JP2017002189A - Modified diene polymer composition, rubber composition for side wall and tire - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a modified diene polymer composition excellent in rolling resistance property while maintaining a balance of rolling resistance property, extrusion processability and cutting resistance a high level.SOLUTION: The invention relates to a modified diene polymer composition containing a rubber component containing a both terminal modified diene polymer (a1) having Mooney relaxation rate measured at 110°C, modification rate and a ratio of weigh average molecular weight Mw and number average molecular weight Mn (Mw/Mn) in predetermined ranges, a specific rubbery polymer (b) and a silica inorganic filler.SELECTED DRAWING: None

Description

  The present invention relates to a modified diene polymer composition, a rubber composition for a sidewall, and a tire.

  In recent years, environmental considerations, such as the suppression of carbon dioxide emissions, have become social demands, and the demand for lower fuel consumption for automobiles has increased. Since the hysteresis loss of the tread portion where the tire is in contact with the ground accounts for 50 to 60% of the rolling resistance of the entire tire, development of rubber materials that can reduce the hysteresis loss of the tread portion has been conventionally performed. Yes.

  The rubbery polymer, carbon black, silica, etc. used for such rubber materials have been developed, and the hysteresis loss of the tread portion has been greatly reduced by the improvement of the compounding technology including these, etc. Rolling resistance is also being greatly reduced.

  However, in order to further reduce the rolling resistance of the tire, when trying to reduce the hysteresis loss only in the tread portion, other performances such as wear resistance and grip performance on wet road surfaces are reduced. Only improvement is limited. Therefore, it has also been proposed to reduce the rolling resistance of the tire by reducing the hysteresis loss of a portion other than the tread portion, for example, the sidewall portion.

  In general, a rubber composition containing a conjugated diene copolymer such as butadiene rubber is used for the tire sidewall in order to improve the cut property.

  For example, Patent Document 1 discloses specific silica for 100 parts by weight of a rubber component composed of 30 to 60% by weight of butadiene rubber polymerized using a neodymium catalyst and 70 to 40% by weight of another diene rubber. Is described, and a rubber composition for a tire sidewall is described which contains 10 to 30 parts by weight of a specific carbon black.

  Patent Document 2 contains a rubber component in which the total content of butadiene rubber modified with a compound represented by a specific formula and butadiene rubber synthesized using a rare earth element-based catalyst is 5 to 95% by mass. A rubber composition for sidewalls is described.

  Patent Document 3 discloses that (A) a conjugated diene-based polymer obtained by polymerizing a conjugated diene compound using an anionic polymerization initiator, or by copolymerizing a conjugated diene compound and an aromatic vinyl compound. The total number of alkoxy groups bonded to the silyl group is 4 or more at the polymerization active terminal of the polymer, and contains 20% by mass or more of a modified conjugated diene polymer obtained by reacting a compound having one or more nitrogen atoms. A rubber composition comprising 30 to 70 parts by mass of a rubber component, and (B) at least one rubbery polymer selected from natural rubber, high-cis polybutadiene rubber, and polyisoprene; A rubber composition for a sidewall containing an inorganic filler is described.

JP 2006-124487 A Japanese Patent No. 5563281 JP 2013-87219 A

  However, in order to improve the rolling resistance characteristics in the sidewall, for example, when a method of reducing the compounding amount of a reinforcing agent such as silica is tried, the shape of the rubber composition is not stable, and the extrusion processability tends to deteriorate. I found out that On the other hand, in order to suppress the deterioration of extrusion processability, an attempt was made to blend a solid resin, and it was found that the rolling resistance characteristic tends to deteriorate. As described above, the rolling resistance characteristic and the extrusion workability are in a contradictory relationship, but the methods described in Patent Documents 1 to 3 described above have insufficient balance of these characteristics, and there is room for further improvement.

  The present invention has been made in view of the above, and provides a modified diene polymer composition having excellent rolling resistance characteristics while maintaining a high balance of rolling resistance characteristics, extrusion processability, and cut resistance. For the purpose.

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

1. (A) Mooney relaxation rate measured at 110 ° C. is 0.45 or less, modification rate is 75% by mass or more, and ratio of weight average molecular weight Mw to number average molecular weight Mn by gel permeation chromatography (GPC) ( 30 to 70 parts by mass of a rubber component (I) including a both-end modified conjugated diene polymer (I 1) having Mw / Mn) of 1.9 or more;
(B) 30 to 70 parts by mass of at least one rubbery polymer (b) selected from the group consisting of natural rubber, high-cis polybutadiene rubber, and polyisoprene;
(C) a silica-based inorganic filler,
A modified diene polymer composition, wherein the content of the both-end modified conjugated diene polymer (a) is 20% by mass or more based on the total mass of the rubber component (a).

2. (A) Mooney relaxation rate measured at 110 ° C. is 0.45 or less, modification rate is 75% by mass or more, and weight average molecular weight Mw and number average molecular weight Mn by gel permeation chromatography (GPC) The ratio (Mw / Mn) of the weight average molecular weight Mw and the number average molecular weight Mn measured by gel permeation chromatography (GPC) with a both-end modified conjugated diene polymer (A1) having a ratio (Mw / Mn) of 1.9 or more And 30-70 parts by mass of the rubber component (I) including the one-end modified conjugated diene polymer (I2) having a 1.9 of 1.9 or more,
(B) 30 to 70 parts by mass of at least one rubbery polymer (b) selected from the group consisting of natural rubber, high-cis polybutadiene rubber, and polyisoprene;
(C) a silica-based inorganic filler,
The total content of the both-end modified conjugated diene polymer (A1) and the one-end modified conjugated diene polymer (I2) is 20% by mass or more based on the total mass of the rubber component (A). A modified diene polymer composition.

3. 3. The above 1 or 2, wherein the both terminal-modified conjugated diene polymer (A1) has a star polymer structure having a nitrogen atom at at least one terminal and centering on a nitrogen-containing alkoxysilane substituent. Modified diene polymer composition.

4). The ratio of the 2nd number average molecular weight calculated | required by GPC-light-scattering-method measurement with respect to the 1st number average molecular weight calculated | required by the gel permeation chromatography measurement of the said both terminal modified | denatured conjugated diene type | system | group polymer (i) is as follows. The modified diene polymer composition according to any one of the above 1 to 3, which is 1.00 or more.

5. The ratio of the second weight average molecular weight determined by GPC-light scattering measurement to the first weight average molecular weight determined by gel permeation chromatography measurement is the above-mentioned both-end-modified conjugated diene-based polymer (ii). The modified diene polymer composition according to any one of the above 1 to 4, which is 1.00 or more.

6). The terminal-modified conjugated diene polymer (A1) has a first number average molecular weight of 200,000 or more and 2,000,000 or less, and the first weight relative to the first number average molecular weight. 6. The modified diene polymer composition according to any one of 1 to 5 above, wherein the average molecular weight ratio is 1.90 or more and 3.50 or less.

7). The modified diene polymer composition according to any one of the above 1 to 6, wherein the both-end-modified conjugated diene polymer (A1) is represented by the following general formula (A) or (B).

（式（Ａ）中、Ｒ²¹〜Ｒ²⁴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、Ｒ²⁵及びＲ²⁶は、各々独立して、炭素数１〜２０のアルキレン基を表し、Ｒ²⁷は、水素原子、炭化水素で置換されたシリル基、炭素数１〜２０のアルキル基、又は炭素数６〜２０のアリール基を表す。ａ及びｃは、各々独立して、１又は２の整数を表し、ｂ及びｄは、各々独立して、０又は１の整数を表し、（ａ＋ｂ）及び（ｃ＋ｄ）は、各々独立して、２以下の整数を表し、（Ｐｏｌｙｍ）は、共役ジエン化合物を重合、又は共役ジエン化合物と芳香族ビニル化合物とを共重合することで得られる共役ジエン系重合体鎖を表し、少なくともその一つの末端に、下記一般式（４）〜（７）から選ばれる少なくとも一つで表される官能基が結合している。複数存在する場合のＲ²¹、及びＲ²³、並びに複数存在する（Ｐｏｌｙｍ）は、各々独立している。）

(In formula (A), R ^{21 to} R ²⁴ each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ²⁵ and R ²⁶ are each independently Represents an alkylene group having 1 to 20 carbon atoms, and R ²⁷ represents a hydrogen atom, a silyl group substituted with a hydrocarbon, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. And c each independently represents an integer of 1 or 2, b and d each independently represents an integer of 0 or 1, and (a + b) and (c + d) each independently represents 2 (Polym) represents a conjugated diene polymer chain obtained by polymerizing a conjugated diene compound or copolymerizing a conjugated diene compound and an aromatic vinyl compound, and at least one end thereof. , Represented by at least one selected from the following general formulas (4) to (7) When there are a plurality of functional groups, R ²¹ and R ²³ and a plurality of (Polym) are independent of each other.

（式（Ｂ）中、Ｒ²⁸〜Ｒ³³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、Ｒ³⁴、Ｒ³⁵、及びＲ³⁶は、各々独立して、炭素数１〜２０のアルキレン基を表し、ａ、ｃ、及びｅは、各々独立して、１又は２の整数を表し、ｂ、ｄ、及びｆは、各々独立して、０又は１の整数を表し、（ａ＋ｂ）、（ｃ＋ｄ）、及び（ｅ＋ｆ）は、各々独立して、２以下の整数を表し、（Ｐｏｌｙｍ）は、共役ジエン化合物を重合、又は共役ジエン化合物と芳香族ビニル化合物とを共重合することで得られる共役ジエン系重合体鎖を表し、少なくともその一つの末端に、下記一般式（４）〜（７）から選ばれる少なくとも一つで表される官能基が結合している。複数存在する場合のＲ²⁸、Ｒ³⁰、及びＲ³²、並びに複数存在する（Ｐｏｌｙｍ）は、各々独立している。）

(In the formula (B), R ^{28 to} R ³³ each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ³⁴ , R ³⁵ , and R ³⁶ are Each independently represents an alkylene group having 1 to 20 carbon atoms, a, c, and e each independently represent an integer of 1 or 2, b, d, and f each independently represent: Represents an integer of 0 or 1, each of (a + b), (c + d), and (e + f) independently represents an integer of 2 or less, and (Polym) is a polymer of a conjugated diene compound or a conjugated diene compound It represents a conjugated diene polymer chain obtained by copolymerizing with an aromatic vinyl compound, and at least one terminal thereof is represented by at least one selected from the following general formulas (4) to (7) R ^28, R ³⁰ in the case where groups are to have. plurality of bonded and R ^32, and a plurality To standing (Polym) are each independent.)

（式（４）中、Ｒ₁₀及びＲ₁₁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ばれる少なくとも１種を表す。Ｒ₁₀及びＲ₁₁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、その場合のＲ₁₀及びＲ₁₁は、炭素数５〜１２の炭化水素基を表し、その一部分に不飽和結合又は分岐構造を有していてもよい。）

(In the formula (4), R ₁₀ and R ₁₁ 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 R ₁₀ and R ₁₁ may be bonded to form a cyclic structure with the adjacent nitrogen atom, and in this case, R ₁₀ and R ₁₁ have 5 to 12 carbon atoms. It represents a hydrocarbon group, and a part thereof may have an unsaturated bond or a branched structure.)

（式（５）中、Ｒ₁₂及びＲ₁₃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ばれる少なくとも１種を表す。Ｒ₁₂及びＲ₁₃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、その場合のＲ₁₂及びＲ₁₃は、炭素数５〜１２の炭化水素基を表し、その一部分に不飽和結合又は分岐構造を有していてもよい。Ｒ₁₄は、炭素数１〜２０のアルキレン基、又は炭素数４〜２０の共役ジエン系化合物に基づく二価の基を表す。）

(In the formula (5), R ₁₂ and R ₁₃ 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 R ₁₂ and R ₁₃ may be bonded to form a cyclic structure with an adjacent nitrogen atom, and R ₁₂ and R _{13 in} this case are each having 5 to 12 carbon atoms. R ₁₄ represents a hydrocarbon group and may have an unsaturated bond or a branched structure in a part of the hydrocarbon group, R ₁₄ is an alkylene group having 1 to 20 carbon atoms, or a divalent compound based on a conjugated diene compound having 4 to 20 carbon atoms. Represents a valent group.)

（式（６）中、Ｒ₁₅及びＲ₁₆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のアリール基からなる群より選ばれる少なくとも１種を表す。Ｒ₁₅及びＲ₁₆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、その場合のＲ₁₅及びＲ₁₆は、結合して炭素数５〜１２のアルキレン基を表し、その一部分に分岐構造を有していてもよい。）

(In the formula (6), R ₁₅ and R ₁₆ 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 an aryl group having 6 to 20 carbon atoms R ₁₅ and R ₁₆ may be bonded to form a cyclic structure with an adjacent nitrogen atom, and R ₁₅ and R _{16 in} this case are bonded to form a carbon number of 5; Represents an alkylene group of ˜12, and a part thereof may have a branched structure.)

（式（７）中、Ｒ₁₇は、炭素数が２〜１２の炭化水素基を表し、その一部分に不飽和結合又は分岐構造を有していてもよい。Ｒ₁₈は、炭素数１〜１２のアルキル基を表し、その一部分に分岐構造を有していてもよい。）

(In the formula (7), R ₁₇ represents a hydrocarbon group having 2 to 12 carbon atoms, and may have an unsaturated bond or a branched structure in a part thereof. R ₁₈ has 1 to 12 carbon atoms. And may have a branched structure in a part thereof.)

8). The both terminal-modified conjugated diene polymer (a) is
A polymerization step in which an organic lithium compound having at least one nitrogen atom in the molecule is used as a polymerization initiator, and at least a conjugated diene compound is polymerized to obtain a conjugated diene polymer;
A modification step of modifying the conjugated diene polymer with a modifier having four or more alkoxy groups bonded to a silyl group in one molecule and a tertiary amino group;
8. The modified diene polymer composition according to any one of 1 to 7 above, which is obtained from a production method having

9. 9. The modified diene polymer composition according to 8 above, wherein the modifying agent includes a modifying agent represented by at least one of the following general formulas (1) to (3).

（式（１）中、Ｒ¹〜Ｒ⁴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、Ｒ⁵は、炭素数１〜１０のアルキレン基を表し、Ｒ⁶は、炭素数１〜２０のアルキレン基を表し、ｍは、１又は２の整数を表し、ｎは、２又は３の整数を表す。（ｍ＋ｎ）は、４以上の整数である。複数存在する場合のＲ¹〜Ｒ⁴は、各々独立している。）

(In Formula (1), R < ¹ > -R < ⁴ > respectively independently represents a C1-C20 alkyl group or a C6-C20 aryl group, and R < ⁵ > is C1-C10 alkylene. R ⁶ represents an alkylene group having 1 to 20 carbon atoms, m represents an integer of 1 or 2, n represents an integer of 2 or 3. (m + n) is an integer of 4 or more When there are a plurality of R ^{1 to} R ⁴ , each is independent.)

（式（２）中、Ｒ¹〜Ｒ⁶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、Ｒ⁷〜Ｒ⁹は、各々独立して、炭素数１〜２０のアルキレン基を表し、ｍ、ｎ、及びｌは、各々独立して、１〜３の整数を表し、（ｍ＋ｎ+ｌ）は、４以上の整数を表す。複数存在する場合のＲ¹〜Ｒ⁶は、各々独立している。）

(In Formula (2), R < ¹ > -R < ⁶ > respectively independently represents a C1-C20 alkyl group or a C6-C20 aryl group, and R < ⁷ > -R < ⁹ > is respectively independently. Represents an alkylene group having 1 to 20 carbon atoms, m, n, and l each independently represent an integer of 1 to 3, and (m + n + 1) represents an integer of 4 or more. R ^{1 to} R ^{6 in the} case are independent of each other.)

（式（３）中、Ｒ¹〜Ｒ⁴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、Ｒ⁵及びＲ⁶は、各々独立して、炭素数１〜２０のアルキレン基を表し、ｍ及びｎは、各々独立して１〜３の整数を表し、（ｍ＋ｎ）は４以上の整数を表し、Ｒ⁷は、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、又は炭化水素基で置換されたシリル基を表す。複数存在する場合のＲ¹〜Ｒ⁴は、各々独立している。）

(In the formula (3), R ¹ ~R ⁴ each independently represent an alkyl group or an aryl group having 6 to 20 carbon atoms having 1 to 20 carbon atoms, R ⁵ and R ⁶ are each independently Represents an alkylene group having 1 to 20 carbon atoms, m and n each independently represent an integer of 1 to 3, (m + n) represents an integer of 4 or more, and R ⁷ represents an integer of 1 to 20 carbon atoms. Represents an alkyl group, an aryl group having 6 to 20 carbon atoms, or a silyl group substituted with a hydrocarbon group, and R ^{1 to} R ^{4 in the} case where a plurality thereof are present are each independent.)

10. The modifier is represented by the formula (1), m is 2, and n is 3, or the formula (2), and m, n, and l are all 3. 10. The modified diene polymer composition according to 9 above, which is a modifier.

11. The modified diene polymer composition according to any one of 8 to 10, wherein the organolithium compound includes an organolithium compound represented by any one of the following general formulas (14) to (17).

（式（１４）中、Ｒ₁₀及びＲ₁₁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ばれる少なくとも１種を表す。Ｒ₁₀及びＲ₁₁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、その場合のＲ₁₀及びＲ₁₁は、炭素数５〜１２の炭化水素基を表し、その一部分に不飽和結合又は分岐構造を有していてもよい。）

(In the formula (14), R ₁₀ and R ₁₁ 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. R ₁₀ and R ₁₁ may be bonded to form a cyclic structure with the adjacent nitrogen atom, and in this case, R ₁₀ and R ₁₁ have 5 to 12 carbon atoms. It represents a hydrocarbon group, and a part thereof may have an unsaturated bond or a branched structure.)

（式（１５）中、Ｒ₁₂及びＲ₁₃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ばれる少なくとも１種を表す。Ｒ₁₂及びＲ₁₃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、その場合のＲ₁₂及びＲ₁₃は、炭素数５〜１２の炭化水素基を表し、その一部分に不飽和結合又は分岐構造を有していてもよい。Ｒ₁₄は、炭素数１〜２０のアルキレン基、又は炭素数４〜２０の共役ジエン系化合物に基づく二価の基を表す。）

(In the formula (15), R ₁₂ and R ₁₃ are each independently an alkyl group having 1 to 12 carbon atoms, cycloalkyl of 3 to 14 carbon atoms, and the group consisting of aralkyl group having 6 to 20 carbon atoms R ₁₂ and R ₁₃ may be bonded to form a cyclic structure with an adjacent nitrogen atom, and R ₁₂ and R _{13 in} this case are each having 5 to 12 carbon atoms. R ₁₄ represents a hydrocarbon group and may have an unsaturated bond or a branched structure in a part of the hydrocarbon group, R ₁₄ is an alkylene group having 1 to 20 carbon atoms, or a divalent compound based on a conjugated diene compound having 4 to 20 carbon atoms. Represents a valent group.)

（式（１６）中、Ｒ₁₅及びＲ₁₆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のアリール基からなる群より選ばれる少なくとも１種を表す。Ｒ₁₅及びＲ₁₆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、その場合のＲ₁₅及びＲ₁₆は、結合して炭素数５〜１２のアルキレン基を表し、その一部分に分岐構造を有していてもよい。）

(In the formula (16), R ₁₅ and R ₁₆ 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 aryl group having 6 to 20 carbon atoms. R ₁₅ and R ₁₆ may be bonded to form a cyclic structure with an adjacent nitrogen atom, and R ₁₅ and R _{16 in} this case are bonded to form a carbon number of 5; Represents an alkylene group of ˜12, and a part thereof may have a branched structure.)

（式（１７）中、Ｒ₁₇は、炭素数が２〜１０の炭化水素基を表し、その一部分に不飽和結合又は分岐構造を有していてもよい。Ｒ₁₈は、炭素数１〜１２のアルキル基を表し、その一部分に分岐構造を有していてもよい。）

(In the formula (17), R ₁₇ represents a hydrocarbon group having 2 to 10 carbon atoms, and a part thereof may have an unsaturated bond or a branched structure. R ₁₈ has 1 to 12 carbon atoms. And may have a branched structure in a part thereof.)

12 The one-end modified conjugated diene polymer (ii) is an alkoxy bonded to a silyl group at the polymerization active terminal of a conjugated diene copolymer obtained by copolymerizing a conjugated diene compound and an aromatic vinyl compound. The modified diene according to any one of the above 2 to 11, which is a one-terminal modified conjugated diene copolymer obtained by reacting a modifying agent having a total number of groups of 4 or more and having one or more nitrogen atoms -Based polymer composition.

13. Any one of 1 to 12 above, containing 0.5 to 300 parts by mass of the (iii) silica-based inorganic filler with respect to a total of 100 parts by mass of the rubber component (A) and the rubbery polymer (B). The modified diene polymer composition as described.

14 The modification according to any one of the above 1 to 13, further comprising (2) 0.5 to 100 parts by mass of carbon black with respect to a total of 100 parts by mass of the rubber component (a) and the rubbery polymer (b). Diene polymer composition.

15. 15. The modified diene polymer composition according to any one of 1 to 14 above, which is a rubber composition for a tire sidewall.

16. A tire comprising a crosslinked product of the modified diene polymer composition according to any one of 1 to 15 above.

  According to the present invention, it is possible to provide a modified diene polymer composition that is excellent in rolling resistance characteristics while maintaining a high balance of rolling resistance characteristics, extrusion processability, and cut resistance.

  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 limited to the following embodiment, It can implement by changing variously within the range of the summary.

  The modified diene polymer composition of the present embodiment comprises (a) a rubber component (a) containing a specific amount of a specific modified conjugated diene polymer, (b) a specific rubbery polymer (b), and ( C) Contains a silica-based inorganic filler.

<< (I) Rubber component >>
In the present embodiment, the modified diene polymer composition includes a rubber component (A). The rubber component (A) has a Mooney relaxation rate measured at 110 ° C. of 0.45 or less, a modification rate of 75% by mass or more, and a weight average molecular weight Mw and number by gel permeation chromatography (GPC). Both-terminal-modified conjugated diene polymer (A1) having an average molecular weight Mn ratio (Mw / Mn) of 1.9 or more (hereinafter simply referred to as “both-terminal-modified conjugated diene polymer (A1)” or “component (B) may also be described. The rubber component (A) contained in the modified diene polymer composition of the present embodiment corresponds to at least one of the following first aspect and second aspect.

  In the first aspect of the present embodiment, the rubber component (A) contains 20% by mass or more of the both terminal-modified conjugated diene polymer (I) based on the total mass of the rubber component (A). The first aspect of this embodiment is particularly excellent in rolling resistance.

  In addition, in the second aspect of the present embodiment, the rubber component (a) is added to the both-end-modified conjugated diene polymer (a), and the weight average molecular weight Mw and number average molecular weight by gel permeation chromatography (GPC). One-terminal-modified conjugated diene polymer (A2) having a Mn ratio (Mw / Mn) of 1.9 or more (hereinafter simply referred to as “one-terminal-modified conjugated diene polymer (A2)” or “component (A 2) ”, and based on the total mass of the rubber component (b), both terminal-modified conjugated diene polymer (b) and one-end modified conjugated diene polymer (b) And 20% by mass or more in total. The second aspect of this embodiment is particularly excellent in extrusion processability when a vulcanized product is used.

  In the present embodiment, the rubber component (A) may correspond to at least one of the first aspect and the second aspect. In addition, in this specification, the description which does not specify an aspect in particular shall apply to both the 1st aspect and the 2nd aspect.

  The modified diene polymer composition of the present embodiment contains 30 to 70 parts by mass of the rubber component (A) and 30 to 70 parts by mass of a rubbery polymer (B) described later. When the rubber component (A) is 30 to 70 parts by mass, the extrusion processing characteristics and the cut resistance are improved. From the viewpoint of the balance of rolling resistance characteristics, extrusion processability, and cut resistance, the contents of the rubber component (A) and the rubbery polymer (B) are 40 to 60 parts by mass and 60 to 40 parts by mass, respectively. It is preferable that Hereinafter, each component will be described.

<Both-terminal-modified conjugated diene polymer (I)>
In the present embodiment, the rubber component (A) includes a both-end-modified conjugated diene polymer (I). The both-end modified conjugated diene polymer (A1) has a Mooney relaxation rate measured at 110 ° C. of 0.45 or less, a modification rate of 75% by mass or more, and gel permeation chromatography (GPC). The ratio (Mw / Mn) of the weight average molecular weight Mw to the number average molecular weight Mn is 1.9 or more.

  In the first aspect of the present embodiment, from the viewpoint of rolling resistance characteristics and extrusion processability, the content of both terminal-modified conjugated diene-based polymer (I) is based on the total mass of the rubber component (I). As long as it is 20 mass% or more, 50 mass% or more is preferable, 80 mass% or more is more preferable, and 100 mass% may be sufficient. Further, in the second aspect of the present embodiment, from the viewpoint of rolling resistance characteristics and extrusion processability, both terminal-modified conjugated diene polymers (A1) and a single-terminal modified conjugated diene polymer (I) described later are used. The total content of 2) may be 20% by mass or more, preferably 50% by mass or more, more preferably 80% by mass or more, and 100% by mass based on the total mass of the rubber component (A). Also good.

  The Mooney relaxation rate (hereinafter referred to simply as “MSR” or “Mooney relaxation rate” by omitting the temperature condition) of the both-end-modified conjugated diene-based polymer (1) at 110 ° C. is 0.45. Or less, preferably 0.42 or less, more preferably 0.40 or less, further preferably 0.38 or less, and still more preferably 0.35 or less. Further, the lower limit of the Mooney relaxation rate is not particularly limited, may be a detection limit value or less, and is preferably 0.15 or more. It is considered that rolling resistance characteristics are exhibited due to the Mooney relaxation rate being 0.45 or less. MSR can be measured by the method described in Examples described later.

  MSR is an indicator of the molecular weight and the number of branches of the modified conjugated diene polymer. For example, as the MSR decreases, the molecular weight and the number of branches of the modified conjugated diene polymer (for example, the number of branches of the star polymer (hereinafter also referred to as “number of arms of the star polymer”)) tend to increase. It is in. When comparing modified conjugated diene polymers having the same Mooney viscosity, which will be described later, since the MSR decreases as the number of branches of the modified conjugated diene polymer increases, the MSR in this case may be used as an index of the degree of branching. it can.

  In order to set the Mooney relaxation rate to 0.45 or less, for example, the weight average molecular weight of the modified conjugated diene polymer is 700,000 or more and the degree of branching is 3 or more, or the weight average of the modified conjugated diene polymer is If the molecular weight is 650,000 or more and the degree of branching is 4 or more, it tends to be 0.45 or less. In order to set the Mooney relaxation rate to 0.40 or less, for example, the weight average molecular weight of the modified conjugated diene polymer is 750,000 or more and the degree of branching is 3 or more, or the modified conjugated diene polymer is If the weight average molecular weight is 700,000 or more and the degree of branching is 4 or more, it tends to be 0.40 or less. Further, the degree of branching can be controlled by, for example, the number of functional groups of the modifier, the amount of modifier added, or the degree of progress of metalation.

  In the present embodiment, the both-end-modified conjugated diene polymer (A1) is measured at 110 ° C. from the viewpoints of workability when used as a vulcanized product and wear resistance when used as a vulcanized product. The Mooney viscosity (hereinafter simply referred to as “Mooney viscosity”, omitting the temperature condition) is preferably 100 or more and 200 or less, more preferably 110 or more and 180 or less, and 120 or more and 160 or less. More preferably it is. The Mooney viscosity can be measured by the method described in Examples described later.

  In the present embodiment, the modification rate, which is an index for modification of the both-end-modified conjugated diene polymer (ii), may be 75% by mass or more, preferably 78% by mass or more, and preferably 80% by mass or more. It is more preferable that it is 85 mass% or more, it is more preferable that it is 88 mass% or more, and it is still more preferable that it is 90 mass% or more. Here, the “modification rate” refers to the ratio (% by mass) of the polymer having a specific functional group in the target conjugated diene polymer. For example, the “modification rate” is represented by a polymer having a nitrogen atom at a polymerization initiation terminal and / or a formula (1), (2), or (3) to be described later, among the target conjugated diene polymers. It is represented by the ratio (mass%) of the modified conjugated diene polymer modified by the modifying agent.

  In this embodiment, the both-end-modified conjugated diene polymer (A1) has a Mooney relaxation rate of 0.45 or less and a modification rate of 75% by mass or more, more preferably a Mooney relaxation rate. Is 0.45 or less, and the modification rate is 78% by mass or more, more preferably, the Mooney relaxation rate is 0.44 or less, and the modification rate is 80% by mass or more, and still more preferably, The Mooney relaxation rate is 0.43 or less, and the modification rate is 85% by mass or more. Even more preferably, the Mooney relaxation rate is 0.42 or less, and the modification rate is 88% by mass or more. Preferably, the Mooney relaxation rate is 0.40 or less and the modification rate is 90% by mass or more.

  In order to obtain a modified conjugated diene polymer having a Mooney relaxation rate of 0.45 or less and a modification rate of 75% by mass or more, for example, a modification initiator, that is, having at least one nitrogen atom in the molecule It is preferable to use an organolithium compound as a polymerization initiator and to modify the polymer with a modifier that gives a specific branching rate after polymerization. At this time, when an organolithium compound having at least one nitrogen atom in the molecule is used as a polymerization initiator, a chain transfer reaction is promoted. It is preferable to control the polymerization conditions.

  In order to make the modification rate of the both-end-modified conjugated diene-based polymer (I) 75% by mass or more, it tends to be controllable by the addition amount and reaction of the modifier. Polymerization is preferably performed using an organolithium compound having at least one nitrogen atom as a polymerization initiator.

  The both terminal-modified conjugated diene polymer (A1) preferably has a star polymer structure having a nitrogen atom at at least one terminal and centering on a nitrogen-containing alkoxysilane substituent. In order to have a nitrogen atom at at least one terminal, for example, in the polymerization step described in the production method described later, there is a tendency that it can be achieved by using a polymerization initiator containing nitrogen. The nitrogen-containing alkoxysilane substituent is preferably a structure derived from a modifier. The “star-shaped polymer structure” in the present specification is a structure in which a plurality of linear molecular chains (arms) are bonded from one branch point. Moreover, it is preferable that one branch point here is couple | bonded with the linear molecular chain containing an at least nitrogen atom and the linear molecular chain containing an alkoxysilane group.

  In this embodiment, the ratio (Mw / Mn) of the first weight average molecular weight (Mw) to the first number average molecular weight (Mn) of the both-end-modified conjugated diene polymer (ii) is 1.90 or more. From the viewpoint of physical properties of the vulcanizate, it is preferably 1.90 or more and 3.50 or less, more preferably 1.93 or more and 3.50 or less, and further preferably 1.93 or more and 3 or less. .40 or less, more preferably 1.95 or more and 2.7 or less, and particularly preferably 1.95 or more and 2.5 or less. Further, the first number average molecular weight (Mn) of the both-end-modified conjugated diene polymer (a) is 200,000 or more and 2,000,000 or less, and (Mw / Mn) is 1.90 or more and 3 More preferably, it is .50 or less. Here, the first number average molecular weight (Mn) and the first weight average molecular weight (Mw) are respectively the polystyrene-equivalent number average molecular weight and weight average molecular weight determined by gel permeation chromatography (GPC) measurement. Say.

  The terminal-modified conjugated diene polymer (A1) preferably has a first number average molecular weight (Mn) of 200,000 or more and 2,000,000 or less from the viewpoint of a balance between performance and processing characteristics. 250,000 or more and 1,500,000 or less, more preferably 300,000 or more and 1,000,000 or less. When the first number average molecular weight (Mn) is 200,000 or more, there is a tendency that the strength when vulcanized can be further improved, and when it is 1,000,000 or less, Tend to be able to further improve the performance. The modified conjugated diene polymer of the present embodiment preferably has a first weight average molecular weight (Mw) of 400,000 or more and 4,000,000 or less from the viewpoint of balance between performance and processability. More preferably, it is 500,000 or more and 3,000,000 or less, and more preferably 600,000 or more and 2,000,000 or less.

  The both-end modified conjugated diene polymer (A) in the present embodiment is determined by GPC-light scattering measurement with respect to the first number average molecular weight (Mn) in terms of polystyrene determined by gel permeation chromatography (GPC) measurement. The ratio (Mn-i / Mn) of the second number average molecular weight (Mn-i) obtained is preferably 1.00 or more, more preferably 1.20 or more, and 1.30 or more. More preferably.

  The first number average molecular weight (Mn) is a polystyrene-equivalent number average molecular weight obtained by gel permeation chromatography (GPC) measurement, and is a relative molecular weight. The relative molecular weight is affected by the rotation radius of the polymer to be measured. On the other hand, the second number average molecular weight is a number average molecular weight (Mn-i) measured by GPC-light scattering method measurement, and is an absolute molecular weight. The absolute molecular weight is not affected by the turning radius of the polymer. Therefore, the second number average molecular weight (Mn-i / Mn) relative to the first number average molecular weight is an index of the branched structure of the polymer and the molecular weight. That is, when (Mn-i / Mn) is 1.00 or more, the molecular weight is high and the structure has a branched structure. The upper limit of (Mn-i / Mn) is not particularly limited, but is preferably 3.00 or less.

  When (Mn-i / Mn) is 1.00 or more, the degree of branching derived from the star-shaped polymer of the resulting modified conjugated diene polymer tends to be improved. In order to obtain a modified conjugated diene polymer having (Mn-i / Mn) of 1.00 or more, for example, it has 3 or more branches and the first number average molecular weight is 300,000 or more. A modified conjugated diene polymer that has a tendency to be obtained by using a modified conjugated diene polymer and that has 4 or more branches and a first number average molecular weight of 320,000 or more is used. Is preferred.

  The both-end-modified conjugated diene polymer (I) used in the present embodiment is measured by GPC-light scattering method for the first weight average molecular weight (Mw) in terms of polystyrene determined by gel permeation chromatography (GPC) measurement. The ratio (Mw-i / Mw) of the second weight average molecular weight (Mw-i) determined by the above is preferably 1.00 or more, more preferably 1.02 or more, and 1.05 or more. More preferably.

  The first weight average molecular weight (Mw) is a polystyrene equivalent weight average molecular weight obtained by gel permeation chromatography (GPC) measurement, and is a relative molecular weight. The relative molecular weight is affected by the rotation radius of the polymer to be measured. On the other hand, the second weight average molecular weight (Mw-i) is an absolute molecular weight obtained by GPC-light scattering measurement. The absolute molecular weight is not affected by the turning radius of the polymer. Therefore, the second weight average molecular weight (Mw-i / Mw) with respect to the first weight average molecular weight is an index of the branched structure of the polymer and the molecular weight. That is, when (Mw−i / Mw) is 1.00 or more, the molecular weight is high and the structure has a branched structure. The upper limit of (Mw-i / Mw) is not particularly limited, but is preferably 2.00 or less.

  When (Mw-i / Mw) is 1.00 or more, the modification rate of the resulting modified conjugated diene polymer tends to be improved. In order to obtain a modified conjugated diene polymer having (Mw-i / Mw) of 1.00 or more, for example, it has 3 or more branches and a first weight average molecular weight (Mw) of 600,000. The modified conjugated diene polymer tends to be obtained as described above. Gel permeation chromatography measurement and GPC-light scattering method measurement can be performed by the methods described in the Examples described later.

  In this embodiment, it is preferable that the both terminal modified conjugated diene polymer (A1) is a both terminal modified conjugated diene polymer represented by the following general formula (A) and / or (B).

式（Ａ）中、Ｒ²¹〜Ｒ²⁴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、Ｒ²⁵及びＲ²⁶は、各々独立して、炭素数１〜２０のアルキレン基を表し、Ｒ²⁷は、水素原子、炭化水素で置換されたシリル基、炭素数１〜２０のアルキル基、又は炭素数６〜２０のアリール基を表す。ａ及びｃは、各々独立して、１又は２の整数を表し、ｂ及びｄは、各々独立して、０又は１の整数を表し、（ａ＋ｂ）及び（ｃ＋ｄ）は、各々独立して、２以下の整数を表し、（Ｐｏｌｙｍ）は、共役ジエン化合物を重合、又は共役ジエン化合物と芳香族ビニル化合物とを共重合することで得られる共役ジエン系重合体鎖を表し、少なくともその一つの末端に、下記一般式（４）〜（７）から選ばれる少なくとも一つで表される官能基が結合している。複数存在する場合のＲ²¹、及びＲ²³、並びに複数存在する（Ｐｏｌｙｍ）は、各々独立している。

In formula (A), R ^{21 to} R ²⁴ each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ²⁵ and R ²⁶ are each independently An alkylene group having 1 to 20 carbon atoms is represented, and R ²⁷ represents a hydrogen atom, a silyl group substituted with a hydrocarbon, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. a and c each independently represent an integer of 1 or 2, b and d each independently represent an integer of 0 or 1, and (a + b) and (c + d) are each independently Represents an integer of 2 or less, and (Polym) represents a conjugated diene polymer chain obtained by polymerizing a conjugated diene compound or copolymerizing a conjugated diene compound and an aromatic vinyl compound, and at least one terminal thereof. And a functional group represented by at least one selected from the following general formulas (4) to (7). When there are a plurality of R ^{21 s} and R ^{23 s} and a plurality of (Polym) s are independent of each other.

In the both-end-modified conjugated diene polymer represented by the formula (A), an Si atom bonded to R ²⁵ is a branch point, and the branch point is a linear molecular chain (arm), R ²⁵ , Since it is bonded to (OR ²¹ ) _3-ab , R ²² _b , and (Polym) _a , the both-end-modified conjugated diene polymer represented by the formula (A) has the above-mentioned “star polymer structure”. ”.

式（Ｂ）中、Ｒ²⁸〜Ｒ³³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、Ｒ³⁴、Ｒ³⁵、及びＲ³⁶は、各々独立して、炭素数１〜２０のアルキレン基を表し、ａ、ｃ、及びｅは、各々独立して、１又は２の整数を表し、ｂ、ｄ、及びｆは、各々独立して、０又は１の整数を表し、（ａ＋ｂ）、（ｃ＋ｄ）、及び（ｅ＋ｆ）は、各々独立して、２以下の整数を表し、（Ｐｏｌｙｍ）は、共役ジエン化合物を重合、又は共役ジエン化合物と芳香族ビニル化合物とを共重合することで得られる共役ジエン系重合体鎖を表し、少なくともその一つの末端に、下記一般式（４）〜（７）から選ばれる少なくとも一つで表される官能基が結合している。複数存在する場合のＲ²⁸、Ｒ³⁰、及びＲ³²、並びに複数存在する（Ｐｏｌｙｍ）は、各々独立している。

In the formula (B), R ^{28 to} R ³³ each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ³⁴ , R ³⁵ , and R ³⁶ each represents Independently represents an alkylene group having 1 to 20 carbon atoms, a, c and e each independently represents an integer of 1 or 2, and b, d and f each independently represents 0; Or an integer of 1, (a + b), (c + d), and (e + f) each independently represents an integer of 2 or less, and (Polym) is a polymer of a conjugated diene compound or a conjugated diene compound and an aromatic Represents a conjugated diene polymer chain obtained by copolymerization with an aromatic vinyl compound, and at least one terminal thereof is represented by at least one functional group selected from the following general formulas (4) to (7) Are joined. R ²⁸ , R ³⁰ , and R ³² in the case where a plurality exist, and a plurality (Polym) are independent from each other.

In the both-end-modified conjugated diene polymer represented by the formula (B), the Si atom bonded to R ³⁴ is a branch point, and the branch point is a linear molecular chain (arm), R ³⁴ , Since it is bonded to (OR ²⁸ ) _3-ab , R ²⁹ _b , and (Polym) _a , the both-end-modified conjugated diene polymer represented by the formula (B) has the above-mentioned “star polymer structure”. ”.

式（４）中、Ｒ₁₀及びＲ₁₁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ばれる少なくとも１種を表す。Ｒ₁₀及びＲ₁₁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、その場合のＲ₁₀及びＲ₁₁は、炭素数５〜１２の炭化水素基を表し、その一部分に不飽和結合又は分岐構造を有していてもよい。

In formula (4), R ₁₀ and R ₁₁ are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aralkyl group having 6 to 20 carbon atoms. It represents at least one selected. R ₁₀ and R ₁₁ may be bonded to form a cyclic structure together with the adjacent nitrogen atom, in which case R ₁₀ and R ₁₁ represent a hydrocarbon group having 5 to 12 carbon atoms, It may have an unsaturated bond or a branched structure.

式（５）中、Ｒ₁₂及びＲ₁₃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ばれる少なくとも１種を表す。Ｒ₁₂及びＲ₁₃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、その場合のＲ₁₂及びＲ₁₃は、炭素数５〜１２の炭化水素基を表し、その一部分に不飽和結合又は分岐構造を有していてもよい。Ｒ₁₄は、炭素数１〜２０のアルキレン基、又は炭素数４〜２０の共役ジエン系化合物に基づく二価の基を表す。

In formula (5), R ₁₂ and R ₁₃ are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aralkyl group having 6 to 20 carbon atoms. It represents at least one selected. R ₁₂ and R ₁₃ may be bonded to form a cyclic structure together with the adjacent nitrogen atom, in which case R ₁₂ and R ₁₃ represent a hydrocarbon group having 5 to 12 carbon atoms, and a part thereof It may have an unsaturated bond or a branched structure. R ₁₄ represents a divalent group based on an alkylene group having 1 to 20 carbon atoms or a conjugated diene compound having 4 to 20 carbon atoms.

式（６）中、Ｒ₁₅及びＲ₁₆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のアリール基からなる群より選ばれる少なくとも１種を表す。Ｒ₁₅及びＲ₁₆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、その場合のＲ₁₅及びＲ₁₆は、結合して炭素数５〜１２のアルキレン基を表し、その一部分に分岐構造を有していてもよい。

In formula (6), R ₁₅ and R ₁₆ are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aryl group having 6 to 20 carbon atoms. It represents at least one selected. R ₁₅ and R ₁₆ may be bonded to form a cyclic structure together with the adjacent nitrogen atom, and R ₁₅ and R _{16 in} this case are bonded to each other to represent an alkylene group having 5 to 12 carbon atoms, A part may have a branched structure.

式（７）中、Ｒ₁₇は、炭素数が２〜１２の炭化水素基を表し、その一部分に不飽和結合又は分岐構造を有していてもよい。Ｒ₁₈は、炭素数１〜１２のアルキル基を表し、その一部分に分岐構造を有していてもよい。

In the formula (7), R ₁₇ represents a hydrocarbon group having 2 to 12 carbon atoms, and a part thereof may have an unsaturated bond or a branched structure. R ₁₈ represents an alkyl group having 1 to 12 carbon atoms, and a part thereof may have a branched structure.

  (Polym) in formula (A) and formula (B) are each independently a conjugated diene polymer obtained by polymerizing a conjugated diene compound or copolymerizing a conjugated diene compound and an aromatic vinyl compound. Represents a chain, and at least one terminal thereof has a functional group represented by at least one selected from the above general formulas (4) to (7). The conjugated diene polymer constituting (Polym) is a conjugated diene polymer obtained by polymerizing a conjugated diene compound or copolymerizing a conjugated diene compound and an aromatic vinyl compound using a polymerization initiator. It is preferable. The details of the conjugated diene polymer will be described later together with the description of the production method.

In formula (A), each of R ^{21 to} R ²⁴ independently preferably represents an alkyl group having 1 to 8 carbon atoms, and more preferably represents an alkyl group having 1 to 4 carbon atoms. R ²⁵ and R ²⁶ each independently preferably represent an alkylene group having 1 to 8 carbon atoms, and more preferably represent an alkylene group having 2 to 4 carbon atoms. R ²⁷ preferably represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably represents a hydrogen atom. Examples of R ^{21 to} R ²⁴ are not limited to the following, but include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group, preferably a methyl group and an ethyl group. . Examples of R ²⁵ and R ²⁶ include a methylene group, an ethylene group, a propylene group, a butylene group, and a pentylene group, and an ethylene group, a propylene group, and a butylene group are preferable. R ²⁷ represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group or an isobutyl group, preferably a hydrogen atom, a methyl group or an ethyl group.

  In the formula (A), the number average molecular weight of the conjugated diene polymer chain portion constituting (Polym) is not particularly limited, but it is preferably independently 250,000 or more and 1,500,000 or less, More preferably, it is 350,000 or more and 900,000 or less.

In the formula (B), R ^{28 to} R ³³ each independently preferably represent an alkyl group having 1 to 8 carbon atoms, and more preferably represent an alkyl group having 1 to 4 carbon atoms. R ³⁴ , R ³⁵ and R ³⁶ each independently preferably represent an alkylene group having 1 to 8 carbon atoms, and more preferably represent an alkylene group having 2 to 4 carbon atoms. Further, as represented by R ²⁸ to R ³³ is not particularly limited, for example, a methyl group, an ethyl group, a propyl group, butyl group, isobutyl group and the like, preferably a methyl group, an ethyl group. Further, R ³⁴ and R ³⁵ are not particularly limited, and examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, and a pentylene group, and an ethylene group, a propylene group, and a butylene group are preferable. .

  In the formula (B), the number average molecular weight of the conjugated diene polymer chain moiety constituting (Polym) is not particularly limited, but it is preferably independently 250,000 or more and 1,500,000 or less, More preferably, it is 350,000 or more and 900,000 or less.

In Formula (4), when at least one of R ₁₀ and R ₁₁ is an alkyl group, the alkyl group is preferably an alkyl group having 1 to 6 carbon atoms. When at least one of R ₁₀ and R ₁₁ represents a cycloalkyl group, the cycloalkyl group is preferably a cycloalkyl group having 5 to 7 carbon atoms. When at least one of R ₁₀ and R ₁₁ is an aralkyl group, the aralkyl group is preferably an aralkyl group having 6 to 8 carbon atoms. In the case where R ₁₀ and R ₁₁ are bonded to form a cyclic structure with the adjacent nitrogen atom, R ₁₀ and R ₁₁ are preferably bonded to each other to represent an alkylene group having 5 to 7 carbon atoms. Further, the groups represented by R ₁₀ and R ₁₁ are not limited to the following, but each independently includes, for example, a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group, preferably a butyl group, An isobutyl group. In the case where R ₁₀ and R ₁₁ are bonded to form a cyclic structure with an adjacent nitrogen atom, R ₁₀ and R ₁₁ are not limited to the following, but include, for example, a methylene group, ethylene Group, propylene group, butylene group, pentylene group and hexylene group, preferably butylene group, pentylene group and hexylene group.

In Formula (5), when at least one of R ₁₂ and R ₁₃ is an alkyl group, the alkyl group preferably represents an alkyl group having 1 to 8 carbon atoms. Examples of the alkyl group include, but are not limited to, a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group, and a butyl group and an isobutyl group are preferable. When R ₁₂ and R ₁₃ are bonded to form a cyclic structure with the adjacent nitrogen atom, the group represented by R ₁₂ and R ₁₃ bonded to each other is not limited to the following, but for example, methylene Group, ethylene group, propylene group, butylene group, pentylene group, and hexylene group. Preferred are butylene group, pentylene group, and hexylene group.

In the formula (5), R ₁₄ preferably represents an alkylene group having 1 to 8 carbon atoms. Examples of R ₁₄ include, but are not limited to, methylene group, ethylene group, propylene group, butylene group, pentylene group, and hexylene group, preferably ethylene group, propylene group, and butylene group. .

In the formula (6), R ₁₅ and R ₁₆ are preferably an alkyl group having 1 to 12 carbon atoms. Examples of the alkyl group are not limited to the following, but examples include a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group, and a methyl group and an ethyl group are preferable.

In Formula (7), R ₁₇ preferably represents an alkylene group having 4 to 6 carbon atoms. R ₁₈ preferably represents an alkyl group having 1 to 4 carbon atoms. R ₁₇ is not limited to the following, and examples thereof include a butylene group, a pentylene group, and a hexylene group, and a pentylene group and a hexylene group are preferable. Examples of R ₁₈ are not limited to the following, and examples include a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group, and a methyl group and an ethyl group are preferable.

<Method for Producing Both-Terminal Modified Conjugated Diene Polymer (I)>
The method for producing the both-end-modified conjugated diene polymer (A1) contained in the modified diene polymer composition of the present embodiment is not particularly limited.
A polymerization step (hereinafter, also simply referred to as “polymerization step”), in which an organic lithium compound having at least one nitrogen atom in the molecule is used as a polymerization initiator, and at least a conjugated diene compound is polymerized to obtain a conjugated diene polymer;
A modification step of modifying the conjugated diene polymer with a modifier having 4 or more alkoxy groups bonded to silyl groups in one molecule and a tertiary amino group (hereinafter also simply referred to as “modification step”); ,
It is preferable to have. The conjugated diene polymer constituting the both-end-modified conjugated diene polymer (a) is a homopolymer of a single conjugated diene compound, a polymer or copolymer of different types of conjugated diene compounds, or a conjugated diene. It is a copolymer of a compound and an aromatic vinyl compound. Hereinafter, the polymerization step and the modification step will be described.

[Polymerization process]
In the polymerization step for producing component (ii), it is preferable to use an organolithium compound having at least one nitrogen atom in the molecule as a polymerization initiator, and at least a conjugated diene compound is polymerized to produce a conjugated diene-based polymer. Get coalesced.

(Polymerization initiator)
The polymerization initiator for producing the both-end-modified conjugated diene polymer (A1) is an organolithium compound having at least one nitrogen atom in the molecule, or a compound having at least one nitrogen atom in the molecule, and A polymerization initiator system containing an organolithium compound can be used. In the polymerization initiator system, an organolithium compound having at least one nitrogen atom in the molecule may be prepared in a predetermined reactor in advance, or in a reactor for performing polymerization or copolymerization described later. The compound having at least one nitrogen atom in the molecule and organolithium may be reacted simultaneously with or before the polymerization or copolymerization.

  The compounds having at least one nitrogen atom in the molecule used for the polymerization initiator system in the production of the both-end-modified conjugated diene polymer (I) are represented by the following general formulas (24) to (26). Compounds can be used.

式（２４）中、Ｒ₁₀及びＲ₁₁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ばれる少なくとも１種を表す。Ｒ₁₀及びＲ₁₁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、その場合のＲ₁₀及びＲ₁₁は、炭素数５〜１２の炭化水素基を表し、その一部分に不飽和結合又は分岐構造を有していてもよい。

In Formula (24), R ₁₀ and R ₁₁ are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aralkyl group having 6 to 20 carbon atoms. It represents at least one selected. R ₁₀ and R ₁₁ may be bonded to form a cyclic structure together with the adjacent nitrogen atom, in which case R ₁₀ and R ₁₁ represent a hydrocarbon group having 5 to 12 carbon atoms, It may have an unsaturated bond or a branched structure.

式（２５）中、Ｒ₁₂及びＲ₁₃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ばれる少なくとも１種を表す。Ｒ₁₂及びＲ₁₃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、その場合のＲ₁₂及びＲ₁₃は、炭素数５〜１２の炭化水素基を表し、その一部分に不飽和結合又は分岐構造を有していてもよい。Ｒ₁₄は、炭素数１〜２０のアルキレン基、又は炭素数４〜２０の共役ジエン系化合物に基づく二価の基を表す。Ｘは、水素原子、Ｃｌ原子、Ｂｒ原子、又はＩ原子を表す。

In Formula (25), R ₁₂ and R ₁₃ are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aralkyl group having 6 to 20 carbon atoms. It represents at least one selected. R ₁₂ and R ₁₃ may be bonded to form a cyclic structure together with the adjacent nitrogen atom, in which case R ₁₂ and R ₁₃ represent a hydrocarbon group having 5 to 12 carbon atoms, and a part thereof It may have an unsaturated bond or a branched structure. R ₁₄ represents a divalent group based on an alkylene group having 1 to 20 carbon atoms or a conjugated diene compound having 4 to 20 carbon atoms. X represents a hydrogen atom, a Cl atom, a Br atom, or an I atom.

式（２６）中、Ｒ₁₅及びＲ₁₆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のアリール基からなる群より選ばれる少なくとも１種を表す。Ｒ₁₅及びＲ₁₆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、その場合のＲ₁₅及びＲ₁₆は、炭素数５〜１２のアルキレン基を表し、その一部分に分岐構造を有していてもよい。

In formula (26), R ₁₅ and R ₁₆ are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aryl group having 6 to 20 carbon atoms. It represents at least one selected. R ₁₅ and R ₁₆ may be bonded to form a cyclic structure together with the adjacent nitrogen atom, in which case R ₁₅ and R ₁₆ represent an alkylene group having 5 to 12 carbon atoms and branched into a part thereof. You may have a structure.

In the formula (24), R ₁₀ and R ₁₁ represent, but are not limited to, for example, methyl group, ethyl group, propyl group, butyl group, octyl group, cyclopropyl group, cyclohexyl group, 3- Examples include phenyl-1-propyl group, isobutyl group, decyl group, heptyl group, and phenyl group. The compound represented by the formula (24) is not limited to the following, but for example, dimethylamine, diethylamine, dibutylamine, dipropylamine, diheptylamine, dihexylamine, dioctylamine, di-2-ethyl Examples include hexylamine, didecylamine, ethylpropylamine, ethylbutylamine, ethylbenzylamine, and methylphenethylamine. The compound represented by the formula (24) is not limited to these, and includes the similar compounds as long as the above conditions are satisfied. The compound represented by the formula (24) is, from the viewpoint of hysteresis loss reduction of the modified diene polymer composition described later, the reduction of unpleasant odor of the modified conjugated diene polymer, and the chain transfer reaction control described later. Dibutylamine and dihexylamine are preferable, and dibutylamine is more preferable.

When R ₁₀ and R ₁₁ are bonded to form a cyclic structure with the adjacent nitrogen atom, the compound represented by the formula (24) is not particularly limited, and examples thereof include piperidine, hexamethyleneimine, aza Examples include cyclooctane, 1,3,3-trimethyl-6-azabicyclo [3.2.1] octane, and 1,2,3,6-tetrahydropyridine. The compound represented by the formula (24) is not limited to these, and includes the similar compounds as long as the above conditions are satisfied. The compound represented by the formula (24) includes a reduction in hysteresis loss of a modified diene polymer composition described later, a viewpoint of reducing unpleasant odor of a modified conjugated diene polymer described later, and a viewpoint of chain transfer reaction control described later. From the above, piperidine, hexamethyleneimine, azacyclooctane and 1,3,3-trimethyl-6-azabicyclo [3.2.1] octane are preferable, piperidine and hexamethyleneimine are more preferable, and piperidine is more preferable. is there.

In the formula (25), R ₁₄ preferably represents an alkylene group having 2 to 16 carbon atoms, more preferably 3 carbon atoms, from the viewpoint of reactivity and interaction with inorganic fillers such as carbon and silica. Represents an alkylene group of 10 to 10. The compound represented by the formula (25) is not limited to the following compounds, but examples thereof include 3-chloro-dimethylpropan-1-amine, 3-chloro-diethylpropane-1-amine, and 3-chloro-dibutylpropane. -1-amine, 3-chloro-dipropylpropan-1-amine, 3-chloro-diheptylpropan-1-amine, 3-chloro-dihexylpropan-1-amine, 3-chloropropyl-ethylhexane-1 -Amine, 3-chloro-didecylpropan-1-amine, 3-chloro-ethylpropan-1-amine, 3-chloro-ethylbutan-1-amine, 3-chloro-ethylpropan-1-amine, benzyl-3 -Chloro-ethylpropan-1-amine, 3-chloro-ethylphenethylpropan-1-amine, 3-chloro-methylphenethyl Propan-1-amine, 1- (3-chloropropyl) piperidine, 1- (3-chloropropyl) hexamethyleneimine, 1- (3-chloropropyl) 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) hexamethyleneimine, 1- (3-chlorohexyl) hexamethyleneimine, 1- (3-Chlorodecyl) hexamethyleneimine. The compound represented by the formula (25) is not limited to these compounds, and includes the similar compounds as long as the above conditions are satisfied. From the viewpoints of reactivity and interaction with inorganic fillers such as carbon and silica, the compound represented by the formula (25) is 3-chloro-dibutylpropan-1-amine, 1- (3-chloropropyl). Hexamethyleneimine is preferable, and 1- (3-chloropropyl) hexamethyleneimine is more preferable.

In Formula (25), when R ₁₄ represents a divalent group based on a conjugated diene compound having any one of the following repeating units (28) to (30), X represents a hydrogen atom.

  When X represents a hydrogen atom, the compound represented by the formula (25) is not limited to the following, but examples thereof include 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-ethylpropyl-2-butenyl-1-amine, N, N-ethylbutyl-2-butenyl-1-amine, N, N-ethylbenzyl-2-butenyl-1- Min, 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- Tenenyl-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- And tetrahydropyridine, (2-methyl-2-butenyl) hexamethyleneimine, (3-methyl-2-butenyl) hexamethyleneimine, and the compound represented by the formula (25) is not limited to these compounds. However, the compound represented by the formula (25) includes N, N-dibutyl-2 from the viewpoint of reducing hysteresis loss of the modified diene polymer composition described later. − Tenenyl 1-amine and 1- (2-butenyl) hexamethyleneimine are preferable, 1- (2-butenyl) piperidine and 1- (2-butenyl) hexamethyleneimine are more preferable, and 1- (2 -Butenyl) piperidine.

  The compound represented by the formula (26) is not limited to the following compounds. For example, N, N-dimethyl-o-toluidine, N, N-dimethyl-m-toluidine, N, N-dimethyl-p- Toluidine, N, N-diethyl-o-toluidine, N, N-diethyl-m-toluidine, N, N-diethyl-p-toluidine, N, N-dipropyl-o-toluidine, N, N-dipropyl-m- Toluidine, N, N-dipropyl-p-toluidine, N, N-dibutyl-o-toluidine, N, N-dibutyl-m-toluidine, N, N-dibutyl-p-toluidine, o-piperidinotoluene, p -Piperidinotoluene, o-pyrrolidinotoluene, p-pyrrolidinotoluene, N, N, N ', N'-tetramethyltoluylenediamine, N, N, N', N'-tetraethyl Ruiylenediamine, N, N, N ′, N′-tetrapropyltoluylenediamine, N, N-dimethylxylidine, N, N-diethylxylidine, N, N-dipropylxylidine, N, N-dimethyl Mesidine, N, N-diethylmesidine, (N, N-dimethylamino) toluylphenylmethylamine, 1- (N, N-dimethylamino) -2-methylnaphthalene, 1- (N, N-dimethylamino) -2-methylanthracene. The compound represented by the formula (26) is not limited to these, and includes the similar compounds as long as the above conditions are satisfied. The compound represented by the formula (26) is preferably N, N-dimethyl-o-toluidine from the viewpoint of reducing the hysteresis loss of the modified diene polymer composition described later.

  The organolithium compound contained in the polymerization initiator system and reacted with the compound having at least one nitrogen atom in the molecule is not limited to the following, but includes, for example, n-butyllithium, sec-butyllithium, tert -Butyl lithium, n-propyl lithium, iso-propyl lithium.

  In this embodiment, the organolithium compound as a polymerization initiator has at least one nitrogen atom in the molecule and can be used as a polymerization initiator for anionic polymerization from the viewpoint of improving the modification rate and improving fuel efficiency. It is preferable that an organic lithium compound represented by at least one of the following general formulas (14) to (17) is included. An organic lithium compound may be used individually by 1 type, and may use 2 or more types together.

式（１４）中、Ｒ₁₀及びＲ₁₁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ばれる少なくとも１種を表す。Ｒ₁₀及びＲ₁₁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、その場合のＲ₁₀及びＲ₁₁は、炭素数５〜１２の炭化水素基を表し、その一部分に不飽和結合又は分岐構造を有していてもよい。

In Formula (14), R ₁₀ and R ₁₁ are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aralkyl group having 6 to 20 carbon atoms. It represents at least one selected. R ₁₀ and R ₁₁ may be bonded to form a cyclic structure together with the adjacent nitrogen atom, in which case R ₁₀ and R ₁₁ represent a hydrocarbon group having 5 to 12 carbon atoms, It may have an unsaturated bond or a branched structure.

式（１５）中、Ｒ₁₂及びＲ₁₃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ばれる少なくとも１種を表す。Ｒ₁₂及びＲ₁₃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、その場合のＲ₁₂及びＲ₁₃は、炭素数５〜１２の炭化水素基を表し、その一部分に不飽和結合又は分岐構造を有していてもよい。Ｒ₁₄は、炭素数１〜２０のアルキレン基、又は炭素数４〜２０の共役ジエン系化合物に基づく二価の基を表す。

In formula (15), R ₁₂ and R ₁₃ are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aralkyl group having 6 to 20 carbon atoms. It represents at least one selected. R ₁₂ and R ₁₃ may be bonded to form a cyclic structure together with the adjacent nitrogen atom, in which case R ₁₂ and R ₁₃ represent a hydrocarbon group having 5 to 12 carbon atoms, and a part thereof It may have an unsaturated bond or a branched structure. R ₁₄ represents a divalent group based on an alkylene group having 1 to 20 carbon atoms or a conjugated diene compound having 4 to 20 carbon atoms.

式（１６）中、Ｒ₁₅及びＲ₁₆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のアリール基からなる群より選ばれる少なくとも１種を表す。Ｒ₁₅及びＲ₁₆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、その場合のＲ₁₅及びＲ₁₆は、結合して炭素数５〜１２のアルキレン基を表し、その一部分に分岐構造を有していてもよい。

In formula (16), R ₁₅ and R ₁₆ are each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aryl group having 6 to 20 carbon atoms. It represents at least one selected. R ₁₅ and R ₁₆ may be bonded to form a cyclic structure together with the adjacent nitrogen atom, and R ₁₅ and R _{16 in} this case are bonded to each other to represent an alkylene group having 5 to 12 carbon atoms, A part may have a branched structure.

式（１７）中、Ｒ₁₇は、炭素数が２〜１０の炭化水素基を表し、その一部分に不飽和結合又は分岐構造を有していてもよい。Ｒ₁₈は、炭素数１〜１２のアルキル基を表し、その一部分に分岐構造を有していてもよい。

In the formula (17), R ₁₇ represents a hydrocarbon group having 2 to 10 carbon atoms, and a part thereof may have an unsaturated bond or a branched structure. R ₁₈ represents an alkyl group having 1 to 12 carbon atoms, and a part thereof may have a branched structure.

In the formula (14), examples of R ₁₀ and R ₁₁ include a methyl group, an ethyl group, a propyl group, a butyl group, and an octyl group. Examples of the compound represented by the formula (14) include ethylpropylaminolithium, ethylbutylaminolithium, ethylbenzylaminolithium, methylphenethylaminolithium and the like. R ₁₀ and R ₁₁ are not limited to these, and include the similar compounds as long as the above conditions are satisfied. From the viewpoint of solubility in a solvent, reduction of hysteresis loss of a modified conjugated diene polymer composition described later, and control of chain transfer reaction described later, examples of the compound represented by formula (14) include dibutylaminolithium, di Hexylaminolithium is preferred, and dibutylaminolithium is more preferred.

In the formula (14), when R ₁₀ and R ₁₁ are bonded to form a cyclic structure with the adjacent nitrogen atom, the organolithium compound represented by the formula (14) is not limited to the following. Are, for example, piperidinolithium, hexamethyleneiminolithium, lithium azacyclooctane, lithium-1,3,3-trimethyl-6-azabicyclo [3.2.1] octane, 1,2,3,6-tetrahydro A pyridino lithium is mentioned. The organolithium compound is not limited to these, and includes the similar compounds as long as the above conditions are satisfied. From the viewpoint of the solubility of the polymerization initiator in the solvent, the reduction in unpleasant odor of the modified conjugated diene polymer described later, and the suppression of the chain transfer reaction, piperidinolithium, hexamethyleneiminolithium, lithium azacyclooctane, Lithium-1,3,3-trimethyl-6-azabicyclo [3.2.1] octane is preferred, more preferably piperidinolithium or hexamethyleneiminolithium, and still more preferably piperidinolithium.

In Formula (15), R ₁₄ represents a divalent group based on an alkylene group having 1 to 20 carbon atoms or a conjugated diene compound having 4 to 20 carbon atoms. The divalent group based on the conjugated diene compound preferably represents a group having a repeating unit represented by at least one selected from the group consisting of the following formulas (18) to (20).

In the formula (15), when R ₁₄ represents an alkylene group, R ₁₄ represents an alkylene group having 2 to 16 carbon atoms from the viewpoint of reactivity and interaction with inorganic fillers such as carbon and silica. Is preferable, and an alkylene group having 3 to 10 carbon atoms is more preferable. When R ₁₄ represents an alkylene group having 1 to 20 carbon atoms, the organolithium compound represented by the formula (15) is not limited to the following, but for example, (3- (dimethylamino) -propyl ) Lithium, (3- (diethylamino) -propyl) lithium, (3- (dipropylamino) -propyl) lithium, (3- (dibutylamino) -propyl) lithium, (3- (dipentylamino) -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, (3 (Ethylbenzylamino) -propyl) lithium, (3- (methylphenethylamino) -propyl) lithium, (4- (dibutylamino) -butyl) lithium, (5- (dibutylamino) -pentyl) lithium, (6- (Dibutylamino) -hexyl) lithium, (10- (dibutylamino) -decyl) lithium, etc. The organolithium compound is not limited to these, and includes analogs of these if the above conditions are satisfied. (3- (Dibutylamino) -propyl) lithium is more preferable from the viewpoints of reactivity and interaction with inorganic fillers such as carbon and silica.

In the formula (15), when R ₁₄ represents a divalent group based on a conjugated diene compound having a repeating unit represented by the formulas (18) to (20), an organolithium compound represented by the formula (15) Although not 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) Thium, (4- (diethylamino) -3-methyl-2-butenyl) lithium, (4- (dibutylamino) -3-methyl-2-butenyl) lithium, (4- (dipropylamino) -3-methyl- 2-butenyl) lithium, (4- (diheptylamino) -3-methyl-2-butenyl) lithium, (4- (dihexylamino) -3-methyl-2-butenyl) lithium. The organolithium compound is not limited to these, and includes the similar compounds as long as the above conditions are satisfied. From the viewpoint of reactivity as an initiator and the viewpoint of chain transfer reaction control described later, 4- (dimethylamino) -2-butenyl) lithium, (4- (diethylamino) -2-butenyl) lithium, (4- ( Dibutylamino) -2-butenyl) lithium is preferred, and (4- (dibutylamino) -2-butenyl) lithium is more preferred.

In the formula (15), when R ₁₂ and R ₁₃ are bonded to form a cyclic structure with the adjacent nitrogen atom, the organolithium compound represented by the formula (15) is not particularly limited. , (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- (Hexamethyneleniminyl) butyl) lithium, (5- (Hexamethineleniminyl) ethyl) Pentyl) lithium, (6- (hexamethineleniminyl) hexyl) lithium, (10- (hexamethylenelenimine) decyl) lithium, (4- (piperidinyl) -2-butenyl) lithium, (4- (hexa) (Methineleniminyl) -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. The organolithium compound is not limited to these, and includes the similar compounds as long as the above conditions are satisfied. From the viewpoint of reactivity and interaction with inorganic fillers such as carbon and silica, and from the viewpoint of chain transfer reaction control to be described later, (3- (piperidinyl) propyl) lithium, (3- (hexamethineleniminyl) propyl ) Lithium, (3- (1,2,3,6-tetrahydropyridinyl) propyl) lithium, (4- (piperidinyl) -2-butenyl) lithium, (4- (hexamethyneleniminyl) -2- Butenyl) lithium is preferred, more preferably (3- (hexamethyleneleniminyl) propyl) lithium, (4- (piperidinyl) -2-butenyl) lithium, (4- (hexamethyleneleniminyl) -2-butenyl) ) Lithium is preferred, and (4- (piperidinyl) -2-butenyl) lithium is more preferred.

  The organic lithium compound represented by the formula (16) is not limited to the following, but examples thereof include N, N-dimethyl-o-toluidinolithium, N, N-dimethyl-m-toluidinolithium, N, N-dimethyl-p-toluidinolithium, N, N-diethyl-o-toluidinolithium, N, N-diethyl-m-toluidinolithium, N, N-diethyl-p-toluidino Lithium, N, N-dipropyl-o-toluidinolithium, N, N-dipropyl-m-toluidinolithium, N, N-dipropyl-p-toluidinolithium, N, N-dibutyl-o-to Louisino lithium, N, N-dibutyl-m-toluidinolithium, N, N-dibutyl-p-toluidinolithium, o-piperidinotruenolithium, p-piperidinotruenolithium, o-pyro Dinotorenolithium, p-pyrrolidinotoluene, N, N, N ′, N′-tetramethyltoluylenediaminolithium, N, N, N ′, N′-tetraethyltoluylenediaminolithium, N, N, N ′ , N′-tetrapropyltoluylenediaminolithium, N, N-dimethylxylidinolithium, N, N-diethylxylidinolithium, N, N-dipropylxylidinolithium, N, N-dimethylmesidinolithium, N, N-diethylmesidinolithium, (N, N-dimethylamino) toluylphenylmethylaminolithium, 1- (N, N-dimethylamino) -2-methylnaphthalenolithium, 1- (N, N-dimethylamino)- 2-methylanthracenolithium is mentioned. The organolithium compound is not limited to these, and includes the similar compounds as long as the above conditions are satisfied. From the viewpoint of polymerization activity, N, N-dimethyl-o-toluidinolithium is more preferable.

  The organolithium compound represented by the formula (17) is not limited to the following compounds. For example, 2- (2-methylpiperidinyl) -1-ethyllithium (for example, trade name “AI” manufactured by FMC) -250 "). The organolithium compound is not limited to these, and includes the similar compounds as long as the above conditions are satisfied.

  Prior to the polymerization step, an organolithium compound having at least one nitrogen atom in the molecule may be prepared in advance, and the method is prepared by any known method.

  The organolithium compound having at least one nitrogen atom in the molecule represented by the formula (14) is obtained by, for example, reacting the compound represented by the formula (24) with the organolithium compound in a hydrocarbon solvent. Obtained by. As the above hydrocarbon solvent, an appropriate solvent such as hexane, cyclohexane or benzene may be selected. The reaction temperature is preferably 0 ° C. or higher and 80 ° C. or lower, preferably 5.0 ° C. or higher and 70 ° C. or lower, more preferably 7.0 ° C. or higher and 50 ° C. or lower from the viewpoint of productivity. Although it does not specifically limit as an organolithium compound made to react with the compound represented by Formula (24), For example, n-butyllithium, sec-butyllithium, tert-butyllithium, n-propyllithium, iso-propyllithium is mentioned. Can be mentioned.

The organolithium compound having at least one nitrogen atom in the molecule represented by the formula (15) is, for example, a compound represented by the formula (25) when R ₁₄ represents an alkylene group having 1 to 20 carbon atoms. And an organic lithium compound are reacted in a hydrocarbon solvent to prepare a lithium amide compound, which is reacted with an alkyl halide represented by the following formula (C), and further reacted with an organic lithium compound. It is done.

式（Ｃ）中、Ｘ¹及びＸ²は、各々独立して、Ｉ原子、Ｂｒ原子、又はＣｌ原子を表し、Ｒ^3aは、炭素数１〜２０のアルキレン基を、好ましくは炭素数２〜１６のアルキレン基、より好ましくは炭素数３〜１０のアルキレン基を表す。

In formula (C), X ¹ and X ² each independently represent an I atom, a Br atom, or a Cl atom, and R ^3a represents an alkylene group having 1 to 20 carbon atoms, preferably 2 to 2 carbon atoms. 16 represents an alkylene group, more preferably an alkylene group having 3 to 10 carbon atoms.

  The compound represented by the formula (C) is not limited to the following, but examples thereof include 1-bromo-3-chloropropane, 1-bromo-4-chlorobutane, 1-bromo-5-chloropentane, and 1-bromo. -6-chlorohexane, 1-bromo-10-chlorodecane, 1-bromo-3-iodopropane, 1-bromo-4-iodobutane, 1-bromo-5-iodopentane, 1-bromo-6-iodohexane, 1 -Bromo-10-iododecane, 1-chloro-3-iodopropane, 1-chloro-4-iodobutane, 1-chloro-5-iodopentane, 1-chloro-6-iodohexane, 1-chloro-10-iododecane Can be mentioned. From the viewpoint of reactivity and safety, the compound represented by the formula (C) is 1-bromo-3-chloropropane, 1-bromo-4-chlorobutane, 1-bromo-5-chloropentane, 1-bromo-6. -Chlorohexane and 1-bromo-10-chlorodecane are preferable, and 1-bromo-3-chloropropane, 1-bromo-4-chlorobutane and 1-bromo-6-chlorohexane are more preferable.

  The reaction temperature when preparing a lithium amide compound using the compound represented by formula (25), the organolithium compound, and the hydrocarbon solvent is the reaction between the compound represented by formula (24) and the organolithium compound. It is the same as the temperature when making it. The reaction temperature at the time of reacting the obtained lithium amide compound with the compound represented by the formula (C) is preferably −78 ° C. or higher and 70 ° C. or lower, more preferably −50 ° C. or higher and 50 ° C. or lower. . Thereafter, the reaction temperature for reacting the obtained compound with the organolithium compound is preferably −78 ° C. or more and 70 ° C. or less, more preferably −50 ° C. or more and 50 ° C. or less. Although it does not specifically limit as an organolithium compound, For example, the thing similar to the organolithium compound made to react with the compound represented by Formula (24) can be used.

  The organolithium compound represented by formula (16) having at least one nitrogen atom in the molecule is obtained by, for example, reacting the compound represented by formula (26) with an organolithium compound in a hydrocarbon solvent, It is obtained by preparing a lithium amide compound, reacting this with an alkyl dihalide represented by the above formula (C), and further reacting with an organic lithium compound.

  The reaction temperature when preparing the lithium amide compound using the compound represented by formula (26), the organolithium compound, and the hydrocarbon solvent is the reaction between the compound represented by formula (24) and the organolithium compound. It is the same as the temperature when making it. The reaction temperature when the compound represented by the formula (C) is reacted with the lithium amide compound is preferably −78 ° C. or higher and 70 ° C. or lower, more preferably −50 ° C. or higher and 50 ° C. or lower. Thereafter, the reaction temperature for reacting the obtained compound with the organolithium compound is preferably −78 ° C. or more and 70 ° C. or less, more preferably −50 ° C. or more and 50 ° C. or less. As the organic lithium compound, the same organic lithium compound that is reacted with the compound represented by the formula (24) can be used.

In the formula (15), when R ₁₄ is a divalent group based on a conjugated diene compound having at least one selected from the repeating units represented by the formulas (18) to (20), preferably It is synthesized by a method including steps (I) to (IV) in order.
(I) A compound represented by formula (25) and an organolithium compound are reacted in a hydrocarbon solvent to synthesize a lithium amide compound.
(II) The obtained lithium amide compound is reacted with butadiene or isoprene in a hydrocarbon solvent.
(III) Lithium is deactivated by adding alcohol, and the product obtained in the above step (II) is distilled under reduced pressure.
(IV) The product obtained by distillation in the above step (III) is reacted with an organolithium compound in a hydrocarbon solvent.

  A lithium amide is prepared using a compound represented by the formula (25), an organolithium compound, and a hydrocarbon solvent. The reaction temperature in step (I) is a reaction between the compound represented by the formula (24) and the organolithium compound. The temperature is the same as the reaction temperature. Alcohols in the above step (III) can be general ones, but those having a low molecular weight are preferable, for example, methanol, ethanol and isopropanol are preferable, and ethanol is more preferable. The reaction temperature in step (IV) is 0 ° C. or higher and 80 ° C. or lower, preferably 10 ° C. or higher and 70 ° C. or lower. As the organic lithium compound, the same organic lithium compound that is reacted with the compound represented by the formula (24) can be used.

(Polar compound)
When preparing an organolithium compound having at least one nitrogen atom in the molecule, a polar compound may be added to the system. There is a tendency to promote the formation and solubilization in hydrocarbon solvents. Examples of the polar compound include, but are not limited to, the following: tertiary monoamines, tertiary diamines, chained or cyclic ethers.

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

  The tertiary diamine is not limited to the following, but examples thereof include 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 include tetramethylhexanediamine, dipiperidinopentane, and dipiperidinoethane.

  Examples of the chain ether 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, and 2,2-bis (3,4,5-trimethyl-2-oxolanyl) propane.

  Among polar compounds, tertiary monoamines such as trimethylamine and triethylamine; tertiary diamines such as N, N, N ′, N′-tetramethylethylenediamine; cyclic ethers such as tetrahydrofuran and 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.

  When adding a polar compound when preparing an organolithium compound, it is preferable to add it within the range of 30 ppm to 50,000 ppm by mass with respect to the solvent used when preparing it, and 200 ppm to 20 ppm. More preferably, it is added within a range of not more than 1,000 ppm by mass. In order to fully express the effect of promoting the reaction and solubilizing in the solvent, addition of 30 ppm by mass or more is preferable, ensuring the freedom of microstructure adjustment in the subsequent polymerization step, and the solvent after polymerization. In consideration of separation from the polymerization solvent in the step of recovering and purifying, it is preferable to add at 50,000 mass ppm or less.

  The conjugated diene polymer before modification uses the above-described organolithium compound having at least one nitrogen atom in the molecule, or a polymerization initiator system containing a compound having at least one nitrogen atom and an organolithium compound. Thus, it is obtained by polymerizing a conjugated diene compound or copolymerizing a conjugated diene compound and an aromatic vinyl compound.

  In the polymerization step, an organolithium compound having at least one nitrogen atom in the molecule is prepared in advance in a predetermined reactor, and polymerization of the conjugated diene compound or copolymerization of the conjugated diene compound and the aromatic vinyl compound is performed. The polymerization reaction may be performed by supplying the reactor to the reactor. Alternatively, a polymerization initiator system may be prepared by mixing a compound having at least one nitrogen atom in the molecule and an organolithium compound using a static mixer or an in-line mixer. When the organolithium compound having at least one nitrogen atom in the molecule is used, the polymerization initiator system may be not only one type but also a mixture of two or more types.

  The polymerization process in the production of the both-end-modified conjugated diene polymer (I) may be carried out by either a batch type or a continuous type, but a high degree of modification, a high molecular weight, and a highly branched conjugated diene. From the viewpoint of stably producing the system polymer, it is preferable to perform polymerization in a continuous manner, and it is more preferable to perform polymerization in a continuous manner in one reactor or two or more connected reactors. At this time, in order to make the modification rate 75% by mass or more and MSR 0.45 or less, for example, the polymerization temperature is 45 ° C. or more and 80 ° C. or less, and the solid content is 16.0% by mass or less. preferable. In order to make the modification rate 78% by mass or more and the MSR 0.45 or less, the polymerization temperature should be controlled in the range of 50 ° C. or more and 80 ° C. or less, and the solid content should be 16.0% by mass or less. preferable. In order to make the modification rate 80% by mass or more and MSR 0.44 or less, the polymerization temperature should be controlled in the range of 50 ° C. or more and 80 ° C. or less, and the solid content should be 16.0% by mass or less. preferable. The feed composition of the organolithium compound is preferably 0.001 mol / L or less with respect to the hydrocarbon solvent. In order to achieve a modification rate of 85% by mass or more and an MSR of 0.43 or less, the polymerization temperature is controlled in the range of 50 ° C. or more and 78 ° C. or less, the solid content is 16.0% by mass or less, and organic The feed composition of the lithium compound is preferably 0.001 mol / L or less with respect to the hydrocarbon solvent. In order to make the modification rate 88% by mass or more and MSR 0.42 or less, the polymerization temperature is 55 ° C. or more and 76 ° C. or less, the solid content is 15.0% by mass or less, and the feed composition of the organolithium compound Is preferably 0.0008 mol / L or less with respect to the hydrocarbon solvent. More preferably, from the viewpoint of appropriately controlling the chain transfer reaction described below, achieving a modification rate of 90% by mass or more and an MSR of 0.40 or less, that is, achieving a high modification rate, high molecular weight, and high branching. Polymerization, the polymerization temperature is 60 ° C. or more and 72 ° C. or less, the solid content is 14.0% by mass or less, the organolithium compound is continuously added, and the feed composition of the organolithium compound is relative to the hydrocarbon solvent. Is preferably 0.00070 mol / L or less.

  The reaction in the polymerization step may be a continuous type or a batch type, but from the viewpoint of production efficiency, a monomer containing a conjugated diene compound and a polymerization initiator (which may be a polymerization initiator system) are placed in a polymerization tank. A continuous system in which the polymer is continuously supplied and continuously polymerized is preferable. In the case of a continuous system, the monomer, solvent, and polymerization initiator (may be a polymerization initiator system) used for polymerization may be fed separately to the polymerization tank, or a mixing tank equipped with a stirrer may be used. The method of using and the method of mixing continuously using a static mixer or a line mixer in piping may be sufficient.

  From the viewpoint of the stability of the organolithium compound, the monomer and polymerization initiator used for polymerization are preferably diluted with a hydrocarbon solvent. About a monomer, it is preferable that solid content is 16 mass% or less. When the polymerization initiator is an organic lithium compound, the feed composition of the organic lithium compound is preferably 0.0010 mol / L or less, more preferably 0.0008 mol / L or less with respect to the hydrocarbon solvent.

  In the polymerization step, from the viewpoint of stable production of a high molecular weight polymer, it is preferable that the polymerization method is continuous and the organolithium compound is 0.0010 mol / L or less with respect to the hydrocarbon solvent.

  When performing polymerization in which a conjugated diene polymer becomes a copolymer of a conjugated diene compound and an aromatic vinyl compound using a polymerization initiator system containing a compound having at least one nitrogen atom in the molecule and an organolithium compound In Makromol. As described in chem 186. 1335-1350 (1985), the chain transfer reaction is promoted by the influence of at least one nitrogen atom in the molecule of the polymerization initiator system, so that the living active terminal is deactivated. In order to increase the modification rate, specific production conditions may be required. As described above, for example, when the polymerization temperature is increased, the chain transfer rate or the chain transfer rate is increased, the number average molecular weight of the obtained polymer is decreased, the degree of branching is increased, the molecular weight distribution is widened, and the aromatics are increased. Since the number of block portions in which 30 or more vinyl units are linked tends to decrease or disappear, MSR tends to decrease. However, it is presumed that the inactivation of the living active terminal is promoted, and if the production conditions are not controlled, the modification rate tends to decrease. Note that, in each of the batch type polymerization method and the continuous type polymerization method, the continuous polymerization method tends to advance the chain transfer reaction.

  The polymerization temperature is preferably in the range where anionic polymerization proceeds, chain transfer reaction is controlled, and the number of blocks in which 30 or more aromatic vinyl compound units are chained is small or absent, and is not particularly limited. From a viewpoint, it is preferable that it is 45 degreeC or more, and it is more preferable that it is 80 degreeC or less from a viewpoint which controls chain transfer reaction and ensures sufficiently the reaction amount of the modifier | denaturant with respect to the active terminal after superposition | polymerization, From the viewpoint that the number of blocks in which 30 or more group vinyl units are linked is small, 50 ° C to 78 ° C is more preferable, and 60 ° C to 75 ° C is more preferable.

  In the polymerization step, from the viewpoint of chain transfer reaction control, the solid is a content of the conjugated diene compound and the aromatic vinyl compound, and the total mass of the solvent, such as the conjugated diene compound and the aromatic vinyl compound. The content (also referred to as “monomer concentration”) is preferably 16% by mass or less, more preferably 15% by mass or less, and still more preferably 14% by mass or less. The lower limit of the solid content is not particularly limited, but is preferably 12.5% by mass or more.

  In the polymerization step, from the viewpoint of chain transfer reaction control and suppression of active terminal deactivation, the polymerization method is continuous, the polymerization temperature is 45 ° C. or higher and 80 ° C. or lower, and the solid content is 16% by mass or less. Is preferred.

(Conjugated diene polymer)
The conjugated diene polymer constituting the both-end-modified conjugated diene polymer (I) of the present embodiment (hereinafter sometimes simply referred to as “conjugated diene polymer”) is a hydrocarbon solvent, It may be obtained by polymerizing at least a conjugated diene compound, and may be obtained by copolymerizing a conjugated diene compound and an aromatic vinyl compound. The conjugated diene polymer is preferably obtained by growing by an anionic polymerization reaction using a continuous polymerization method using an organolithium compound having at least one nitrogen atom in the molecule as a polymerization initiator. In particular, the conjugated diene polymer is more preferably a polymer having an active end obtained by a growth reaction by living anion polymerization. Thereby, a modified conjugated diene polymer having a high modification rate can be obtained.

(Conjugated diene compounds)
The conjugated diene compound used for constituting the conjugated diene polymer is not particularly limited as long as it is a polymerizable monomer. For example, 1,3-butadiene, isoprene, 2,3-dimethyl- Examples include 1,3-butadiene, 1,3-pentadiene, 3-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, and 1,3-butadiene is more preferable. These may be used alone or in combination of two or more.

(Aromatic vinyl compound)
The aromatic vinyl compound is not limited to the following as long as it is a monomer copolymerizable with a conjugated diene compound. For example, styrene, p-methylstyrene, α-methylstyrene, vinylethylbenzene, vinylxylene, vinyl Naphthalene and diphenylethylene are mentioned. 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 step is preferably performed in a polymerization solvent. Examples of the polymerization solvent include hydrocarbon solvents such as saturated hydrocarbons and aromatic hydrocarbons. Specific hydrocarbon solvents include, but are not limited to, aliphatic hydrocarbons such as butane, pentane, hexane, and heptane; alicyclic carbons such as cyclopentane, cyclohexane, methylcyclopentane, and methylcyclohexane. Hydrogen: Hydrocarbons composed of aromatic hydrocarbons such as benzene, toluene and xylene and mixtures thereof.

  The conjugated diene compound, the aromatic vinyl compound, and the polymerization solvent are each treated alone or mixed with these mixed solutions in advance before being subjected to a polymerization reaction by reacting the organometallic compound with allenes and acetylenes that are impurities. You can also keep it. Thereby, inhibition of polymerization by impurities can be prevented, the active terminal amount of the polymer becomes high, a sharper molecular weight distribution (Mw / Mn) can be achieved, and a higher modification rate tends to be achieved. ,preferable.

  In the polymerization reaction of the conjugated diene polymer, a polar compound may be added. Polar compounds tend to copolymerize an aromatic vinyl compound with a conjugated diene compound at random, and can also be used as a vinylating agent for controlling the microstructure of the conjugated diene moiety. It is also effective in improving the polymerization rate.

  Examples of polar compounds include, but are not limited to, tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dimethoxybenzene, 2,2-bis (2-oxolanyl). ) Ethers such as propane; Tertiary amine compounds such as tetramethylethylenediamine, dipiperidinoethane, trimethylamine, triethylamine, pyridine, quinuclidine; potassium-t-amylate, potassium-t-butylate, sodium-t-butylate, Examples include 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, Although it can select according to the objective etc., it is preferable that they are 0.01 mol or more and 100 mol or less with respect to 1 mol of polymerization initiators. An appropriate amount of such a polar compound (vinylating agent) can be used as a regulator of the microstructure of the polymer conjugated diene moiety depending on the desired vinyl bond amount. Many polar compounds simultaneously have an effective randomizing effect in the copolymerization of conjugated diene compounds and aromatic vinyl compounds, and tend to be used to adjust the distribution of aromatic vinyl compounds and adjust the amount of styrene block It is in. 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 interrupted during the copolymerization. Alternatively, a method of adding them may be used.

  The amount of the conjugated diene in the conjugated diene polymer of the present embodiment is not particularly limited, but is preferably 50% by mass or more and 100% by mass or less, and more preferably 60% by mass or more and 80% by mass or less. . The amount of bonded aromatic vinyl in the conjugated diene polymer of the present embodiment is not particularly limited, but is preferably 0% by mass to 50% by mass, and more preferably 20% by mass to 40% by mass. Is more preferable. If the amount of bound conjugated diene and amount of bound aromatic vinyl are in the above ranges, a vulcanizate that has a better balance between low hysteresis loss and wet skid resistance, and that is more satisfactory in wear resistance and fracture strength can be obtained. It tends to be possible. 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 measures according to the method as described in the Example mentioned later.

  The amount of vinyl bonds in the conjugated diene bond unit is not particularly limited, but is preferably 10 mol% or more and 75 mol% or less, and more preferably 25 mol% or more and 65 mol% or less. When the vinyl bond amount is in the above range, a vulcanizate having a further excellent balance between low hysteresis loss and wet skid resistance and more satisfactory wear resistance and fracture strength tends to be obtained. Here, when the modified conjugated diene polymer is a copolymer of butadiene and styrene, in the butadiene bond unit by the method of Hampton (RR Hampton, Analytical Chemistry, 21, 923 (1949)). The vinyl bond amount (1,2-bond amount) can be determined. Specifically, it is measured by the method described in the examples described later.

  The conjugated diene polymer may be a random copolymer or a block copolymer. Examples of the random copolymer include, but are not limited to, for example, butadiene-isoprene random copolymer, butadiene-styrene random copolymer, isoprene-styrene random copolymer, butadiene-isoprene-styrene random copolymer. Is mentioned. 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, a taper (gradient) random in which the composition is distributed in a tapered shape. A copolymer is 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.

  The block copolymer is not limited to the following, for example, a 2-type block copolymer consisting of 2 blocks, a 3-type block copolymer consisting of 3 blocks, and a 4-type block copolymer consisting of 4 blocks. Coalesce is mentioned. 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. When expressed, it is represented by an S-B2 type block copolymer, an S-B-S3 type block copolymer, an S-B-S-B4 type block copolymer, or the like.

  In the above equation, the boundaries of each block need not 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.

  In the present embodiment, the conjugated diene polymer obtained by the production method described above may be further hydrogenated in an inert solvent to convert all or part of the double bonds to saturated hydrocarbons. Good. In that case, heat resistance and weather resistance are improved, and the product tends to be prevented from being deteriorated when processed at a high temperature. 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 (also simply referred to as “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 polymer is preferably 3.0 mol% or more and 70 mol% or less, more preferably 5.0 mol% or more and 65 mol% or less. More preferably, it is from mol% to 60 mol%. 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 mol% or less, It is more preferably 30 mol% or less, and further preferably 20 mol% or less. 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 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. Examples of the hydrogenation catalyst include 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. Examples include homogeneous catalysts such as the catalyst used. 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 are not limited to the following. For example, (1) supported heterogeneity in which a metal such as Ni, Pt, Pd, or Ru is supported on carbon, silica, alumina, diatomaceous earth, or the like. (2) so-called Ziegler type hydrogenation catalysts using (2) organic acid salts such as Ni, Co, Fe, Cr, transition metal salts such as acetylacetone salts and reducing agents such as organic aluminum, and (3) Ti So-called organometallic complexes such as organometallic compounds such as Ru, Rh and Zr. Furthermore, as hydrogenation catalysts, for example, Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 1-337970, Japanese Patent Publication No. 1-53851, Examples thereof include hydrogenation catalysts described in Japanese Patent Publication No. 2-9041 and Japanese Patent Application Laid-Open No. 8-109219. A preferable hydrogenation catalyst includes a reaction mixture of a titanocene compound and a reducing organometallic compound.

  If the conjugated diene compound 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 by mass or less, more preferably 100 ppm by mass or less, and 50 ppm by mass or less based on the total amount of the conjugated diene compound. More preferably. Examples of allenes include propadiene and 1,2-butadiene. Examples of acetylenes include ethyl acetylene and vinyl acetylene.

  Low hysteresis when the microstructure (the amount of each bond in the modified conjugated diene polymer) is in the above range and the glass transition temperature of the conjugated diene polymer is in the range of −45 ° C. or higher and −15 ° C. or lower. A more excellent vulcanizate can be obtained due to the balance between loss and wet skid resistance.

  When the conjugated diene polymer constituting the both-end-modified conjugated diene polymer (I) used in the present embodiment is a copolymer of a conjugated diene compound and an aromatic vinyl compound, a unit of the aromatic vinyl compound It is preferable that the number of blocks having a chain of 30 or more is small or absent. Specifically, when the copolymer is a butadiene-styrene copolymer, the method described in Kolthoff (method described in IM KOLTHOFF, et al., J. Polym. Sci. 1, 429 (1946)). In a known method for decomposing a polymer and analyzing the amount of polystyrene insoluble in methanol, a block in which 30 or more aromatic vinyl units are chained is preferably 5.0% by mass or less based on the total amount of the polymer, More preferably, it is 3.0 mass% or less.

[Modification step]
In the method for producing a both-end-modified conjugated diene polymer (I) used in the present embodiment, the conjugated diene polymer obtained by the polymerization step is modified so that the modification rate is 75% by mass or more. In the modification step, the conjugated diene polymer is preferably modified with a modifying agent having 4 or more alkoxy groups bonded to a silyl group and a tertiary amino group in one molecule.

(Modifier)
The modifying agent is not limited to the following, and examples thereof include 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-silacycloheptanthris (3-trimethoxysilylpropyl) amine, tris (3-methyldimethoxysilylpropyl) amine, tris (3-triethoxysilyl) Propyl) amine and tris (3-methyldiethoxysilylpropyl) amine.

  From the viewpoint of fuel saving performance, the modifier preferably contains a modifier represented by at least one of the following general formulas (1) to (3). A modifier may be used individually by 1 type, and may use 2 or more types together.

式（１）中、Ｒ¹〜Ｒ⁴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、Ｒ⁵は、炭素数１〜１０のアルキレン基を表し、Ｒ⁶は、炭素数１〜２０のアルキレン基を表し、ｍは、１又は２の整数を表し、ｎは、２又は３の整数を表す。（ｍ＋ｎ）は、４以上の整数である。複数存在する場合のＲ¹〜Ｒ⁴は、各々独立している。

In formula (1), R ^{1 to} R ⁴ each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ⁵ is an alkylene group having 1 to 10 carbon atoms. R ⁶ represents an alkylene group having 1 to 20 carbon atoms, m represents an integer of 1 or 2, and n represents an integer of 2 or 3. (M + n) is an integer of 4 or more. When there are a plurality of R ^{1 to} R ⁴ , each is independent.

式（２）中、Ｒ¹〜Ｒ⁶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、Ｒ⁷〜Ｒ⁹は、各々独立して、炭素数１〜２０のアルキレン基を表し、ｍ、ｎ、及びｌは、各々独立して、１〜３の整数を表し、（ｍ＋ｎ+ｌ）は、４以上の整数を表す。複数存在する場合のＲ¹〜Ｒ⁶は、各々独立している。

In formula (2), R ^{1 to} R ⁶ each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ^{7 to} R ⁹ are each independently Represents an alkylene group having 1 to 20 carbon atoms, m, n and l each independently represent an integer of 1 to 3, and (m + n + 1) represents an integer of 4 or more. When there are a plurality of R ^{1 to} R ⁶ , each is independent.

式（３）中、Ｒ¹〜Ｒ⁴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、Ｒ⁵及びＲ⁶は、各々独立して、炭素数１〜２０のアルキレン基を表し、ｍ及びｎは、各々独立して、１〜３の整数を表し、（ｍ＋ｎ）は、４以上の整数を表し、Ｒ⁷は、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、又は炭化水素基で置換されたシリル基を表す。複数存在する場合のＲ¹〜Ｒ⁴は、各々独立している。

In Formula (3), R ^{1 to} R ⁴ each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ⁵ and R ⁶ are each independently Represents an alkylene group having 1 to 20 carbon atoms, m and n each independently represent an integer of 1 to 3, (m + n) represents an integer of 4 or more, and R ⁷ represents an integer of 1 to 20 carbon atoms. Or an aryl group having 6 to 20 carbon atoms, or a silyl group substituted with a hydrocarbon group. When there are a plurality of R ^{1 to} R ⁴ , each is independent.

  The modifying agent represented by the formula (1) is not limited to the following, but 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-dimethoxymethylsilylpropyl) -1-aza -2-silacyclopentane, 2,2-diethoxy-1- (3-diethoxyethylsilylpropyl) -1-aza-2-silacyclopentane, 2-methoxy, 2-methyl- -(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-diethoxyethylsilylpropyl) -1- Aza-2-silacyclopentane. Among these, from the viewpoints of reactivity and interaction between the functional group of the modifier and an inorganic filler such as silica, and from the viewpoint of processability, m represents 2 in the formula (1), and n is Those representing 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 modifier of formula (1) is reacted with the polymerization active terminal are not particularly limited, but it is preferably 0 to 120 ° C. for 30 seconds or more. Alkali metal compounds and / or alkaline earths in which the total number of moles of alkoxy groups bonded to silyl groups in the compound of the modifier represented by formula (1) constitutes a polymerization initiator (or a polymerization initiator system) It is preferably in the range of 0.6 to 3.0 times the number of moles added of the metal compound, more preferably in the range of 0.8 to 2.5 times, more preferably 0.8 or more It is more preferable that the range is 2.0 times or less. From the viewpoint of obtaining a sufficient modification rate and molecular weight and branched structure, the resulting modified conjugated diene polymer is preferably 0.6 times or more, and the polymer ends are coupled to each other for improved processability. In addition to preferably obtaining the polymer component, it is preferably 3.0 times or less from the viewpoint of the modifier cost.

  The modifier represented by the formula (2) is not limited to the following, but examples include tris (3-trimethoxysilylpropyl) amine, tris (3-methyldimethoxysilylpropyl) amine, tris (3-tri Ethoxysilylpropyl) amine, tris (3-methyldiethoxysilylpropyl) amine, tris (trimethoxysilylmethyl) amine, tris (2-trimethoxysilylethyl) amine, tris (4-trimethoxysilylbutyl) amine It is done. Among these, it is preferable that n, m, and l all represent 3 from the viewpoint of reactivity and interaction between the functional group of the modifier and an inorganic filler such as silica, and workability. . Preferable specific examples include tris (3-trimethoxysilylpropyl) amine and tris (3-triethoxysilylpropyl) amine.

  There are no particular limitations on the reaction temperature, reaction time, etc. when the modifier represented by formula (2) is reacted with the polymerization active terminal, but the reaction may be carried out at 0 ° C. or higher and 120 ° C. or lower for 30 seconds or longer. preferable. An alkali metal compound in which the total number of alkoxy groups bonded to the silyl group in the compound of the modifier represented by the formula (2) constitutes the above-described polymerization initiator (which may be a polymerization initiator system); / Is preferably in the range of 0.6 to 3.0 times the number of moles of the alkaline earth metal compound, more preferably in the range of 0.8 to 2.5 times, More preferably, it is in the range of 0.8 times or more and 2.0 times or less. From the viewpoint of obtaining a sufficient modification rate and molecular weight and branched structure in the modified conjugated diene polymer, it is preferably 0.6 times or more, and the branched polymer is obtained by coupling the polymer ends to improve processability. In addition to preferably obtaining the components, it is preferably 3.0 times or less from the viewpoint of the modifier cost.

  The modifier represented by the formula (3) is not limited to the following, but examples thereof include bis (3- (methylamino) propyl) trimethoxysilane and bis (3- (ethylamino) propyl) trimethoxysilane. Bis (3- (propylamino) propyl) trimethoxysilane and bis (3- (butylamino) propyl) trimethoxysilane. Among these, n and m are preferably 3 from the viewpoints of reactivity and interaction between the functional group of the modifier and an inorganic filler such as silica, and processability. Preferable specific examples include bis (3- (methylamino) propyl) trimethoxysilane and bis (3- (ethylamino) propyl) trimethoxysilane.

  There are no particular limitations on the reaction temperature, reaction time, and the like when the modifier represented by formula (3) is reacted with the polymerization active terminal, but the reaction may be performed at 0 ° C. or higher and 120 ° C. or lower for 30 seconds or longer. preferable.

  The modifier is a viewpoint of obtaining a modified conjugated diene polymer having an excellent balance of high modification rate, high molecular weight, and high branching and fuel saving performance, workability, and wear resistance as a vulcanized product. From the group consisting of a modifier represented by formula (1), wherein m is 2 and n is 3, and a modifier represented by formula (2) and m, n, and l are all 3 It is preferable to include at least one kind.

  The total number of moles of alkoxy groups bonded to the silyl group in the compound of the modifier represented by the formula (3) is an alkali metal compound and / or alkaline earth of a polymerization initiator (which may be a polymerization initiator system). It is preferably in the range of 0.6 to 3.0 times the number of moles of metal group compound added, more preferably in the range of 0.8 to 2.5 times. More preferably, it is in the range of 2 to 2.0 times. From the viewpoint of obtaining a sufficient modification rate and molecular weight and branched structure, the resulting modified conjugated diene polymer is preferably 0.6 times or more, and the polymer ends are coupled to each other for improved processability. In addition to preferably obtaining the polymer component, it is preferably 3.0 times or less from the viewpoint of the modifier cost.

  From the viewpoint of improving the modification rate, in the modification step, the content of the monomer containing the conjugated diene compound is preferably 100 ppm to 50,000 ppm by mass with respect to the total amount of all monomers and the polymer. 200 mass ppm or more and 10,000 mass ppm or less is more preferable, and 300 mass ppm or more and 5000 mass ppm or less is more preferable. The content of the monomer containing the conjugated diene compound in the solution can be measured by the method described in the examples described later.

  In the method for producing the both-end-modified conjugated diene polymer (I) used in the present embodiment, after the modification reaction, a deactivator, a neutralizing agent, etc. are added to the polymer solution as necessary. It may be added. Examples of the quenching agent include, but are not limited to, water; alcohols such as methanol, ethanol, and isopropanol. Examples of the neutralizing agent include, but are not limited to, carboxylic acids such as stearic acid, oleic acid, and versatic acid; aqueous solutions of inorganic acids, and carbon dioxide.

  The both-end-modified conjugated diene polymer (I) used in the present embodiment should be added with a rubber stabilizer from the viewpoint of preventing gel formation after polymerization and improving stability during processing. Is preferred. The rubber stabilizer is not limited to the following, and known ones can be used. For example, 2,6-di-tert-butyl-4-hydroxytoluene (BHT), n-octadecyl-3 Antioxidants such as-(4'-hydroxy-3 ', 5'-di-tert-butylphenol) propinate and 2-methyl-4,6-bis [(octylthio) methyl] phenol are preferred.

  In order to further improve the processability of the both-end-modified conjugated diene polymer (A1) used in this embodiment, process oil is added to the both-end-modified conjugated diene polymer (A1) as necessary. can do. The method for adding the process oil to the both-end-modified conjugated diene polymer (a) is not limited to the following, but the process oil is added to the polymer solution and mixed to obtain an oil-extended polymer solution. A method of removing the solvent is preferred. Examples of the process oil include aroma oil, naphthenic oil, and paraffin oil. 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 replacement oil include TDAE (Treated Distillate Aromatic Extracts), MES (Middle Extraction Solt), and RAS (Mild Extraction Solt), as described in Kautschuk Gummi Kunststoffe 52 (12) 799 (1999). The addition amount of the process oil is not particularly limited, but is preferably 10 parts by mass or more and 60 parts by mass, and more preferably 15 parts by mass or more and 37.5 parts by mass or less with respect to 100 parts by mass of the modified conjugated diene polymer.

[Desolvation step]
As a method for obtaining the both-end-modified conjugated diene polymer (I) of this embodiment from the polymer solution, a known method can be used. As the method, for example, after separating the solvent by steam stripping or the like, the polymer is filtered and further dehydrated and dried to obtain the polymer, concentrated in a flushing tank, and further a vent extruder, etc. And a method of directly devolatilizing with a drum dryer or the like.

  The both terminal-modified conjugated diene polymer (A1) may be used alone or in combination of two or more.

<One-terminal modified conjugated diene polymer (ii)>
In the second aspect of the present embodiment, in the modified diene polymer composition, the weight average molecular weight determined by gel permeation chromatography together with the both-end modified conjugated diene polymer (A1) in the rubber component (A). Mw / number average molecular weight Mn ratio Mw / Mn is a one-end modified conjugated diene polymer (ii) (hereinafter simply referred to as “one-end modified conjugated diene polymer (ii)” or “ Component (I2) "), and the total content of both terminal-modified conjugated diene polymer (I1) and one-end modified conjugated diene polymer (I2) is It is 20 mass% or more on the basis of the total mass of component (I). Here, it is assumed that the “one-end modified conjugated diene polymer (ii)” does not include the both-end modified conjugated diene polymer.

  In the second aspect of the present embodiment, the rubber component (a) contains both terminal-modified conjugated diene polymer (a1) and one terminal-modified conjugated diene polymer (a2), The total content of the terminal-modified conjugated diene polymer (ii) and the one-terminal modified conjugated diene polymer (ii) may be 20 mass% or more based on the total mass of the rubber component (ii). 50 mass% or more is preferable, 80 mass% or more is more preferable, and 100 mass% may be sufficient. Further, in the second aspect of the present embodiment, the rubber component (A) includes both terminal-modified conjugated diene polymer (A1) and one terminal-modified conjugated diene polymer (I2). The content of the terminal-modified conjugated diene polymer (A) is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass based on the total mass of the rubber component (A). % Or more.

  Hereinafter, the one-end modified conjugated diene polymer (A2) will be described.

  The conjugated diene compound used for producing the conjugated diene polymer constituting the one-end modified conjugated diene polymer (ii) 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-methyl-1,3-pentadiene, 1,3-heptadiene, 1,3-hexadiene, etc. Can be mentioned. Among these, 1,3-butadiene and isoprene are preferable from the viewpoint of industrial availability, and 1,3-butadiene is more preferable. These may be used alone or in combination of two or more.

  The aromatic vinyl compound used for producing the conjugated diene polymer constituting the one-end modified conjugated diene polymer (ii) may be any monomer that can be copolymerized with the conjugated diene compound, It does not specifically limit, For example, styrene, p-methylstyrene, (alpha) -methylstyrene, vinyl ethylbenzene, vinyl xylene, vinyl naphthalene, diphenylethylene etc. are mentioned. Among these, styrene is preferable from the viewpoint of industrial availability. These may be used alone or in combination of two or more.

  In the present embodiment, monomers other than the conjugated diene compound and the aromatic vinyl compound can be copolymerized within a range not impairing the effect. Examples of such other monomers include ethylenically unsaturated carboxylic acid ester monomers such as isopropyl (meth) acrylate, N-butyl (meth) acrylate, and t-butyl (meth) acrylate, ethylene, propylene, and isobutylene. Olefin monomers such as vinylcyclohexane, and non-conjugated diene monomers such as 1,4-pentadiene and 1,4-hexadiene. Examples of such a copolymer include 1,3-butadiene-styrene-isopropyl (meth) acrylate copolymer, 1,3-butadiene-styrene-N-butyl (meth) acrylate copolymer, 1,3 -Butadiene-styrene-t-butyl (meth) acrylate copolymer, 1,3-butadiene-styrene-ethylene copolymer, 1,3-butadiene-styrene-propylene copolymer, 1,3-butadiene-styrene- Isobutylene copolymer, 1,3-butadiene-styrene-vinylcyclohexane copolymer, 1,3-butadiene-styrene-1,4-pentadiene copolymer, 1,3-butadiene-styrene-1,4-hexadiene copolymer A polymer etc. are mentioned.

  The conjugated diene polymer constituting the one-end modified conjugated diene polymer (ii) 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, a taper (gradient) random in which the composition is distributed in a tapered shape. A copolymer 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. When represented by “B”, a type 2 block copolymer represented by S—B, a type 3 block copolymer represented by S—B—S, and a type 4 represented by S—B—S—B Examples thereof include block copolymers.

  In the above, the boundary of each block does not necessarily need 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 uniformly distributed or may be distributed 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.

  In this embodiment, the conjugated diene polymer having a functional group may be further hydrogenated in an inert solvent to convert all or part of the double bonds to saturated hydrocarbons. In that case, heat resistance and weather resistance are further 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.

  More specifically, the hydrogenation rate (ie, “hydrogenation rate”) of the unsaturated double bond based on the conjugated diene compound can be arbitrarily selected according to the purpose, and is not particularly limited. For example, when the modified conjugated diene polymer composition of this embodiment is used as a vulcanized rubber, from the viewpoint of vulcanizability, the double of the conjugated diene part of the one-end modified conjugated diene polymer (ii) is used. It is preferred that some bonds remain. In this case, the hydrogenation rate of the conjugated diene part in the polymer is preferably 3 to 70 mol%, more preferably 5 to 65 mol%, and still more preferably 10 to 60 mol%. 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 mol% or less, More preferably, it is 30 mol% or less, and further preferably 20 mol% or less. 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 catalysts for hydrogenating unsaturated double bonds based on conjugated diene compounds include: (a) supported type in which a metal such as Ni, Pt, Pd, Ru is supported on carbon, silica, alumina, diatomaceous earth, or the like. A heterogeneous hydrogenation catalyst, (b) a so-called Ziegler-type hydrogenation catalyst using an organic acid salt such as Ni, Co, Fe, Cr or a transition metal salt such as acetylacetone salt and a reducing agent such as organic aluminum; ) So-called organometallic complexes such as organometallic compounds such as Ti, Ru, Rh and Zr. For example, as a hydrogenation catalyst, Japanese Patent Publication No. 42-008704, Japanese Patent Publication No. 43-006636, Japanese Patent Publication No. 63-004841, Japanese Patent Publication No. 01-037970, Japanese Patent Publication No. 01-053851, Japanese Patent Publication No. 02- Hydrogenation catalysts described in Japanese Patent Application Laid-Open No. 009041 and Japanese Patent Application Laid-Open No. 08-109219 can be used. Among these, preferable hydrogenation catalysts include a reaction mixture of a titanocene compound and a reducing organometallic compound.

  The anionic polymerization initiator used as the polymerization initiator when producing the one-end modified conjugated diene polymer (ii) is not particularly limited as long as it functions as a polymerization initiator, and examples thereof include alkali metal compounds and alkalis. Examples include earth metal compounds.

  Although it does not specifically limit as an alkali metal compound used as an anionic polymerization initiator, An organolithium compound is preferable. Examples of the organolithium compound include a low molecular weight compound, a solubilized oligomeric organolithium compound, a compound composed of a carbon-lithium bond in a bonding mode between an organic group and lithium, and a compound composed of a tin-lithium bond.

  Although it does not specifically limit as an organic lithium compound, For example, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, n-hexyl lithium, benzyl lithium, phenyl lithium, stilbene lithium, etc. are mentioned.

  As the organic lithium compound, n-butyllithium and sec-butyllithium are preferable from the viewpoint of industrial availability and ease of control of the polymerization reaction. These organolithium compounds may be used alone or in combination of two or more.

  Examples of other alkali metal compounds include organic sodium compounds, organic potassium compounds, organic rubidium compounds, and organic cesium compounds. Specific examples include sodium naphthalene and potassium naphthalene. In addition, alkoxides such as lithium, sodium, and potassium, sulfonates, carbonates, amides, and the like can be given. Moreover, you may use together with another organometallic compound.

  The alkaline earth metal compound used as the anionic polymerization initiator is not particularly limited, and examples thereof include organic magnesium compounds, organic calcium compounds, and organic strontium compounds. Further, alkaline earth metal alkoxides, sulfonates, carbonates, amides and other compounds may be used. These organic alkaline earth metal compounds may be used in combination with the above-described alkali metal compounds and other organic metal compounds.

  In this embodiment, the conjugated diene polymer constituting the one-end-modified conjugated diene polymer (ii) is obtained by anionic polymerization reaction using the above-described alkali metal compound and / or alkaline earth metal compound as a polymerization initiator. Those obtained by growth are preferred. In particular, the conjugated diene polymer is more preferably a polymer having an active end obtained by a growth reaction by living anion polymerization. Thereby, a modified conjugated diene polymer having a high modification rate can be obtained.

  Although it does not specifically limit as a polymerization mode, It can carry out by polymerization modes, such as a batch type and a continuous type. In the continuous mode, one or two or more connected reactors can be used. The reactor is not particularly limited, and for example, a tank type with a stirrer, a tube type, or the like can be used.

  Usually, allenes, acetylenes and the like are contained as impurities in the conjugated diene compound (monomer) used for the production of the conjugated diene polymer constituting the one-end modified conjugated diene polymer (ii). And there is a possibility of inhibiting the denaturation 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.

  The polymerization reaction for producing the conjugated diene polymer is preferably performed in a solvent. Examples of the solvent include 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; Examples thereof include hydrocarbons composed of a mixture thereof. Treatment of allenes and acetylenes, which are impurities, with an organometallic compound before being subjected to a polymerization reaction tends to yield a polymer having a high concentration of active terminals, and a high modification rate is achieved. It is preferable because of its tendency.

  In the polymerization reaction of the conjugated diene polymer, a polar compound may be added. An aromatic vinyl compound can be randomly copolymerized with a conjugated diene compound, and can also be used as a vinylating agent for controlling the microstructure of the conjugated diene portion. In addition, there is an effect of improving the polymerization rate.

  The polar compound is not particularly limited. For example, tetrahydrofuran, diethyl ether, 1,4-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 N, N ′, N′-tetramethylethylenediamine, 1,2-dipiperidinoethane, trimethylamine, triethylamine, pyridine, quinuclidine; potassium-t-amylate Alkali metal alkoxide compounds such as potassium tert-butylate, sodium tert-butylate and sodium amylate; phosphine compounds such as triphenylphosphine Rukoto can. 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 the usage-amount of a polar compound is 0.01-100 mol with respect to 1 mol of polymerization initiators. Such a polar compound can be used in an appropriate amount depending on the desired vinyl bond amount as a microstructure modifier (vinylating agent) of the conjugated diene moiety in the conjugated diene polymer. Many polar compounds simultaneously have an effective randomizing effect in the copolymerization of a conjugated diene compound and an aromatic vinyl compound, and the amount of the aromatic vinyl compound block such as adjustment of the distribution of the aromatic vinyl compound and the amount of styrene block can be reduced. It can be used as an adjusting agent for adjusting.

  As a method for randomizing the conjugated diene compound and the aromatic vinyl compound, for example, as described in JP-A-59-140221, a conjugated diene compound (1,3-3- A method of intermittently adding a part of the addition amount of butadiene or the like) may be used.

  The polymerization temperature is not particularly limited as long as it is a temperature at which anionic polymerization proceeds. For example, in the case of living anionic polymerization, it is usually preferably 0 ° C. or higher from the viewpoint of productivity, and is 120 ° C. or lower from the viewpoint of sufficiently securing the reaction amount of the modifier with respect to the active terminal after completion of polymerization. It is preferable. Further, from the viewpoint of preventing cold flow of the conjugated diene polymer, a polyfunctional aromatic vinyl compound such as divinylbenzene may be used in order to control the degree of branching.

  The amount of bonded conjugated diene in the one-end modified conjugated diene polymer (ii) contained in the modified diene polymer composition of the present embodiment is not particularly limited, but is preferably 50 to 100% by mass, For example, when used for tire sidewall applications, it is more preferably 90-100% by mass, and for example, when used for tire tread applications, it is more preferably 60-80% by mass. The amount of bonded aromatic vinyl in the one-end modified conjugated diene polymer (ii) contained in the modified diene polymer composition of the present embodiment is not particularly limited, but is 0 to 50% by mass. Is preferable, and it is more preferable that it is 20-40 mass%.

  If the amount of bound conjugated diene and bound aromatic vinyl in the one-end-modified conjugated diene polymer (ii) is within the above range, the balance between rolling resistance characteristics and wet skid resistance is further improved and wear resistance is also satisfactory. A vulcanizate can be obtained. Here, the amount of bonded aromatic vinyl can be measured by ultraviolet absorption of a phenyl group, whereby the amount of bonded conjugated diene can also be determined. Specifically, it can measure by the method according to the Example mentioned later.

  Moreover, the amount of vinyl bonds in the conjugated diene bond unit is not particularly limited, but is preferably 10 to 75 mol%, and 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 can be obtained. Here, when the modified conjugated diene polymer is a copolymer of butadiene and styrene, the butadiene bond unit in the butadiene bond unit is obtained by the method of Hampton (RR Hampton, Analytical Chemistry, 21, 923 (1949)). A vinyl bond amount (1,2-bond amount) can be determined.

  The microstructure (the amount of the conjugated conjugated diene, the amount of the conjugated aromatic vinyl and the amount of the vinyl bond in the conjugated diene bonding unit) is in the above range, and the glass transition temperature of the copolymer is in the range of −45 to −15 ° C. In some cases, a better vulcanizate can be obtained due to the balance between rolling resistance characteristics and wet skid resistance.

  When the conjugated diene polymer is a conjugated diene-aromatic vinyl copolymer, it is preferable that the number of blocks in which 30 or more aromatic vinyl units are linked is small or absent. Specifically, when the copolymer is a butadiene-styrene copolymer, the method described in Kolthoff (method described in IM KOLTHOFF, et al., J. Polym. Sci. 1, 429 (1946)). In a known method for decomposing a polymer and analyzing the amount of polystyrene insoluble in methanol, the block in which 30 or more aromatic vinyl units are chained is preferably 5% by mass or less based on the total amount of the polymer, More preferably, it is 3 mass% or less.

  The method for producing the one-end modified conjugated diene polymer (ii) is a modification step in which a conjugated diene polymer having an active end is obtained by the method as described above, and then the active end is reacted with a modifier. It is preferable to contain. Although it does not specifically limit as a modifier, For example, the number of the alkoxy groups couple | bonded with the silyl group is one or more, and the total of the alkoxy group couple | bonded with the silyl group and the compound which has two or more tertiary amino groups is 4 And a compound having one or more nitrogen atoms, and at least one of them is preferable. Among the modifiers, the total number of alkoxy groups bonded to the silyl group is 4 or more, and a compound having one or more nitrogen atoms is more preferable.

  Examples of the “compound having a total of 4 or more alkoxy groups bonded to a silyl group and having one or more nitrogen atoms” used in the modifier include, for example, the following formulas (31), (32), and ( 33).

（一般式（３１）中、Ｒ¹〜Ｒ⁴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、Ｒ⁵は炭素数１〜１０のアルキレン基を表し、Ｒ⁶は炭素数１〜２０のアルキレン基を表す。ｍは１又は２の整数であり、ｎは２又は３の整数である。（ｍ＋ｎ）は、４以上の整数である。複数存在する場合のＲ¹〜Ｒ⁴は、各々独立している。）

(In General Formula (31), R ^{1 to} R ⁴ each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ⁵ is an alkylene having 1 to 10 carbon atoms. R ⁶ represents an alkylene group having 1 to 20 carbon atoms, m is an integer of 1 or 2, n is an integer of 2 or 3. (m + n) is an integer of 4 or more. When there are a plurality of R ^{1 to} R ⁴ , each is independent.)

（一般式（３２）中、Ｒ⁷〜Ｒ¹⁰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、Ｒ¹¹及びＲ¹²は、各々独立して、炭素数１〜２０のアルキレン基を表し、Ｒ¹³及びＲ¹⁴は、各々独立して、炭素数１〜６のアルキレン基を表し、かつ隣接する２つのＮとともに５員環以上の環構造を形成する。ｐ及びｑは、各々独立して、２又は３の整数である。）

(In General Formula (32), R ^{7 to} R ¹⁰ each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ¹¹ and R ¹² are each independently Each represents an alkylene group having 1 to 20 carbon atoms, R ¹³ and R ¹⁴ each independently represents an alkylene group having 1 to 6 carbon atoms, and a ring structure having a 5-membered ring or more together with two adjacent N atoms. P and q are each independently an integer of 2 or 3.)

（一般式（３３）中、Ｘ¹及びＸ²は、各々独立して、炭素数１〜２０のアルコキシ基を表し、Ｒ¹⁵及びＲ¹⁶は、各々独立して、炭素数１〜２０のアルキル基を表し、Ａ¹及びＡ²は、各々独立して、単結合又は炭素数１〜２０のアルキレン基を表し、Ａ³は下記式（ａ）又は（ｂ）で表される基を表し、複数の、Ｘ¹、Ｘ²、Ｒ¹⁵、Ｒ¹⁶、Ａ¹、Ａ²又はＡ³が存在するときは、それらは、各々同一であっても異なっていてもよい。ｒ及びｓは、各々独立して、０〜３の整数であり、ｔは０〜２０の整数であり、ｔが２以上の場合、（Ａ¹−Ａ³−Ａ²）で表される複数の繰り返し単位は、各々同一であっても異なっていてもよい。）

(In General Formula (33), X ¹ and X ² each independently represent an alkoxy group having 1 to 20 carbon atoms, and R ¹⁵ and R ¹⁶ are each independently alkyl having 1 to 20 carbon atoms. A ¹ and A ² each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms, A ³ represents a group represented by the following formula (a) or (b), When a plurality of X ¹ , X ² , R ¹⁵ , R ¹⁶ , A ¹ , A ² or A ³ are present, they may be the same or different, and r and s are each Independently, it is an integer of 0 to 3, t is an integer of 0 to 20, and when t is 2 or more, the plurality of repeating units represented by (A ¹ -A ³ -A ² ) are each They may be the same or different.)

（一般式（ａ）中、Ｒ¹⁷は水素原子又は炭素数１〜２０のアルキル基を表す。なお、Ａ³が一般式（ａ）で表される場合、（ｒ＋ｓ）は５又は６である。）

(In the general formula (a), R ¹⁷ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. When A ³ is represented by the general formula (a), (r + s) is 5 or 6. .)

（一般式（ｂ）中、Ａ⁴は単結合又は炭素数１〜２０のアルキレン基を表し、Ｘ³は炭素数１〜２０のアルコキシ基を表す。Ｒ¹⁸は炭素数１〜２０のアルキル基を表し、複数のＸ³又はＲ¹⁸が存在するときは、それらは、各々同一であっても異なっていてもよい。ｕは０〜３の整数である。なお、Ａ³が一般式（ｂ）で表される場合、［ｒ＋（ｔ×ｕ）＋ｓ］は５以上の整数である。）

(In the general formula (b), A ⁴ represents a single bond or an alkylene group having 1 to 20 carbon atoms, X ³ represents an alkoxy group having 1 to 20 carbon atoms, and R ¹⁸ represents an alkyl group having 1 to 20 carbon atoms. When a plurality of X ³ or R ¹⁸ are present, they may be the same or different from each other, u is an integer of 0 to 3, and A ³ is represented by the general formula (b ), [R + (t × u) + s] is an integer of 5 or more.)

  Examples of the modifier represented by the general formula (31) include 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane and 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-dimethoxymethylsilylpropyl) -1-aza-2-silacyclopentane, 2 , 2-Diethoxy-1- (3-diethoxyethylsilylpropyl) -1-aza-2-silacyclopentane, 2-methoxy, 2-methyl-1- (3-trimethoxysilane Rupropyl) -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-diethoxyethylsilylpropyl) -1-aza-2-silacyclopentane Etc. Among these, those in which m is 2 and n is 3 are preferable from the viewpoint of rolling resistance characteristics and extrusion workability. Specifically, 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane, 2,2-diethoxy-1- (3-triethoxysilylpropyl) -1 -Aza-2-silacyclopentane is more preferred.

  Examples of the modifier represented by the general formula (32) include 1,4-bis [3- (trimethoxysilyl) propyl] piperazine, 1,4-bis [3- (triethoxysilyl) propyl] piperazine, 1,4-bis [3- (dimethoxymethylsilyl) propyl] piperazine, 1,3-bis [3- (trimethoxysilyl) propyl] imidazolidine, 1,3-bis [3- (triethoxysilyl) propyl] Imidazolidine, 1,3-bis [3- (diemethoxyethylsilyl) propyl] imidazolidine, 1,3-bis [3- (trimethoxysilyl) propyl] hexahydropyrimidine, 1,3-bis [3- ( Triethoxysilyl) propyl] hexahydropyrimidine, 1,3-bis [3- (tributoxysilyl) propyl] -1,2,3,4-tetrahi Ropirimijin, and the like. Among these, those in which p and q are 3 are preferable from the viewpoint of rolling resistance characteristics and extrusion workability. Specifically, 1,4-bis [3- (trimethoxysilyl) propyl] piperazine, 1,4-bis [3- (triethoxysilyl) propyl] piperazine, 1,3-bis [3- (trimethoxy Silyl) propyl] imidazolidine, 1,3-bis [3- (triethoxysilyl) propyl] imidazolidine, 1,3-bis [3- (trimethoxysilyl) propyl] hexahydropyrimidine, 1,3-bis [ 3- (triethoxysilyl) propyl] hexahydropyrimidine and 1,3-bis [3- (tributoxysilyl) propyl] -1,2,3,4-tetrahydropyrimidine are preferred, and among these, 1,4 -Bis [3- (trimethoxysilyl) propyl] piperazine, 1,4-bis [3- (triethoxysilyl) propyl] piperazine Masui.

In the general formula (33), examples of the modifier in which A ³ is represented by the general formula (a) include bis (3-trimethoxysilylpropyl) methylamine, bis (3-triethoxysilylpropyl) methylamine, Bis (3-trimethoxysilylpropyl) ethylamine, bis (3-triethoxysilylpropyl) ethylamine, bis (3-trimethoxysilylpropyl) propylamine, bis (3-triethoxysilylpropyl) propylamine, bis (3- Trimethoxysilylpropyl) butylamine, bis (3-triethoxysilylpropyl) butylamine, bis (3-trimethoxysilylpropyl) phenylamine, bis (3-triethoxysilylpropyl) phenylamine, bis (3-trimethoxysilylpropyl) ) Benzylamine, bis (3-tri Toxisilylpropyl) benzylamine, bis (trimethoxysilylmethyl) methylamine, bis (triethoxysilylmethyl) methylamine, bis (2-trimethoxysilylethyl) methylamine, bis (2-triethoxysilylethyl) methylamine Bis (triethoxysilylmethyl) propylamine, bis (2-triethoxysilylethyl) propylamine and the like. In the case of general formula (b), tris (trimethoxysilylmethyl) amine, tris (2-triethoxy And silylethyl) amine, tris (3-trimethoxysilylpropyl) amine, and tris (3-triethoxysilylpropyl) amine. Among these, those in which r, s, and u are 3 are preferable from the viewpoints of rolling resistance characteristics and extrusion processability. Specifically, bis (3-trimethoxysilylpropyl) methylamine, bis (3-triethoxysilylpropyl) methylamine, bis (3-trimethoxysilylpropyl) ethylamine, bis (3-triethoxysilylpropyl) ethylamine Bis (3-trimethoxysilylpropyl) propylamine, bis (3-triethoxysilylpropyl) propylamine, bis (3-trimethoxysilylpropyl) butylamine, bis (3-triethoxysilylpropyl) butylamine, bis (3 -Trimethoxysilylpropyl) phenylamine, bis (3-triethoxysilylpropyl) phenylamine, bis (3-trimethoxysilylpropyl) benzylamine, bis (3-triethoxysilylpropyl) benzylamine, bis (trimethoxy Rylmethyl) methylamine, bis (triethoxysilylmethyl) methylamine, bis (2-trimethoxysilylethyl) methylamine, bis (2-triethoxysilylethyl) methylamine, bis (triethoxysilylmethyl) propylamine, bis (2-triethoxysilylethyl) propylamine, tris (trimethoxysilylmethyl) amine, tris (2-triethoxysilylethyl) amine, tris (3-trimethoxysilylpropyl) amine, tris (3-triethoxysilylpropyl) ) Amine is more preferred.

  As the modifier, the number of alkoxy groups bonded to the silyl group is one or more, the compound having two or more tertiary amino groups, and the total number of alkoxy groups bonded to the silyl group is four or more, one or more Among the compounds having a nitrogen atom of 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane, 2,2-diethoxy-1- (3-triethoxysilyl) Propyl) -1-aza-2-silacyclopentane is even more preferred. In the modification reaction, the above-described modifiers may be used alone or in combination of two or more.

  There are no particular limitations on the reaction temperature, reaction time, and the like when the above-described modifier is reacted with the active terminal of the conjugated diene polymer, but it is usually preferable to react at 0 to 20 ° C. for 30 seconds or longer. .

  In the above-described modifier, the total number of moles of alkoxy groups bonded to silyl groups in the compound is 0.8 to 3 times the number of moles of alkali metal compound and / or alkaline earth metal compound added as a polymerization initiator. The range is preferably 1 to 2.5 times, more preferably 1 to 2 times. The resulting modified conjugated diene polymer is preferably 0.8 times or more from the viewpoint of obtaining a sufficient modification rate, and a branched polymer component is obtained by coupling polymer ends to improve processability. Is preferably 3 times or less from the viewpoint of the cost of the modifier.

In the present embodiment, as shown as the specific compound, the “alkyl group” in formulas (31) to (33) is generally a hydrocarbon represented by C _n H _{2n + 2} to H Represents a group having a monovalent bond, and may be linear or branched. The “alkylene group” represents a group having a divalent bond obtained by further removing H from an alkyl group. The “alkoxy group” represents a group in which an alkyl group is bonded to an oxygen atom. The “aryl group” in formulas (31) to (33) means a group having an aromatic ring in which carbon atoms of 1 to 20 carbon atoms are arranged in a ring, and even if it is a single ring, it has a plurality of rings. The plurality of rings may be condensed rings. Examples of the aryl group include a phenyl group and a naphthalene group.

  From the viewpoint of making the effect of this embodiment more excellent, the polymer having a functional group component (one-end modified conjugate modified with a compound represented by the formula (31), (32), or (33)) The diene polymer) is preferably 5% by mass or more, more preferably 20% by mass or more, and still more preferably 50% by mass with respect to the total amount of the polymer having the functional group component and the unmodified conjugated diene polymer. It is preferable to produce a one-end-modified conjugated diene-based polymer so as to be a polymer containing at least% (that is, a polymer having a modification rate within this range). As a method for quantifying a polymer having a functional group component, it can be measured by chromatography capable of separating a functional group-containing modified component and a non-modified component. As a method using this chromatography, there is a method in which a GPC column using a polar substance such as silica adsorbing a functional group component as a filler is used and the internal standard of the non-adsorbed component is used for comparison.

  In the method for producing the one-end modified conjugated diene polymer (ii), a deactivation agent, a neutralizing agent and the like may be added to the polymer solution as necessary after the modification reaction. Examples of the quenching agent include water; alcohols such as methanol, ethanol, and isopropanol. Examples of the neutralizing agent include carboxylic acids such as stearic acid, oleic acid, and versatic acid; aqueous solutions of inorganic acids, carbon dioxide gas, and the like.

  In addition, a rubber stabilizer is added to the one-end modified conjugated diene polymer (ii) from the viewpoint of preventing gel formation in the finishing step after polymerization or after polymerization, and from the viewpoint of improving stability during processing. It is preferable to do. The stabilizer for rubber is not particularly limited, and known ones can be used, but 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.

  Moreover, in order to further improve the workability of the modified conjugated diene polymer composition of this embodiment, process oil can be added to the one-end modified conjugated diene polymer (ii) 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 10-60 mass parts with respect to 100 mass parts of modified conjugated diene polymers, and 20-37.5 mass parts is preferable.

  As a method for obtaining the one-end-modified conjugated diene polymer (ii) from the polymer solution, a known method can be used. For example, after separating the solvent by steam stripping or the like, the polymer is separated by filtration, further dehydrated and dried to obtain the polymer, concentrated in a flushing tank, and further devolatilized by a vent extruder or the like. The method, the method of devolatilizing directly with a drum dryer etc. are mentioned.

<Other rubbery polymers>
In the present embodiment, the rubber component (I) is a rubber other than the above-mentioned both-end-modified conjugated diene polymer (A1) and one-end-modified conjugated diene polymer (I2) as long as the characteristics of the present invention are satisfied. A polymer (hereinafter sometimes referred to as “other rubbery polymer”) may be included. The other rubbery polymer is not particularly limited. For example, another rubbery polymer having a ratio (Mw / Mn) of weight average molecular weight Mw to number average molecular weight Mn by gel permeation chromatography is 1.9 or more. And / or other non-modified rubbery polymers (including diene polymers and non-diene polymers). The rubber component (a) does not include (b) a polymer belonging to a rubber-like polymer.

  Such other rubbery polymer is not particularly limited, and examples thereof include conjugated dienes other than the above-mentioned both-end-modified conjugated diene polymer (A1) and one-end-modified conjugated diene polymer (I2). Polymer or hydrogenated product thereof, random copolymer of conjugated diene compound and vinyl aromatic compound or hydrogenated product thereof, block copolymer of conjugated diene compound and vinyl aromatic compound or hydrogenated product thereof And non-diene polymers.

  Specifically, butadiene rubber or its hydrogenated product, styrene-butadiene rubber or its hydrogenated product, styrene-butadiene block copolymer or its hydrogenated product, styrene-isoprene block copolymer or its hydrogenated product, etc. Examples thereof include styrene elastomers, acrylonitrile-butadiene rubber or hydrogenated products 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, fluorine rubber, 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 provided with a functional group having polarity such as a hydroxyl group other than the modified conjugated diene polymer. 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.

<< (B) Rubbery polymer >>
The modified diene polymer composition of the present embodiment comprises (b) at least one rubber-like polymer selected from natural rubber, high-cis polybutadiene rubber, and polyisoprene rubber. ) "Or" rubbery polymer (b) "). The modified diene polymer composition of the present embodiment includes 30 to 70 parts by mass of a rubber component (A) and 30 to 70 parts by mass of a component (B).

  Natural rubber is a substance mainly composed of cis-type polyisoprene contained in rubber tree sap, and is produced by addition polymerization in vivo. In visual inspection, it is classified into grades of international standards RSS1 to RSS5.

  Polyisoprene rubber is a kind of synthetic rubber that is polyisoprene obtained by chemically polymerizing isoprene. There are some structural differences between polyisoprene rubber and natural rubber polyisoprene. First, synthetic polyisoprene contained in polyisoprene rubber cannot obtain a 100% cis isomer at present and contains a small amount of trans isomer. Natural rubber contains trace amounts of proteins and fatty acids in addition to polyisoprene, but synthetic polyisoprene has no such impurities. Examples of the polyisoprene rubber include JSR (trade name) JSR IR1220 manufactured by JSR Corporation.

  High-cis polybutadiene rubber is, for example, polybutadiene produced by solution polymerization using a Ziegler-Natta type coordination catalyst based on titanium, cobalt, and nickel, or in the presence of an alkyl lithium compound. Polybutadiene having a high amount of 1,4-cis bonds, such as UBEPOL (registered trademark) BR manufactured by Ube Industries, Ltd., and the like.

  In the modified diene polymer composition, the amount of the rubber component (A) is 30 to 70 parts by mass and the amount of the rubbery polymer (B) is 30 to 70 parts by mass. The characteristics and cut resistance are further improved. From the viewpoint of a balance between rolling resistance characteristics, extrusion processability, and cut resistance, the blending amounts of the rubber component (A) and the rubbery polymer (B) are preferably 40 to 60 parts by mass and 60 to 40, respectively. Part by mass.

<< (C) Silica-based inorganic filler >>
The modified diene polymer composition of the present embodiment includes (c) a silica-based inorganic filler (also referred to as “component (c)” in the present specification).

  From the viewpoint of developing the rolling resistance characteristics, the extrusion processability, and the viewpoint of making the cut resistance practically sufficient, the compounding amount of the silica-based inorganic filler is determined by the rubber component (A) and the rubber-like polymer ( (B) as 100 parts by mass, preferably 0.5 to 300 parts by mass, more preferably 5 to 200 parts by mass, and still more preferably 20 to 100 parts by mass.

The silica-based inorganic filler is not particularly limited, but may be a known, solid particles preferably comprise SiO ₂ or Si ₃ Al as a constituent unit, the main structural units of SiO ₂ or Si ₃ Al More preferably, it is a component. Here, “main component” means containing 50% by mass or more of the target component 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 inorganic fibrous materials such as silica, clay, talc, mica, diatomaceous earth, wollastonite, montmorillonite, zeolite, and glass fiber. In addition, a silica-based inorganic filler having a hydrophobic surface or a mixture of a silica-based inorganic filler and a non-silica inorganic filler can also be used. Among these, silica and glass fiber are preferable from the viewpoints of strength, wear resistance, and the like, and silica is more preferable. Examples of silica include dry silica, wet silica, and synthetic silicate silica. Among these, wet silica is preferable.

  Examples of the dry silica include those obtained by reacting purified silicon tetrachloride in a high-temperature flame and having higher purity, finer particles, and extremely low moisture compared to the wet type. It is widely used as a raw material for fillers, resin thickeners, reinforcing agents, powder fluidizers and ceramics.

  As wet silica, for example, sodium silicate using silica sand as a raw material, neutralizing the aqueous solution to deposit silica, filtering and drying, a fluffy and light white powder is given in appearance. In general, it is used as a reinforcing filler for synthetic rubber, prevention of powdering and consolidation of liquids such as agricultural chemicals, prevention of back-through of printing ink for lightweight paper, paint, ink thickening and anti-sagging, thermal insulation, and abrasive. .

In the modified conjugated diene polymer composition, 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 from the viewpoint of obtaining more excellent rolling resistance characteristics. 170-250 m ² / g is more preferable.

<< Other >>
<Carbon black>
In the modified diene polymer composition of the present embodiment, the total amount of the rubber component (A) and the rubber-like polymer (B) is 100 parts by mass. It is preferable to contain -100 mass parts.

The carbon black is not particularly limited, and for example, carbon black of each class such as SRF, FEF, HAF, ISAF, and SAF can be used. Among these, a carbon black having a nitrogen adsorption specific surface area of 50 m ² / g or more and a dibutyl phthalate (DBP) oil absorption of 80 mL / 100 g or more is preferable from the viewpoint of extrusion moldability and rolling resistance characteristics.

  The blending amount of carbon black is from 0.5 to about 100 parts by mass of the total of the rubber component (A) and the rubbery polymer (B) from the viewpoint of the balance of rolling resistance characteristics, extrusion processability, and cut resistance. 100 mass parts is preferable, 3-100 mass parts is more preferable, and 5-50 mass parts is still more preferable.

<Metal oxide and metal hydroxide>
The modified diene polymer composition of the present embodiment may contain a metal oxide or a metal hydroxide in addition to the silica-based inorganic filler and carbon black. The metal oxide is a solid particle having a chemical unit M _x O _y (M represents a metal atom, and x and y each independently represents an integer of 1 to 6) as a main component of a structural unit. 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.

<Silane coupling agent>
The modified diene polymer composition of this embodiment may contain a silane coupling agent. The silane coupling agent has an affinity or binding group for each of the rubber component, the rubber-like polymer, and the silica-based inorganic filler, and has a function of tightly interacting the two. In general, a compound having a sulfur bond portion, an alkoxysilyl group, and a silanol group portion in one molecule is used.

  Although the silane coupling agent is not limited to the following, for example, 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, Silane coupling agents containing mercapto groups such as NXTZ60, NXT silane, bis- [3- (triethoxysilyl) -propyl] -tetrasulfide, bis- [3- (triethoxysilyl) -propyl] -disulfide, bis -[2- (triethoxysilane) ) -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 tetrasulfide 3-trimethoxysilylpropyl benzothiazolyl tetrasulfide, 3-triethoxysilylpropyl benzoyl tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis (3-di Ethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide, and the like. Among them, bis- [3- (triethoxysilyl) -propyl] -disulfide, ethoxy (3-mercaptopropyl) bis (3,6,9,12,15-pentaoxaoctacosan-1-yloxy) silane [Evonik] -Degussa: Si363], Momentive's NXT-Z30, NXT-Z45, NXTZ60, silane coupling agents containing mercapto groups such as NXT silane, bis- [3- (triethoxysilyl) -propyl]- Tetrasulfide is preferable because of its high reinforcing effect. These silane coupling agents can be used singly or in combination of two or more.

  The compounding amount of the silane coupling agent is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, with the total of the rubber component (A) and the rubbery polymer (B) being 100 parts by mass. 1 to 15 parts by mass is more preferable. 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.

<Rubber softener>
The modified diene polymer composition of the present embodiment may contain a rubber softener 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 modified conjugated diene-aromatic vinyl copolymer, those having an appropriate aromatic content are preferred because they tend to be familiar with the copolymer.

  The blending amount of the rubber softener is preferably 0 to 100 parts by weight, more preferably 10 to 90 parts by weight, with respect to 100 parts by weight in total of the rubber component (A) and the rubbery polymer (B). 90 parts by mass is more preferable. If the blending amount of the rubber softener is too large, bleeding out tends to occur, and the surface of the composition may become sticky.

<< Method for Producing Modified Diene Polymer Composition >>
In the method for producing the modified diene polymer composition of the present embodiment, the rubber component (A), the rubber-like polymer (B), the silica-based inorganic filler (C) containing the modified conjugated diene polymer, if desired, The method of mixing additives such as carbon black and other fillers, silane coupling agents, and rubber softeners is not particularly limited. For example, a melt kneading method using a general blender such as an open roll, a Banbury mixer, a kneader, a single screw extruder, a twin screw extruder, a multi-screw extruder, etc., each component is dissolved and mixed, and then the solvent is heated The method of removing etc. are mentioned. 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 the modified conjugated diene polymer and various compounding agents at a time and a method of mixing in multiple times can be applied.

  The modified diene polymer composition may be a vulcanized rubber composition obtained by vulcanizing a non-vulcanized modified diene polymer composition with a vulcanizing agent. 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, preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the rubber component containing the modified conjugated diene polymer. A conventionally known method can be applied as the vulcanization method, and the vulcanization temperature is usually 120 to 200 ° C, preferably 140 to 180 ° C.

  In vulcanization, a vulcanization accelerator may be used as necessary. As the vulcanization accelerator, conventionally known materials can be used, for example, sulfenamide, guanidine, thiuram, aldehyde-amine, aldehyde-ammonia, thiazole, thiourea, dithiocarbamate, etc. And vulcanization accelerators. As the vulcanization aid, zinc white, stearic acid or the like can be used. The usage-amount of a vulcanization accelerator is 0.01-20 mass parts normally with respect to a total of 100 mass parts with the said rubber component (ii) and the said rubber-like polymer (b), 0.1-15 Part by mass is preferred. The amount of the vulcanization aid used is 0.01 to 20 parts by mass and 0.1 to 15 parts by mass with respect to 100 parts by mass in total of the rubber component (A) and the rubbery polymer (B). Is preferred.

  The modified diene polymer composition of the present embodiment includes other softening agents and fillers other than those described above, as well as heat resistance stabilizers, antistatic agents, and weather resistance stability, within the range not impairing the purpose of the present embodiment. Various additives such as an agent, an anti-aging agent, a coloring agent, 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, weathering stabilizer, anti-aging agent, colorant, and lubricant.

  A tire can be manufactured by a normal method using the modified diene polymer composition of the present embodiment. For example, the modified diene polymer composition of the present embodiment may be a rubber composition for a tire sidewall. That is, a tire can be manufactured by making a side wall etc. using the said modified | denatured diene type resin composition, bonding together with another member, and heat-pressing using a tire molding machine. A tire including a crosslinked product of the modified diene resin composition is preferred. By using the modified diene resin composition of the present embodiment, it is possible to produce a tire having an excellent balance of rolling resistance characteristics, extrusion processability, and cut resistance, and particularly excellent rolling resistance characteristics.

  The present embodiment will be described in more detail with reference to the following examples and comparative examples, but the present invention is not limited to the following examples. The sample was analyzed by the method shown below.

(1) (Physical Properties (1)) Bound Styrene Amount As a sample, 100 mg of a modified conjugated diene polymer was diluted to 100 mL with chloroform and dissolved to obtain a measurement sample. The amount of bound styrene (mass%) was measured by absorption at 254 nm by the phenyl group of styrene (manufactured by Shimadzu Corporation: UV-2450).

(2) (Physical property (2)) 1,2-vinyl bond amount As a 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 was placed in the cell to prepare a solution cell. Using a solution cell, the infrared spectrum was measured in the range of 600 to 1000 cm ⁻¹ , and the 1,2-vinyl bond amount of the butadiene portion was determined from the absorbance at a predetermined wave number according to the formula of the Hampton method (Japan). Spectroscopic Co., Ltd .: FT-IR230).

(3) (Physical Properties (3)) Mooney Viscosity of Polymer and Mooney Relaxation Rate Using a polymer before addition of a modifier or a modified conjugated diene polymer as a sample, a Mooney viscometer (trade name “Kamishima Seisakusho” VR1132 "), and in accordance with JIS K6300 (ISO 289-1) and ISO 289-4, the Mooney viscosity of the conjugated diene polymer before the addition of the modifier and the conjugated diene polymer after the modification, and the modified conjugated diene polymer weight The Mooney relaxation rate of the coalescence was measured. The measurement temperature was 110 ° C. Moreover, in the case of the sample extended using process oil, it measured at 100 degreeC. First, after preheating the sample for 1 minute, the rotor was rotated at 2 rpm, the torque after 4 minutes was measured, and the measured value was taken as Mooney viscosity (ML _{(1 + 4)} ). Thereafter, when the modified conjugated diene polymer was used as a sample, the rotation of the rotor was immediately stopped, and the torque every 0.1 second for 1.6 to 5 seconds was recorded in Mooney units after the stop. The slope of the straight line when the time (seconds) was log-log plotted was determined, and the absolute value thereof was taken as the Mooney relaxation rate (MSR).

(4) (Physical property (4)) Modification rate By applying the property of adsorbing the modified diene polymer component to a gel permeation chromatography (hereinafter also referred to as “GPC”) column using silica gel as a filler. The modification rate of the modified conjugated diene polymer was measured. A sample solution containing a modified conjugated diene polymer as a sample and a low molecular weight internal standard polystyrene is used to determine the amount of adsorption to the silica column from the difference between the chromatogram measured with the polystyrene gel column and the chromatogram measured with the silica gel column. Measurements were made to determine the denaturation rate.

・ Preparation of sample for measurement:
As a sample, 10 mg of a modified conjugated diene polymer and 5 mg of standard polystyrene were dissolved in 20 mL of tetrahydrofuran (THF) to prepare a measurement sample.

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

・ GPC measurement conditions using silica gel column:
Using THF as an eluent, 200 μL of a measurement sample was injected into a GPC apparatus and measured. The column used was DuPont Zorbax. The chromatogram was measured using a silica gel gel column with a column oven temperature of 40 ° C. and a THF flow rate of 0.5 mL / min using a Tosoh HLC8020 RI detector.

・ Method of calculating denaturation rate:
Sample with 100 as the total peak area of the chromatogram using the polystyrene gel column, P1 as the peak area of the sample, P2 as the peak area of the standard polystyrene, and 100 as the entire peak area of the chromatogram using the silica column The modification ratio (%) was obtained from the following formula, with the area of P3 being P3 and the peak area of standard polystyrene being P4.
Denaturation rate (%) = [1- (P2 × P3) / (P1 × P4)] × 100
(However, P1 + P2 = P3 + P4 = 100)

(5) (Physical property 5) Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)
The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the modified conjugated diene polymer were measured using a permeation GPC apparatus in which three columns each having a polystyrene gel as a filler were connected. The weight average molecular weight (Mw) and the number average molecular weight (Mn) were obtained from a calibration curve using standard polystyrene, and the index of molecular weight distribution (Mw / Mn) was calculated from the ratio of the weight average molecular weight and the number average molecular weight. . Tetrahydrofuran (THF) was used as the eluent.

  The column used was a guard column: Tosoh TSKguardcolumn HHR-H, column: Tosoh TSKgel G6000HHR, TSKgel G5000HHR, TSKgel G4000HHR. The molecular weight was measured using an RI detector of HLC8020 manufactured by Tosoh under conditions of an oven temperature of 40 ° C. and a THF flow rate of 1.0 mL / min. 10 mg of a modified conjugated diene polymer as a sample was dissolved in 20 mL of THF to obtain a measurement solution, and 200 μL of this measurement solution was injected into the apparatus for measurement.

(6) (Physical property 6) Molecular weight measured by GPC-light scattering method (absolute molecular weight)
Using a modified conjugated diene polymer as a sample, a chromatogram was measured using a GPC-light scattering measuring apparatus in which three columns with a polystyrene gel as a filler were connected, and based on the solution viscosity and light scattering method. The weight average molecular weight (Mw-i) and the number average molecular weight (Mn-i) were determined (these are also called "absolute molecular weights"). As an eluent, a mixed solution of tetrahydrofuran and triethylamine (THF in TEA: 5 mL of triethylamine was mixed with 1 L of tetrahydrofuran to prepare) was used.

  The column used was a guard column: a trade name “TSKguardcolumn HHR-H” manufactured by Tosoh Corporation, and a column: a trade name “TSKgel G6000HHR”, “TSKgel G5000HHR”, “TSKgel G4000HHR” manufactured by Tosoh Corporation. A GPC-light scattering measurement device (trade name “Viscotek TDAmax” manufactured by Malvern) was used under the conditions of an oven temperature of 40 ° C. and a THF flow rate of 1.0 mL / min. 10 mg of a sample was dissolved in 20 mL of THF to prepare a measurement solution, and 200 μL of the measurement solution was injected into a GPC measurement device and measured.

(7) (Physical property 7) Glass transition temperature (Tg)
The glass transition temperature of the modified conjugated diene polymer was measured according to ISO 22768: 2006. The DSC curve was recorded while raising the temperature within a predetermined temperature range, and the peak top (Infection point) of the DSC differential curve was taken as the glass transition temperature.

(8) Monomer concentration during modification reaction The “monomer concentration during modification reaction” in Table 1 is the ratio of the monomer to the total amount of all monomers and polymers during the modification reaction. (Mass ppm). The monomer concentration during the modification reaction was determined by gas chromatography (GC) by measuring the amount of monomers (aromatic vinyl compound and conjugated diene compound) remaining in various samples after polymerization.

(9) (Evaluation 1) Extrusion workability About the skin (surface shape) of the rubber after passing through the roll of the unvulcanized rubber composition prepared by the method shown in Examples and Comparative Examples, five panelists visually observed, Each panelist was rated at a maximum of 5 points, with an overall rating of 25 points. The closer to 25 points, the better the extrusion processability. 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.

(10) (Evaluation 2) Mooney Viscosity of Unvulcanized Rubber Composition After preheating the unvulcanized rubber composition as a sample at 100 ° C. for 1 minute according to JIS K6300-1, using a Mooney viscometer The Mooney viscosity after rotating the rotor at 2 revolutions per minute for 4 minutes was measured. Each measurement was indexed with the result of Comparative Example 1 taken as 100. It shows that it is excellent in workability, so that a value is small.

(11) (Evaluation 3) Rolling Resistance Characteristics Using a vulcanized rubber sheet as a measurement sample, a viscoelasticity tester (ARES G-2) manufactured by TA Instrument Co., Ltd. was used, and viscoelastic parameters were measured in a torsion mode. The comparative example 1 was set to 100, and each measured value was indexed. 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 (low fuel consumption). A smaller value indicates better rolling resistance characteristics.

(12) (Evaluation 4) Cut resistance Measured according to JIS-K-6252, with Comparative Example 1 as the control (“◯”), “◎” means better than this, “O” was evaluated as “x” when it was worse than Comparative Example 1.

[Production Example 1]
The internal volume is 10 L, the ratio of internal height (L) to diameter (D) (L / D) is 4.0, has an inlet at the bottom, an outlet at the top, a stirrer and Two autoclaves having a temperature adjusting jacket were connected. 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 29.0 g / min, styrene at 18.9 g / min, and n-hexane at 180.2 g / min. Immediately before this mixed solution enters the first reactor, n-butyllithium for impurity inactivation treatment is supplied at 0.087 mmol / min and mixed with a static mixer, and then the bottom of the first reactor is added. Continuously fed. Further, 2,2-bis (2-oxolanyl) propane as a polar substance at a rate of 0.018 g / min, piperidinolithium (also referred to as “1-lithiopiperidine”) as a preliminarily prepared lithium amide as a polymerization initiator. ) And n-butyllithium mixed solution (molar ratio of piperidinolithium to n-butyllithium was 0.75: 0.25. Hereinafter, this mixed solution as a polymerization initiator was referred to as “LA-1”. Is also supplied to the bottom of the first reactor at a rate of 0.180 mmol / min, and the reactor internal temperature is maintained at 67 ° C. 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 72 ° C., and further fed to the static mixer from the top of the second reactor. A small amount of the copolymer solution before the addition of the modifier is withdrawn from the outlet of the second reactor, an antioxidant (BHT) is added so as to be 0.2 g per 100 g of the polymer, and then the solvent is removed. The Mooney viscosity was measured and found to be 62.

  Next, the modifier 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane (Table) shown in Table 1 was added to the copolymer solution continuously flowing in the static mixer. Among them, abbreviated as “AS-1”) was added at a rate of 0.047 mmol / min to carry out a denaturing reaction. 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 copolymer (hereinafter also referred to as “modified SBR-A”) was obtained.

  As a result of analysis of the modified SBR-A, the Mooney viscosity at 110 ° C. was 128, the amount of bound styrene was 35% by mass, the amount of vinyl bonds (1,2-bond amount) in the butadiene bond unit was 40 mol%, and the modification rate was 92 It was 1 mass%. Other physical properties of the modified SBR-A are also shown in Table 1.

[Production Example 2]
2,2-Dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane (“AS-1”) was converted to tris (3-trimethoxysilylpropyl) amine (“ In the same manner as in Production Example 1, except that the amount added was changed to 0.032 mmol / min, the two-terminal modified conjugated diene copolymer (hereinafter referred to as “modified SBR—”) was used. B ”). Table 1 shows the physical properties of the modified SBR-B.

[Production Example 3]
Two autoclaves with an internal volume of 10L, an internal height-to-diameter ratio (L / D) of 4, an inlet at the bottom, an outlet at the top, and a stirrer and a temperature adjustment jacket are connected in series. The first group was a polymerization reactor and the second group was a denaturing reactor.

  Premixed 1,3-butadiene from which impurities such as moisture have been removed in advance under the conditions of 29.0 g / min, styrene 18.9 g / min, n-hexane 180.2 g / min, and then impurity inactivation treatment N-Butyllithium was further mixed with a static mixer immediately before entering the first reactor, and continuously fed to the bottom of the first reactor at 0.087 mmol / min. 2,2-bis (2-oxolanyl) propane was fed at a rate of 0.018 g / min, and n-butyllithium was used as a polymerization initiator at a rate of 0.180 mmol / min at the bottom of the first reactor. The polymerization reaction was continued such that the temperature in the reactor was 72 ° C. and the temperature at the reactor outlet was 90 ° C.

  The temperature of the second modification reactor was kept at 85 ° C., and 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane (in the table, “AS -1 ") was added from the bottom of the second reactor at a rate of 0.047 mmol / min to carry out a modification (coupling) reaction.

  Antioxidant (BHT) was continuously added to the polymer solution flowing out from the top of the second reactor at a rate of 0.248 g per 100 g of polymer at a rate of 0.048 g / min (n-hexane solution). After terminating the reaction, the solvent was removed to obtain a modified conjugated diene polymer solution. Further, the solvent was removed from the modified conjugated diene polymer solution with a drum dryer to obtain a one-end modified conjugated diene copolymer (hereinafter also referred to as “modified SBR-C”). Table 1 shows the physical properties of the modified SBR-C.

[material]
In Examples 1 to 8 and Comparative Example 1 described later, the following materials were used.
・ Both-end modified conjugated diene copolymer (modified SBR-A)
-Both-end modified conjugated diene copolymer (modified SBR-B)
・ One-end modified conjugated diene copolymer (modified SBR-C)
・ Natural rubber (# RSS3)
・ High cis polybutadiene (manufactured by Ube Industries, UBEPOL BR150)
Silica (Evonik Degussa Japan Co., Ltd., Ultrasil 7000GR, Nitrogen adsorption specific surface area: 175 m ² / g)
・ Silane coupling agent (Si69, manufactured by Evonik Degussa Japan)
・ Carbon black (Tokai Carbon Co., Ltd., Seast KH (N339))
・ Process oil (manufactured by JX Nippon Oil & Energy, NC140)
・ Zinc flower (Mitsui Metal Mining Co., Ltd., Zinc flower No. 1)
・ Stearic acid and wax (Onouchi Shinsei Chemical Co., Ltd., Sunnock)
・ Anti-aging agent (N-isopropyl-N′-phenyl-p-phenylenediamine)
・ Sulfur / vulcanization accelerator 1 (N-cyclohexyl-2-benzothiazylsulfinamide)
・ Vulcanization accelerator 2 (diphenylguanidine)

[Example 1]
According to the formulation shown in Table 2, kneading was carried out by the following method to obtain an unvulcanized rubber composition and a vulcanized rubber sheet. Using a kneader (with an internal volume of 0.5 L) equipped with a temperature control device, the modified conjugated diene polymer (modified SBR-A) under the conditions of a filling rate of 60% and a rotor rotational speed of 50 rpm as the first stage kneading And modified SBR-B), natural rubber, silica, silane coupling agent, and process oil were kneaded for 4 minutes. At this time, the discharge temperature was adjusted to 155 to 160 ° C. by temperature control of the kneader to obtain a blend.

  Next, as the second stage kneading, the mixture obtained above was cooled to room temperature, carbon black, zinc white, stearic acid, wax, and anti-aging agent were added and kneaded for 3 minutes in the kneader. Also in this case, the discharge temperature was adjusted to 155 to 160 ° C. by temperature control of the kneader.

  The discharge temperature was controlled by measuring the temperature of each formulation discharged from the kneader after kneading. The compound discharged from the kneader was immediately passed 6 times through a 10 inch φ open roll to prepare a sheet-like unvulcanized rubber composition, cooled, and then evaluated for extrusion processability.

  Furthermore, after heating the unvulcanized rubber composition using an oven at 70 ° C. for 30 minutes, as a third stage kneading, sulfur and a vulcanization accelerator were added using a 10 inch φ open roll set at 70 ° C. In addition, kneading was performed to obtain an unvulcanized rubber composition. A part was taken out from this unvulcanized rubber composition, and the extrusion processability and the Mooney viscosity of the unvulcanized rubber composition were 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. The rolling resistance characteristics and cut resistance of the vulcanized rubber sheet were evaluated.

[Example 2]
The compounding amounts of “both terminal modified conjugated diene copolymer (modified SBR-A)”, “both terminal modified conjugated diene copolymer (modified SBR-B)”, and “natural rubber (# RSS3)” An unvulcanized rubber composition and a vulcanized rubber sheet were prepared in the same manner as in Example 1 except that they were 30 parts by mass, 30 parts by mass, and 40 parts by mass, respectively, and extrusion processability, Mooney viscosity, rolling Resistance characteristics and cut resistance were evaluated.

[Example 3]
The compounding amounts of “both terminal modified conjugated diene copolymer (modified SBR-A)”, “both terminal modified conjugated diene copolymer (modified SBR-B)”, and “natural rubber (# RSS3)” An unvulcanized rubber composition and a vulcanized rubber sheet were produced in the same manner as in Example 1 except that they were 20 parts by mass, 20 parts by mass, and 60 parts by mass, respectively, and extrusion processability, Mooney viscosity, rolling Resistance characteristics and cut resistance were evaluated.

[Example 4]
The compounding amounts of “both terminal modified conjugated diene copolymer (modified SBR-A)”, “both terminal modified conjugated diene copolymer (modified SBR-B)”, and “natural rubber (# RSS3)” An unvulcanized rubber composition and a vulcanized rubber sheet were prepared in the same manner as in Example 1 except that they were 15 parts by mass, 15 parts by mass, and 70 parts by mass, respectively, and extrusion processability, Mooney viscosity, rolling Resistance characteristics and cut resistance were evaluated.

[Example 5]
Instead of “both end modified conjugated diene copolymer (modified SBR-B)”, 20 parts by mass of “one end modified conjugated diene copolymer (modified SBR-C)” prepared in Production Example 3 was used. Except for this, an unvulcanized rubber composition and a vulcanized rubber sheet were prepared in the same manner as in Example 3, and extrusion processability, Mooney viscosity, rolling resistance characteristics, and cut resistance were evaluated.

[Example 6]
28 parts by mass of “both terminal-modified conjugated diene copolymer (modified SBR-A)” was used in Production Example 3 instead of “both terminal modified conjugated diene copolymer (modified SBR-B)”. An unvulcanized rubber composition and a vulcanized rubber sheet were produced in the same manner as in Example 3 except that 12 parts by mass of “one-end modified conjugated diene copolymer (modified SBR-C)” was used, and extrusion processability The Mooney viscosity, rolling resistance characteristics, and cut resistance were evaluated.

[Example 7]
Unvulcanized in the same manner as in Example 3 except that 30 parts by mass of “natural rubber (# RSS3)” and 30 parts by mass of “High cis polybutadiene (UBEPOL BR150) manufactured by Ube Industries, Ltd.” are used. A rubber composition and a vulcanized rubber sheet were prepared and evaluated for extrusion processability, Mooney viscosity, rolling resistance characteristics, and cut resistance.

[Comparative Example 1]
Instead of “both terminal modified conjugated diene copolymer (modified SBR-A)” and “both terminal modified conjugated diene copolymer (modified SBR-B)”, the “one terminal modified conjugate” prepared in Production Example 3 was used. Except for using 40 parts by mass of “diene copolymer (modified SBR-C)”, an unvulcanized rubber composition and a vulcanized rubber sheet were prepared in the same manner as in Example 3, and extrusion processability, Mooney viscosity, The rolling resistance characteristics and cut resistance were evaluated.

  Table 2 shows the compositions of Examples 1 to 7 and Comparative Example 1. Table 3 shows the evaluation results of extrusion processability, Mooney viscosity, rolling resistance characteristics, and cut resistance in Examples 1 to 7 and Comparative Example 1.

  According to the present invention, it is possible to obtain a rubber composition for a sidewall having an excellent balance of extrusion processability, rolling resistance characteristics, and cut resistance, and using this, the rolling resistance characteristics and cut resistance can be obtained. An excellent tire can be obtained.

Claims (16)

(A) Mooney relaxation rate measured at 110 ° C. is 0.45 or less, modification rate is 75% by mass or more, and weight average molecular weight Mw and number average molecular weight Mn by gel permeation chromatography (GPC) 30 to 70 parts by mass of a rubber component (A) including a both-end modified conjugated diene polymer (A1) having a ratio (Mw / Mn) of 1.9 or more;
(B) 30 to 70 parts by mass of at least one rubbery polymer (b) selected from the group consisting of natural rubber, high-cis polybutadiene rubber, and polyisoprene;
(C) a silica-based inorganic filler,
A modified diene polymer composition, wherein the content of the both-end modified conjugated diene polymer (a) is 20% by mass or more based on the total mass of the rubber component (a). (A) Mooney relaxation rate measured at 110 ° C. is 0.45 or less, modification rate is 75% by mass or more, and weight average molecular weight Mw and number average molecular weight Mn by gel permeation chromatography (GPC) The ratio (Mw / Mn) of the weight average molecular weight Mw and the number average molecular weight Mn measured by gel permeation chromatography (GPC) with a both-end modified conjugated diene polymer (A1) having a ratio (Mw / Mn) of 1.9 or more And 30-70 parts by mass of the rubber component (I) including the one-end modified conjugated diene polymer (I2) having a 1.9 of 1.9 or more,
(B) 30 to 70 parts by mass of at least one rubbery polymer (b) selected from the group consisting of natural rubber, high-cis polybutadiene rubber, and polyisoprene;
(C) a silica-based inorganic filler,
The total content of the both-end modified conjugated diene polymer (A1) and the one-end modified conjugated diene polymer (I2) is 20% by mass or more based on the total mass of the rubber component (A). A modified diene polymer composition.   The both-end-modified conjugated diene polymer (A1) has a star-shaped polymer structure having a nitrogen atom at at least one terminal and centering on a nitrogen-containing alkoxysilane substituent. The modified diene polymer composition as described.   The ratio of the 2nd number average molecular weight calculated | required by GPC-light-scattering-method measurement with respect to the 1st number average molecular weight calculated | required by the gel permeation chromatography measurement of the said both terminal modified conjugated diene type polymer (a) is The modified diene polymer composition according to any one of claims 1 to 3, which is 1.00 or more.   The ratio of the second weight average molecular weight determined by GPC-light scattering measurement to the first weight average molecular weight determined by gel permeation chromatography measurement is the above-mentioned both-end-modified conjugated diene-based polymer (ii). The modified diene polymer composition according to any one of claims 1 to 4, which is 1.00 or more.   The terminal-modified conjugated diene polymer (A1) has a first number average molecular weight of 200,000 or more and 2,000,000 or less, and the first weight relative to the first number average molecular weight. The modified diene polymer composition according to any one of claims 1 to 5, wherein the ratio of the average molecular weight is 1.90 or more and 3.50 or less. The modified diene polymer composition according to any one of claims 1 to 6, wherein the both terminal-modified conjugated diene polymer (A1) is represented by the following general formula (A) or (B).

(In formula (A), R ^{21 to} R ²⁴ each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ²⁵ and R ²⁶ are each independently Represents an alkylene group having 1 to 20 carbon atoms, and R ²⁷ represents a hydrogen atom, a silyl group substituted with a hydrocarbon, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. And c each independently represents an integer of 1 or 2, b and d each independently represents an integer of 0 or 1, and (a + b) and (c + d) each independently represents 2 (Polym) represents a conjugated diene polymer chain obtained by polymerizing a conjugated diene compound or copolymerizing a conjugated diene compound and an aromatic vinyl compound, and at least one end thereof. , Represented by at least one selected from the following general formulas (4) to (7) When there are a plurality of functional groups, R ²¹ and R ²³ and a plurality of (Polym) are independent of each other.

(In the formula (B), R ^{28 to} R ³³ each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ³⁴ , R ³⁵ , and R ³⁶ are Each independently represents an alkylene group having 1 to 20 carbon atoms, a, c, and e each independently represent an integer of 1 or 2, b, d, and f each independently represent: Represents an integer of 0 or 1, each of (a + b), (c + d), and (e + f) independently represents an integer of 2 or less, and (Polym) is a polymer of a conjugated diene compound or a conjugated diene compound It represents a conjugated diene polymer chain obtained by copolymerizing with an aromatic vinyl compound, and at least one terminal thereof is represented by at least one selected from the following general formulas (4) to (7) R ^28, R ³⁰ in the case where groups are to have. plurality of bonded and R ^32, and a plurality To standing (Polym) are each independent.)

(In the formula (4), R ₁₀ and R ₁₁ 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 R ₁₀ and R ₁₁ may be bonded to form a cyclic structure with the adjacent nitrogen atom, and in this case, R ₁₀ and R ₁₁ have 5 to 12 carbon atoms. It represents a hydrocarbon group, and a part thereof may have an unsaturated bond or a branched structure.)

(In the formula (5), R ₁₂ and R ₁₃ 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 R ₁₂ and R ₁₃ may be bonded to form a cyclic structure with an adjacent nitrogen atom, and R ₁₂ and R _{13 in} this case are each having 5 to 12 carbon atoms. R ₁₄ represents a hydrocarbon group and may have an unsaturated bond or a branched structure in a part of the hydrocarbon group, R ₁₄ is an alkylene group having 1 to 20 carbon atoms, or a divalent compound based on a conjugated diene compound having 4 to 20 carbon atoms. Represents a valent group.)

(In the formula (6), R ₁₅ and R ₁₆ 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 an aryl group having 6 to 20 carbon atoms R ₁₅ and R ₁₆ may be bonded to form a cyclic structure with an adjacent nitrogen atom, and R ₁₅ and R _{16 in} this case are bonded to form a carbon number of 5; Represents an alkylene group of ˜12, and a part thereof may have a branched structure.)

(In the formula (7), R ₁₇ represents a hydrocarbon group having 2 to 12 carbon atoms, and may have an unsaturated bond or a branched structure in a part thereof. R ₁₈ has 1 to 12 carbon atoms. And may have a branched structure in a part thereof.) The both terminal-modified conjugated diene polymer (a) is
A polymerization step in which an organic lithium compound having at least one nitrogen atom in the molecule is used as a polymerization initiator, and at least a conjugated diene compound is polymerized to obtain a conjugated diene polymer;
A modification step of modifying the conjugated diene polymer with a modifier having four or more alkoxy groups bonded to a silyl group in one molecule and a tertiary amino group;
The modified diene polymer composition according to any one of claims 1 to 7, which is obtained from a production method having the following. The modified diene polymer composition according to claim 8, wherein the modifying agent includes a modifying agent represented by at least one of the following general formulas (1) to (3).

(In Formula (1), R < ¹ > -R < ⁴ > respectively independently represents a C1-C20 alkyl group or a C6-C20 aryl group, and R < ⁵ > is C1-C10 alkylene. R ⁶ represents an alkylene group having 1 to 20 carbon atoms, m represents an integer of 1 or 2, n represents an integer of 2 or 3. (m + n) is an integer of 4 or more When there are a plurality of R ^{1 to} R ⁴ , each is independent.)

(In Formula (2), R < ¹ > -R < ⁶ > respectively independently represents a C1-C20 alkyl group or a C6-C20 aryl group, and R < ⁷ > -R < ⁹ > is respectively independently. Represents an alkylene group having 1 to 20 carbon atoms, m, n, and l each independently represent an integer of 1 to 3, and (m + n + 1) represents an integer of 4 or more. R ^{1 to} R ^{6 in the} case are independent of each other.)

(In the formula (3), R ¹ ~R ⁴ each independently represent an alkyl group or an aryl group having 6 to 20 carbon atoms having 1 to 20 carbon atoms, R ⁵ and R ⁶ are each independently Represents an alkylene group having 1 to 20 carbon atoms, m and n each independently represent an integer of 1 to 3, (m + n) represents an integer of 4 or more, and R ⁷ represents an integer of 1 to 20 represents an alkyl group having 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a silyl group substituted with a hydrocarbon group, and when there are a plurality of R ^{1 to} R ⁴ each independently.   The modifier is represented by the formula (1), m is 2, and n is 3, or the formula (2), and m, n, and l are all 3. The modified diene polymer composition according to claim 9, which is a modifier. The modified diene polymer composition according to any one of claims 8 to 10, wherein the organolithium compound includes an organolithium compound represented by any one of the following general formulas (14) to (17). object.

(In the formula (14), R ₁₀ and R ₁₁ 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. R ₁₀ and R ₁₁ may be bonded to form a cyclic structure with the adjacent nitrogen atom, and in this case, R ₁₀ and R ₁₁ have 5 to 12 carbon atoms. It represents a hydrocarbon group, and a part thereof may have an unsaturated bond or a branched structure.)

(In the formula (15), R ₁₂ and R ₁₃ are each independently an alkyl group having 1 to 12 carbon atoms, cycloalkyl of 3 to 14 carbon atoms, and the group consisting of aralkyl group having 6 to 20 carbon atoms R ₁₂ and R ₁₃ may be bonded to form a cyclic structure with an adjacent nitrogen atom, and R ₁₂ and R _{13 in} this case are each having 5 to 12 carbon atoms. R ₁₄ represents a hydrocarbon group and may have an unsaturated bond or a branched structure in a part of the hydrocarbon group, R ₁₄ is an alkylene group having 1 to 20 carbon atoms, or a divalent compound based on a conjugated diene compound having 4 to 20 carbon atoms. Represents a valent group.)

(In the formula (16), R ₁₅ and R ₁₆ 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 aryl group having 6 to 20 carbon atoms. R ₁₅ and R ₁₆ may be bonded to form a cyclic structure with an adjacent nitrogen atom, and R ₁₅ and R _{16 in} this case are bonded to form a carbon number of 5; Represents an alkylene group of ˜12, and a part thereof may have a branched structure.)

(In the formula (17), R ₁₇ represents a hydrocarbon group having 2 to 10 carbon atoms, and a part thereof may have an unsaturated bond or a branched structure. R ₁₈ has 1 to 12 carbon atoms. And may have a branched structure in a part thereof.)   The one-end modified conjugated diene polymer (ii) is an alkoxy bonded to a silyl group at the polymerization active terminal of a conjugated diene copolymer obtained by copolymerizing a conjugated diene compound and an aromatic vinyl compound. The total number of groups is 4 or more, and is a one-end-modified conjugated diene copolymer obtained by reacting a modifying agent having one or more nitrogen atoms. Modified diene polymer composition.   Any one of Claims 1-12 containing 0.5-300 mass parts of said (iii) silica type inorganic fillers with respect to a total of 100 mass parts of said rubber component (I) and said rubber-like polymer (B). The modified diene polymer composition according to one item.   14. The composition according to claim 1, further comprising (2) 0.5 to 100 parts by mass of carbon black with respect to a total of 100 parts by mass of the rubber component (A) and the rubbery polymer (B). The modified diene polymer composition as described.   The modified diene polymer composition according to any one of claims 1 to 14, which is a rubber composition for a tire sidewall.   A tire comprising a crosslinked product of the modified diene polymer composition according to any one of claims 1 to 15.