminolithium.

一般式（８）中、Ｒ¹及びＲ²は、各々独立して、炭素数１〜１２のアルキル基、炭素数３〜１４のシクロアルキル基、及び炭素数６〜２０のアラルキル基からなる群より選択されるいずれかを表す。Ｒ³は、炭素数１〜２０のアルキレン基、又は下記式（３）〜（５）からなる群から選ばれるいずれかを表す。

In General Formula (8), R ¹ and R ² are each independently a group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aralkyl group having 6 to 20 carbon atoms. Represents one selected from R ³ represents an alkylene group having 1 to 20 carbon atoms or any one selected from the group consisting of the following formulas (3) to (5).

In the general formula (8), when R ³ is an alkylene group having 1 to 20 carbon atoms, R ³ has 2 carbon atoms from the viewpoint of reactivity and interaction with inorganic fillers such as carbon black and silica. -16 is preferable, More preferably, it is 3-10.

In the general formula (8), when R ³ is an alkylene group having 1 to 20 carbon atoms, the compound represented by the general formula (8) is not limited to the following. (Dimethylamino) -propyl) lithium, (3- (diethylamino) -propyl) lithium, (3- (dipropylamino) -propyl) lithium, (3- (dibutylamino) -propyl) lithium, (3- (dipentyl) Amino) -propyl) lithium, (3- (dihexylamino) -propyl) lithium, (3- (dioctylamino) -propyl) lithium, (3- (ethylhexylamino) -propyl) lithium, (3- (didecylamino) -Propyl) lithium, (3- (ethylpropylamino-propyl) lithium, (3- (ethylbutylamino-propyl) lithium, ( -(Ethylbenzylamino) -propyl) lithium, (3- (methylphenethylamino) -propyl) lithium, (4- (dibutylamino) -butyl) lithium, (5- (dibutylamino) -pentyl) lithium, (6 -(Dibutylamino) -hexyl) lithium, (10- (dibutylamino) -decyl) lithium and the like.

In the general formula (8), when R ³ is an alkylene group having 1 to 20 carbon atoms, the compound represented by the general formula (8) includes reactivity with inorganic fillers such as carbon black and silica, and mutual interaction. From the viewpoint of action, (3- (dibutylamino) -propyl) lithium is more preferable.

In the general formula (8), when R ³ is any one selected from the group consisting of the above formulas (3) to (5), the compound represented by the general formula (8) is limited to the following. For example, (4- (dimethylamino) -2-butenyl) lithium, (4- (diethylamino) -2-butenyl) lithium, (4- (dibutylamino) -2-butenyl) lithium, (4 -(Dipropylamino) -2-butenyl) lithium, (4- (diheptylamino) -2-butenyl) lithium, (4- (dihexylamino) -2-butenyl) lithium, (4- (dioctylamino) -2-butenyl) lithium, (4- (di-2-ethylhexylamino) -2-butenyl) lithium, (4- (didecylamino) -2-butenyl) lithium, (4- (ethylpropylamino) 2-butenyl) lithium, (4- (ethylbutylamino) -2-butenyl) lithium, (4- (ethylbenzylamino) -2-butenyl) lithium, (4- (methylphenethylamino) -2-butenyl) lithium , (4- (dimethylamino) -2-methyl-2-butenyl) lithium, (4- (diethylamino) -2-methyl-2-butenyl) lithium, (4- (dibutylamino) -2-methyl-2- Butenyl) lithium, (4- (dipropylamino) -2-methyl-2-butenyl) lithium, (4- (diheptylamino) -2-methyl-2-butenyl) lithium, (4- (dihexylamino) 2-methyl-2-butenyl) lithium, (4- (dimethylamino) -3-methyl-2-butenyl) lithium, (4- (diethylamino) -3-methyl Ru-2-butenyl) lithium, (4- (dibutylamino) -3-methyl-2-butenyl) lithium, (4- (dipropylamino) -3-methyl-2-butenyl) lithium, (4- (di Heptylamino) -3-methyl-2-butenyl) lithium and (4- (dihexylamino) -3-methyl-2-butenyl) lithium.

In the general formula (8), when R ³ is any one selected from the group consisting of the above formulas (3) to (5), the compound represented by the general formula (8) may be used as a polymerization initiator. From the viewpoint of reactivity, 4- (dimethylamino) -2-butenyl) lithium, (4- (diethylamino) -2-butenyl) lithium, or (4- (dibutylamino) -2-butenyl) lithium is preferred, and more Preferred is (4- (dibutylamino) -2-butenyl) lithium.

In the general formula (8), R ¹ and R ² may form a cyclic structure together with the adjacent nitrogen atom bonded to, in which case, R ¹ and R ^2, the total number of carbon atoms 5-12 And may have an unsaturated bond or a branched structure.

In the general formula (8), when R ¹ and R ² are bonded to form a cyclic structure with the adjacent nitrogen atom, the compound represented by the general formula (8) is not limited to the following. For example, (3- (piperidinyl) propyl) lithium, (3- (hexamethyleneiminyl) propyl) lithium, (3- (heptamethyleneiminyl) propyl) lithium, (3- (octamethyleneiminyl) ) Propyl) lithium, (3- (1,3,3-trimethyl-6-azabicyclo (3.2.1) octanyl) propyl) lithium, (3- (1,2,3,6-tetrahydropyridinyl) Propyl) lithium, (2- (hexamethineleniminyl) ethyl) lithium, (4- (hexamethineleniminyl) butyl) lithium, (5- (hexamethinelenimine) Nyl) pentyl) lithium, (6- (hexamethineleniminyl) hexyl) lithium, (10- (hexamethylenelenimine) decyl) lithium, (4- (piperidinyl) -2-butenyl) lithium, (4- (Hexamethineleniminyl) -2-butenyl) lithium, (4- (heptamethyleneiminyl) -2-butenyl) lithium, (4- (octamethyleneiminyl) -2-butenyl) lithium, (4- ( 1,3,3-trimethyl-6-azabicyclo (3.2.1) octanyl) -2-butenyl) lithium, (4- (1,2,3,6-tetrahydropyridinyl) -2-butenyl) lithium , (4- (hexamethineleniminyl) -2-methyl-2-butenyl) lithium, (4- (hexamethyleneleniminyl) -3-methyl-2-butenyl) Lithium and the like.

In the general formula (8), when R ¹ and R ² are bonded to form a cyclic structure with the adjacent nitrogen atom, the compound represented by the general formula (8) includes inorganic compounds such as carbon black and silica. From the viewpoint of reactivity and interaction with the filler, (3- (piperidinyl) propyl) lithium, (3- (hexamethyleneleniminyl) propyl) lithium, (3- (1,2,3,6- Tetrahydropyridinyl) propyl) lithium, (4- (piperidinyl) -2-butenyl) lithium, or (4- (hexamethylenelenimyl) -2-butenyl) lithium is preferred, (3- (piperidinyl) propyl) Lithium, (4- (piperidinyl) -2-butenyl) lithium, (3- (hexamethineleniminyl) propyl) lithium, or (4- (hexamethinelenine) Minyl) -2-butenyl) lithium is more preferred.

<Method for Preparing Polymerization Initiator (a1)>
The compound (a1) which is a polymerization initiator can be obtained by mixing the compound represented by the general formula (1) or (2) and the organic lithium compound in an arbitrary solvent.

  Examples of the solvent include, but are not limited to, hydrocarbon solvents such as hexane, cyclohexane, and benzene. The reaction temperature is preferably 0 to 80 ° C, and preferably 10 to 70 ° C from the viewpoint of productivity.

  In the polymerization step, a compound (a1) which is a polymerization initiator, preferably a compound represented by the general formula (7) or (8) is prepared in advance in a predetermined reactor, and polymerization of a conjugated diene compound is performed. Or you may supply to the reactor which copolymerizes a conjugated diene compound and an aromatic vinyl compound, may perform a polymerization reaction, and prepares a compound (a1) in the reactor for performing the polymerization or copolymerization mentioned later. Then, a predetermined monomer (a conjugated diene compound or an aromatic vinyl compound) may be supplied to the reactor to perform polymerization or copolymerization, or a reactor for performing polymerization or copolymerization described later. Among them, the preparation of the compound (a1) which is a polymerization initiator and the polymerization or copolymerization of monomers may be performed simultaneously.

  The compound represented by the general formula (7) can be obtained, for example, by reacting the compound represented by the general formula (1) with an organolithium compound in a hydrocarbon solvent.

  The compound represented by the general formula (8) can be obtained, for example, by reacting the compound represented by the general formula (2) with an organolithium compound in a hydrocarbon solvent.

  When preparing the compound represented by the general formula (7) or (8), a polar compound may be added to the system. Thereby, the acceleration | stimulation of the production | generation of the compound represented by General formula (7) or (8) and the solubilization effect to a hydrocarbon solvent are acquired.

  Examples of polar compounds include tertiary monoamines, tertiary diamines, chain or cyclic ethers, and the like.

  Examples of the tertiary monoamine include, but are not limited to, trimethylamine, triethylamine, methyldiethylamine, 1,1-dimethoxytrimethylamine, 1,1-diethoxytrimethylamine, 1,1-diethoxytriethylamine, N, Examples thereof include N-dimethylformamide diisopropyl acetal and N, N-dimethylformamide dicyclohexyl acetal.

  Examples of the tertiary diamine include, but are not limited to, for example, N, N, N ′, N′-tetramethyldiaminomethane, N, N, N ′, N′-tetramethylethylenediamine, N, N , N ′, N′-tetramethylpropanediamine, N, N, N ′, N′-tetramethyldiaminobutane, N, N, N ′, N′-tetramethyldiaminopentane, N, N, N ′, N Examples thereof include compounds such as' -tetramethylhexanediamine, dipiperidinopentane, and dipiperidinoethane.

  Examples of chain ethers include, but are not limited to, dimethyl ether, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene dimethyl ether.

  Examples of the cyclic ether include, but are not limited to, tetrahydrofuran, bis (2-oxolanyl) ethane, 2,2-bis (2-oxolanyl) propane, 1,1-bis (2-oxolanyl) ethane. 2,2-bis (2-oxolanyl) butane, 2,2-bis (5-methyl-2-oxolanyl) propane, 2,2-bis (3,4,5-trimethyl-2-oxolanyl) propane, etc. Compounds.

  Among polar compounds, from the viewpoint of promoting the formation of the compound of formula (7) or (8) and solubilizing effect on hydrocarbons, tertiary monoamines such as trimethylamine, triethylamine, and tertiary diamines such as N, N, N ', N'-tetramethylethylenediamine, tetrahydrofuran which is a cyclic ether, or 2,2-bis (2-oxolanyl) propane is preferred. A polar compound may be used individually by 1 type, and may be used in combination of 2 or more type.

  Moreover, when adding a polar compound when preparing the compound represented by the general formula (7) or (8), within a range of 30 to 50,000 ppm by weight with respect to the solvent used for the preparation. It is preferable to add, and it is more preferable to add within the range of 200 to 20,000 ppm by weight.

  In order to fully express the effect of promoting the reaction and solubilization in the solvent, the polar compound is preferably added in an amount of 30 ppm by weight or more based on the solvent, and in the polymerization step of the both-end-modified diene polymer. In consideration of securing the degree of freedom of microstructure adjustment and separation from the polymerization solvent in the step of recovering and purifying the solvent after polymerization, it is preferably added at 50,000 ppm by weight or less.

  A polymerization initiator (a1) may be used individually by 1 type, and 2 or more types of mixtures may be sufficient as it.

  The polymerization mode of the modified conjugated diene polymer is not particularly limited, and examples thereof include a batch system or a continuous system in one reactor or two or more connected reactors.

  The both-end-modified conjugated diene polymer is a polymer having an active end obtained by a growth reaction by living anion polymerization using the compound represented by the formula (7) or (8) as a polymerization initiator (a1). It is preferable to perform a modification step with a nitrogen atom-containing compound (a2) described later on this active terminal, whereby a high-modification-terminated both-terminal modified conjugated diene polymer is obtained.

<Conjugated diene compounds>
The terminal-modified conjugated diene polymer may be a polymer obtained by polymerizing at least a conjugated diene compound. The conjugated diene compound is not particularly limited as long as it is a polymerizable monomer. For example, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 3- Examples include methyl-1,3-pentadiene, 1,3-heptadiene, 1,3-hexadiene and the like. Among these, 1,3-butadiene and isoprene are preferable from the viewpoint of industrial availability. These may be used alone or in combination of two or more.

  If the conjugated diene compound used in the polymerization step contains allenes, acetylenes or the like as impurities, there is a risk of inhibiting the modification reaction described later. Therefore, the total content concentration (mass) of these impurities is preferably 200 ppm or less, more preferably 100 ppm or less, and even more preferably 50 ppm or less.

  Examples of allenes include propadiene and 1,2-butadiene. Examples of acetylenes include ethyl acetylene and vinyl acetylene.

<Aromatic vinyl compound>
The both-end modified conjugated diene polymer may be obtained by modifying a copolymer of a conjugated diene compound and an aromatic vinyl compound. The aromatic vinyl compound is not particularly limited as long as it is a monomer copolymerizable with a conjugated diene compound. For example, styrene, p-methylstyrene, α-methylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene, diphenyl Examples include ethylene. Among these, styrene is preferable from the viewpoint of industrial availability. These may be used alone or in combination of two or more.

<solvent>
The polymerization reaction of both terminal-modified conjugated diene polymers is preferably performed in a solvent (hereinafter also referred to as “polymerization solvent”). Examples of the solvent include, but are not limited to, hydrocarbon solvents such as saturated hydrocarbons and aromatic hydrocarbons. Specifically, aliphatic hydrocarbons such as butane, pentane, hexane, and heptane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; And hydrocarbons composed of a mixture thereof.

<Treatment of impurities in raw materials>
The conjugated diene compound, the aromatic vinyl compound, and the polymerization solvent described above are each alone or a mixture thereof before being subjected to a polymerization reaction in advance, the impurities such as allenes and acetylenes are converted into organometallic compounds. It is preferable to react and process. Thereby, inhibition of polymerization by the impurities can be prevented, the active terminal amount of the polymer becomes high, a sharper molecular weight distribution can be achieved, and a higher modification rate tends to be achieved.

<Polar compound>
In the polymerization reaction of the both-end modified conjugated diene polymer, a polar compound may be added. By adding a polar compound, an aromatic vinyl compound can be randomly copolymerized with a conjugated diene compound, and the polar compound should also be used as a vinylating agent for controlling the microstructure of the conjugated diene moiety. Can do. It is also effective in improving the polymerization rate.

  Although it does not specifically limit as a polar compound, For example, tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dimethoxybenzene, 2,2-bis (2- Ethers such as oxolanyl) propane; tertiary amine compounds such as tetramethylethylenediamine, dipiperidinoethane, trimethylamine, triethylamine, pyridine, quinuclidine; potassium tert-amylate, potassium tertbutylate, sodium tertbutylate And alkali metal alkoxide compounds such as sodium amylate; and phosphine compounds such as triphenylphosphine. These polar compounds may be used alone or in combination of two or more.

  The usage-amount of a polar compound is not specifically limited, It can select according to the objective etc. Usually, it is preferable that it is 0.01-100 mol with respect to 1 mol of polymerization initiators.

  Such a polar compound (vinylating agent) can be used by selecting an appropriate amount in order to obtain a desired vinyl bond amount, as a regulator of the microstructure of the conjugated diene portion of the both-end modified conjugated diene polymer. it can. Many polar compounds simultaneously have an effective randomizing effect in the copolymerization of a conjugated diene compound and an aromatic vinyl compound, and can be used as an adjustment of the distribution of the aromatic vinyl compound and an adjuster of the styrene block amount. As a method for randomizing the conjugated diene compound and the aromatic vinyl compound, for example, as described in JP-A-59-140221, a part of 1,3-butadiene is intermittently produced during the copolymerization. You may use the method of adding to.

<Polymerization temperature>
The polymerization temperature in the polymerization step of the both-end-modified conjugated diene polymer is not particularly limited as long as the living anion polymerization proceeds. From the viewpoint of productivity, it is preferably 0 ° C. or higher, and after the polymerization is completed. From the viewpoint of sufficiently ensuring the reaction amount of the modifier with respect to the active terminal, it is preferably 120 ° C. or lower.

<Nitrogen atom-containing compound (a2)>
The nitrogen atom-containing compound (a2) is not particularly limited as long as it is a compound that contains one or more nitrogen atoms in the molecule and can modify the active terminal of the conjugated diene polymer. As the nitrogen atom-containing compound (a2), the total number of alkoxy groups bonded to the silyl group is 4 or more, a compound having one or more nitrogen atoms, N, N, N ′, such as tetramethyldiaminobenzophenone, N'-tetradialkyldiamino-benzophenones, N, N'-dialkylamino-benzaldehydes such as tetramethyldiamino-benzaldehyde, 1,3-dialkyl-2-imidazolids such as 1,3-dimethyl-2-imidazolidinone Examples include ridinones, 1-alkyl substituted pyrrolidinones, 1-aryl substituted pyrrolidinones, and dialkyl-carbodiimides and dicycloalkyl-carbodiimides having about 5 to 20 carbon atoms.

  The nitrogen atom-containing compound (a2) is more preferably a compound represented by the following general formula (6).

In General Formula (6), R ^{4 to} R ⁷ each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ⁸ is an alkylene group having 3 to 10 carbon atoms. R ⁹ represents an alkylene group having 1 to 20 carbon atoms, m is an integer of 1 or 2, and n is an integer of 2 or 3.

  The nitrogen atom-containing compound (a2) represented by the general formula (6) is not limited to the following. For example, 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1- Aza-2-silacyclopentane, 2,2-diethoxy-1- (3-triethoxysilylpropyl) -1-aza-2-silacyclopentane, 2,2-dimethoxy-1- (4-trimethoxysilylbutyl) ) -1-Aza-2-silacyclohexane, 2,2-dimethoxy-1- (5-trimethoxysilylpentyl) -1-aza-2-silacycloheptane, 2,2-dimethoxy-1- (3-dimethoxy) Methylsilylpropyl) -1-aza-2-silacyclopentane, 2,2-diethoxy-1- (3-diethoxyethylsilylpropyl) -1-aza-2-silacyclopentane 2-methoxy, 2-methyl-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane, 2-ethoxy, 2-ethyl-1- (3-triethoxysilylpropyl) -1- Aza-2-silacyclopentane, 2-methoxy, 2-methyl-1- (3-dimethoxymethylsilylpropyl) -1-aza-2-silacyclopentane, 2-ethoxy, 2-ethyl-1- (3- And diethoxyethylsilylpropyl) -1-aza-2-silacyclopentane.

  Among these, from the viewpoint of reactivity and interaction between the functional group of the nitrogen atom-containing compound (a2) and an inorganic filler such as silica, and from the viewpoint of workability, in the general formula (6), m is 2, Those in which n is 3 are preferred. Specifically, 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane, 2,2-diethoxy-1- (3-triethoxysilylpropyl) -1 -Aza-2-silacyclopentane is preferred.

  The reaction temperature, reaction time, and the like when the nitrogen atom-containing compound (a2) is reacted with the polymerization active terminal of the conjugated diene polymer are not particularly limited, but are reacted at 0 to 120 ° C. for 30 seconds or longer. Is preferred.

  In the nitrogen atom-containing compound (a2), the total number of moles of alkoxy groups bonded to the silyl group in the compound represented by the general formula (6) is 0. 0 of the number of moles of lithium contained in the polymerization initiator (a1). The range is preferably 6 to 3 times, more preferably 0.8 to 2.5 times, and even more preferably 0.8 to 2 times. From the viewpoint of obtaining a sufficient modification rate in the both-end-modified conjugated diene-based polymer, it is preferably 0.6 times or more, and a branched polymer component is obtained by coupling polymer ends to improve processability. Is preferable, and from the viewpoint of cost, it is preferably 3 times or less.

<Deactivator, neutralizer, etc.>
If necessary, a deactivator, a neutralizing agent and the like may be added to the polymer solution containing the both terminal-modified conjugated diene polymer. The quenching agent is not particularly limited, and examples thereof include water, alcohols such as methanol, ethanol, and isopropanol. The neutralizing agent is not particularly limited, and examples thereof include carboxylic acids such as stearic acid, oleic acid, and versatic acid; aqueous solutions of inorganic acids, carbon dioxide gas, and the like.

  As a method for obtaining a both-end modified conjugated diene polymer from a polymer solution containing the both-end modified conjugated diene polymer, a known method can be used. For example, after separating the solvent by steam stripping or the like, the both-end modified conjugated diene polymer is filtered off, and further dehydrated and dried to obtain a both-end modified conjugated diene polymer, and concentrated in a flushing tank. Furthermore, a method of devolatilization with a vent extruder or the like, a method of devolatilization directly with a drum dryer, or the like can be mentioned.

<Microstructure and Properties of Both-Terminal Modified Conjugated Diene Polymer>
(Binding conjugated diene content)
The amount of bound conjugated diene in the both-end modified conjugated diene polymer is not particularly limited, but is preferably 50 to 100% by mass, and more preferably 60 to 80% by mass.

(Amount of bonded aromatic vinyl)
The amount of bonded aromatic vinyl in the both-end conjugated diene polymer is not particularly limited, but is preferably 0 to 50% by mass, and more preferably 20 to 40% by mass.

  When the amount of bound conjugated diene and amount of bound aromatic vinyl are within the above ranges, a vulcanizate having a further excellent balance between rolling resistance characteristics and wet skid resistance and satisfying wear resistance and breaking strength can be obtained.

  Here, the amount of bonded aromatic vinyl can be measured by ultraviolet absorption of a phenyl group, and the amount of bonded conjugated diene can also be obtained from this. Specifically, it can measure by the method according to the Example mentioned later.

(Vinyl bond amount)
The amount of vinyl bonds in the conjugated diene bond unit of the both terminal conjugated diene polymer is not particularly limited, but is preferably 10 to 75 mol%, more preferably 25 to 65 mol%.

  When the vinyl bond amount is in the above range, a vulcanizate having a further excellent balance between rolling resistance characteristics and wet skid resistance and satisfying wear resistance and fracture strength can be obtained.

  Here, when the both terminal-modified conjugated diene polymer is a copolymer of butadiene and styrene, a butadiene bond unit is obtained by the method of Hampton (RR Hampton, Analytical Chemistry, 21, 923 (1949)). The vinyl bond content (1,2-bond content) can be determined.

(Polymer structure of both terminal-modified conjugated diene polymers)
When the both terminal-modified conjugated diene polymer is a copolymer of a conjugated diene compound and another monomer, it may be a random copolymer or a block copolymer.

  Examples of the random copolymer include a butadiene-isoprene random copolymer, a butadiene-styrene random copolymer, an isoprene-styrene random copolymer, and a butadiene-isoprene-styrene random copolymer.

  The composition distribution of each monomer in the copolymer chain is not particularly limited. For example, a completely random copolymer close to a statistical random composition, or a tapered (gradient) random copolymer in which the composition is distributed in a tapered shape. A polymer etc. are mentioned. The bonding mode of the conjugated diene, that is, the composition of 1,4-bonds, 1,2-bonds, etc. may be uniform or distributed.

  Examples of the block copolymer include a 2 type block copolymer comprising 2 blocks, a 3 type block copolymer comprising 3 blocks, and a 4 type block copolymer comprising 4 blocks. For example, a block composed of an aromatic vinyl compound such as styrene is represented by S, and a block composed of a conjugated diene compound such as butadiene or isoprene and / or a block composed of a copolymer of an aromatic vinyl compound and a conjugated diene compound is represented by B. In terms of block copolymer, the type 2 block copolymer represented by the structure (SB), the type 3 block copolymer represented by the structure (SBS), and the structure (S 4 type block copolymer represented by -BSB) and the like.

  In the above structure, the boundaries between the blocks do not necessarily have to be clearly distinguished. For example, when the block B is a copolymer of an aromatic vinyl compound and a conjugated diene compound, the aromatic vinyl compound in the block B may be distributed uniformly or in a tapered shape. Further, a plurality of portions where the aromatic vinyl compound is uniformly distributed and / or portions where the aromatic vinyl compound is distributed in a tapered shape may coexist in the block B. Furthermore, a plurality of segments having different aromatic vinyl compound contents may coexist in the block B. When a plurality of blocks S and blocks B are present in the copolymer, the structures such as molecular weight and composition thereof may be the same or different.

(Molecular weight of both-end-modified conjugated diene polymer)
The molecular weight of the both-end-modified conjugated diene polymer (weight average molecular weight: in terms of polystyrene) is 200,000 to from the viewpoint of performance such as processability and tensile properties of the modified conjugated diene polymer composition of the present embodiment. 2 million is preferable, and more preferably 250,000 to 1,500,000.

  The molecular weight distribution (weight average molecular weight / number average molecular weight) is preferably 1.0 to 3.0, more preferably 1.1 to 2.5, from the viewpoint of processability and rolling resistance characteristics.

  The weight average molecular weight is determined by, for example, measuring the chromatogram using GPC using three columns with a polystyrene gel as a filler, as described later, and using a calibration curve using standard polystyrene. It can be calculated.

(Modification rate)
In the present specification, “modification rate” means a conjugated diene polymer in which at least one terminal is modified among conjugated diene polymers to be measured (one-side modified conjugated diene polymer and both terminal modified conjugated diene). The ratio (mass%) of the total of the polymer. The both-end-modified conjugated diene polymer is excellent in the balance between rolling resistance characteristics and wet skid resistance, and from the viewpoint of obtaining a vulcanizate having practically sufficient wear resistance and fracture strength, the modification rate is preferably 50. It is 80 mass% or more, More preferably, it is 85 mass% or more more preferably.

(Hydrogen addition rate)
The both terminal-modified conjugated diene polymer may be hydrogenated.

  By further hydrogenating the both-end-modified conjugated diene polymer in an inert solvent, all or part of the double bond can be converted to a saturated hydrocarbon. In that case, heat resistance and weather resistance are improved, and deterioration of the product when processed at a high temperature can be prevented. As a result, it exhibits even better performance in various applications such as automotive applications. The hydrogenation rate of the unsaturated double bond based on the conjugated diene compound (ie, “hydrogenation rate”) can be arbitrarily selected according to the purpose, and is not particularly limited.

  When used as a vulcanized rubber, it is preferable that the double bond of the conjugated diene part partially remains. From this viewpoint, the hydrogenation rate of the conjugated diene part in the terminal-modified conjugated diene polymer contained in the modified conjugated diene polymer composition of the present embodiment is preferably 3 to 70%, preferably 5 to 65. % Is more preferable, and 10 to 60% is further more preferable.

  The hydrogenation rate of the aromatic double bond based on the aromatic vinyl compound in the copolymer of the conjugated diene compound and the aromatic vinyl compound is not particularly limited, but is preferably 50% or less, 30 % Or less is more preferable, and 20% or less is still more preferable.

  The hydrogenation rate can be determined by a nuclear magnetic resonance apparatus (NMR).

  The hydrogenation method is not particularly limited, and a known method can be used.

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

  As the hydrogenation catalyst, a heterogeneous catalyst such as a catalyst in which a noble metal is supported on a porous inorganic substance; a catalyst in which a salt such as nickel or cobalt is solubilized and reacted with organic aluminum or the like, or a metallocene such as titanocene is used. Examples thereof include homogeneous catalysts such as catalysts. Among these, a titanocene catalyst is preferable from the viewpoint of selecting mild hydrogenation conditions. The hydrogenation of the aromatic group can be performed by using a noble metal supported catalyst.

  Specific examples of the hydrogenation catalyst include (1) a supported heterogeneous hydrogenation catalyst in which a metal such as Ni, Pt, Pd, or Ru is supported on carbon, silica, alumina, diatomaceous earth, or the like. (2) Ni, A so-called Ziegler type hydrogenation catalyst using a transition metal salt such as an organic acid salt such as Co, Fe or Cr or an acetylacetone salt and a reducing agent such as organoaluminum, and (3) an organic metal such as Ti, Ru, Rh or Zr. Examples include so-called organometallic complexes such as compounds. For example, as a hydrogenation catalyst, JP-B-42-8704, JP-B-43-6636, JP-B-63-4841, JP-B-1-37970, JP-B-1-53851, JP-B-2-9041 And hydrogenation catalysts described in JP-A-8-109219 can be used. A preferred hydrogenation catalyst is a reaction mixture of a titanocene compound and a reducing organometallic compound.

<Rubber stabilizer>
It is preferable to add a stabilizer for rubber to the both-end-modified conjugated diene-based polymer from the viewpoint of preventing gel formation in the finishing step after polymerization and improving the stability during processing.

  The stabilizer for rubber is not particularly limited, and known ones can be used. For example, 2,6-di-tert-butyl-4-hydroxytoluene (BHT), n-octadecyl-3- (4 '-Hydroxy-3', 5'-di-tert-butylphenol) propinate, 2-methyl-4,6-bis ((octylthio) methyl) phenol and the like are preferable.

<Process oil>
In order to further improve the processability of the modified conjugated diene polymer, process oil can be added to the modified conjugated diene polymer as necessary.

  The method for adding the process oil to the modified conjugated diene polymer is not particularly limited, but a method in which the process oil is added to the polymer solution and mixed to remove the solvent from the oil-extended polymer solution is preferable. Examples of the process oil include aroma oil, naphthenic oil, paraffin oil and the like. Among these, from the viewpoint of environmental safety, oil bleed prevention and wet grip characteristics, an aromatic substitute oil having a polycyclic aromatic (PCA) component of 3% by mass or less by the IP346 method is preferable.

  Examples of the aroma substitute oil include TDAE (Treated Distillate Aromatic Extracts) shown in Kautschuk Gummi Kunststoffe 52 (12) 799 (1999), MES (Mil Extraction Solvate), etc., and R e s, e.

  Although the addition amount of process oil is not specifically limited, Usually, it is 0-60 mass parts with respect to 100 mass parts of modified conjugated diene polymers, and 0-37.5 mass parts is preferable.

<Rubber polymer>
(A) The rubber component containing both terminal-modified conjugated diene polymers may contain other rubber-like polymers in addition to the above-mentioned both terminal-modified conjugated diene polymers, as long as the characteristics of the present invention are satisfied. Good.

  The rubbery polymer is not particularly limited, and for example, a conjugated diene polymer or a hydrogenated product thereof, a random copolymer of a conjugated diene compound and a vinyl aromatic compound, or a hydrogenated product thereof, and a conjugated diene compound. Examples thereof include block copolymers with vinyl aromatic compounds, hydrogenated products thereof, and non-diene polymers.

  Specifically, the rubber-like polymer includes butadiene rubber or a hydrogenated product thereof, styrene-butadiene rubber or a hydrogenated product thereof, styrene-butadiene block copolymer or a hydrogenated product thereof, and styrene-isoprene block copolymer. Or a styrene-type elastomer such as a hydrogenated product thereof, acrylonitrile-butadiene rubber, or a hydrogenated product thereof.

  Examples of the non-diene polymer include ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-butene-diene rubber, ethylene-butene rubber, ethylene-hexene rubber, ethylene-octene rubber and other olefin elastomers, butyl rubber, brominated butyl rubber, Acrylic rubber, fluororubber, silicone rubber, chlorinated polyethylene rubber, epichlorohydrin rubber, α, β-unsaturated nitrile-acrylic ester-conjugated diene copolymer rubber, urethane rubber, polysulfide rubber and the like can be mentioned.

  The various rubber-like polymers described above may be modified rubbers to which functional groups having polarity such as hydroxyl groups and amino groups are added. The weight average molecular weight is preferably 2,000 to 2,000,000, more preferably 5,000 to 1,500,000, from the viewpoint of the balance between performance and processing characteristics. These rubbery polymers may be used alone or in combination of two or more.

<(B) Silica-based inorganic filler>
In the manufacturing method of the modified conjugated diene polymer composition of the present embodiment, 30 to 30 parts of silica-based inorganic filler is added to 100 parts by mass of the rubber component (component (A)) containing both terminal-modified conjugated diene polymers. Mix 300 parts by weight.

  The compounding amount of the silica-based inorganic filler with respect to 100 parts by mass of the rubber component containing the both-end modified conjugated diene polymer is 30 parts by mass or more from the viewpoint of manifesting the effects of the present invention, while the inorganic filler is sufficiently dispersed. From the viewpoint of making the composition have sufficient workability and mechanical strength, the amount is 300 parts by mass or less. Preferably it is 40-200 mass parts, More preferably, it is 55-100 mass parts.

The silica-based inorganic filler is not particularly limited, it can be a known, SiO _2, or preferably solid particles containing Si ₃ Al as a constituent unit, SiO _2, or the constitutional unit Si ₃ Al More preferably, the main component is used. Here, “main component” means that 50% by mass or more of SiO ₂ or Si ₃ Al is contained in the silica-based inorganic filler. The silica-based inorganic filler preferably contains 70% by mass or more, more preferably 80% by mass or more of SiO ₂ or Si ₃ Al.

  Specific examples of the silica-based inorganic filler include silica, clay, talc, mica, diatomaceous earth, wollastonite, montmorillonite, zeolite, and inorganic fibrous substances such as glass fiber.

  Moreover, as a silica type inorganic filler, the mixture of the silica type inorganic filler which hydrophobized the surface, and inorganic fillers other than a silica type inorganic filler and a silica type can also be used. Among these, silica or glass fiber is preferable and silica is more preferable from the viewpoints of strength, wear resistance, and the like.

  Examples of the silica include dry silica, wet silica, and synthetic silicate silica. Among these, wet silica is preferable.

From the viewpoint of obtaining a modified conjugated diene polymer composition having more excellent rolling resistance characteristics, the nitrogen adsorption specific surface area determined by the BET adsorption method of the silica-based inorganic filler is preferably 100 to 300 m ² / g. 160 to 250 m ² / g, more preferably 170 to 190 m ² / g.

<(C) Silane coupling agent>
In the method for producing the modified conjugated diene polymer composition of the present embodiment, 100 parts by mass of the rubber component (component (A)) containing the both-end modified conjugated diene polymer is used with a silane coupling agent (component (C )) 0.03-90 parts by mass are blended.

  The silane coupling agent has a function of tightly interacting the rubber component (component (A)) containing the both-end-modified conjugated diene polymer and the silica-based inorganic filler (component (B)). , Having an affinity or binding group for each of the rubber component containing both terminal-modified conjugated diene polymer and the silica-based inorganic filler, and in general, a sulfur bond portion, an alkoxysilyl group, and a silanol A compound having a base portion in one molecule is used.

  The compounding quantity of a silane coupling agent is 0.03-90 mass parts with respect to 100 mass parts of rubber components containing a both-ends modified conjugated diene polymer, 0.15-60 mass parts is preferable, 3- More preferred is 45 parts by mass. When the blending amount of the silane coupling agent is within the above range, the addition effect of the silane coupling agent can be made more remarkable.

  Examples of the silane coupling agent include, but are not limited to, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, Ethoxy (3-mercaptopropyl) bis (3,6,9,12,15-pentaoxaoctacosan-1-yloxy) silane (Evonik Degussa: Si363), Momentive NXT-Z30, NXT-Z45 , NXTZ60, silane coupling agents containing a mercapto group such as NXT silane, bis- (3- (triethoxysilyl) -propyl) -tetrasulfide, bis- (3- (triethoxysilyl) -propyl) -disulfide, Bis- (2- (triethoxy Silyl) -ethyl) -tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis- (2- (triethoxysilyl) -ethyl) -tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, Bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl -N, N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetras Fido, 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzoyltetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis (3- Diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide and the like.

  Of these, silane coupling agents include bis- (3- (triethoxysilyl) -propyl) -disulfide and ethoxy (3-mercaptopropyl) bis (3,6,9,12,15) from the viewpoint of reinforcing effect. Silane coupling agents containing mercapto groups such as pentaoxaoctacosan-1-yloxy) silane (Evonik Degussa: Si363), Momentive NXT-Z30, NXT-Z45, NXTZ60, NXT silane, etc. -(3- (Triethoxysilyl) -propyl) -tetrasulfide is preferred. These silane coupling agents can be used singly or in combination of two or more.

<(D) Vulcanization accelerator, anti-aging agent>
In the method for producing the modified conjugated diene polymer composition of the present embodiment, a vulcanization acceleration aid and / or an antioxidant (component (D)) is blended. The modified conjugated diene polymer composition may contain at least one selected from the group consisting of a vulcanization accelerating aid and an antiaging agent, and preferably contains both a vulcanization accelerating aid and an antiaging agent. Is done.

  Examples of the vulcanization acceleration aid include, but are not limited to, metal oxide salts such as zinc oxide and magnesium oxide, fatty acids such as stearic acid and dehydrated castor oil fatty acid, and zinc carbonate. These vulcanization accelerating aids can be used alone or in combination of two or more. From the viewpoint of effectively completing vulcanization, it is more preferable to use a combination of zinc oxide and stearic acid.

  From the viewpoint of effectively completing vulcanization, the blending amount of the vulcanization accelerating aid is 0.5 to 15 with respect to 100 parts by mass of the rubber component (component (A)) containing both terminal-modified conjugated diene polymers. Mass parts are preferred, 1.0 to 10 parts by mass are more preferred, and 1.5 to 5 parts by mass are even more preferred.

  The anti-aging agent is not limited to the following, but examples thereof include p- (p-toluenesulfonylamide) -diphenylamine, diphenylamines such as octylated diphenylamine, N- (1,3-dimethylbutyl) -N P-phenylene such as' -phenyl-p-phenylenediamine (6PPD), N-phenyl-N'-isopropyl-p-phenylenediamine (IPPD), and N, N'-di-2-naphthyl-p-phenylenediamine A diamine system etc. are mentioned. These anti-aging agents can be used singly or in combination of two or more.

  The blending amount of the anti-aging agent is a rubber component (component (component (the component (the component (the improvement of heat-resistant oxidation resistance, ozone deterioration resistance, and display resistance deterioration))) from the viewpoint of economic resistance. A)) 0.1-15 mass parts is preferable with respect to 100 mass parts, 0.5-10 mass parts is more preferable, and 1-5 mass parts is further more preferable.

Next, a method for producing the modified conjugated diene polymer composition of this embodiment will be described.
<Process [I], Process [B]>
The method for producing the modified conjugated diene polymer composition of the present embodiment is as follows:
Step [a]: Step of kneading component (A), component (B), component (C), and component (D) at the same time, or step [b]: Mixing component (A) and component (D) A step of kneading the first kneaded product, component (B) and component (C) after kneading to produce a first kneaded product is included. In the present specification, the step of preparing the first kneaded product after kneading the component (A) and the component (D) in the step [b] is referred to as “first stage”, and the first kneading is performed. The stage in which the product, component (B) and component (C) are kneaded may be referred to as “the latter stage”.

  In the step [A], the components (A) to (D) may be obtained by kneading a part or all of each component at the same time, preferably all of the components (A) to (D). Are kneaded at the same time.

  In the preceding stage of the step [b], all or part of the component (A) and all or part of the component (D) may be kneaded, preferably all of the component (A) and component (D). All or a part is kneaded, and more preferably, all of the component (A) and all of the component (D) are kneaded. In the latter stage of the step [b], all or part of the first kneaded material produced in the former stage, all or part of the component (B), and all or part of the component (C) may be kneaded. Well, preferably all of the first kneaded product, all of component (B), and all of component (C) are kneaded.

  Moreover, what is necessary is just to mix | blend at least 1 sort (s) chosen from the group which consists of a vulcanization acceleration | stimulation adjuvant and anti-aging agent as a component (D) in a process [I] or a process [B]. Only one of them may be blended in this step, and both the vulcanization acceleration aid and the anti-aging agent may be blended at the same time.

  In the modified conjugated diene polymer composition, the rubber component containing (A) both terminal-modified conjugated diene polymer and (B) silica-based inorganic filler, Therefore, the reaction between the silica-based inorganic filler and the silane coupling agent is not hindered and can be sufficiently reacted, and the dispersibility is improved. As a result, in the modified conjugated diene polymer composition of interest, it is possible to obtain an improved balance of processability, rolling resistance characteristics, wet skid resistance, tensile characteristics, and wear resistance, as compared with the conventional ones.

  Here, the rubber component (component (A)) containing the both-end-modified conjugated diene polymer used in step [b] or step [b] is a component (component (A) before step [b] or step [b]). Only step A) may be masticated in advance, or step [ii] or step [b] may be performed without mastication, but component (A) may be carried out before step [ii] or step [b]. It is preferable to pour only.

  Although the kneading | mixing temperature in process [I] or process [B] is not specifically limited, For example, the range of 120-170 degreeC is preferable. By kneading at 120 to 170 ° C. in step [b] or step [b], the reaction rate of (B) silica-based inorganic filler and (C) silane coupling agent is improved, and dispersibility is increased. it can. The kneading temperature is preferably selected according to the type of (C) silane coupling agent.

  For example, when the (C) silane coupling agent has 3 or more sulfur atoms in its molecular structure, the kneading temperature is preferably in the range of 120 to 160 ° C, and in the range of 140 to 150 ° C. Is more preferable.

  Although it does not specifically limit as a silane coupling agent which has three or more sulfur atoms in molecular structure, Specifically, bis- (2- (triethoxysilyl) -ethyl) -tetrasulfide and bis- ( 3- (triethoxysilyl) -propyl) -tetrasulfide and the like.

  For example, when (C) the silane coupling agent has 1 to 2 sulfur atoms in its molecular structure, the kneading temperature is preferably in the range of 140 to 170 ° C, and in the range of 150 to 160 ° C. It is more preferable that

  The silane coupling agent having 1 to 2 sulfur atoms in the molecular structure is not particularly limited, and specific examples include bis- (3- (triethoxysilyl) -propyl) -disulfide.

  In the step [b] or [b], the kneading time after reaching a desired temperature, for example, 150 to 160 ° C. or 140 to 150 ° C., selected as described above, during kneading. It is preferably 2 to 8 minutes, and more preferably 2 to 5 minutes. Thereby, the balance of each physical property of a modified conjugated diene type polymer composition can be raised more.

  In the step [b], (A) a rubber component containing a both-end-modified conjugated diene polymer and (D) a vulcanization accelerator and / or an anti-aging agent are blended and kneaded in the previous stage. The first kneaded product is once discharged from a closed kneader such as a Banbury mixer, and then the first kneaded product, the component (B) and the component (C) discharged from the closed kneader at a later stage. ) May be put into a kneader or the like that is the same as or different from the preceding stage, or the first kneaded product is not discharged from the closed kneader, and subsequently (B) a silica-based inorganic filler, And (C) a silane coupling agent may be blended and kneaded. In addition, from the viewpoint of workability in the process [b] (the cohesiveness of the discharged material), the first kneaded product is not discharged from the closed kneader, and (B) a silica-based inorganic filler and (C) a silane cup It is preferable to mix and knead the ring agent.

  In the step [b], the temperature and the kneading time in the previous stage depend on the kneading time of the entire step [b], but (D) the dispersibility of the vulcanization accelerating aid and / or anti-aging agent From a viewpoint, 120-170 degreeC and 0.5 minute-3 minutes are preferable.

  In the production method of the modified conjugated diene polymer composition of the present embodiment, as a method of kneading various materials, a conventionally known method can be applied and is not limited to the following, but for example, open A melt kneading method using a general blender such as a roll, a Banbury mixer, a kneader, a single screw extruder, a twin screw extruder, a multi-screw extruder, etc., and after dissolving and mixing the components, the solvent is removed by heating. Methods and the like.

  Of these, a melt kneading method using a roll, a Banbury mixer, a kneader, or an extruder is preferred from the viewpoint of productivity and good kneading properties. In addition, any of a method of kneading various materials at a time and a method of kneading in a plurality of times can be applied.

<Others>
<(E) Carbon black>
Moreover, the manufacturing method of the modified | denatured diene polymer composition of this embodiment is further from viewpoints of coloring property, workability, etc. with respect to 100 mass parts of rubber components containing the said (A) modified conjugated diene polymer. E) It is preferable to include the process of mix | blending 0.5-100 mass parts of carbon black.

Although it does not specifically limit as carbon black, For example, carbon black of each class, such as SRF, FEF, HAF, ISAF, SAF, can be used. Among these, from the viewpoint of workability and rolling resistance characteristics, the nitrogen adsorption specific surface area is preferably 50 m ² / g or more, the dibutyl phthalate (DBP) oil absorption is preferably 80 mL / 100 g or more, and the nitrogen adsorption specific surface area is 90 m ² / g or more and DBP oil absorption is more preferably 80 mL / 100 g or more.

  The blending amount of carbon black with respect to 100 parts by mass of the rubber component containing the both-end modified conjugated diene polymer is 0.5% by mass or more from the viewpoint of expressing the performance required for uses such as dry grip properties and conductive tires, 100 parts by mass or less is preferable from the viewpoint of dispersibility, more preferably 3 to 100 parts by mass, and still more preferably 5 to 50 parts by mass.

  (E) The timing of blending the carbon black is not particularly limited. For example, in the latter stage of the step [ii] or the step [b], the carbon black is blended and kneaded together with the components to be blended, or the step [ii] Or it is preferable to mix | blend and knead | mix further with the kneaded material obtained by the process [b]. From the viewpoint of further improving rolling resistance characteristics and wet skid resistance, it is more preferable to mix and knead carbon black together with (B) a silica-based inorganic filler and (C) a silane coupling agent.

<Metal oxide, metal hydroxide>
In the method for producing the modified conjugated diene polymer composition of the present embodiment, a metal oxide and / or a metal hydroxide may be blended and kneaded.

Metal oxide refers to solid particles having the chemical formula MxO _y (M represents a metal atom, and x and y each represents an integer of 1 to 6) as a main component of a structural unit, and is limited to the following. Although not intended, for example, alumina, titanium oxide, magnesium oxide, zinc oxide or the like can be used. A mixture of a metal oxide and an inorganic filler other than the metal oxide can also be used. The metal hydroxide is not particularly limited, and examples thereof include aluminum hydroxide, magnesium hydroxide, and zirconium hydroxide.

<Rubber softener>
In the method for producing the modified conjugated diene polymer composition of the present embodiment, a rubber softener may be contained in order to improve processability.

  As the rubber softener, mineral oil or a liquid or low molecular weight synthetic softener is suitable. The mineral oil rubber softener called process oil or extender oil used for softening, increasing volume and improving processability of rubber is a mixture of aromatic ring, naphthene ring and paraffin chain. A paraffin chain having 50% or more carbon atoms in the total carbon is called paraffinic, a naphthene ring having 30 to 45% carbon is naphthenic, and an aromatic carbon having more than 30% aromatic is aromatic. It is called a system.

  As the rubber softener used together with the rubber component containing the (A) both-end-modified conjugated diene polymer used in the production method of the present embodiment, those having an appropriate aromatic content tend to be familiar with the copolymer. Therefore, it is preferable.

  The blending amount of the rubber softening agent is preferably 0 to 100 parts by weight, more preferably 10 to 90 parts by weight, and more preferably 30 to 90 parts by weight based on 100 parts by weight of the rubber component containing the (A) both-end-modified conjugated diene polymer. Part by mass is more preferable. If the blending amount of the rubber softener exceeds 100 parts by mass with respect to 100 parts by mass of the rubber component, bleeding out tends to occur, and the composition surface may become sticky.

<wax>
In the method for producing the modified conjugated diene polymer composition of the present embodiment, a wax may be blended. Conventionally known waxes can be used as the wax, and examples thereof include natural waxes and petroleum waxes. The amount of the wax used is usually 0.5 to 5 parts by mass, preferably 1 to 2 parts by mass with respect to 100 parts by mass of the rubber component containing the (A) both-end-modified conjugated diene polymer.

<Vulcanizing agent>
In the method for producing the modified conjugated diene polymer composition of the present embodiment, a vulcanized composition may be obtained by adding a vulcanizing agent and performing a vulcanization treatment.

  As the vulcanizing agent, for example, radical generators such as organic peroxides and azo compounds, oxime compounds, nitroso compounds, polyamine compounds, sulfur and sulfur compounds can be used. Sulfur compounds include sulfur monochloride, sulfur dichloride, disulfide compounds, polymeric polysulfur compounds, and the like.

  The amount of the vulcanizing agent used is usually 0.01 to 20 parts by mass, and 0.1 to 15 parts by mass with respect to 100 parts by mass of the rubber component containing the (A) both-end modified conjugated diene polymer. preferable. As the vulcanization method, a conventionally known method can be applied, and the vulcanization temperature is usually 120 to 200 ° C, preferably 140 to 180 ° C.

<Vulcanization accelerator>
In vulcanization, a vulcanization accelerator may be used as necessary.

  As the vulcanization accelerator, conventionally known materials can be used, and are not limited to the following, but for example, sulfenamide-based, guanidine-based, thiuram-based, aldehyde-amine-based, aldehyde-ammonia-based, Examples thereof include vulcanization accelerators such as thiazole, thiourea, and dithiocarbamate.

  The amount of the vulcanization accelerator used is usually 0.01 to 20 parts by mass, and 0.1 to 15 parts by mass with respect to 100 parts by mass of the rubber component containing (A) both-end-modified conjugated diene polymer. preferable.

  Further, in the method for producing the modified conjugated diene polymer composition of the present embodiment, other softeners and fillers other than those described above, as long as the purpose of the present embodiment is not impaired, Various additives such as an antistatic agent, a weather resistance stabilizer, a colorant, and a lubricant may be used. As other softeners, known softeners can be used. Specific examples of other fillers include calcium carbonate, magnesium carbonate, aluminum sulfate, and barium sulfate. Known materials can be used as the above heat stabilizer, antistatic agent, weather stabilizer, colorant, and lubricant.

  In the method for producing the modified conjugated diene polymer composition of the present embodiment, the timing of adding other components (excluding the vulcanizing agent) other than the components (A) to (D) is not particularly limited. [B], or may be kneaded together before or after step [b], or at least one selected from the group consisting of components (A) to (D) and other components are kneaded in advance. Then, the step [ii] or the step [b] may be performed, and the kneaded product obtained in the step [ii] or the step [b] is mixed with other components and further kneaded. Also good.

  The modified conjugated diene polymer obtained by the production method of the present embodiment can be used, for example, as a rubber composition for a base tread, and a tire can be produced by a usual method. That is, a base tread is produced using the modified conjugated diene polymer composition obtained by the production method of the present embodiment, bonded together with other members, and heated and pressurized using a tire molding machine, thereby producing a tire. Can be manufactured. In addition, by using the modified conjugated diene polymer composition obtained by the production method of the present embodiment as a material for tire treads, the workability, rolling resistance characteristics, wet skid resistance, tensile characteristics, and wear resistance are improved. A tire with excellent balance can be obtained.

  Hereinafter, although a specific example and a comparative example are given and this embodiment is described in detail, this embodiment is not limited to the following examples. First, structural analysis methods of both end or one-side modified conjugated diene polymers (hereinafter collectively referred to as “modified conjugated diene polymers”) used in Examples and Comparative Examples, and Examples and Comparative Examples. A method for measuring physical properties of the modified conjugated diene polymer composition is shown below.

[(1) Bonded styrene content]
As a measurement sample, 100 mg of a modified conjugated diene polymer was made up to 100 mL with chloroform, dissolved, and used as a measurement sample. Using UV-2450 manufactured by Shimadzu Corporation as a measuring instrument, the amount of ultraviolet (UV) absorbed at a wavelength of 254 nm by the phenyl group of styrene was measured, and the amount of bound styrene (% by mass) was measured.

[(2) 1,2-vinyl bond amount]
As a measurement sample, 50 mg of a modified conjugated diene polymer was dissolved in 10 mL of carbon disulfide to prepare a measurement sample. A measurement sample is put in a measurement cell to produce a solution cell, and an infrared spectrum is measured in the range of 600 to 1000 cm ⁻¹ using JAFT Co., Ltd. product: FT-IR230 as a measuring instrument. The 1,2-vinyl bond amount (mol%) was determined according to the calculation formula of the Hampton method (R. R. Hampton, Analytical Chemistry, 21, 923 (1949)) by the absorbance at the wave number.

[(3) Molecular weight]
The chromatogram of the modified conjugated diene polymer was measured using a gel permeation chromatography (hereinafter, also referred to as “GPC”) measuring apparatus in which three columns each having a polystyrene gel as a filler were connected, and standard polystyrene. The weight average molecular weight (Mw) and the number average molecular weight (Mn) were determined based on a calibration curve using. Tetrahydrofuran (THF) was used as the eluent. Moreover, molecular weight distribution (Mw / Mn) was calculated | required from ratio of the obtained number average molecular weight (Mn) and weight average molecular weight (Mw).

  As a column, TSKguardcolumn HHR-H manufactured by Tosoh Corporation was used as a guard column, and TSKgel G6000HHR, TSKgel G5000HHR, and TSKgel G4000HHR manufactured by Tosoh Corporation were used as columns. The molecular weight was measured using an RI detector (“HLC8020” manufactured by Tosoh Corporation) under conditions of an oven temperature of 40 ° C. and a THF flow rate of 1.0 mL / min.

  As a measurement sample, 10 mg of a modified conjugated diene polymer was dissolved in 20 mL of THF to prepare a measurement solution. 200 μL of the measurement solution was injected into the GPC measurement apparatus and measured.

[(4) Denaturation rate]
The modification rate was measured by applying the property of adsorbing the modified conjugated diene polymer component to a GPC column using silica gel as a filler. As shown below, a sample solution containing a sample and a low molecular weight internal standard polystyrene was prepared, and a chromatogram measured with a polystyrene gel column and a chromatogram measured with a silica column were measured. The amount of adsorption onto the column was measured to determine the denaturation rate. A commercially available standard polystyrene having a molecular weight of 5000 was used as the low molecular weight internal standard polystyrene.

(Preparation of sample solution)
As a sample for measurement, 10 mg of a modified conjugated diene polymer whose active terminal was modified after the modification step and 5 mg of standard polystyrene were dissolved in 20 mL of THF to prepare a sample solution.

(Measurement of chromatogram using polystyrene gel column)
Using THF as an eluent, 200 μL of the sample solution was injected into the apparatus for measurement.
The column used was guard column: TSKguardcolumn HHR-H manufactured by Tosoh Corporation, column: Tosoh TSKgel G6000HHR, TSKgel G5000HHR, TSKgel G4000HHR.
A chromatogram was measured using a RI gel detector (HLC8020 manufactured by Tosoh Corporation) under conditions of a column oven temperature of 40 ° C. and a THF flow rate of 1.0 mL / min, and measured with a polystyrene gel column.

(Measurement of chromatogram using silica gel column)
Using THF as an eluent, 200 μL of sample was injected into the apparatus for measurement.
As the column, guard column: DIOL 4.6 × 12.5 mm 5 micron, column: Zorbax PSM-1000S, PSM-300S, PSM-60S were used. Using a RI detector with a column oven temperature of 40 ° C. and a THF flow rate of 0.5 mL / min and a CCP8020 series build-up GPC system manufactured by Tosoh Corporation: AS-8020, SD-8022, CCPS, CO-8020, RI-8021 The chromatogram measured with a silica gel column was obtained.

(Calculation method of denaturation rate)
The total peak area of the chromatogram measured with the polystyrene gel column is 100, the peak area of the sample is P1, the peak area of the standard polystyrene is P2, and the entire peak area of the chromatogram measured with the silica column is 100. Assuming that the peak area of the sample was P3 and the peak area of the standard polystyrene was P4, the modification rate (mass%) was obtained from the following formula.
Denaturation rate (mass%) = (1− (P2 × P3) / (P1 × P4)) × 100

[(5) Mooney viscosity]
Using a Mooney viscometer, the measurement was performed according to JIS K6300-1. The sample after preheating at 100 ° C. for 1 minute was measured for viscosity after rotating the rotor at 2 revolutions per minute for 4 minutes. The smaller the value, the smaller the viscosity and the better the workability.

  The Mooney viscosity of the modified conjugated diene polymer (SBR (1) to (3)) described in Table 1 and the Mooney viscosity of the unvulcanized rubber composition described in Table 3 are in accordance with the method for measuring this Mooney viscosity. Measured.

[(6) Collectability of waste]
An unvulcanized rubber composition after the first stage of kneading, produced by the methods shown in Examples and Comparative Examples, was used as a measurement sample. Five panelists observe visually about the collection (shape) of the discharged material immediately after discharging from the Banbury mixer (immediately after the kneading by the Banbury mixer in the first stage of mixing and discharging), 5 per panelist. Evaluation was made with a perfect score of 25 points. The closer to 25 points, the better the workability after extrusion. The scoring criteria were as follows.
5 points: The discharge is only a large lump and the unity is very good.
4 points: Most of the emission is a large lump and well organized.
3 points: Slightly many small lumps in the discharge, and the unity is a little bad.
2 points: The discharge has many small lumps and is not well organized.
1 point: The discharge is very small and the unity is very bad.

[(7) Rolling resistance characteristics (RR)]
Vulcanized rubber sheets obtained in the examples and comparative examples were used as measurement samples. Using a viscoelasticity tester (ARES-G2) manufactured by TA Instruments, viscoelasticity parameters were measured in torsion mode. Tan δ measured at 50 ° C. with a frequency of 10 Hz and a strain of 3% was used as an index of rolling resistance characteristics (fuel economy). Each measured value was indexed with Comparative Example 1 as 100 for Examples 1 to 6 and Comparative Examples 1 and 2, and indexed with Comparative Example 3 as 100 for Example 7 and Comparative Example 3. A smaller value indicates better rolling resistance characteristics.

[(8) Wet skid resistance (WET)]
Vulcanized rubber sheets obtained in the examples and comparative examples were used as measurement samples. Using a viscoelasticity tester (ARES-G2) manufactured by TA Instruments, viscoelasticity parameters were measured in torsion mode. Tan δ measured at 0 ° C. with a frequency of 10 Hz and a strain of 1% was used as an indicator of wet skid resistance. Each measured value was indexed with Comparative Example 1 as 100 for Examples 1 to 6 and Comparative Examples 1 and 2, and indexed with Comparative Example 3 as 100 for Example 7 and Comparative Example 3. Larger values indicate better wet skid resistance.

[(9) Tensile properties]
Vulcanized rubber sheets obtained in the examples and comparative examples were used as measurement samples. The tensile breaking strength (TB) and the tensile breaking elongation (EB) were measured by the tensile test method of JIS K6251. The product of the tensile strength at break (TB, unit: MPa) and the tensile elongation at break (EB, unit:%) was taken as tensile characteristics. Each measured value was indexed with Comparative Example 1 as 100 for Examples 1 to 6 and Comparative Examples 1 and 2, and indexed with Comparative Example 3 as 100 for Example 7 and Comparative Example 3. Larger values indicate better tensile properties.

[(10) Abrasion resistance]
Vulcanized rubber sheets obtained in the examples and comparative examples were used as measurement samples. Using an Akron abrasion tester (manufactured by Yasuda Seiki Seisakusho), the amount of wear at a load of 44.1 N and 3000 rotations was measured according to JIS K6264-2. Each measured value was indexed with Comparative Example 1 as 100 for Examples 1 to 6 and Comparative Examples 1 and 2, and indexed with Comparative Example 3 as 100 for Example 7 and Comparative Example 3. Smaller values indicate less wear and better wear resistance.

[(11) Balance of physical properties]
Processability of unvulcanized rubber composition in each example and comparative example (Mooney viscosity and discharged mass), and physical properties of vulcanized rubber sheet (rolling resistance characteristics, wet skid resistance, tensile characteristics, abrasion resistance) ), The physical property balance was evaluated as follows. The physical property balance indicates that it is excellent in the order of ◎, ○, Δ, ×.

  The balance of physical properties “◎” is that the unvulcanized rubber composition has a Mooney viscosity of 89 or less, the discharge unity property is 18 to 25 points, the rolling resistance characteristic of the vulcanized rubber sheet is an index of 96 or less, and the wet skid resistance is an index of 100. As mentioned above, it was set as the case where all the conditions whose tensile property is the index 105 or more and abrasion resistance are the index 101 or less are satisfied.

  The physical property balance “◯” indicates that the unvulcanized rubber composition has a Mooney viscosity of 99 or less, the discharge unity property is 15 to 25 points, the rolling resistance property of the vulcanized rubber sheet is an index of 99 or less, and the wet skid resistance is an index of 97. As described above, “◎” is excluded from the cases where the tensile properties are all equal to or greater than 102 and the wear resistance is all that satisfies the index of 105 or less.

  The balance of physical properties “Δ” is that the Mooney viscosity of the unvulcanized rubber composition is 105 or less, the discharge unity is 12 to 25 points, the rolling resistance characteristic of the vulcanized rubber sheet is the index 110 or less, and the wet skid resistance is the index 94. As described above, “◎” and “◯” are excluded from the cases where the tensile properties are 95 or more and the wear resistance is 110 or less.

  The physical property balance “×” was set to the case where the above conditions “」 ”to“ Δ ”were not satisfied.

[Production Example of Modified Conjugated Diene Polymer]
(Production Example 1)
An autoclave having an internal volume of 10 L, an internal height-to-diameter ratio (L / D) of 4, an inlet at the bottom, an outlet at the top, a stirrer and a temperature adjusting jacket is 2 Group-linked. Furthermore, one static mixer was connected downstream from the outlet of the second reactor. 1,3-butadiene, from which impurities such as moisture had been previously removed, was mixed at 17.1 g / min, styrene at 9.6 g / min, and n-hexane at 162.3 g / min. Immediately before this mixed solution enters the first reactor, n-butyllithium for impurity deactivation treatment is supplied at 0.079 mmol / min and mixed with a static mixer, and then the bottom of the first reactor Continuously fed. Furthermore, a mixed solution of hexamethyleneiminolithium and n-butyllithium (hexamethyleneimino) was used as a polymerization initiator (a1) at a rate of 0.016 g / min as a polar compound at a rate of 0.016 g / min. The molar ratio of lithium to n-butyllithium was set to 0.75: 0.25) at a rate of 0.158 mmol / min to the bottom of the first reactor, and the reactor internal temperature was set to 68 ° C. Retained. The polymer solution was continuously withdrawn from the top of the first reactor, continuously fed to the bottom of the second reactor, and the reaction was continued at 71 ° C., and further fed to the static mixer from the top of the second reactor. To a copolymer solution continuously flowing in a static mixer, 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane was added as a nitrogen atom-containing compound (a2). The denaturation reaction was carried out at a rate of 072 mmol / min. Antioxidant (BHT) is continuously added to the polymer solution flowing out from the static mixer so that the amount is 0.2 g per 100 g of the polymer, the modification reaction is terminated, and then the solvent is removed. A system polymer solution was obtained.

  Further, process oil (manufactured by JX Nippon Mining & Energy Co., Ltd., trade name “NC140”) was mixed with the both-end-modified conjugated diene polymer solution, and then the solvent was removed with a drum dryer. A modified conjugated diene polymer (hereinafter also referred to as “modified SBR (1)”) was obtained.

  As a result of analyzing the modified SBR (1), the modification rate of the both-end-modified conjugated diene polymer was 88%, the Mooney viscosity at 100 ° C. was 73, the amount of bonded styrene was 35% by mass, the amount of bonded butadiene was 65% by mass, The 1,2-vinyl bond content was 42 mol%, the weight average molecular weight Mw was 800,000, and the molecular weight distribution was 2.4. The process oil content of the modified SBR (1) was 20.0% by mass.

(Production Example 2)
An autoclave having an internal volume of 10 L and equipped with a stirrer and a jacket and capable of temperature control was used as a reactor, and impurities were previously removed. 762 g of 1,3-butadiene, 268 g of styrene, 4710 g of cyclohexane, 2,2 as a polar compound -1.30 g of bis (2-oxolanyl) propane was put into the reactor, and the reactor internal temperature was kept at 42 ° C. As a polymerization initiator (a1), a mixed solution of piperidine (3.0 mmol) and n-butyllithium (1.1 mmol) was supplied to the reactor. After the start of the polymerization reaction, the temperature inside the reactor started to rise due to the exotherm caused by the polymerization, and the final temperature inside the reactor reached 79 ° C. Two minutes after reaching the peak of the reaction temperature, 0.55 mmol of 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane was added to the reactor as the nitrogen atom-containing compound (a2). The denaturation reaction was carried out for 5 minutes. After adding 2.1 g of an antioxidant (2,6-di-tert-butyl-4-hydroxytoluene; BHT) to this polymer solution, the solvent was removed by steam stripping, and both ends modified conjugated diene system A polymer solution was obtained.

  Further, after mixing process oil (trade name “NC140” manufactured by JX Nippon Mining & Energy Co., Ltd.) with the both-end-modified conjugated diene polymer solution, the solvent is removed with a drum dryer, and both-end-modified conjugated diene system is obtained. A polymer “hereinafter also referred to as“ modified SBR (2) ”” was obtained.

  As a result of analyzing the modified SBR (2), the modification rate of the both-end-modified conjugated diene polymer was 87%, the Mooney viscosity at 100 ° C. was 50, the amount of bonded styrene was 26% by mass, the amount of bonded butadiene was 74% by mass, The 1,2-vinyl bond amount was 56 mol%, the weight average molecular weight Mw was 554,000, and the molecular weight distribution was 1.2. The process oil content of the modified SBR (2) was 20.0% by mass.

(Production Example 3)
One side modified SBR “F3420” manufactured by Asahi Kasei Chemicals Co., Ltd. (the total number of alkoxy groups having one or more nitrogen atoms in the silyl group and bonded to the silyl group at the polymerization active terminal of the conjugated diene polymer is 4 or more) A modified SBR (3) was a one-side modified conjugated diene polymer (polymer) modified with a compound, and 25 parts by mass of process oil (SRAE) was added to 100 parts by mass of the polymer.

  As a result of analyzing the modified SBR (3), the modification rate of the one-end modified conjugated diene polymer was 88%, Mooney viscosity at 100 ° C. was 91, the amount of bound styrene was 35% by weight, the amount of bound butadiene was 75% by weight, The 1,2-vinyl bond amount was 42 mol%, the weight average molecular weight Mw was 790,000, and the molecular weight distribution was 2.0. The process oil content of the modified SBR (3) was 20.0% by mass.

  Table 1 below shows the structures and physical properties of the modified SBR (1) to (3) described above.

Example 1
According to the composition shown below, an unvulcanized rubber composition (unvulcanized product) and a vulcanized rubber composition (vulcanized product) were obtained.
Modified SBR (1) (both end-modified conjugated diene copolymer produced in (Production Example 1)): 125.0 parts by mass (both ends modified conjugated diene polymer 100 parts by mass and process oil 25 parts by mass )
-Silica (Evonik Degussa, Ultrasil 7000GR): 75 parts by mass-Silane coupling agent (Evonik Degussa, Si75): 6 parts by mass-Process oil (manufactured by JX Nippon Mining & Energy Corporation, trade name " NC140 "): 2 parts by mass, carbon black (manufactured by Tokai Carbon Co., Ltd., Seast KH (N339)): 5 parts by mass, vulcanization acceleration aid 1 (stearic acid): 1.0 part by mass, vulcanization acceleration aid Agent 2 (zinc oxide): 2.5 parts by mass Wax: (Sannok, manufactured by Ouchi Shinsei Chemical Co., Ltd.): 1.5 parts by mass Anti-aging agent (N-isopropyl-N′-phenyl-p -Phenylenediamine): 2.0 parts by mass, sulfur: 2.2 parts by mass, vulcanization accelerator 1 (N-cyclohexyl-2-benzothiazylsulfinamide): 1.7 parts by mass, vulcanization accelerator 2 ( Zife Ruguanijin): 2.0 parts by weight

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

(First stage of kneading)
Modified SBR (1) using a Kobe Steel Banbury mixer “Mixtron BB2” (with an internal capacity of 1430 cc) equipped with a temperature control device under the conditions of a 60% filling rate and a rotor rotational speed of 80 rpm. For 30 seconds.

  Thereafter, silica, silane coupling agent, process oil, carbon black, vulcanization acceleration aid (stearic acid and zinc oxide), and anti-aging agent were simultaneously blended and kneaded. Subsequently, kneading was performed for 2 minutes after the material instruction temperature reached 150 ° C., while controlling the material instruction temperature in the Banbury mixer to 150 to 160 ° C. by controlling the temperature of the mixer. Then, without discharging the kneaded product, while controlling the material instruction temperature in the Banbury mixer to 150 to 160 ° C., the wax is blended and kneaded for 1 minute, and the compound (discharge temperature 150 to 160 ° C.) is Banbury. It discharged | emitted from the mixer and obtained the unvulcanized rubber composition. At this time, the state of the unvulcanized rubber composition was observed (the collectability of the discharged matter). Then, the compound was immediately passed 6 times through a 10 inch φ open roll to obtain a sheet-like unvulcanized rubber composition.

  In each example and comparative example, the blending amount of the process oil in the first kneading step is the total blending amount of the process oil contained in the modified SBR and the process oil blended in the first kneading step. 27 parts by mass with respect to 100 parts by mass of the both-end-modified conjugated diene polymer contained in.

(2nd kneading stage)
Next, as the second stage of kneading, the sheet-like unvulcanized rubber composition obtained by the first stage of kneading is cooled to room temperature, and then kneaded again for 3 minutes using the Banbury mixer. did. Also in this case, the temperature of the discharge (formulation) was adjusted to 150 to 160 ° C. by controlling the temperature of the mixer. And after discharging | emitting the said compound from a Banbury mixer, the compound was immediately passed 6 times through a 10 inch (phi) open roll, and it was set as the sheet-like unvulcanized rubber composition.

(3rd stage of kneading)
Furthermore, after heating the sheet-like unvulcanized rubber composition using an oven at 70 ° C. × 30 minutes, as a third stage of kneading, sulfur and vulcanization are performed with a 10-inch φ open roll set at 70 ° C. An accelerator was added and kneaded for 2 minutes to obtain an unvulcanized rubber composition. A part of the unvulcanized rubber composition was taken out and the Mooney viscosity of the unvulcanized rubber composition was measured.

  Thereafter, the other remaining of the unvulcanized rubber composition was vulcanized with a vulcanization press at 160 ° C. for 20 minutes to obtain a vulcanized rubber sheet. After vulcanization, the rolling resistance characteristics (RR), wet skid resistance (WET), tensile characteristics, and abrasion resistance of the vulcanized rubber sheet were evaluated.

(Examples 2-7) and (Comparative Examples 1-3)
As shown in Table 2, the type of the modified SBR to be blended and the order of blending the compounds were changed, and unvulcanized rubber compositions and vulcanized rubber sheets of Examples 2 to 7 and Comparative Examples 1 to 3 were obtained. . In Table 2, the materials summarized in the row of “kneading time” indicate that they were blended almost simultaneously. The evaluation results are shown in Table 3.

  The both-end modified conjugated diene polymer composition obtained by the production method of the present invention can be used as materials for various members such as tire treads, footwear, and industrial articles.

Claims (5)

(A) 100 parts by mass of a rubber component (component (A)) containing a both-end-modified conjugated diene polymer;
(B) Silica-based inorganic filler (component (B)) 30 to 300 parts by mass;
(C) 0.03-90 parts by mass of a silane coupling agent (component (C)),
(D) a vulcanization acceleration aid and / or an anti-aging agent (component (D)),
A method for producing a modified conjugated diene polymer composition comprising a kneading step of kneading
The kneading step includes
Step [a]: Step of kneading component (A), component (B), component (C), and component (D) at the same time, or step [b]: Mixing component (A) and component (D) A method for producing a modified conjugated diene polymer composition, comprising a step of kneading the first kneaded product, component (B) and component (C) after kneading to produce a first kneaded product. The terminal-modified conjugated diene polymer is
An active terminal of a conjugated diene polymer polymerized using a polymerization initiator (a1) containing a compound represented by the following general formula (1) or (2) and an organolithium compound;
A nitrogen atom-containing compound (a2);
The manufacturing method of the modified conjugated diene polymer composition of Claim 1 which is a both-ends modified conjugated diene polymer obtained by making this react.

(In General Formula (1), R ¹ and R ² each independently comprise an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aralkyl group having 6 to 20 carbon atoms. R ¹ and R ² may be bonded to form a cyclic structure with the adjacent nitrogen atom, in which case R ¹ and R ² have a total number of carbon atoms It represents 5-12 hydrocarbon groups and may have an unsaturated bond or a branched structure.)

(In the general formula (2), R ¹ and R ² are the same as R ¹ and R ² in the general formula (1) in, R ³ is an alkylene group having 1 to 20 carbon atoms, or the following formula ( 3) to any one selected from the group consisting of (5), and when R ³ is an alkylene group having 1 to 20 carbon atoms, X is any selected from the group consisting of Cl, Br and I In the case where R ³ is any one selected from the group consisting of the following formulas (3) to (5), X represents a hydrogen atom.)

The method for producing a modified conjugated diene polymer composition according to claim 1 or 2, wherein the nitrogen atom-containing compound (a2) is a compound represented by the following general formula (6).

(In General Formula (6), R ^{4 to} R ⁷ each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ⁸ is an alkylene having 3 to 10 carbon atoms. R ⁹ represents an alkylene group having 1 to 20 carbon atoms, m is an integer of 1 or 2, and n is an integer of 2 or 3.)   Any of Claims 1-3 including the process of kneading | mixing (E) carbon black 0.5-100 mass parts with respect to 100 mass parts of rubber components containing said (A) both terminal modified conjugated diene type polymer. A method for producing the modified conjugated diene polymer composition according to claim 1.   The manufacturing method of the modified conjugated diene polymer composition of Claim 4 including the process of knead | mixing the said component (B), a component (C), and the said (E) carbon black simultaneously.