JP2016017097A - Modified conjugated diene-based polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a modified conjugated diene-based polymer composition which allows even a silica-based inorganic filler-containing vulcanized product obtained therefrom to have an excellent balance between low hysteresis loss properties and wet skid resistance or excellent fracture strength and satisfy practically-sufficient processability, wear resistance and even drive stability.SOLUTION: The modified conjugated diene-based polymer composition contains: a modified conjugated diene-based copolymer (A) which has a functional group shown by a predetermined general formula at one end thereof and an alkoxysilyl group and an amine-containing functional group at another end thereof, which end is made different from the end having the group shown by the predetermined general formula and which contains an aromatic vinyl compound-derived unit; and a modified conjugated diene-based polymer (B) which has the functional group shown by the predetermined general formula at one end thereof and the alkoxysilyl group and the amine-containing functional group at another end thereof, which end is made different from the end having the group shown by the predetermined general formula and which does not contain the aromatic vinyl compound-derived unit.SELECTED DRAWING: None

Description

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

  In recent years, environmental considerations such as the suppression of carbon dioxide emissions have become social demands. Specifically, demands for reducing fuel consumption for automobiles are increasing. Under such circumstances, there has been a demand for the development of a material having low rolling resistance as a material for automobile tires, particularly tire treads in contact with the ground.

  On the other hand, from the viewpoint of safety, development of materials having excellent wet skid resistance and practically sufficient wear resistance and fracture characteristics is required. Conventionally, carbon black, silica, and the like have been used as reinforcing fillers for tire treads.

  When silica is used, there is an advantage that low hysteresis loss and wet skid resistance can be improved. On the other hand, since silica with a hydrophilic surface has a low affinity with a conjugated diene rubber and has a disadvantage of poor dispersibility compared with carbon black, with respect to carbon black with a hydrophobic surface, In order to improve dispersibility or to provide a bond between silica and rubber, a silane coupling agent must be added separately.

  Furthermore, in recent years, the dispersibility of silica in rubber materials has been improved by introducing functional groups having affinity and reactivity with silica at the end of rubber molecules having high mobility. Attempts have been made to reduce hysteresis loss by sealing the part with a bond with silica particles.

  For example, conventionally, a modified diene rubber obtained by reacting a modifier having a glycidylamino group with a polymer end (see, for example, Patent Document 1) or a glycidoxyalkoxysilane reacted with a polymer end. Modified diene rubber obtained (for example, see Patent Document 2), and further modified diene rubber obtained by reacting an alkoxysilane containing an amino group with the polymer terminal (for example, see Patent Documents 3 and 4), And proposals for compositions of these with silica.

  In addition, the diene rubber is polymerized by using a polyfunctional anionic polymerization initiator and then modified with a modifier such as a glycidylamino group to increase the number of functionalized polymer ends. A technique for improving the performance of a composition composed of silica and silica, that is, silica dispersibility and reducing hysteresis loss (see, for example, Patent Document 5) has also been proposed.

International Publication No.01 / 23467 Japanese Patent Application Laid-Open No. 07-233217 JP 2001-158834 A JP 2003-171418 A JP 2006-306962 A

  However, with the further increase in demand for fuel efficiency in recent years, development of a rubber composition with further reduced hysteresis loss has been required. Moreover, since the dispersibility of silica increases, the rigidity or dynamic elastic modulus decreases, and the steering stability tends to deteriorate. Therefore, there is a need for a modified diene rubber that improves the balance of low hysteresis loss and wet skid resistance by improving the dispersibility of silica and further suppresses the decrease in dynamic elastic modulus.

  The present invention has been made in view of the above-described problems of the prior art, and is excellent in balance between low hysteresis loss and wet skid resistance and fracture strength even when a vulcanizate containing a silica-based inorganic filler is used. Another object of the present invention is to provide a modified conjugated diene polymer composition that also satisfies practically sufficient processability, wear resistance, and steering stability.

  As a result of intensive studies to solve the above problems, the inventors of the present invention include a composition containing a modified conjugated diene copolymer (A) having a specific terminal and a modified conjugated diene polymer (B) having a specific terminal. Even if it contains inorganic fillers, especially silica-based inorganic fillers, and even vulcanized products, it has an excellent balance between low hysteresis loss and wet skid resistance and fracture strength, and is practically sufficient. As a result, it was found that satisfactory processability, wear resistance, and steering stability can be satisfied, and the present invention has been completed.

（前記一般式（１）中、Ｒ１及びＲ２は、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択されるいずれかであり、同一であっても異なっていてもよい。ここで、Ｒ１及びＲ２は、結合して隣接した窒素原子とともに環状構造を形成していてもよく、その場合のＲ１及びＲ２は、合計の炭素数が４〜１２の炭化水素基である。Ｒ１及びＲ２は、不飽和結合を有していても、分岐構造を有していてもよい。）。
［２］
前記変性共役ジエン系共重合体（Ａ）及び前記変性共役ジエン系重合体（Ｂ）が、それぞれ下記一般式（２）〜（８）のいずれかで表される、［１］に記載の変性共役ジエン系重合体組成物：

（前記一般式（２）中、Ｒ３〜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のアリール基であり、Ｒ７及びＲ８は、各々独立して、炭素数１〜２０のアルキレン基であり、Ｒ９は水素又は炭化水素で置換されたシリル基である。ａ及びｃは、各々独立して１又は２の整数であり、ｂ及びｄは、各々独立して０又は１の整数であり、ａ＋ｂ及びｃ＋ｄは２以下の整数である。ここで、一般式（２）が変性共役ジエン系共重合体（Ａ）である場合、Ｐｏｌｙｍは、芳香族ビニル化合物由来の単位を含む共役ジエン系共重合体であり、一般式（２）が変性共役ジエン系重合体（Ｂ）である場合、Ｐｏｌｙｍは、芳香族ビニル化合物由来の単位を含まない共役ジエン系重合体であり、Ｐｏｌｙｍの少なくとも一つの末端が前記一般式（１）で表される官能基である。Ｒ３〜Ｒ６が複数存在するときは、それらは各々同一であっても異なっていてもよい。）

（前記一般式（３）中、Ｒ１０〜Ｒ１３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のアリール基であり、Ｒ１４及びＲ１５は、各々独立して炭素数１〜２０のアルキレン基であり、ｅ及びｇは、各々独立して０〜２の整数であり、ｅ又はｇのどちらかが１以上である。ｆ及びｈは、各々独立して０又は１の整数であり、ｅ＋ｆ及びｇ＋ｈは２以下の整数である。ここで、一般式（３）が変性共役ジエン系共重合体（Ａ）である場合、Ｐｏｌｙｍは、芳香族ビニル化合物由来の単位を含む共役ジエン系共重合体であり、一般式（３）が変性共役ジエン系重合体（Ｂ）である場合、Ｐｏｌｙｍは、芳香族ビニル化合物由来の単位を含まない共役ジエン系重合体であり、複数あってもよいＰｏｌｙｍの少なくとも一つの末端が前記一般式（１）で表される官能基である。ｉは０〜２０の整数であり、ｉが２以上の場合、（Ｒ１４−Ａ１−Ｒ１５）で表される複数の繰り返し単位は、同じであってもよく相異なるものであってもよい。Ａ１は下記一般式（ａ）、（ｂ）、（ｃ）のいずれかで表される基である。Ｒ１０〜Ｒ１３が複数存在するときは、それらは各々同一であっても異なっていてもよい。）

（前記一般式（ａ）において、Ｒ１６及びＲ１７は、各々独立して、炭素数１〜２０のアルキレン基であり、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。）

（前記一般式（ｂ）において、Ｒ１８は炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基及び活性水素を持たないヘテロ原子で置換されている炭素数１〜２０の炭化水素基からなる群より選ばれるいずれかである。）

（前記一般式（ｃ）において、Ｒ１８は炭素数１〜２０のアルキレン基であり、Ｒ１９及びＲ２０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のアリール基である。ｊは０〜２の整数であり、ｋは０又は１の整数であり、ｊ＋ｋは２以下の整数である。ここで、一般式（３）が変性共役ジエン系共重合体（Ａ）である場合、Ｐｏｌｙｍは、芳香族ビニル化合物由来の単位を含む共役ジエン系共重合体であり、一般式（３）が変性共役ジエン系重合体（Ｂ）である場合、Ｐｏｌｙｍは、芳香族ビニル化合物由来の単位を含まない共役ジエン系重合体であり、複数あってもよいＰｏｌｙｍの少なくとも一つの末端が前記一般式（１）で表される官能基である。Ｒ１９、Ｒ２０が複数存在するときは、それらは各々同一であっても異なっていてもよい。）

（前記一般式（４）中、Ｒ２１、Ｒ２２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のアリール基であり、Ｒ２３、Ｒ２４は、各々独立して、炭素数１〜２０のアルキレン基であり、Ｒ２５、Ｒ２６、Ｒ２７は、各々独立して、Ｓｉ、Ｏ又はＮを含み、活性水素を持たない有機基で置換されていてもよい炭素数１〜２０の炭化水素基である。ｌは１又は２の整数であり、ｍは０又は１の整数であり、ｌ＋ｍは２以下の整数である。ここで、一般式（４）が変性共役ジエン系共重合体（Ａ）である場合、Ｐｏｌｙｍは、芳香族ビニル化合物由来の単位を含む共役ジエン系共重合体であり、一般式（４）が変性共役ジエン系重合体（Ｂ）である場合、Ｐｏｌｙｍは、芳香族ビニル化合物由来の単位を含まない共役ジエン系重合体であり、複数あってもよいＰｏｌｙｍの少なくとも一つの末端が前記一般式（１）で表される官能基である。Ｒ２１、Ｒ２２が複数存在するときは、それらは各々同一であっても異なっていてもよい。）

（前記一般式（５）中、Ｒ２８、Ｒ２９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のアリール基であり、Ｒ３０は炭素数１〜２０のアルキレン基であり、Ｒ３１、Ｒ３２は、各々独立して炭素数１〜６の２価の炭化水素基であって、隣接する２つのＮとともに５員環以上の環構造をなし、Ｒ３３は炭素数１〜２０の炭化水素基、活性水素を持たないヘテロ原子で置換されている炭素数１〜２０の炭化水素基、又は３有機置換シリル基であり、ｎは１又は２の整数であり、ｏは０又は１の整数であり、ｎ＋ｏは２以下の整数である。ここで、一般式（５）が変性共役ジエン系共重合体（Ａ）である場合、Ｐｏｌｙｍは、芳香族ビニル化合物由来の単位を含む共役ジエン系共重合体であり、一般式（５）が変性共役ジエン系重合体（Ｂ）である場合、Ｐｏｌｙｍは、芳香族ビニル化合物由来の単位を含まない共役ジエン系重合体であり、複数あってもよいＰｏｌｙｍの少なくとも一つの末端が前記一般式（１）で表される官能基である。Ｒ２８、Ｒ２９が複数存在するときは、それらは各々同一であっても異なっていてもよい。）

（前記一般式（６）中、Ｒ３４、Ｒ３５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のアリール基であり、Ｒ３６は炭素数１〜２０のアルキレン基であり、Ｒ３７、Ｒ３８は、各々独立して炭素数１〜６の２価の炭化水素基であって、隣接する２つのＮとともに５員環以上の環構造をなし、Ｒ３９、Ｒ４０は、各々独立して炭素数１〜２０の炭化水素基、活性水素を持たないヘテロ原子で置換されている炭素数１〜２０の炭化水素基、又は３有機置換シリル基であり、ｍは１又は２の整数であり、ｑは０又は１の整数であり、ｐ＋ｑは２以下の整数である。ここで、一般式（６）が変性共役ジエン系共重合体（Ａ）である場合、Ｐｏｌｙｍは、芳香族ビニル化合物由来の単位を含む共役ジエン系共重合体であり、一般式（６）が変性共役ジエン系重合体（Ｂ）である場合、Ｐｏｌｙｍは、芳香族ビニル化合物由来の単位を含まない共役ジエン系重合体であり、複数あってもよいＰｏｌｙｍの少なくとも一つの末端が前記一般式（１）で表される官能基である。Ｒ３４、Ｒ３５が複数存在するときは、それらは各々同一であっても異なっていてもよい。）

（前記一般式（７）において、Ａ２は三級アミン、ピリジン、シアン及びイミンからなる群より選ばれる少なくとも一種の官能基を有する一価の基であり、Ｒ４１及びＲ４２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のアリール基であり、Ｒ４３は炭素数１〜２０のアルキレン基である。ｒは１又は２の整数であり、ｓは０又は１の整数である。ここで、一般式（７）が変性共役ジエン系共重合体（Ａ）である場合、Ｐｏｌｙｍは、芳香族ビニル化合物由来の単位を含む共役ジエン系共重合体であり、一般式（７）が変性共役ジエン系重合体（Ｂ）である場合、Ｐｏｌｙｍは、芳香族ビニル化合物由来の単位を含まない共役ジエン系重合体であり、複数あってもよいＰｏｌｙｍの少なくとも一つの末端が前記一般式（１）で表される官能基である。Ｒ４１、Ｒ４２が複数存在するときは、それらは各々同一であっても異なっていてもよい。）

（前記一般式（８）において、Ｒ４４は炭素数１〜２０のアルキル基又は炭素数６〜２０のアリール基であり、Ｒ４５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素数１〜２０のアルコキシ基であり、Ｒ４６は炭素数１〜２０のアルキレン基である。Ｒ４７及びＲ４８は、各々独立に水素であるか、炭化水素で置換されたシリル基である。ｔは１〜２の整数であり、ｕは０〜１の整数であり、ｖは１〜１０の整数である。ｗはｖが１の時は３−ｔ−ｕであり、ｖが２以上のときは２−ｔである。ここで、一般式（８）が変性共役ジエン系共重合体（Ａ）である場合、Ｐｏｌｙｍは、芳香族ビニル化合物由来の単位を含む共役ジエン系共重合体であり、一般式（８）が変性共役ジエン系重合体（Ｂ）である場合、Ｐｏｌｙｍは、芳香族ビニル化合物由来の単位を含まない共役ジエン系重合体であり、複数あってもよいＰｏｌｙｍの少なくとも一つの末端が前記一般式（１）で表される官能基である。Ｒ４４、Ｒ４５が複数存在するときは、それらは各々同一であっても異なっていてもよい。）。
［３］
リチウムアミド化合物を用いて、炭化水素溶媒中、共役ジエン化合物と芳香族ビニル化合物とを共重合させた後、得られた重合体の活性末端に、２つ以上のアルコキシ基で置換されたシリル基と１つ以上の窒素原子を有する化合物を反応させて得られた変性共役ジエン系共重合体（Ａ１）と、
リチウムアミド化合物を用いて、炭化水素溶媒中、共役ジエン化合物を重合させた後、得られた重合体の活性末端に、２つ以上のアルコキシ基で置換されたシリル基と１つ以上の窒素原子を有する化合物とを反応させて得られた変性共役ジエン重合体（Ｂ１）と、
を含む、変性共役ジエン系重合体組成物。
［４］
２つ以上のアルコキシ基で置換されたシリル基と１つ以上の窒素原子を有する化合物が、下記一般式（１１）〜（１８）のいずれかで表される化合物である、［３］に記載の変性共役ジエン系重合体組成物。

（前記一般式（１１）中、Ｒ５１〜Ｒ５４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、Ｒ５８及びＲ５９は、各々独立して、炭素数１〜２０のアルキレン基を表し、ｍ１は１又は２の整数であり、ｎ１は２又は３の整数である。ここで、Ｒ５１〜Ｒ５４が複数存在するときは、それらは各々同一であっても異なっていてもよい。）

（前記一般式（１２）中、Ｒ６１〜Ｒ６４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、Ｒ６８及びＲ６９は、各々独立して、炭素数１〜２０のアルキレン基を表し、Ｒ６８、Ｒ６９及びＡ６１が複数存在するときは、それらは各々同一であっても異なっていてもよい。ｍ２及びｎ２は、それぞれ０〜３の整数である。ｐ２は０〜２０の整数であり、ｐ２が２以上の場合、（Ｒ６９−Ａ６１−Ｒ６８）で表される複数の繰り返し単位は、相異なるものであってもよい。Ｒ６１〜Ｒ６４が、複数存在するときは、それらは、各々同一であっても異なっていてもよい。Ａ６１は下記一般式（ｄ）、（ｅ）、（ｆ）のいずれかで表される基である。）

（前記一般式（ｄ）において、Ｒ７０及びＲ７１は、各々独立して、炭素数１〜２０のアルキレン基であり、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。）

（前記一般式（ｅ）において、Ｒ８７は炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、活性水素を持たないヘテロ原子で置換されている炭素数１〜２０の炭化水素基、及び３有機置換シリル基からなる群より選ばれるいずれかである。）

（前記一般式（ｆ）において、Ｒ９０は炭素数１〜２０のアルキレン基であり、Ｒ９５及びＲ９６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のアリール基である。ｒ１は０〜３の整数である。）

（前記一般式（１３）中、Ｒ１０１、Ｒ１０２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、Ｒ１０８、Ｒ１０９は、各々独立して、炭素数１〜２０のアルキレン基を表し、Ｒ１１２、Ｒ１１３、Ｒ１１４は、各々独立して、Ｓｉ、Ｏ、又はＮを含み、活性水素を持たない有機基で置換されていてもよい炭素数１〜２０の炭化水素基である。ｉ３は１〜３の整数である。Ｒ１０１、Ｒ１０２が、複数存在するときは、それらは、各々同一であっても異なっていてもよい。）

（前記一般式（１４）中、Ｒ２０１、Ｒ２０２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のアリール基であり、Ｒ２０９は炭素数１〜２０のアルキレン基であり、Ｒ２１０、Ｒ２１１は、各々独立して、炭素数１〜６の２価の炭化水素基であって、隣接する２つのＮとともに５員環以上の環構造をなし、Ｒ２１５は炭素数１〜２０の炭化水素基、活性水素を持たないヘテロ原子で置換されている炭素数１〜２０の炭化水素基、又は３有機置換シリル基であり、ｍ４は２又は３の整数である。Ｒ２０１、Ｒ２０２が、複数存在するときは、それらは、各々同一であっても異なっていてもよい。）

（前記一般式（１５）中、Ｒ３０１、Ｒ３０２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のアリール基であり、Ｒ３０９は炭素数１〜２０のアルキレン基であり、Ｒ３１０、Ｒ３１１は、各々独立して、炭素数１〜６の２価の炭化水素基であって、隣接する２つのＮとともに５員環以上の環構造をなし、Ｒ３１５、Ｒ３１６は、各々独立して、炭素数１〜２０の炭化水素基、活性水素を持たないヘテロ原子で置換されている炭素数１〜２０の炭化水素基、又は３有機置換シリル基であり、ｍ５は２又は３の整数である。Ｒ３０１、Ｒ３０２が複数存在するときは、それらは各々同一であっても異なっていてもよい。）

（前記一般式（１６）において、Ａ４００は三級アミン、ピリジン、シアン、イミンからなる群より選ばれる少なくとも一種の官能基を有する一価の基であり、Ｒ４０１及びＲ４０２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のアリール基であり、Ｒ４０８は炭素数１〜２０のアルキレン基である。ｍ６は２又は３の整数である。Ｒ４０１、Ｒ４０２が複数存在するときは、それらは各々同一であっても異なっていてもよい。）

（前記一般式（１７）において、Ｒ５０１、Ｒ５０２、Ｒ５０６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、Ｒ５０８は炭素数１〜２０のアルキレン基を表す。Ｒ５０３、Ｒ５０４及びＲ５０５は、各々独立に炭素数１〜２０のアルキル基又はアリール基であるか、又はそれらの２つは互いに結合してそれらが結合しているケイ素原子とともに環を形成してもよい。ｍ７は１〜２の整数であり、ｆ７は１〜１０の整数である。Ｒ５０１〜Ｒ５０５、Ｒ５０８が、複数存在するときは、それらは、各々同一であっても異なっていてもよい。）

（前記一般式（１８）において、Ｒ６０１、Ｒ６０２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、Ｒ６０８は炭素数１〜２０のアルキレン基を表す。Ｒ６０３、Ｒ６０４及びＲ６０５は、各々独立に炭素数１〜２０のアルキル基又はアリール基であるか、又はそれらの２つは互いに結合してそれらが結合しているケイ素原子とともに環を形成してもよい。ｍ８は１〜２の整数である。Ｒ６０１は、各々同一であっても異なっていてもよい。）。
［５］
前記変性共役ジエン系共重合体（Ａ）及び前記変性共役ジエン系重合体（Ｂ）の合計１００質量部に対して、シリカ系無機充填剤０．５〜３００質量部をさらに含む、［１］〜［４］のいずれかに記載の変性共役ジエン系重合体組成物。
［６］
前記変性共役ジエン系共重合体（Ａ）及び前記変性共役ジエン系重合体（Ｂ）の合計１００質量部に対してシリカ系無機充填剤７５質量部をさらに含む変性共役ジエン系重合体組成物であって、当該変性共役ジエン系重合体組成物を加硫物とした際、５０℃、周波数１０Ｈｚにおける、ひずみ０．１％と１０％で測定した貯蔵弾性率の差（ΔＧ´）が、０．８ＭＰａ以下である、［１］〜［４］のいずれかに記載の変性共役ジエン系重合体組成物。 The present invention is as follows.
[1]
It has a functional group represented by the following general formula (1) at the terminal and an alkoxysilyl group and an amine at a terminal different from the terminal having the functional group represented by the following general formula (1). A modified conjugated diene copolymer (A) having a functional group and a unit derived from an aromatic vinyl compound;
It has a functional group represented by the following general formula (1) at the terminal and an alkoxysilyl group and an amine at a terminal different from the terminal having the functional group represented by the following general formula (1). A modified conjugated diene polymer (B) having a functional group that does not contain a unit derived from an aromatic vinyl compound, and
Modified conjugated diene polymer composition containing:

(In the general formula (1), R1 and R2 are any 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. R1 and R2 may be bonded to form a cyclic structure with the adjacent nitrogen atom, in which case R1 and R2 are the total of It is a hydrocarbon group having a carbon number of 4 to 12. R1 and R2 may have an unsaturated bond or a branched structure.
[2]
The modification according to [1], wherein the modified conjugated diene copolymer (A) and the modified conjugated diene polymer (B) are each represented by any one of the following general formulas (2) to (8). Conjugated diene polymer composition:

(In the general formula (2), R3 to R6 are each independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R7 and R8 are each independently carbon. An alkylene group having a number of 1 to 20, R9 is a silyl group substituted with hydrogen or hydrocarbon, a and c are each independently an integer of 1 or 2, and b and d are each independently And a + b and c + d are integers equal to or less than 2. Here, when the general formula (2) is the modified conjugated diene copolymer (A), Polym is an aromatic vinyl compound. When the general formula (2) is a modified conjugated diene polymer (B), Polym is a conjugated diene-based polymer containing no unit derived from an aromatic vinyl compound. And at least one end of Polym is When serial is a functional group represented by the general formula (1) .R3~R6 there are multiple, they may be each independently selected from the same.)

(In the general formula (3), R10 to R13 are each independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R14 and R15 are each independently a carbon number. 1 to 20 alkylene groups, e and g are each independently an integer of 0 to 2, and either e or g is 1 or more, and f and h are each independently 0 or 1 E + f and g + h are integers equal to or less than 2. Here, when the general formula (3) is the modified conjugated diene copolymer (A), Polym is a unit derived from an aromatic vinyl compound. When the general formula (3) is a modified conjugated diene polymer (B), Polym is a conjugated diene polymer that does not contain a unit derived from an aromatic vinyl compound, At least one end of Polym which may be plural Is a functional group represented by the general formula (1), i is an integer of 0 to 20, and when i is 2 or more, the plurality of repeating units represented by (R14-A1-R15) are: A1 is a group represented by any one of the following general formulas (a), (b), and (c), and when there are a plurality of R10 to R13. Each may be the same or different.)

(In the general formula (a), R16 and R17 are each independently an alkylene group having 1 to 20 carbon atoms, and together with two adjacent Ns, form a ring structure of five or more members.)

(In the general formula (b), R18 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a hydrocarbon group having 1 to 20 carbon atoms substituted with a hetero atom having no active hydrogen. Any one selected from the group consisting of

(In the general formula (c), R18 is an alkylene group having 1 to 20 carbon atoms, and R19 and R20 are each independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. J is an integer of 0 to 2, k is an integer of 0 or 1, and j + k is an integer of 2 or less, wherein the general formula (3) is a modified conjugated diene copolymer (A) In this case, Polym is a conjugated diene copolymer containing a unit derived from an aromatic vinyl compound, and when General Formula (3) is a modified conjugated diene polymer (B), Polym is an aromatic vinyl. It is a conjugated diene polymer that does not contain a compound-derived unit, and at least one terminal of Polym may be a functional group represented by the general formula (1) When there are a plurality of R19 and R20 They are each identical And it may be different as well.)

(In the general formula (4), R21 and R22 are each independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R23 and R24 are each independently carbon. An alkylene group having 1 to 20 carbon atoms, and R25, R26, and R27 each independently include Si, O, or N, and may be substituted with an organic group having no active hydrogen. A hydrocarbon group, wherein l is an integer of 1 or 2, m is an integer of 0 or 1, and l + m is an integer of 2 or less, wherein the general formula (4) is a modified conjugated diene-based copolymer In the case of the compound (A), Polym is a conjugated diene copolymer containing units derived from an aromatic vinyl compound, and when the general formula (4) is a modified conjugated diene polymer (B), Polym is Conjugated dienes that do not contain units derived from aromatic vinyl compounds At least one terminal of the polym that is a combination and may be a plurality is a functional group represented by the general formula (1) When there are a plurality of R21 and R22, they may be the same or different. May be.)

(In the general formula (5), R28 and R29 are each independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R30 is an alkylene group having 1 to 20 carbon atoms. , R31 and R32 are each independently a divalent hydrocarbon group having 1 to 6 carbon atoms, and together with two adjacent Ns, form a ring structure of five or more members, and R33 has 1 to 20 carbon atoms. A hydrocarbon group, a hydrocarbon group having 1 to 20 carbon atoms substituted with a heteroatom having no active hydrogen, or an organically substituted silyl group, n is an integer of 1 or 2, and o is 0 or 1 N + o is an integer equal to or less than 2. Here, when the general formula (5) is the modified conjugated diene copolymer (A), Polym is a conjugate containing a unit derived from an aromatic vinyl compound. This is a diene copolymer, and the general formula (5) is a modified conjugated diene. In the case of the polymer (B), Polym is a conjugated diene polymer that does not contain a unit derived from an aromatic vinyl compound, and at least one terminal of the Polym that may be plural is represented by the general formula (1). When there are a plurality of R28 and R29, they may be the same or different.)

(In the general formula (6), R34 and R35 are each independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R36 is an alkylene group having 1 to 20 carbon atoms. , R37 and R38 are each independently a divalent hydrocarbon group having 1 to 6 carbon atoms, and form a ring structure of 5 or more members with two adjacent Ns, and R39 and R40 each independently And a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms substituted with a heteroatom having no active hydrogen, or a 3 organic substituted silyl group, m is an integer of 1 or 2 And q is an integer of 0 or 1, and p + q is an integer of 2 or less, where, when general formula (6) is a modified conjugated diene copolymer (A), Polym is an aromatic vinyl Conjugated diene copolymer containing a compound-derived unit When 6) is a modified conjugated diene polymer (B), Polym is a conjugated diene polymer that does not contain a unit derived from an aromatic vinyl compound, and at least one terminal of Polym, which may be plural, is the above-mentioned This is a functional group represented by the general formula (1) .When there are a plurality of R34 and R35, they may be the same or different.

(In the general formula (7), A2 is a monovalent group having at least one functional group selected from the group consisting of a tertiary amine, pyridine, cyan and imine, and R41 and R42 are each independently, An alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, R43 is an alkylene group having 1 to 20 carbon atoms, r is an integer of 1 or 2, and s is an integer of 0 or 1. Here, when the general formula (7) is the modified conjugated diene copolymer (A), Polym is a conjugated diene copolymer containing a unit derived from an aromatic vinyl compound, and the general formula ( When 7) is a modified conjugated diene polymer (B), Polym is a conjugated diene polymer that does not contain a unit derived from an aromatic vinyl compound, and at least one terminal of Polym may be plural. General formula 1) it is a functional group represented by .R41, when R42 is plurally present, they may be each independently selected from the same.)

(In the general formula (8), R44 is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R45 is an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms. Or an alkoxy group having 1 to 20 carbon atoms, and R46 is an alkylene group having 1 to 20 carbon atoms, and R47 and R48 are each independently hydrogen or a silyl group substituted with a hydrocarbon. Is an integer from 1 to 2, u is an integer from 0 to 1, v is an integer from 1 to 10. w is 3-tu when v is 1, and v is 2 or more. Here, when general formula (8) is a modified conjugated diene copolymer (A), Polym is a conjugated diene copolymer containing units derived from an aromatic vinyl compound. Yes, when the general formula (8) is a modified conjugated diene polymer (B), Pol m is a conjugated diene polymer containing no unit derived from an aromatic vinyl compound, and at least one terminal of Polym, which may be plural, is a functional group represented by the general formula (1) R44, When a plurality of R45 are present, they may be the same or different.
[3]
A silyl group in which a conjugated diene compound and an aromatic vinyl compound are copolymerized in a hydrocarbon solvent using a lithium amide compound, and then substituted at the active terminal of the polymer with two or more alkoxy groups And a modified conjugated diene copolymer (A1) obtained by reacting a compound having one or more nitrogen atoms,
After polymerizing a conjugated diene compound in a hydrocarbon solvent using a lithium amide compound, a silyl group substituted with two or more alkoxy groups and one or more nitrogen atoms at the active terminal of the obtained polymer A modified conjugated diene polymer (B1) obtained by reacting a compound having
A modified conjugated diene polymer composition comprising:
[4]
[3] The compound having a silyl group substituted with two or more alkoxy groups and one or more nitrogen atoms is a compound represented by any one of the following general formulas (11) to (18). Modified conjugated diene polymer composition.

(In the general formula (11), R51 to R54 each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R58 and R59 each independently represent carbon. Represents an alkylene group of 1 to 20, m1 is an integer of 1 or 2, and n1 is an integer of 2 or 3. Here, when there are a plurality of R51 to R54, they are the same. May be different.)

(In the general formula (12), R61 to R64 each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R68 and R69 each independently represent carbon. Represents an alkylene group of 1 to 20, and when a plurality of R68, R69 and A61 are present, they may be the same or different, and m2 and n2 are each an integer of 0 to 3. p2 is an integer of 0 to 20, and when p2 is 2 or more, the plurality of repeating units represented by (R69-A61-R68) may be different from each other. And each of them may be the same or different, and A61 is a group represented by any one of the following general formulas (d), (e), and (f).)

(In the general formula (d), R70 and R71 are each independently an alkylene group having 1 to 20 carbon atoms, and together with two adjacent Ns, form a ring structure of five or more members.)

(In the general formula (e), R87 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms substituted by a hetero atom having no active hydrogen. And any one selected from the group consisting of three organic substituted silyl groups.)

(In the general formula (f), R90 is an alkylene group having 1 to 20 carbon atoms, and R95 and R96 are each independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. R1 is an integer of 0 to 3.)

(In the general formula (13), R101 and R102 each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R108 and R109 each independently represent carbon. Represents an alkylene group having 1 to 20 carbon atoms, and R112, R113, and R114 each independently contains Si, O, or N, and may be substituted with an organic group having no active hydrogen. I3 is an integer of 1 to 3. When a plurality of R101 and R102 are present, they may be the same or different.

(In the general formula (14), R201 and R202 are each independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R209 is an alkylene group having 1 to 20 carbon atoms. , R210, and R211 are each independently a divalent hydrocarbon group having 1 to 6 carbon atoms, and together with two adjacent Ns, form a ring structure of five or more members, and R215 has 1 to 20 carbon atoms. A hydrocarbon group having 1 to 20 carbon atoms substituted with a hetero atom having no active hydrogen, or a 3 organic substituted silyl group, m4 is an integer of 2 or 3. R201 and R202 are , When there are a plurality, they may be the same or different.)

(In the general formula (15), R301 and R302 are each independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R309 is an alkylene group having 1 to 20 carbon atoms. , R310 and R311 are each independently a divalent hydrocarbon group having 1 to 6 carbon atoms, and together with two adjacent Ns, form a ring structure of five or more members, and R315 and R316 each independently And a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms substituted with a heteroatom having no active hydrogen, or a 3 organic substituted silyl group, and m5 is 2 or 3 (When there are a plurality of R301 and R302, they may be the same or different.)

(In the general formula (16), A400 is a monovalent group having at least one functional group selected from the group consisting of tertiary amine, pyridine, cyan, and imine, and R401 and R402 are each independently An alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, R408 is an alkylene group having 1 to 20 carbon atoms, m6 is an integer of 2 or 3. There are a plurality of R401 and R402. Sometimes they may be the same or different.)

(In the general formula (17), R501, R502 and R506 each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R508 represents an alkylene having 1 to 20 carbon atoms. R503, R504 and R505 are each independently an alkyl group or aryl group having 1 to 20 carbon atoms, or two of them are bonded to each other to form a ring together with the silicon atom to which they are bonded. M7 is an integer of 1 to 2, and f7 is an integer of 1 to 10. When a plurality of R501 to R505 and R508 are present, they may be the same or different. May be.)

(In the general formula (18), R601 and R602 each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R608 represents an alkylene group having 1 to 20 carbon atoms. R603, R604 and R605 are each independently an alkyl group or aryl group having 1 to 20 carbon atoms, or two of them are bonded to each other to form a ring together with the silicon atom to which they are bonded. M8 is an integer of 1 to 2. R601 may be the same or different.
[5]
It further includes 0.5 to 300 parts by mass of a silica-based inorganic filler with respect to 100 parts by mass in total of the modified conjugated diene copolymer (A) and the modified conjugated diene polymer (B) [1] -Modified conjugated diene polymer composition according to any one of [4].
[6]
A modified conjugated diene polymer composition further comprising 75 parts by mass of a silica-based inorganic filler with respect to a total of 100 parts by mass of the modified conjugated diene copolymer (A) and the modified conjugated diene polymer (B). When the modified conjugated diene polymer composition was vulcanized, the difference in storage modulus (ΔG ′) measured at a strain of 0.1% and 10% at 50 ° C. and a frequency of 10 Hz was 0. The modified conjugated diene polymer composition according to any one of [1] to [4], which is 8 MPa or less.

  According to the present invention, even when it is a vulcanizate containing a silica-based inorganic filler, it is excellent in balance between low hysteresis loss and wet skid resistance and fracture strength, practically sufficient workability, wear resistance, Provided is a modified conjugated diene polymer composition that also satisfies steering stability.

  Hereinafter, modes for carrying out the present invention (hereinafter referred to as the present embodiment) will be described in detail. The present invention is not limited to this embodiment, and can be implemented with various modifications within the scope of the gist.

[Modified Conjugated Diene Polymer Composition]
The modified conjugated diene polymer composition in the present embodiment includes a modified conjugated diene copolymer (A) and a modified conjugated diene polymer (B). That is, the modified conjugated diene polymer composition in this embodiment has a functional group represented by the following general formula (1) at a terminal and a functional group represented by the following general formula (1). A modified conjugated diene copolymer (A) having a functional group containing an alkoxysilyl group and an amine at a terminal different from the terminal and containing a unit derived from an aromatic vinyl compound, and the following at the terminal: A functional group having an alkoxysilyl group and an amine at a terminal different from the terminal having a functional group represented by the general formula (1) and having a functional group represented by the following general formula (1) And a modified conjugated diene polymer (B) containing no unit derived from an aromatic vinyl compound.

（前記一般式（１）中、Ｒ１及びＲ２は、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択されるいずれかであり、同一であっても異なっていてもよい。ここで、Ｒ１及びＲ２は、結合して隣接した窒素原子とともに環状構造を形成していてもよく、その場合のＲ１及びＲ２は、合計の炭素数が４〜１２の炭化水素基である。）

(In the general formula (1), R1 and R2 are any 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. R1 and R2 may be bonded to form a cyclic structure with the adjacent nitrogen atom, in which case R1 and R2 are the total of (It is a hydrocarbon group having 4 to 12 carbon atoms.)

(Modified Conjugated Diene Copolymer (A) and Modified Conjugated Diene Polymer (B))
The modified conjugated diene copolymer (A) and the modified conjugated diene polymer (B) in the present embodiment have a functional group represented by the general formula (1) at the terminal, and the general formula (1). A functional group containing an alkoxysilyl group and an amine at a terminal different from the terminal having a functional group represented by The modified conjugated diene copolymer (A) contains aromatic vinyl-derived units, while the modified conjugated diene polymer (B) does not contain aromatic vinyl-derived units. Are distinguished.

  In the general formula (1), R1 and R2 are any 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. Yes, they may be the same or different. Here, R1 and R2 may combine to form a cyclic structure together with the adjacent nitrogen atom, and R1 and R2 in that case are hydrocarbon groups having 4 to 12 carbon atoms in total. R1 and R2 may have an unsaturated bond or may have a branched structure.

  The modified conjugated diene copolymer (A) and / or the modified conjugated diene polymer (B) has low hysteresis loss when the modified conjugated diene polymer composition of the present embodiment is used as a vulcanizate. From the viewpoint, any of the following general formulas (2) to (8) is preferable. From the same viewpoint, the modified conjugated diene copolymer (A) and the modified conjugated diene polymer (B) are more preferably any of the following general formulas (2) to (8).

（前記一般式（２）中、Ｒ３〜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のアリール基であり、Ｒ７及びＲ８は、炭素数１〜２０のアルキレン基であり、Ｒ９は水素又は炭化水素で置換されたシリル基である。ａ及びｃは、各々独立して１又は２の整数であり、ｂ及びｄは、各々独立して０又は１の整数であり、ａ＋ｂ及びｃ＋ｄは２以下の整数である。ここで、一般式（２）が変性共役ジエン系共重合体（Ａ）である場合、Ｐｏｌｙｍは、芳香族ビニル化合物由来の単位を含む共役ジエン系共重合体であり、一般式（２）が変性共役ジエン系重合体（Ｂ）である場合、Ｐｏｌｙｍは、芳香族ビニル化合物由来の単位を含まない共役ジエン系重合体であり、Ｐｏｌｙｍの少なくとも一つの末端が前記一般式（１）で表される官能基である。Ｒ３〜Ｒ６が複数存在するときは、それらは各々同一であっても異なっていてもよい。）

（前記一般式（３）中、Ｒ１０〜Ｒ１３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のアリール基であり、Ｒ１４及びＲ１５は、各々独立して炭素数１〜２０のアルキレン基であり、ｅ及びｇは、各々独立して０〜２の整数であり、ｅ又はｇのどちらかが１以上である。ｆ及びｈは、各々独立して０又は１の整数であり、ｅ＋ｆ及びｇ＋ｈは２以下の整数である。ここで、一般式（３）が変性共役ジエン系共重合体（Ａ）である場合、Ｐｏｌｙｍは、芳香族ビニル化合物由来の単位を含む共役ジエン系共重合体であり、一般式（３）が変性共役ジエン系重合体（Ｂ）である場合、Ｐｏｌｙｍは、芳香族ビニル化合物由来の単位を含まない共役ジエン系重合体であり、複数あってもよいＰｏｌｙｍの少なくとも一つの末端が前記一般式（１）で表される官能基である。ｉは０〜２０の整数であり、ｉが２以上の場合、（Ｒ１４−Ａ１−Ｒ１５）で表される複数の繰り返し単位は、同じであってもよく相異なるものであってもよい。Ａ１は下記一般式（ａ）、（ｂ）、（ｃ）のいずれかで表される基である。Ｒ１０〜Ｒ１３が複数存在するときは、それらは各々同一であっても異なっていてもよい。）

（前記一般式（ａ）において、Ｒ１６及びＲ１７は、各々独立して、炭素数１〜２０のアルキレン基であり、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。）

（前記一般式（ｂ）において、Ｒ１８は炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基及び活性水素を持たないヘテロ原子で置換されている炭素数１〜２０の炭化水素基からなる群より選ばれるいずれかである。）

（前記一般式（ｃ）において、Ｒ１８は炭素数１〜２０のアルキレン基であり、Ｒ１９及びＲ２０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のアリール基である。ｊは０〜２の整数であり、ｋは０又は１の整数であり、ｊ＋ｋは２以下の整数である。ここで、一般式（３）が変性共役ジエン系共重合体（Ａ）である場合、Ｐｏｌｙｍは、芳香族ビニル化合物由来の単位を含む共役ジエン系共重合体であり、一般式（３）が変性共役ジエン系重合体（Ｂ）である場合、Ｐｏｌｙｍは、芳香族ビニル化合物由来の単位を含まない共役ジエン系重合体であり、複数あってもよいＰｏｌｙｍの少なくとも一つの末端が前記一般式（１）で表される官能基である。Ｒ１９、Ｒ２０が複数存在するときは、それらは各々同一であっても異なっていてもよい。）

（前記一般式（４）中、Ｒ２１、Ｒ２２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のアリール基であり、Ｒ２３、Ｒ２４は、各々独立して、炭素数１〜２０のアルキレン基であり、Ｒ２５、Ｒ２６、Ｒ２７は、各々独立して、Ｓｉ、Ｏ又はＮを含み、活性水素を持たない有機基で置換されていてもよい炭素数１〜２０の炭化水素基である。ｌは１又は２の整数であり、ｍは０又は１の整数であり、ｌ＋ｍは２以下の整数である。ここで、一般式（４）が変性共役ジエン系共重合体（Ａ）である場合、Ｐｏｌｙｍは、芳香族ビニル化合物由来の単位を含む共役ジエン系共重合体であり、一般式（４）が変性共役ジエン系重合体（Ｂ）である場合、Ｐｏｌｙｍは、芳香族ビニル化合物由来の単位を含まない共役ジエン系重合体であり、複数あってもよいＰｏｌｙｍの少なくとも一つの末端が前記一般式（１）で表される官能基である。Ｒ２１、Ｒ２２が複数存在するときは、それらは各々同一であっても異なっていてもよい。）

（前記一般式（５）中、Ｒ２８、Ｒ２９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のアリール基であり、Ｒ３０は炭素数１〜２０のアルキレン基であり、Ｒ３１、Ｒ３２は、各々独立して炭素数１〜６の２価の炭化水素基であって、隣接する２つのＮとともに５員環以上の環構造をなし、Ｒ３３は炭素数１〜２０の炭化水素基、活性水素を持たないヘテロ原子で置換されている炭素数１〜２０の炭化水素基、又は３有機置換シリル基であり、ｎは１又は２の整数であり、ｏは０又は１の整数であり、ｎ＋ｏは２以下の整数である。ここで、一般式（５）が変性共役ジエン系共重合体（Ａ）である場合、Ｐｏｌｙｍは、芳香族ビニル化合物由来の単位を含む共役ジエン系共重合体であり、一般式（５）が変性共役ジエン系重合体（Ｂ）である場合、Ｐｏｌｙｍは、芳香族ビニル化合物由来の単位を含まない共役ジエン系重合体であり、複数あってもよいＰｏｌｙｍの少なくとも一つの末端が前記一般式（１）で表される官能基である。Ｒ２８、Ｒ２９が複数存在するときは、それらは各々同一であっても異なっていてもよい。）

（前記一般式（６）中、Ｒ３４、Ｒ３５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のアリール基であり、Ｒ３６は炭素数１〜２０のアルキレン基であり、Ｒ３７、Ｒ３８は、各々独立して炭素数１〜６の２価の炭化水素基であって、隣接する２つのＮとともに５員環以上の環構造をなし、Ｒ３９、Ｒ４０は、各々独立して炭素数１〜２０の炭化水素基、活性水素を持たないヘテロ原子で置換されている炭素数１〜２０の炭化水素基、又は３有機置換シリル基であり、ｍは１又は２の整数であり、ｑは０又は１の整数であり、ｐ＋ｑは２以下の整数である。ここで、一般式（６）が変性共役ジエン系共重合体（Ａ）である場合、Ｐｏｌｙｍは、芳香族ビニル化合物由来の単位を含む共役ジエン系共重合体であり、一般式（６）が変性共役ジエン系重合体（Ｂ）である場合、Ｐｏｌｙｍは、芳香族ビニル化合物由来の単位を含まない共役ジエン系重合体であり、複数あってもよいＰｏｌｙｍの少なくとも一つの末端が前記一般式（１）で表される官能基である。Ｒ３４、Ｒ３５が複数存在するときは、それらは各々同一であっても異なっていてもよい。）

（前記一般式（７）において、Ａ２は三級アミン、ピリジン、シアン及びイミンからなる群より選ばれる少なくとも一種の官能基を有する一価の基であり、Ｒ４１及びＲ４２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のアリール基であり、Ｒ４３は炭素数１〜２０のアルキレン基である。ｒは１又は２の整数であり、ｓは０又は１の整数である。ここで、一般式（７）が変性共役ジエン系共重合体（Ａ）である場合、Ｐｏｌｙｍは、芳香族ビニル化合物由来の単位を含む共役ジエン系共重合体であり、一般式（７）が変性共役ジエン系重合体（Ｂ）である場合、Ｐｏｌｙｍは、芳香族ビニル化合物由来の単位を含まない共役ジエン系重合体であり、複数あってもよいＰｏｌｙｍの少なくとも一つの末端が前記一般式（１）で表される官能基である。Ｒ４１、Ｒ４２が複数存在するときは、それらは各々同一であっても異なっていてもよい。）

（前記一般式（８）において、Ｒ４４は炭素数１〜２０のアルキル基又は炭素数６〜２０のアリール基であり、Ｒ４５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素数１〜２０のアルコキシ基であり、Ｒ４６は炭素数１〜２０のアルキレン基である。Ｒ４７及びＲ４８は、各々独立に水素であるか、炭化水素で置換されたシリル基である。ｔは１〜２の整数であり、ｕは０〜１の整数であり、ｖは１〜１０の整数である。ｗはｖが１の時は３−ｔ−ｕであり、ｖが２以上のときは２−ｔである。ここで、一般式（８）が変性共役ジエン系共重合体（Ａ）である場合、Ｐｏｌｙｍは、芳香族ビニル化合物由来の単位を含む共役ジエン系共重合体であり、一般式（８）が変性共役ジエン系重合体（Ｂ）である場合、Ｐｏｌｙｍは、芳香族ビニル化合物由来の単位を含まない共役ジエン系重合体であり、複数あってもよいＰｏｌｙｍの少なくとも一つの末端が前記一般式（１）で表される官能基である。Ｒ４４〜Ｒ４８が複数存在するときは、それらは各々同一であっても異なっていてもよい。）

(In said general formula (2), R3-R6 are respectively independently a C1-C20 alkyl group or a C6-C20 aryl group, and R7 and R8 are C1-C20. An alkylene group, R9 is a silyl group substituted with hydrogen or hydrocarbon, a and c are each independently an integer of 1 or 2, and b and d are each independently 0 or 1; It is an integer, and a + b and c + d are integers equal to or less than 2. Here, when the general formula (2) is a modified conjugated diene copolymer (A), Polym includes a unit derived from an aromatic vinyl compound. When it is a conjugated diene copolymer and the general formula (2) is a modified conjugated diene polymer (B), Polym is a conjugated diene polymer that does not contain a unit derived from an aromatic vinyl compound. At least one terminal of the general formula (1 When in a functional group represented by .R3~R6 there are multiple, they may be each independently selected from the same.)

(In the general formula (3), R10 to R13 are each independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R14 and R15 are each independently a carbon number. 1 to 20 alkylene groups, e and g are each independently an integer of 0 to 2, and either e or g is 1 or more, and f and h are each independently 0 or 1 E + f and g + h are integers equal to or less than 2. Here, when the general formula (3) is the modified conjugated diene copolymer (A), Polym is a unit derived from an aromatic vinyl compound. When the general formula (3) is a modified conjugated diene polymer (B), Polym is a conjugated diene polymer that does not contain a unit derived from an aromatic vinyl compound, At least one end of Polym which may be plural Is a functional group represented by the general formula (1), i is an integer of 0 to 20, and when i is 2 or more, the plurality of repeating units represented by (R14-A1-R15) are: A1 is a group represented by any one of the following general formulas (a), (b), and (c), and when there are a plurality of R10 to R13. Each may be the same or different.)

(In the general formula (a), R16 and R17 are each independently an alkylene group having 1 to 20 carbon atoms, and together with two adjacent Ns, form a ring structure of five or more members.)

(In the general formula (b), R18 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a hydrocarbon group having 1 to 20 carbon atoms substituted with a hetero atom having no active hydrogen. Any one selected from the group consisting of

(In the general formula (c), R18 is an alkylene group having 1 to 20 carbon atoms, and R19 and R20 are each independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. J is an integer of 0 to 2, k is an integer of 0 or 1, and j + k is an integer of 2 or less, wherein the general formula (3) is a modified conjugated diene copolymer (A) In this case, Polym is a conjugated diene copolymer containing a unit derived from an aromatic vinyl compound, and when General Formula (3) is a modified conjugated diene polymer (B), Polym is an aromatic vinyl. It is a conjugated diene polymer that does not contain a compound-derived unit, and at least one terminal of Polym may be a functional group represented by the general formula (1) When there are a plurality of R19 and R20 They are each identical And it may be different as well.)

(In the general formula (4), R21 and R22 are each independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R23 and R24 are each independently carbon. An alkylene group having 1 to 20 carbon atoms, and R25, R26, and R27 each independently include Si, O, or N, and may be substituted with an organic group having no active hydrogen. A hydrocarbon group, wherein l is an integer of 1 or 2, m is an integer of 0 or 1, and l + m is an integer of 2 or less, wherein the general formula (4) is a modified conjugated diene-based copolymer In the case of the compound (A), Polym is a conjugated diene copolymer containing units derived from an aromatic vinyl compound, and when the general formula (4) is a modified conjugated diene polymer (B), Polym is Conjugated dienes that do not contain units derived from aromatic vinyl compounds At least one terminal of the polym that is a combination and may be a plurality is a functional group represented by the general formula (1) When there are a plurality of R21 and R22, they may be the same or different. May be.)

(In the general formula (5), R28 and R29 are each independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R30 is an alkylene group having 1 to 20 carbon atoms. , R31 and R32 are each independently a divalent hydrocarbon group having 1 to 6 carbon atoms, and together with two adjacent Ns, form a ring structure of five or more members, and R33 has 1 to 20 carbon atoms. A hydrocarbon group, a hydrocarbon group having 1 to 20 carbon atoms substituted with a heteroatom having no active hydrogen, or an organically substituted silyl group, n is an integer of 1 or 2, and o is 0 or 1 N + o is an integer equal to or less than 2. Here, when the general formula (5) is the modified conjugated diene copolymer (A), Polym is a conjugate containing a unit derived from an aromatic vinyl compound. This is a diene copolymer, and the general formula (5) is a modified conjugated diene. In the case of the polymer (B), Polym is a conjugated diene polymer that does not contain a unit derived from an aromatic vinyl compound, and at least one terminal of the Polym that may be plural is represented by the general formula (1). When there are a plurality of R28 and R29, they may be the same or different.)

(In the general formula (6), R34 and R35 are each independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R36 is an alkylene group having 1 to 20 carbon atoms. , R37 and R38 are each independently a divalent hydrocarbon group having 1 to 6 carbon atoms, and form a ring structure of 5 or more members with two adjacent Ns, and R39 and R40 each independently And a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms substituted with a heteroatom having no active hydrogen, or a 3 organic substituted silyl group, m is an integer of 1 or 2 And q is an integer of 0 or 1, and p + q is an integer of 2 or less, where, when general formula (6) is a modified conjugated diene copolymer (A), Polym is an aromatic vinyl Conjugated diene copolymer containing a compound-derived unit When 6) is a modified conjugated diene polymer (B), Polym is a conjugated diene polymer that does not contain a unit derived from an aromatic vinyl compound, and at least one terminal of Polym, which may be plural, is the above-mentioned This is a functional group represented by the general formula (1) .When there are a plurality of R34 and R35, they may be the same or different.

(In the general formula (7), A2 is a monovalent group having at least one functional group selected from the group consisting of a tertiary amine, pyridine, cyan and imine, and R41 and R42 are each independently, An alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, R43 is an alkylene group having 1 to 20 carbon atoms, r is an integer of 1 or 2, and s is an integer of 0 or 1. Here, when the general formula (7) is the modified conjugated diene copolymer (A), Polym is a conjugated diene copolymer containing a unit derived from an aromatic vinyl compound, and the general formula ( When 7) is a modified conjugated diene polymer (B), Polym is a conjugated diene polymer that does not contain a unit derived from an aromatic vinyl compound, and at least one terminal of Polym may be plural. General formula 1) it is a functional group represented by .R41, when R42 is plurally present, they may be each independently selected from the same.)

(In the general formula (8), R44 is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R45 is an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms. Or an alkoxy group having 1 to 20 carbon atoms, and R46 is an alkylene group having 1 to 20 carbon atoms, and R47 and R48 are each independently hydrogen or a silyl group substituted with a hydrocarbon. Is an integer from 1 to 2, u is an integer from 0 to 1, v is an integer from 1 to 10. w is 3-tu when v is 1, and v is 2 or more. Here, when general formula (8) is a modified conjugated diene copolymer (A), Polym is a conjugated diene copolymer containing units derived from an aromatic vinyl compound. Yes, when the general formula (8) is a modified conjugated diene polymer (B), Pol m is a conjugated diene polymer containing no unit derived from an aromatic vinyl compound, and at least one terminal of Polym, which may be plural, is a functional group represented by the general formula (1). When a plurality of R48s are present, they may be the same or different.)

(Production method of modified conjugated diene copolymer (A) and modified conjugated diene polymer (B))
The modified conjugated diene copolymer (A) is obtained by, for example, copolymerizing a conjugated diene compound and an aromatic vinyl compound in a hydrocarbon solvent using a lithium amide compound, and then obtaining an active terminal of the obtained polymer. And a silyl group substituted with two or more alkoxy groups and a compound having one or more nitrogen atoms. The modified conjugated diene copolymer obtained by the production method is also referred to as (A1) modified conjugated diene (co) polymer, modified conjugated diene (co) polymer (A1), and (A1) component. .

  The modified conjugated diene polymer (B) is obtained by polymerizing a conjugated diene compound in a hydrocarbon solvent using, for example, a lithium amide compound, and then adding two or more alkoxy groups to the active terminal of the obtained polymer. It is obtained by reacting a substituted silyl group with a compound having one or more nitrogen atoms. Further, the modified conjugated diene polymer obtained by the production method is also referred to as (B1) modified conjugated diene polymer, modified conjugated diene polymer (B1), and (B1) component.

  As described above, the modified conjugated diene copolymer composition in this embodiment was obtained after copolymerizing a conjugated diene compound and an aromatic vinyl compound in a hydrocarbon solvent using a lithium amide compound. A modified conjugated diene copolymer (A1) obtained by reacting a compound having one or more nitrogen atoms with a silyl group substituted with two or more alkoxy groups at the active terminal of the polymer, lithium amide After polymerizing a conjugated diene compound in a hydrocarbon solvent using the compound, the resulting polymer has a silyl group substituted with two or more alkoxy groups and one or more nitrogen atoms at the active end of the polymer. And a modified conjugated diene polymer (B1) obtained by reacting the compound.

  Hereinafter, "modified conjugated diene copolymer (A)" and "modified conjugated diene polymer (B)", "modified conjugated diene copolymer (A1)" and "modified conjugated diene polymer (B1)" And “modified conjugated diene-based (co) polymer”.

<Lithium amide compound>
The lithium amide compound for obtaining a modified conjugated diene-based (co) polymer is a compound having an N-Li structure. The lithium amide compound is, for example, a compound represented by the following general formula (9).

  R1 and R2 in the formula (9) are any 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. , May be the same or different. R1 and R2 may combine to form a cyclic structure together with the adjacent nitrogen atom, and R1 and R2 in that case are hydrocarbon groups having a total carbon number of 4 to 12. R1 and R2 may have an unsaturated bond or may have a branched structure.

  Examples of the compound represented by the formula (9) include 1-lithiopyrrolidine, 1-lithiopiperidine, 1-lithioazacycloheptane, 1-lithioazacyclooctane, 1-lithioazacycloundecane, lithium diethylamide, lithium Dibutylamide, lithium dihexylamide, 6-lithio-1,3,3-trimethyl-6-azabicyclo [3.2.1] octane, lithium ethylbutyramide, lithium ethylhexylamide, lithium butylhexylamide, lithium methylphenylamide, Examples thereof include lithium benzylmethylamide and 1-lithio-1,2,3,4-tetrahydropyridine. In addition, the compound represented by said Formula (9) is not limited to these, If the said conditions are satisfy | filled, those similar will be included.

  From the viewpoint of reducing the hysteresis loss of the modified conjugated diene polymer composition of the present embodiment, examples of the compound represented by the formula (9) include 1-lithiopyrrolidine, 1-lithiopiperidine, 1-lithioazacycloheptane, Lithium dibutylamide, 6-lithio-1,3,3-trimethyl-6-azabicyclo [3.2.1] octane and 1-lithio-1,2,3,4-tetrahydropyridine are preferred. More preferred are 1-lithiopyrrolidine, 1-lithiopiperidine and 1-lithioazacycloheptane, and more preferred are 1-lithiopiperidine and 1-lithioazacycloheptane.

  The lithium amide compound can be synthesized by a known method, and can be obtained, for example, by reacting a secondary amine and an organolithium compound in a hydrocarbon solvent. Examples of the hydrocarbon solvent include, but are not limited to, hydrocarbon solvents such as saturated hydrocarbons and aromatic hydrocarbons. Specifically, aliphatic hydrocarbons such as butane, 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. Examples of the secondary amine include, but are not limited to, compounds represented by the following general formula (10).

  In Formula (10), R1 and R2 are any 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. Yes, they may be the same or different. R1 and R2 may combine to form a cyclic structure together with the adjacent nitrogen atom, in which case R1 and R2 are hydrocarbon groups having 4 to 12 carbon atoms in total. R1 and R2 may have an unsaturated bond or may have a branched structure.

  Examples of the compound represented by the formula (10) include pyrrolidine, piperidine, azacycloheptane, azacyclooctane, azacycloundecane, diethylamine, dibutylamine, dihexylamine, 1,3,3-trimethyl-6-azabicyclo. [3.2.1] Octane, ethylbutylamine, ethylhexylamine, butylhexylamine, methylphenylamine, benzylmethylamine, 1,2,3,4-tetrahydropyridine and the like. The compound represented by the formula (10) is not limited to these, and includes the similar compounds as long as the above conditions are satisfied.

  From the viewpoint of reducing the hysteresis loss of the modified conjugated diene polymer composition of the present embodiment, examples of the compound represented by the formula (10) include pyrrolidine, piperidine, azacycloheptane, dibutylamine, 1,3,3- Trimethyl-6-azabicyclo [3.2.1] octane and 1,2,3,4-tetrahydropyridine are preferred. More preferred are pyrrolidine, piperidine, and azacycloheptane. More preferred are piperidine and azacycloheptane.

  Examples of the organolithium compound include, but are not limited to, n-butyllithium, sec-butyllithium, tert-butyllithium, n-propyllithium, iso-propyllithium, and the like.

<Hydrocarbon solvent>
The hydrocarbon solvent for obtaining the modified conjugated diene (co) polymer is not limited to the following, and examples thereof 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.

<Conjugated diene compound>
The conjugated diene compound used for the synthesis of the modified conjugated diene-based (co) polymer is not limited to the following, and examples thereof include 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene. 1,3-pentadiene, 3-methyl-1,3-pentadiene, 1,3-heptadiene, 1,3-hexadiene and the like. These may be used alone or in combination of two or more. Preferred compounds include 1,3-butadiene and isoprene.

  From the viewpoint of preventing inhibition of the modification reaction when producing the modified conjugated diene-based (co) polymer, it is preferable to reduce the content of impurities such as allenes and acetylenes in the conjugated diene compound. That is, the total content concentration (mass) of these impurities is preferably 200 ppm or less, more preferably 100 ppm or less, and even more preferably 50 ppm or less. Examples of allenes include propadiene and 1,2-butadiene. Examples of acetylenes include ethyl acetylene and vinyl acetylene.

<Aromatic vinyl compound>
The aromatic vinyl compound used for the synthesis of the modified conjugated diene copolymer (A) and the modified conjugated diene copolymer (A1) is not limited to the following, but examples thereof include styrene and p-methylstyrene. , Α-methylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene, diphenylethylene and the like. These may be used alone or in combination of two or more. A preferred compound is styrene.

  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. Examples of the organometallic compound include, but are not limited to, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, n-propyl lithium, iso-propyl lithium, and the like.

<Polar compound>
In the polymerization reaction before the modification of the modified conjugated diene (co) polymer, a polar compound may be added. The polar compound is preferably used for randomly copolymerizing an aromatic vinyl compound with a conjugated diene compound. Polar compounds can also be used as vinylating agents for controlling the microstructure of the conjugated diene moiety. It is also effective in improving the polymerization rate. Examples of the polar compound include, but are not limited to, tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, dimethoxybenzene, 2,2-bis (2 Ethers such as -oxolanyl) propane; tertiary amine compounds such as tetramethylethylenediamine, dipiperidinoethane, trimethylamine, triethylamine, pyridine, quinuclidine; potassium-t-amylate, potassium-t-butyrate, sodium-t- Examples include alkali metal alkoxide compounds such as butyrate and sodium amylate; and phosphine compounds such as triphenylphosphine. Each of these polar compounds may be used alone or in combination of two or more.

<Structure of Modified Conjugated Diene Polymer>
The amount of bonded vinyl aromatic compound in the modified conjugated diene copolymer (A1) and the modified conjugated diene copolymer (A1) in the modified conjugated diene copolymer is a viewpoint of low hysteresis loss when a vulcanized product is used. Therefore, it is preferably 10% to 50%, more preferably 15% to 45%, and still more preferably 20% to 40%. The amount of the bound vinyl aromatic compound can be calculated by measuring the absorption spectrum of the vinyl aromatic compound using ultraviolet rays (UV) as described in the examples described later.

  The weight average molecular weight of the modified conjugated diene-based (co) polymer is preferably 20,000 to 2,000,000 from the viewpoint of processability and low hysteresis loss when vulcanized, and is preferably 50,000. To 1,500,000, more preferably 100,000 to 1,000,000. A weight average molecular weight can be measured by the method described in the Example mentioned later.

  The molecular weight distribution (Mn / Mw) of the modified conjugated diene-based (co) polymer is preferably 1.0 to 4.0 from the viewpoint of processability and low hysteresis loss when used as a vulcanizate. More preferably, it is from 1 to 3.5, and even more preferably from 1.1 to 3.0. The molecular weight distribution can be measured by the method described in Examples described later.

  When the polymer before modification of the modified conjugated diene (co) polymer is a copolymer, it may be a random copolymer or a block copolymer. The random copolymer is not limited to the following. For example, in the case of a butadiene-isoprene random copolymer, a modified conjugated diene copolymer (A), and a modified conjugated diene polymer (A1). Butadiene-styrene random copolymer, isoprene-styrene random copolymer, butadiene-isoprene-styrene random copolymer, and the like. Examples of the composition distribution of each monomer in the copolymer chain include a completely random copolymer having a statistically random composition, or a tapered random copolymer having a tapered composition distribution. The bonding mode of the conjugated diene, that is, the composition such as 1,4-bond and 1,2-bond may be uniform or distributed.

  Examples of the block copolymer include a 2-type block copolymer having 2 blocks, a 3-type block copolymer having 3 blocks, and a 4-type block copolymer having 4 blocks. For example, a block composed of an aromatic vinyl compound such as styrene is represented by S, and a block composed of a conjugated diene compound such as butadiene or isoprene and / or a block composed of a copolymer of an aromatic vinyl compound and a conjugated diene compound is represented by B. And an S—B2 type block copolymer, an S—B—S3 type block copolymer, a S—B—S—B4 type block copolymer, and the like. In the above equation, the boundaries of each block need not be clearly distinguished.

  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. In the block B, a plurality of portions where the aromatic vinyl compound is uniformly distributed and / or a plurality of portions where the aromatic vinyl compound is distributed in a tapered shape may coexist. In the block B, a plurality of segments having different aromatic vinyl compound contents may coexist.

  When a plurality of blocks S and B are present in the block copolymer, the structures such as molecular weight and composition thereof may be the same or different.

More generally, the block copolymer includes, for example, a structure represented by the following general formula.
(SB) n, S- (BS) n, B- (SB) n, (SB) m-X,
[(SB) n] m-X, [(BS) n-B] m-X, [(SB) n-S] m-X
(In the structural examples of the block copolymer, n is an integer of 1 or more, preferably an integer of 1 to 5. m is an integer of 2 or more, preferably an integer of 2 to 11. X is a coupling agent. Or the residue of the polyfunctional initiator, and the structure of the polymer chain bonded to X may be the same or different.)

  In the present embodiment, the block copolymer before modification of the modified conjugated diene copolymer (A) and the modified conjugated diene polymer (A1) is an arbitrary mixture of those having the structure represented by the above general formula. But you can.

  When the modified conjugated diene polymer composition of the present embodiment is used as a rubber composition for a tire tread, the modified conjugated diene copolymer (A) is used from the viewpoint of obtaining a rubber composition that is more excellent in low hysteresis loss. In the modified conjugated diene copolymer (A1), the polymer before modification is preferably a random copolymer. In the case where the conjugated diene polymer (A) and the modified conjugated diene polymer (A1) before modification are conjugated diene-aromatic vinyl copolymers, the block of the chain in which 30 or more aromatic vinyl units are linked. It is preferable that the number is small or absent. Specifically, when the conjugated diene polymer before the modification of the component (A) and the component (A1) is a butadiene-styrene copolymer, the method of Kolthoff (IM KOLTHOFF, et al., J. MoI. 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 linked, It is preferably 5% by mass or less, and more preferably 3% by mass or less, based on the total amount of the polymer.

  The polymer before modification of the modified conjugated diene-based (co) polymer is preferably obtained by growing by the anionic polymerization reaction using the above-described lithium amide compound or organic lithium compound as a polymerization initiator. In particular, the polymer before modification is more preferably a polymer having an active end obtained by a growth reaction by living anion polymerization. Thereby, a modified conjugated diene-based (co) 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 type, one or two or more connected reactors can be used. The reactor may be a tank type with a stirrer or a tube type.

  Further, the vinyl bond amount in the conjugated diene bond unit of the modified conjugated diene-based (co) polymer is not limited to the following, but is preferably 10 to 75 mol%, and preferably 25 to 65 mol%. More preferably. If the vinyl bond content is in the above range, a vulcanizate that has a further excellent balance between low hysteresis loss and wet skid resistance and that satisfies wear resistance and fracture strength tends to be obtained. Here, when the modified conjugated diene copolymer (A) and the modified conjugated diene copolymer (A1) are copolymers containing butadiene and styrene, the method of Hampton (RR Hampton, Analytical Chemistry, 21, 923 (1949)), the vinyl bond amount (1,2-bond amount) in the butadiene bond unit can be determined. When the modified conjugated diene-based (co) polymer is a polymer having butadiene as a polymerization monomer, the vinyl bond amount (1,2-vinyl bond amount) in the butadiene bond unit is determined by the Morero method. Can do. Low hysteresis loss when the microstructure (the amount of each vinyl bond in the modified conjugated diene-based (co) polymer) is in the above range and the glass transition temperature of the polymer is in the range of −45 to −15 ° C. There is a tendency that a more excellent vulcanizate can be obtained by the balance between the property and the wet skid resistance. Regarding the glass transition temperature, in accordance with ISO 22768: 2006, a DSC curve is recorded while raising the temperature in a predetermined temperature range, and the peak top (Inflection point) of the DSC differential curve is defined as the glass transition temperature.

  The modified conjugated diene-based (co) polymer may be one obtained by converting all or part of the double bonds of the polymer into saturated hydrocarbons. Modified conjugated diene (co) polymers in which all or part of these double bonds are converted to saturated hydrocarbons have improved heat resistance and weather resistance. In addition, it tends to be able to prevent, change the mobility of the molecule, or improve the compatibility with other polymer compounds. As a result, such hydrogenated modified conjugated diene-based (co) polymers are preferred because they tend to exhibit better performance in various applications such as automotive applications. 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. When obtaining a modified conjugated diene (co) polymer having good heat aging resistance and weather resistance, the hydrogenation rate of the unsaturated double bond based on the conjugated diene compound in the modified conjugated diene (co) polymer is 70. % Is preferably exceeded. More preferably 75% or more, still more preferably 85% or more, and still more preferably 90% or more. Further, from the viewpoint of improving thermal stability, molecular mobility, or compatibility with the resin, the hydrogenation rate in the modified conjugated diene (co) polymer is preferably 3% to 70%, more preferably 5%. % To 65%, more preferably 10% to 60%. 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 the hydrogenation rate may be 50% or less. Preferably, it is 30% or less, more preferably 20% or less. The hydrogenation rate can be measured by a nuclear magnetic resonance apparatus (NMR).

  As a hydrogenation method, a known method can be used. A particularly suitable hydrogenation method is a method in which gaseous hydrogen is blown into the polymer solution in the presence of a catalyst. The catalyst is not limited to the following, but as the heterogeneous catalyst, a catalyst in which a noble metal is supported on a porous inorganic substance is used. As the homogeneous catalyst, a salt of nickel, cobalt or the like is solubilized, organic aluminum, etc. And a catalyst using a metallocene such as titanocene. Of these catalysts, titanocene catalysts that can select particularly mild hydrogenation conditions are preferred.

  Hydrogenation of an aromatic group (aromatic double bond) can be performed by using a noble metal supported catalyst. For example, (1) a supported heterogeneous hydrogenation catalyst in which a metal such as Ni, Pt, Pd, or Ru is supported on carbon, silica, alumina, diatomaceous earth, or the like (2) Ni, Co, Fe, Cr, or the like So-called Ziegler type hydrogenation catalyst using transition metal salt such as organic acid salt or acetylacetone salt and reducing agent such as organoaluminum, (3) so-called organometallic complex such as organometallic compound such as Ti, Ru, Rh, Zr Etc. Specific examples include 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 and Japanese Patent Publication No. 2-5. The hydrogenation catalyst described in Japanese Patent Application Laid-Open No. 9041 and Japanese Patent Application Laid-Open No. 8-109219 can be used. A preferred hydrogenation catalyst is a reaction mixture of a titanocene compound and a reducing organometallic compound.

  The polymerization temperature of the modified conjugated diene-based (co) polymer before the modification is not particularly limited as long as the living anion polymerization proceeds, but from the viewpoint of productivity, it is preferably 0 ° C. or higher. From the viewpoint of sufficiently securing the reaction amount of the modifier with respect to the active terminal after completion of the polymerization, it is preferably 120 ° C. or lower.

  The modified conjugated diene-based (co) polymer in the present embodiment can be obtained by modifying the polymerization active terminal with a predetermined modifier. More specifically, after obtaining a conjugated diene-based (co) polymer having an active end by the above-described method, a silyl group substituted with two or more alkoxy groups at the active end and one or more nitrogen By reacting the compound having atoms, the modified conjugated diene-based (co) polymer in the present embodiment is obtained.

<Compound having a silyl group substituted with two or more alkoxy groups and one or more amines>
In the present embodiment, after obtaining a conjugated diene polymer having an active end by the method described above, the active end has a silyl group substituted with two or more alkoxy groups and one or more amines. A modified conjugated diene (co) polymer can be obtained by reacting a compound (hereinafter also referred to as a modifier). That is, the modified conjugated diene polymer composition of this embodiment is obtained by copolymerizing a conjugated diene compound and an aromatic vinyl compound in a hydrocarbon solvent using a lithium amide compound, and then A modified conjugated diene copolymer (A1) obtained by reacting a compound having one or more nitrogen atoms with a silyl group substituted with two or more alkoxy groups at the active end, and a lithium amide compound are used. Then, after polymerizing a conjugated diene compound in a hydrocarbon solvent, a compound having one or more nitrogen atoms and a silyl group substituted with two or more alkoxy groups at the active end of the obtained polymer. And a modified conjugated diene polymer (B1) obtained by the reaction. Examples of the compound having a silyl group substituted with two or more alkoxy groups and one or more amines in the molecule used for the modification reaction include the following formulas (11) to (18).

  In the general formula (11), R51 to R54 each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R58 and R59 each independently represent a carbon number. 1 to 20 alkylene groups, m1 is an integer of 1 or 2, and n1 is an integer of 2 or 3. When a plurality of R51 to R54 are present, they may be the same or different from each other.

  The modifying agent represented by the general formula (11) 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-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane, 2-ethoxy-2-ethyl-1- (3-triethoxysilylpropyl) -1-aza-2- Silacyclopentane, 2-methoxy-2-methyl-1- (3-dimethoxymethylsilylpropyl) -1-aza-2-silacyclopentane, 2-ethoxy-2-ethyl-1- (3-diethoxyethylsilyl) Propyl) -1-aza-2-silacyclopentane and the like. Among these, m1 is 2, from the viewpoint of reactivity and interaction between the functional group of the modifier and an inorganic filler such as silica, and from the viewpoint of processability of the modified conjugated diene polymer composition of the present embodiment. Those in which n1 is 3 are preferred. Specifically, 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane, 2,2-diethoxy-1- (3-triethoxysilylpropyl) -1 -Aza-2-silacyclopentane is preferred.

  In the general formula (12), R61 to R64 each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R68 and R69 are alkylene having 1 to 20 carbon atoms. Represents a group, and when there are a plurality of R68, R69 and A61, they may be the same or different. m2 and n2 are each an integer of 0 to 3. p2 is an integer of 0 to 20, and when p2 is 2 or more, the plurality of repeating units represented by (R69-A61-R68) may be different from each other. When there are a plurality of R61 to R64, they may be the same or different. A61 is a group represented by any one of the following general formulas (d), (e), and (f).

  In the general formula (d), R70 and R71 are each independently an alkylene group having 1 to 20 carbon atoms, and together with two adjacent Ns, form a ring structure of five or more members.

  In the general formula (e), R87 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms substituted with a hetero atom having no active hydrogen, And 3 selected from the group consisting of organically substituted silyl groups.

  In the general formula (f), R90 is an alkylene group having 1 to 20 carbon atoms, and R95 and R96 are each independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. . r1 is an integer of 0-3.

  Examples of the modifier represented by the general formula (12) include the following compounds. That is, A61 in the general formula (12) is not limited to the following as a compound of the general formula (d). For example, 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- The [3- (tributoxysilyl) propyl] -1,2,3,4-tetrahydropyrimidine-like.

  In addition, A61 in the general formula (12) is not limited to the following compounds as the general formula (e), but examples thereof include bis (3-triethoxysilylpropyl) methylamine, bis ( 3-triethoxysilylpropyl) ethylamine, bis (3-triethoxysilylpropyl) propylamine, bis (3-triethoxysilylpropyl) butylamine, bis (3-triethoxysilylpropyl) phenylamine, bis (3-triethoxy Silylpropyl) benzylamine, bis (triethoxysilylmethyl) methylamine, bis (2-triethoxysilylethyl) methylamine, bis (triethoxysilylmethyl) propylamine, bis (2-triethoxysilylethyl) propylamine and Compatible with these triethoxysilyl compounds Trimethoxysilyl compounds, bis (3-trimethoxysilylpropyl) N-trimethylsilylamine, bis (3-triethoxysilylpropyl) N-trimethylsilylamine, bis (2-triethoxysilylethyl) N-trimethylsilylamine compounds, etc. Can be mentioned.

  Furthermore, A61 in the general formula (12) is not limited to the following as the compound of the general formula (f), but examples thereof include tris (triethoxysilylmethyl) amine, tris (2-tri And ethoxysilylethyl) amine, tris (3-triethoxysilylpropyl) amine, and trimethoxysilyl compounds corresponding to these triethoxysilyl compounds.

  Among these, m2 and n2 from the viewpoints of the reactivity and interaction between the functional group of the modifier and an inorganic filler such as silica, and the processability of the modified conjugated diene polymer composition of the present embodiment. Is preferably 3. Specifically, 1,4-bis [3- (trimethoxysilyl) propyl] piperazine, 1,4-bis [3- (triethoxysilyl) propyl] piperazine, bis (3-trimethoxysilylpropyl) N— Trimethylsilylamine, bis (3-triethoxysilylpropyl) N-trimethylsilylamine, bis (3-triethoxysilylpropyl) methylamine, bis (3-triethoxysilylpropyl) ethylamine, and tris (triethoxysilylmethyl) amine are preferred. .

  In the general formula (13), R101 and R102 each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R108 and R109 each independently represent a carbon number. Represents an alkylene group having 1 to 20 carbon atoms, and each of R112, R113, and R114 independently includes Si, O, or N, and has 1 to 20 carbon atoms which may be substituted with an organic group having no active hydrogen. It is a hydrocarbon group. i3 is an integer of 1 to 3. When there are a plurality of R101 and R102, they may be the same or different.

  Examples of the compound represented by the general formula (13) include, but are not limited to, N- [2- (trimethoxysilanyl) -ethyl] -N, N ′, N′-trimethyl. Ethane-1,2-diamine, N- [2- (dimethoxymethylsilanyl) -ethyl] -N-ethyl-N ′, N′-dimethylethane-1,2-diamine, N- [3- (trimethoxy Silanyl) -propyl] -N, N ', N'-trimethylpropane-1,3-diamine, N- [3- (dimethoxymethylsilanyl) -propyl] -N-ethyl-N', N'-dimethyl Propane-1,3-diamine, N- [3- (triethoxysilanyl) -propyl] -N, N ′, N′-triethyl-2-methylpropane-1,3-diamine, N- [3- ( Dimethoxymethylsilanyl) -propyl]- , N, N ′, N′-tetramethylpropane-1,3-diamine, N- (2-dimethylaminoethyl) -N ′-[2- (trimethoxysilanyl) -ethyl] -N, N′- Dimethylethane-1,2-diamine, N- [2- (diethoxypropylsilanyl) -ethyl] -N ′-(3-ethoxypropyl) -N, N′-dimethylethane-1,2-diamine, N -[2- (Trimethoxysilanyl) -ethyl] -N'-methoxymethyl-N, N'-dimethylethane-1,2-diamine, N- [2- (trimethoxysilanyl) -ethyl] -N , N′-dimethyl-N ′-(2-trimethylsilanylethyl) -ethane-1,2-diamine, N- [2- (triethoxysilanyl) -ethyl] -N, N′-diethyl-N ′ -(2-Dibutylmethoxysilanylethyl) -eta 1,2-diamine, and the like. Among these, from the viewpoint of the reactivity and interaction between the functional group of the modifier and an inorganic filler such as silica, and the viewpoint of the processability of the modified conjugated diene polymer composition of the present embodiment, N- [ 2- (Trimethoxysilanyl) -ethyl] -N, N ′, N′-trimethylethane-1,2-diamine is preferred.

  In the general formula (14), R201 and R202 are each independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, R209 is an alkylene group having 1 to 20 carbon atoms, R210 and R211 are each independently a divalent hydrocarbon group having 1 to 6 carbon atoms, and together with two adjacent Ns, form a ring structure of five or more members, and R215 has 1 to 20 carbon atoms. It is a hydrocarbon group, a C1-C20 hydrocarbon group substituted with a hetero atom having no active hydrogen, or a 3 organic substituted silyl group, and m4 is an integer of 2 or 3. When there are a plurality of R201 and R202, they may be the same or different.

  The compound represented by the general formula (14) is not limited to the following, and examples thereof include 1- [3- (triethoxysilyl) propyl] -4-methylpiperazine, 1- [3- ( Diethoxyethylsilyl) propyl] -4-methylpiperazine, 1- [3- (trimethoxysilyl) propyl] -3-methylimidazolidine, 1- [3- (diethoxyethylsilyl) propyl] -3-ethylimidazo Lysine, 1- [3- (triethoxysilyl) propyl] -3-methylhexahydropyrimidine, 1- [3- (dimethoxymethylsilyl) propyl] -3-methylhexahydropyrimidine, 3- [3- (tributoxy) Silyl) propyl] -1-methyl-1,2,3,4-tetrahydropyrimidine, 3- [3- (dimethoxymethylsilyl) propyl] 1-ethyl-1,2,3,4-tetrahydropyrimidine, 1- (2-ethoxyethyl) -3- [3- (trimethoxysilyl) propyl] imidazolidine, (2- {3- [3- (tri Methoxysilyl) propyl] tetrahydropyrimidin-1-yl} ethyl) dimethylamine, 1- [3- (triethoxysilyl) propyl] -4- (trimethylsilyl) piperazine, 1- [3- (dimethoxymethylsilyl) propyl]- 4- (trimethylsilyl) piperazine, 1- [3- (tributoxysilyl) propyl] -4- (trimethylsilyl) piperazine, 1- [3- (diethoxyethylsilyl) propyl] -3- (triethylsilyl) imidazolidine, 1- [3- (triethoxysilyl) propyl] -3- (trimethylsilyl) imidazolidine, 1 [3- (Dimethoxymethylsilyl) propyl] -3- (trimethylsilyl) hexahydropyrimidine, 1- [3- (triethoxysilyl) propyl] -3- (trimethylsilyl) hexahydropyrimidine, 1- [4- (triethoxy Silyl) butyl] -4- (trimethylsilyl) piperazine and the like. From the viewpoint of reactivity and interaction between the functional group of the modifier and an inorganic filler such as silica, and from the viewpoint of processability of the modified conjugated diene polymer composition of the present embodiment, among these, 1- [3 -(Triethoxysilyl) propyl] -4-methylpiperazine, 1- [3- (trimethoxysilyl) propyl] -3-methylimidazolidine, 1- [3- (triethoxysilyl) propyl] -3-methylhexa Hydropyrimidine, 1- [3- (triethoxysilyl) propyl] -4- (trimethylsilyl) piperazine, 1- [3- (triethoxysilyl) propyl] -3- (trimethylsilyl) imidazolidine, 1- [3- ( Triethoxysilyl) propyl] -3- (trimethylsilyl) hexahydropyrimidine is preferably used, and 1- [3- (triethoxysilyl) propyl is used. Propyl] -4-methylpiperazine, 1- [3- (triethoxysilyl) propyl] -4- (trimethylsilyl) piperazine is more preferable.

  In the general formula (15), R301 and R302 are each independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R309 is an alkylene group having 1 to 20 carbon atoms, R310 and R311 are each independently a divalent hydrocarbon group having 1 to 6 carbon atoms, and form a ring structure of 5 or more members with two adjacent Ns, and R315 and R316 each independently A hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms substituted with a heteroatom having no active hydrogen, or a 3 organic substituted silyl group, and m5 is an integer of 2 or 3 It is. When there are a plurality of R301 and R302, they may be the same or different.

  The compound represented by the general formula (15) is not limited to the following. For example, 2- [3- (trimethoxysilyl) propyl] -1,3-dimethylimidazolidine, 2- ( Diethoxyethylsilyl) -1,3-diethylimidazolidine, 2- (triethoxysilyl) -1,4-diethylpiperazine, 2- (dimethoxymethylsilyl) -1,4-dimethylpiperazine, 5- (triethoxysilyl) ) -1,3-dipropylhexahydropyrimidine, 5- (diethoxyethylsilyl) -1,3-diethylhexahydropyrimidine, {2- [3- (2-dimethylaminoethyl) -2- (ethyldimethoxysilyl) ) -Imidazolidin-1-yl] -ethyl} -dimethylamine, 5- (trimethoxysilyl) -1,3-bis- (2-methoxy) Til) -hexahydropyrimidine, 5- (ethyldimethoxysilyl) -1,3-bis- (2-trimethylsilylethyl) -hexahydropyrimidine) -1,3-dimethylimidazolidine, 2- (3-diethoxyethyl) Silyl-propyl) -1,3-diethylimidazolidine, 2- (3-triethoxysilyl-propyl) -1,4-diethylpiperazine, 2- (3-dimethoxymethylsilyl-propyl) -1,4-dimethylpiperazine 5- (3-triethoxysilyl-propyl) -1,3-dipropylhexahydropyrimidine, 5- (3-diethoxyethylsilyl-propyl) -1,3-diethylhexahydropyrimidine, {2- [3 -(2-Dimethylaminoethyl) -2- (3-ethyldimethoxysilyl-propyl) -imidazolidine 1-yl] -ethyl} -dimethylamine, 5- (3-trimethoxysilyl-propyl) -1,3-bis- (2-methoxyethyl) -hexahydropyrimidine, 5- (3-ethyldimethoxysilyl-propyl) ) -1,3-bis- (2-trimethylsilylethyl) -hexahydropyrimidine, 2- [3- (trimethoxysilyl) propyl] -1,3-bis (trimethylsilyl) imidazolidine, 2- (diethoxyethylsilyl) ) -1,3-bis (triethylsilyl) imidazolidine, 2- (triethoxysilyl) -1,4-bis (trimethylsilyl) piperazine, 2- (dimethoxymethylsilyl) -1,4-bis (trimethylsilyl) piperazine, 5- (triethoxysilyl) -1,3-bis (tripropylsilyl) hexahydropyrimidine etc. Can be mentioned. Among these, from the viewpoint of the reactivity and interaction between the functional group of the modifier and an inorganic filler such as silica, and the viewpoint of the processability of the modified conjugated diene polymer composition of the present embodiment, among these, 2- [ 3- (Trimethoxysilyl) propyl] -1,3-dimethylimidazolidine and 2- [3- (trimethoxysilyl) propyl] -1,3- (bistrimethylsilyl) imidazolidine are preferred.

  In the general formula (16), A400 is a monovalent group having at least one functional group selected from the group consisting of tertiary amine, pyridine, cyan and imine, and R401 and R402 each independently represent carbon It is a C1-C20 alkyl group or a C6-C20 aryl group, and R408 is a C1-C20 alkylene group. m6 is an integer of 2 or 3. When there are a plurality of R401 and R402, they may be the same or different.

  The compound represented by the general formula (16) is not limited to the following, but for example, [3- (1-hexamethyleneimino) propyl] triethoxysilane, [(1-hexamethyleneimino) Methyl] triethoxysilane, [2- (1-hexamethyleneimino) ethyl] triethoxysilane, [3- (1-pyrrolidinyl) propyl] triethoxysilane, [3- (1-heptamethyleneimino) propyl] tri Ethoxysilane, [3- (1-dodecamethyleneimino) propyl] triethoxysilane, 1- [3- (triethoxysilyl) propyl] -4,5-dihydroimidazole, 3- [10- (triethoxysilyl) decyl -4-oxazoline and trimethoxysilyl compounds corresponding to these triethoxysilyl compounds, methyl Triethoxysilyl compounds, ethyl diethoxy silyl compounds, methyldimethoxysilyl compounds, ethyl dimethoxy silyl compounds, and the like. [3- (dimethylamino) propyl] triethoxysilane, [3- (diethylamino) propyl] triethoxysilane, [2- (dimethylamino) ethyl] triethoxysilane, [3- (dibutylamino) propyl] tri Ethoxysilane, [(3-methyl-3-ethylamino) propyl] triethoxysilane and trimethoxysilyl compounds, methyldiethoxysilyl compounds, ethyldiethoxysilyl compounds, methyldimethoxysilyl compounds corresponding to these triethoxysilyl compounds And ethyldimethoxysilyl compounds. Furthermore, 2- (triethoxysilylethyl) pyridine and trimethoxysilyl compounds corresponding to these triethoxysilyl compounds, methyldiethoxysilyl compounds, ethyldiethoxysilyl compounds, methyldimethoxysilyl compounds, ethyldimethoxysilyl compounds and the like can be mentioned. It is done. 2-cyanoethyltriethoxysilane, 3-cyanopropyltriethoxysilane, 11-cyanoundecyltriethoxysilane and trimethoxysilyl compounds corresponding to these triethoxysilyl compounds, methyldiethoxysilyl compounds, ethyldiethoxysilyl compounds, Examples thereof include a methyldimethoxysilyl compound and an ethyldimethoxysilyl compound. Among these, from the viewpoint of reactivity and interaction between the functional group of the modifier and an inorganic filler such as silica, and from the viewpoint of processability of the modified conjugated diene polymer composition of the present embodiment, 3-cyano Propyltriethoxysilane is preferred.

  In the general formula (16), when A402 contains imine, the compound represented by the general formula (16) is not limited to the following. For example, N- (1,3-dimethylbutylidene ) -3- (Triethoxysilyl) -1-propanamine, N- (1-methylethylidene) -3- (triethoxysilyl) -1-propanamine, N-ethylidene-3- (triethoxysilyl) -1 -Propanamine, N- (1-methylpropylidene) -3- (triethoxysilyl) -1-propanamine, N- (4-N, N-dimethylaminobenzylidene) -3- (triethoxysilyl) -1 -Propanamine, N- (cyclohexylidene) -3- (triethoxysilyl) -1-propanamine and trimethoxysilanes corresponding to these triethoxysilyl compounds Le compounds, methyldiethoxysilyl compounds, ethyl diethoxy silyl compounds, methyldimethoxysilyl compounds, ethyl dimethoxy silyl compounds, and the like.

  In the general formula (17), R501, R502, and R506 each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R508 represents an alkylene group having 1 to 20 carbon atoms. Represents. R503, R504 and R505 are each independently an alkyl group or aryl group having 1 to 20 carbon atoms, or two of them may be bonded to each other to form a ring together with the silicon atom to which they are bonded. Good. m7 is an integer of 1 to 2, and f7 is an integer of 1 to 10. When there are a plurality of R501 to R505 and R508, they may be the same or different.

  The compound represented by the general formula (17) is not limited to the following, but for example, N, N-bis (trimethylsilyl) aminopropyltriethoxysilane, N, N-bis (trimethylsilyl) aminoethyl Examples include triethoxysilane, trimethoxysilyl compounds corresponding to these triethoxysilyl compounds, methyldiethoxysilyl compounds, ethyldiethoxysilyl compounds, methyldimethoxysilyl compounds, and ethyldimethoxysilyl compounds.

  In the general formula (18), R601 and R602 each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R608 represents an alkylene group having 1 to 20 carbon atoms. . R603, R604 and R605 are each independently an alkyl group or aryl group having 1 to 20 carbon atoms, or two of them may be bonded to each other to form a ring together with the silicon atom to which they are bonded. Good. m8 is an integer of 1-2. R601 may be the same or different.

  Examples of the compound represented by the general formula (18) include, but are not limited to, for example, 1-trimethylsilyl-2,2-diethoxy-1-aza-2-silacyclopentane and diethoxy thereof. Examples include dimethoxysilyl compounds, methylethoxysilyl compounds, ethylethoxysilyl compounds, methylmethoxysilyl compounds, ethylmethoxysilyl compounds corresponding to silyl compounds.

  These modifiers may be used alone or in combination of two or more.

  The reaction temperature, reaction time, and the like when the above-described modifier is reacted with the polymerization active terminal are not particularly limited, but are preferably reacted at 0 to 120 ° 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, and more preferably 1 to 2 times. The obtained (A) modified conjugated diene polymer is preferably 0.8 times or more in order to obtain a sufficient modification rate, and the branched polymer component is produced by coupling polymer ends to improve processability. It is preferable to make it 3 times or less from the viewpoint of the modifier cost.

  In the method for producing a modified conjugated diene (co) polymer, 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 deactivator 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, carbon dioxide gas, and the like.

  Further, the modification rate of the modified conjugated diene (co) polymer used in the present embodiment (GPC (gel permeation chromatography) using a silica gel as a filler) From the viewpoint of reducing hysteresis loss of the modified conjugated diene polymer composition, the ratio is preferably 50 to 100%, more preferably 70 to 100%, and still more preferably 80 to 100%. The modified conjugated diene-based (co) polymer has a silyl group modified with an amine derived from lithium amide at the polymerization initiation terminal and further substituted with at least two or more alkoxy groups at the polymerization termination terminal and one or more amines. Since it is modified with a compound, the modification rate obtained using GPC using a silica gel as a filler described later represents the ratio of the polymer in which at least one of the start terminal and the end terminal is modified. More specifically, it can be determined by the method described in Examples described later.

  Further, the modified conjugated diene-based (co) polymer used in the present embodiment is added with a rubber stabilizer from the viewpoint of preventing gel formation in the finishing step after polymerization and from the viewpoint of improving stability during processing. It is preferable. It does not specifically limit as a stabilizer for rubber | gum, A well-known thing can be used. Examples of the rubber stabilizer include, but are not limited to, 2,6-di-tert-butyl-4-hydroxytoluene (BHT), n-octadecyl-3- (4′-hydroxy-3 ′), for example. , 5'-di-tert-butylphenol) propinate, 2-methyl-4,6-bis [(octylthio) methyl] phenol and the like are preferred.

  In order to improve the processability of the modified conjugated diene (co) polymer, an extender oil can be added to the modified conjugated diene (co) polymer as necessary. The method of adding the extender oil to the modified conjugated diene-based (co) polymer is not particularly limited, but the method of adding the extender oil to the polymer solution and mixing to remove the solvent from the oil-extended polymer solution. Is preferred. Examples of the extending oil include, but are not limited to, 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 RAE and the like in addition to TDAE and MES shown in Kautschuk Gummi Kunststoff 52 (12) 799 (1999). Although the addition amount of extending oil is not specifically limited, 10-60 mass parts is preferable with respect to 100 mass parts of modified conjugated diene type (co) polymers, and 20-37.5 mass parts is more preferable.

  The modified conjugated diene-based (co) polymer can be used as a material for the modified conjugated diene-based polymer composition of the present embodiment by being obtained from a polymer solution after polymerization. As a method for obtaining the modified conjugated diene-based (co) polymer 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.

(Composition of modified conjugated diene polymer composition)
In the modified conjugated diene polymer composition of the present embodiment, the blending ratio (mass ratio) of the component (A) and the component (B) described above is the modified conjugated diene copolymer (A) / modified conjugated diene system. The polymer (B) is preferably 10/90 to 90/10, more preferably 30/70 to 90/10, and still more preferably 50/50 to 80/20. When the blending ratio of the modified conjugated diene copolymer (A) / modified conjugated diene polymer (B) is in the above range, the balance between low hysteresis loss and wet skid resistance is further improved, and wear resistance and fracture are improved. There is a tendency to obtain a vulcanizate that is even more satisfactory in strength.

  The modified conjugated diene polymer composition of this embodiment is suitably used as a vulcanizate. The vulcanized product may be, for example, the modified conjugated diene polymer composition of this embodiment, an inorganic filler such as silica-based inorganic filler or carbon black, if necessary, and the modified conjugated diene polymer of this embodiment. It is mixed with a rubbery polymer other than the above, a silane coupling agent, a rubber softening agent, a vulcanizing agent, a vulcanization accelerator / auxiliary, etc. to obtain a modified conjugated diene polymer composition, and then heated to be added. It is obtained by sulfuration. Among these, a modified conjugated diene polymer composition containing a silica inorganic filler is preferable. When a vulcanized product is obtained by dispersing a silica-based inorganic filler in the modified conjugated diene polymer composition of the present embodiment, it has an excellent balance between low hysteresis loss and wet skid resistance and is practical. In addition, it has sufficient wear resistance and breaking strength, and can impart excellent workability. The modified conjugated diene polymer composition of the present embodiment also includes a silica-based inorganic filler as a reinforcing filler even when used for vulcanized rubber applications such as tires, automobile parts such as vibration-proof rubber, and shoes. It is preferable.

  In the modified conjugated diene polymer composition of the present embodiment, rubbery polymers other than the modified conjugated diene copolymer (A) and the modified conjugated diene polymer (B) described above can be used in combination. Such a rubbery polymer is not limited to the following, but, for example, a conjugated diene (co) polymer or a hydrogenated product thereof, a random copolymer of a conjugated diene compound and a vinyl aromatic compound. Examples thereof include a combined polymer or a hydrogenated product thereof, a block copolymer of a conjugated diene compound and a vinyl aromatic compound, or a hydrogenated product thereof, a non-diene polymer, and natural rubber. Specifically, butadiene rubber or hydrogenated product thereof, isoprene rubber or hydrogenated product thereof, styrene-butadiene rubber or hydrogenated product thereof, styrene-butadiene block copolymer or hydrogenated product thereof, styrene-isoprene block copolymerized Examples thereof include styrene-based elastomers such as coalescence or hydrogenated products thereof, acrylonitrile-butadiene rubber, or hydrogenated products thereof.

  Examples of the non-diene polymer include, but are not limited to, ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-butene-diene rubber, ethylene-butene rubber, ethylene-hexene rubber, ethylene-octene rubber, and the like. Olefin-based elastomers: butyl rubber, brominated butyl rubber, acrylic rubber, fluoro rubber, silicone rubber, chlorinated polyethylene rubber, epichlorohydrin rubber, α, β-unsaturated nitrile-acrylic ester-conjugated diene copolymer rubber, urethane rubber, many Examples thereof include sulfurized rubber.

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

The silica-based inorganic filler is not particularly limited and known ones can be used. For example, solid particles containing SiO ₂ or Si ₃ Al as a constituent unit are preferable, and SiO ₂ or Si ₃ Al Is more preferably the main component of the structural unit. Examples of the silica-based inorganic filler include, but are not limited to, inorganic fiber materials such as silica, clay, talc, mica, diatomaceous earth, wollastonite, montmorillonite, zeolite, and glass fiber. It is done. 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 viewpoint of reinforcing properties, and silica is more preferable. Examples of silica include dry silica, wet silica, and synthetic silicate silica. Among these, wet silica is preferable from the viewpoint of an excellent balance between the effect of improving fracture characteristics and wet skid resistance.

In the modified conjugated diene polymer composition of this embodiment, from the viewpoint of obtaining practically good wear resistance and fracture characteristics, the nitrogen adsorption specific surface area required by the BET adsorption method of the silica-based inorganic filler is 100 to 300 m. it is preferably ² / g, and more preferably 170~250m ² / g. Further, if necessary, the specific surface area is relatively small (for example, a silica-based inorganic filler having a specific surface area of 200 m ² / g or less) and the specific surface area is relatively large (for example, a silica-based inorganic material having a specific surface area of 200 m ² / g or more). And a filler) can be used in combination. In this case, there is a tendency that good wear resistance and fracture characteristics can be well balanced with low hysteresis loss.

  As described above, the compounding amount of the silica-based inorganic filler in the modified conjugated diene polymer composition is 100 parts by mass of the total amount of the modified conjugated diene copolymer (A) and the modified conjugated diene polymer (B). On the other hand, it is preferable that it is 0.5-300 mass parts, 5-200 mass parts is more preferable, and 20-100 mass parts is further more preferable. The compounding quantity of a silica type inorganic filler shall be 0.5 mass part or more with respect to 100 mass parts of total amounts of the said (A) component and (B) component from a viewpoint from which the addition effect of an inorganic filler expresses. On the other hand, from the viewpoint of sufficiently dispersing the inorganic filler and making the workability and mechanical strength of the composition practically sufficient, it is preferably 300 parts by mass or less.

  Further, the vulcanizate of the modified conjugated diene polymer composition of the present embodiment has a storage elasticity measured at a frequency of 10 Hz, strains of 0.1% and 10% at 50 ° C. from the viewpoint of improving dispersibility of silica and the like. The difference in rate (ΔG ′) is preferably 0.8 MPa or less. That is, a modified conjugated diene polymer composition further comprising 75 parts by mass of a silica-based inorganic filler with respect to a total of 100 parts by mass of the modified conjugated diene copolymer (A) and the modified conjugated diene polymer (B). When the modified conjugated diene polymer composition is a vulcanized product, the difference in storage elastic modulus (ΔG ′) measured at 50 ° C. and a frequency of 10 Hz at strains of 0.1% and 10%, It is preferably 0.8 MPa or less. From the same viewpoint, ΔG ′ is more preferably 0.7 MPa or less, and further preferably 0.6 MPa or less. The ΔG ′ can be obtained by the method described in the examples described later.

The modified conjugated diene polymer composition of the present embodiment may contain carbon black. The carbon black is not particularly limited, and for example, carbon blacks of each class such as SRF, FEF, HAF, ISAF, and SAF can be used. Among these, carbon black having a nitrogen adsorption specific surface area of 50 m ² / g or more and a DBP (Di-butyl phthalate) oil absorption of 80 mL / 100 g is preferable. The compounding amount of the carbon black is preferably 0.5 to 100 parts by mass, more preferably 3 to 100 parts by mass, with respect to 100 parts by mass of the rubber component including the component (A) and the component (B). Part by mass is more preferable. The amount of carbon black is preferably 0.5 parts by mass or more with respect to 100 parts by mass of the rubber component, from the viewpoint of expressing the performance required for applications such as tires such as dry grip performance and conductivity. From the viewpoint of properties, the content is preferably 100 parts by mass or less.

Further, the modified conjugated diene polymer composition may contain a metal oxide or a metal hydroxide in addition to the silica-based inorganic filler and carbon black. The metal oxide refers to solid particles having the chemical formula M _x O _y (M represents a metal atom, and x and y each represents an integer of 1 to 6) as a main component of a structural unit, and is particularly limited. However, 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.

  The modified conjugated diene polymer composition may contain a silane coupling agent. The silane coupling agent has a function of tightly interacting the rubber component and the silica-based inorganic filler, and has an affinity or binding group for each of the rubber component and the silica-based inorganic filler. In general, a compound having a sulfur bond portion, an alkoxysilyl group, and a silanol group portion in one molecule is used. Specifically, bis- [3- (triethoxysilyl) -propyl] -tetrasulfide, bis- [3- (triethoxysilyl) -propyl] -disulfide, bis- [2- (triethoxysilyl) -ethyl ] -Tetrasulfide etc. are mentioned. 0.1-30 mass parts is preferable with respect to 100 mass parts of silica type inorganic fillers mentioned above, as for the compounding quantity of a silane coupling agent, 0.5-20 mass parts is more preferable, and 1-15 mass parts is. Further preferred. When the blending amount of the silane coupling agent is within the above range, the addition effect of the silane coupling agent tends to be more remarkable.

  In order to improve processability, the modified conjugated diene polymer composition may contain a rubber softener. 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 polymer composition of the present embodiment, those having an appropriate aromatic content are preferred because they tend to be familiar with the copolymer. The compounding amount of the rubber softener is a rubber component containing the modified conjugated diene polymer composition of the present embodiment (that is, the modified conjugated diene copolymer (A) and the modified conjugated diene polymer (B). 0-100 mass parts is preferable with respect to 100 mass parts, 10-90 mass parts is more preferable, and 30-90 mass parts is further more preferable. When the compounding amount of the rubber softener is 100 parts by mass or less with respect to 100 parts by mass of the rubber component, it is preferable because bleeding tends to be effectively prevented and stickiness on the composition surface tends to be effectively prevented.

  The above-mentioned components (A), (B), and other rubbery polymers, silica-based inorganic fillers, carbon black and other fillers, silane coupling agents, rubber softeners, and other additives are mixed. The method 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. The method of removing by heating, 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. Also, any of a method of kneading the modified conjugated diene-based (co) polymer and various compounding agents at a time and a method of mixing in multiple times can be applied.

  The modified conjugated diene polymer composition obtained as described above may be a vulcanized composition that has been vulcanized 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 usage-amount of a vulcanizing agent is 0.01-20 mass parts normally with respect to 100 mass parts of rubber components containing (A) component and (B) component, and 0.1-15 mass parts is preferable. 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 And the like. Further, 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 100 mass parts of rubber components containing (A) component and (B) component, and 0.1-15 mass parts is preferable.

  The modified conjugated diene-based polymer composition of the present embodiment includes other softeners and fillers other than those described above, as well as heat resistance stabilizers, antistatic agents, and weather resistance, as long as the purpose of the present embodiment is not impaired. Various additives such as a stabilizer, an anti-aging agent, a colorant, and a lubricant may be used. As other softeners, known softeners can be used. Specific examples of other fillers include calcium carbonate, magnesium carbonate, aluminum sulfate, and barium sulfate. Known materials can be used as the above heat stabilizer, antistatic agent, weathering stabilizer, anti-aging agent, colorant, and lubricant.

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

(1) Amount of bound styrene A sample was used as a chloroform solution, and the amount of bound styrene (mass%) was measured by absorption at UV254 nm by the phenyl group of styrene (manufactured by Shimadzu Corporation: UV-2450).

(2) Microstructure of butadiene moiety (1,2-vinyl bond content)
The sample is a carbon disulfide solution, a solution cell is used, the infrared spectrum is measured in the range of 600 to 1000 cm −1, and the microstructure of the butadiene part is determined by the absorbance at a predetermined wave number according to the calculation formula of the Hampton method or Morello method (Manufactured by JASCO Corporation: FTIR230).

(3) Mooney viscosity According to JIS K 6300, preheating was performed at 100 ° C. for 1 minute, and the viscosity after 4 minutes was measured.

(4) Weight average molecular weight, number average molecular weight, and molecular weight distribution A chromatogram was measured using a gel permeation chromatography (GPC) using three columns each having a polystyrene gel as a packing material. A weight average molecular weight (Mw) and a number average molecular weight (Mn) were obtained from a calibration curve using polystyrene, and a molecular weight distribution index (Mw / Mn) was calculated from the ratio of the weight average molecular weight to the number average molecular weight.

  Tetrahydrofuran (THF) was used as the eluent. As the column, guard column: Tosoh TSKguardcolumn HHR-H, column: Tosoh TSKgel G6000HHR, TSKgel G5000HHR, TSKgel G4000HHR were used. 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. A sample of 10 mg was dissolved in 20 mL of THF, and 200 μL of this solution was injected into the apparatus for measurement.

(5) Modification rate Applying the property that the modified component is adsorbed on a GPC column with silica gel as a filler, using a sample solution containing a sample and standard polystyrene with a molecular weight of 5000 (polystyrene does not adsorb on the column), GPC of the polystyrene gel column and silica column (guard column: DIOL 4.6 × 12.5 mm 5 micron, column: Zorbax PSM-1000S, PSM-300S, PSM-60S, oven temperature 40 ° C., THF flow rate 0.5 mL / Min) GPC (Tosoh CCP8020 series build-up GPC system: AS-8020, SD-8022, CCPS, CO-8020, RI-8021) both chromatograms were measured using an RI detector, Measure the amount adsorbed on the silica column from the difference between the two and denature The rate was determined. As a sample, 10 mg was dissolved in 20 mL of THF together with 5 mg of standard polystyrene, and 200 μL was injected for measurement.

  As a specific procedure, the peak area of the chromatogram using the polystyrene column is set to 100, the peak area of the standard polystyrene is P2, the peak area of the standard polystyrene is P2, and the peak area of the chromatogram using the silica column is P1. Assuming 100 as a whole, the peak area of the sample was P3, the peak area of standard polystyrene was P4, and the modification rate (%) was calculated by the formula [1- (P2 × P3) / (P1 × P4)] × 100. .

[Production of Modified Copolymer SB1 (Component A)]
An autoclave with an internal volume of 5 liters and a temperature-controllable autoclave equipped with a stirrer and a jacket is used as a reactor, and 265 g of butadiene, 93 g of styrene, 2030 g of cyclohexane from which impurities have been previously removed, and 2,2-bis (2 -Oxolanyl) propane 4.1 mmol was charged into the reactor and the temperature in the reactor was kept at 50C.

  The c-hex solution of 1-lithiopiperidine was supplied to the reactor so that the amount of lithium added was 5.1 mmol. After the start of the reaction, the temperature in the reactor started to rise due to the exotherm due to polymerization, and the final temperature in the reactor reached 78 ° C.

  After completion of the polymerization reaction, 0.9 mmol of 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane was added to the reactor, and the temperature was maintained at 78 ° C. for 5 minutes. A denaturation reaction was performed. After adding 1.0 g of an antioxidant (2,6-di-t-butyl-p-cresol: BHT) to this polymer solution, the solvent is removed by steam stripping, and drying treatment is performed by a dryer. Then, a styrene-butadiene copolymer (sample SB1) having a modifying component was obtained.

  As a result of analyzing sample SB1, the amount of bound styrene was 27% by mass and the amount of bound butadiene was 73% by mass. The Mooney viscosity of Sample SB1 was 61. The 1,2-bond content of the microstructure of the butadiene portion determined by calculation according to the Hampton method from the measurement result using an infrared spectrophotometer was 57%. Moreover, the modification | denaturation rate calculated | required from GPC using a silica type adsorption column was 98%. The analysis result of sample SB1 is shown in Table 1 below.

[Production of Modified Copolymer SB2-9 (Component A)]
The kind of the lithium amide compound, the addition amount of the lithium amide compound, the addition amount of the polar substance, the kind of the modifier, the addition amount of the modifier are adjusted as shown in Table 1 below, and the production conditions are the same as described above. As a method, samples SB2 to SB9 were obtained.

[Production of Modified Copolymer SB10]
An autoclave with an internal volume of 5 liters and a temperature-controllable autoclave equipped with a stirrer and a jacket is used as a reactor, and 265 g of butadiene, 93 g of styrene, 2030 g of cyclohexane from which impurities have been previously removed, and 2,2-bis (2 -Oxolanyl) propane 2.3 mmol was put into the reactor and the temperature in the reactor was kept at 50 ° C.

  An n-butyllithium n-hex solution was supplied to the reactor so that the amount of lithium added was 2.3 mmol. After the start of the reaction, the temperature in the reactor started to rise due to the exotherm due to polymerization, and the final temperature in the reactor reached 78 ° C.

  After completion of the polymerization reaction, 1.3 mmol of N- [2- (trimethoxysilanyl) -ethyl] -N, N ′, N′-trimethylethane-1,2-diamine was added to the reactor, A denaturation reaction was carried out for 5 minutes under temperature conditions. After adding 1.0 g of an antioxidant (2,6-di-t-butyl-p-cresol: BHT) to this polymer solution, the solvent is removed by steam stripping, and drying treatment is performed by a dryer. Then, a styrene-butadiene copolymer (sample SB10) having a modifying component was obtained.

  As a result of analyzing sample SB10, the amount of bonded styrene was 26 mass%, and the amount of bonded butadiene was 74 mass%. The Mooney viscosity of Sample SB1 was 60. The 1,2-bond amount of the microstructure of the butadiene portion determined by calculation according to the Hampton method from the measurement result using an infrared spectrophotometer was 58%. Moreover, the modification | denaturation rate calculated | required from GPC using a silica type adsorption column was 88%. The analysis results of sample SB10 are shown in Table 1 below.

[Production of Modified Polymerization B1 (Component B)]
Using an autoclave with an internal volume of 5 liters and a temperature-controllable autoclave equipped with a stirrer and a jacket as a reactor, 358 g of butadiene from which impurities have been removed in advance, 2030 g of cyclohexane, 2,2-bis (2-oxolanyl) as a polar substance 0.040 mmol of propane was put into the reactor, and the temperature in the reactor was kept at 45 ° C.

  The c-hex solution of 1-lithiopiperidine was supplied to the reactor so that the amount of lithium added was 4.0 mmol. After the reaction started, the temperature in the reactor started to rise due to the exotherm due to polymerization, and the final temperature in the reactor reached 80 ° C.

  After completion of the polymerization reaction, 0.9 mmol of 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane was added to the reactor, and the temperature was maintained at 80 ° C. for 5 minutes. A denaturation reaction was performed. After adding 1.0 g of an antioxidant (2,6-di-t-butyl-p-cresol: BHT) to this polymer solution, the solvent is removed by steam stripping, and drying treatment is performed by a dryer. Then, a styrene-butadiene copolymer (sample B1) having a modifying component was obtained.

  As a result of analyzing sample SB1, Mooney viscosity was 60. The 1,2-bond content of the microstructure of the butadiene portion determined by calculation according to the Hampton method from the measurement result using an infrared spectrophotometer was 13%. Moreover, the modification | denaturation rate calculated | required from GPC using a silica type adsorption column was 99%. The analysis results of Sample B1 are shown in Table 2 below.

[Production of Modified Copolymer B2-9 (Component B)]
The type of lithium amide, the amount of lithium amide added, the amount of polar substance added, the type of modifier, the amount of modifier added are adjusted as shown in Table 2 below, and the manufacturing conditions are the same as described above. Samples B2-9 were obtained.

[Production of Modified Copolymer B10]
Using an autoclave with an internal volume of 5 liters and a temperature-controllable autoclave equipped with a stirrer and a jacket as a reactor, 358 g of butadiene from which impurities have been removed in advance, 2030 g of cyclohexane, 2,2-bis (2-oxolanyl) as a polar substance 0.024 mmol of propane was put into the reactor, and the temperature in the reactor was kept at 45 ° C.

  An n-butyl solution of n-butyllithium was supplied to the reactor so that the amount of lithium added was 2.4 mmol. After the reaction started, the temperature in the reactor started to rise due to the exotherm due to polymerization, and the final temperature in the reactor reached 80 ° C.

  After completion of the polymerization reaction, 0.7 mmol of 2,2-dimethoxy-1- (3-trimethoxysilylpropyl) -1-aza-2-silacyclopentane was added to the reactor, and the temperature was maintained at 80 ° C. for 5 minutes. A denaturation reaction was performed. After adding 1.0 g of an antioxidant (2,6-di-t-butyl-p-cresol: BHT) to this polymer solution, the solvent is removed by steam stripping, and drying treatment is performed by a dryer. Then, a styrene-butadiene copolymer (sample B1) having a modifying component was obtained.

  As a result of analyzing sample SB1, Mooney viscosity was 61. The 1,2-bond content of the microstructure of the butadiene portion determined by calculation according to the Hampton method from the measurement result using an infrared spectrophotometer was 13%. Moreover, the modification | denaturation rate calculated | required from GPC using a silica type adsorption column was 89%. The analysis results of Sample B1 are shown in Table 2 below.

[Examples 1-11, Comparative Examples 1-2]
Using the samples shown in Tables 1 and 2 (samples SB1 to SB10 and samples B1 to B10) as raw rubber, modified conjugated diene polymer compositions containing the respective raw rubbers were obtained according to the formulation shown below.
SB (conjugated diene polymer (A)): 70 parts by mass B (modified conjugated diene polymer (B)): 30 parts by mass Silica (Evonik Degussa, trade name “Ultrasil 7000GR”, nitrogen Adsorption specific surface area: 175 m2 / g): 75 parts by mass Silane coupling agent (Evonik Degussa, trade name “Si75” (tetraethoxysilylpropyl disulfide): 6 parts by mass Process oil oil (JX Nippon Oil & Energy Corporation) Manufactured, trade name “NC140”): 42 parts by mass, carbon black (manufactured by Tokai Carbon Co., Ltd., trade name “Seast KH (N339)”, iodine adsorption amount 90 g / kg, CTAB specific surface area 95 m 2 / g): 5 parts by mass Zinc Hana (Mitsui Metal Mining Co., Ltd., trade name “Zinc Hana 1”): 2.5 parts by mass, stearic acid: 1.0 part by mass, wax: (Shin Ouchi Made by Chemical Industry Co., Ltd., trade name “Sannok”, yellowish white granular, solidification point 65 ° C. or higher, specific gravity 0.93: 1.5 parts by mass / anti-aging agent (N-isopropyl-N′-phenyl-p-phenylenediamine ): 2.0 parts by mass, sulfur: 2.2 parts by mass, vulcanization accelerator (N-cyclohexyl-2-benzothiazylsulfinamide): 1.7 parts by mass, vulcanization accelerator (diphenylguanidine): 2 .0 parts by mass

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

  Using a kneader (with an internal volume of 0.5 L) equipped with a temperature control device, as a first stage kneading, under conditions of a filling rate of 65% and a rotor rotation speed of 50 rpm, a modified conjugated diene polymer (modified SBR1), silica An inorganic filler (silica), a silane coupling agent, and process oil were kneaded for 4 minutes. At this time, the temperature of the kneader was controlled, and the modified conjugated diene polymer composition was obtained at a discharge temperature (formulation) of 155 to 160 ° C.

  Next, as the second stage kneading, the blend 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 (formulation) was adjusted to 155 to 160 ° C. by controlling the temperature of the mixer. And after discharging | emitting the said compound from a kneader, the compound was immediately passed 6 times through a 10 inch diameter open roll to prepare a sheet-like unvulcanized rubber composition, and after cooling, the workability was evaluated.

  Furthermore, after heating the unvulcanized composition using an oven at 70 ° C. for 30 minutes, as a third stage of kneading, sulfur and a vulcanization accelerator were added with a 10 inch φ open roll set at 70 ° C. And kneaded to obtain a composition. Thereafter, the remainder of the composition was vulcanized with a vulcanization press at 160 ° C. for 20 minutes to obtain a vulcanized product. After vulcanization, the physical properties of the rubber composition were measured. The physical property measurement results are shown in Table 3 below.

[Comparative Example 3]
A vulcanizate was obtained in the same manner as in Example 1 except that non-modified BR (polybutadiene “Ubepol U150” manufactured by Ube Industries, Ltd.) was used instead of the modified butadiene polymer. After vulcanization, the physical properties of the rubber composition were measured. The physical property measurement results are shown in Table 3 below.

[Comparative Example 4]
A vulcanizate was obtained in the same manner as in Example 1 except that natural rubber (NR) was used instead of the modified butadiene polymer. After vulcanization, the physical properties of the rubber composition were measured. The physical property measurement results are shown in Table 3 below.

  The physical properties of the rubber composition were measured by the following methods.

<Bound rubber amount>
Formulation after completion of the second stage kneading step: About 0.2 gram was cut into a square of about 1 mm, put into a Harris basket (100 mesh wire mesh), and the weight was measured. Then, after being immersed in toluene for 24 hours, a drying treatment was performed and the weight was measured. The amount of rubber bound to the filler (modified conjugated diene polymer + natural rubber) was calculated from the amount of the undissolved component, and the ratio of the rubber bound to the filler to the amount of rubber in the first blend was determined.

<Formulation Mooney viscosity>
Using a Mooney viscometer, according to JIS K6300-1, after preheating at 130 ° C. for 1 minute, the rotor was rotated at 2 revolutions per minute, and the viscosity after 4 minutes was measured. Each measured value was indexed with Comparative Example 2 as 100 for each Example and Comparative Example. It shows that it is excellent in workability, so that a value is small.

<Tensile elongation / breaking strength>
It was measured by the tensile test method of JIS K6251. Each measured value was indexed with Comparative Example 2 as 100 for each Example and Comparative Example. It shows that it is excellent in fracture resistance, so that a numerical value is large.

<Viscoelastic parameters>
A viscoelasticity tester (ARES) manufactured by Rheometrics Scientific was used to measure viscoelastic parameters in torsional mode.

  Further, tan δ measured at 0 ° C. with a frequency of 10 Hz and a strain of 1% was used as an index of wet grip performance. A larger value indicates better wet grip performance. About each measured value of each Example and a comparative example, the comparative example 2 was set to 100, and was indexed.

  Further, tan δ measured at 50 ° C. with a frequency of 10 Hz and a strain of 3% was used as an index of fuel saving characteristics. Larger values indicate better fuel economy. About each measured value of each Example and a comparative example, the comparative example 2 was set to 100, and was indexed.

  G ′ measured at 50 ° C. with a frequency of 10 Hz and a strain of 3% was used as an indicator of steering stability. The larger the value, the better the steering stability. About each measured value of each Example and a comparative example, the comparative example 2 was set to 100, and was indexed. Further, the difference in storage elastic modulus (G ′) between strains of 0.1% and 10% was used as an index of the Payne effect as ΔG ′. The smaller the value, the better the dispersibility of the filler such as silica. About each measured value of each Example and a comparative example, the comparative example 2 was set to 100, and was indexed.

<Abrasion resistance>
Using an Akron abrasion tester, the amount of wear at a load of 6 pounds and 1000 revolutions was measured, and the measured values of each Example and Comparative Example were indexed with Comparative Example 2 as 100. A larger index indicates better wear resistance.

  As shown in Table 3, the modified conjugated diene polymer compositions of Examples 1 to 11 were obtained by using a polymer modified with a modifier that does not correspond to the desired modifier of this embodiment. Compared with the compositions of Examples 1 to 4, the tan δ (strain 3%) at 50 ° C. is low, so the hysteresis loss is low, the tire has low rolling resistance, and the tan δ (strain 1) at 0 ° C. %) Was high and it was confirmed that the wet skid resistance was excellent. Further, since G ′ at 50 ° C. was sufficiently high, it was confirmed that high fuel economy performance was exhibited while ensuring practically sufficient steering stability. Furthermore, the compound Mooney viscosity is sufficiently low, so that it has practically sufficient processability, and because it has sufficiently good tensile strength and wear resistance, it is confirmed that it has practically sufficient mechanical properties. It was done.

  The modified conjugated diene polymer composition of the present invention is excellent in balance of physical properties such as wet skid characteristics, low hysteresis loss, wear resistance, fracture strength, and handling stability and processability even when combined with an inorganic filler. Therefore, it has industrial applicability in fields such as automobile interior / exterior products, anti-vibration rubber, belts, footwear, foams, various industrial parts, and tire applications.

Claims (6)

It has a functional group represented by the following general formula (1) at the terminal and an alkoxysilyl group and an amine at a terminal different from the terminal having the functional group represented by the following general formula (1). A modified conjugated diene copolymer (A) having a functional group and a unit derived from an aromatic vinyl compound;
It has a functional group represented by the following general formula (1) at the terminal and an alkoxysilyl group and an amine at a terminal different from the terminal having the functional group represented by the following general formula (1). A modified conjugated diene polymer (B) having a functional group that does not contain a unit derived from an aromatic vinyl compound, and
Modified conjugated diene polymer composition containing:

(In the general formula (1), R1 and R2 are any 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. R1 and R2 may be bonded to form a cyclic structure with the adjacent nitrogen atom, in which case R1 and R2 are the total of It is a hydrocarbon group having a carbon number of 4 to 12. R1 and R2 may have an unsaturated bond or a branched structure. The modification | denaturation of Claim 1 to which the said modified conjugated diene type | system | group copolymer (A) and the said modified conjugated diene type polymer (B) are each represented by either of the following general formula (2)-(8). Conjugated diene polymer composition:

(In the general formula (2), R3 to R6 are each independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R7 and R8 are each independently carbon. An alkylene group having a number of 1 to 20, R9 is a silyl group substituted with hydrogen or hydrocarbon, a and c are each independently an integer of 1 or 2, and b and d are each independently And a + b and c + d are integers equal to or less than 2. Here, when the general formula (2) is the modified conjugated diene copolymer (A), Polym is an aromatic vinyl compound. When the general formula (2) is a modified conjugated diene polymer (B), Polym is a conjugated diene-based polymer containing no unit derived from an aromatic vinyl compound. And at least one end of Polym is When serial is a functional group represented by the general formula (1) .R3~R6 there are multiple, they may be each independently selected from the same.)

(In the general formula (3), R10 to R13 are each independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R14 and R15 are each independently a carbon number. 1 to 20 alkylene groups, e and g are each independently an integer of 0 to 2, and either e or g is 1 or more, and f and h are each independently 0 or 1 E + f and g + h are integers equal to or less than 2. Here, when the general formula (3) is the modified conjugated diene copolymer (A), Polym is a unit derived from an aromatic vinyl compound. When the general formula (3) is a modified conjugated diene polymer (B), Polym is a conjugated diene polymer that does not contain a unit derived from an aromatic vinyl compound, At least one end of Polym which may be plural Is a functional group represented by the general formula (1), i is an integer of 0 to 20, and when i is 2 or more, the plurality of repeating units represented by (R14-A1-R15) are: A1 is a group represented by any one of the following general formulas (a), (b), and (c), and when there are a plurality of R10 to R13. Each may be the same or different.)

(In the general formula (a), R16 and R17 are each independently an alkylene group having 1 to 20 carbon atoms, and together with two adjacent Ns, form a ring structure of five or more members.)

(In the general formula (b), R18 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a hydrocarbon group having 1 to 20 carbon atoms substituted with a hetero atom having no active hydrogen. Any one selected from the group consisting of

(In the general formula (c), R18 is an alkylene group having 1 to 20 carbon atoms, and R19 and R20 are each independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. J is an integer of 0 to 2, k is an integer of 0 or 1, and j + k is an integer of 2 or less, wherein the general formula (3) is a modified conjugated diene copolymer (A) In this case, Polym is a conjugated diene copolymer containing a unit derived from an aromatic vinyl compound, and when General Formula (3) is a modified conjugated diene polymer (B), Polym is an aromatic vinyl. It is a conjugated diene polymer that does not contain a compound-derived unit, and at least one terminal of Polym may be a functional group represented by the general formula (1) When there are a plurality of R19 and R20 They are each identical And it may be different as well.)

(In the general formula (4), R21 and R22 are each independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R23 and R24 are each independently carbon. An alkylene group having 1 to 20 carbon atoms, and R25, R26, and R27 each independently include Si, O, or N, and may be substituted with an organic group having no active hydrogen. A hydrocarbon group, wherein l is an integer of 1 or 2, m is an integer of 0 or 1, and l + m is an integer of 2 or less, wherein the general formula (4) is a modified conjugated diene-based copolymer In the case of the compound (A), Polym is a conjugated diene copolymer containing units derived from an aromatic vinyl compound, and when the general formula (4) is a modified conjugated diene polymer (B), Polym is Conjugated dienes that do not contain units derived from aromatic vinyl compounds At least one terminal of the polym that is a combination and may be a plurality is a functional group represented by the general formula (1) When there are a plurality of R21 and R22, they may be the same or different. May be.)

(In the general formula (5), R28 and R29 are each independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R30 is an alkylene group having 1 to 20 carbon atoms. , R31 and R32 are each independently a divalent hydrocarbon group having 1 to 6 carbon atoms, and together with two adjacent Ns, form a ring structure of five or more members, and R33 has 1 to 20 carbon atoms. A hydrocarbon group, a hydrocarbon group having 1 to 20 carbon atoms substituted with a heteroatom having no active hydrogen, or an organically substituted silyl group, n is an integer of 1 or 2, and o is 0 or 1 N + o is an integer equal to or less than 2. Here, when the general formula (5) is the modified conjugated diene copolymer (A), Polym is a conjugate containing a unit derived from an aromatic vinyl compound. This is a diene copolymer, and the general formula (5) is a modified conjugated diene. In the case of the polymer (B), Polym is a conjugated diene polymer that does not contain a unit derived from an aromatic vinyl compound, and at least one terminal of the Polym that may be plural is represented by the general formula (1). When there are a plurality of R28 and R29, they may be the same or different.)

(In the general formula (6), R34 and R35 are each independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R36 is an alkylene group having 1 to 20 carbon atoms. , R37 and R38 are each independently a divalent hydrocarbon group having 1 to 6 carbon atoms, and form a ring structure of 5 or more members with two adjacent Ns, and R39 and R40 each independently And a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms substituted with a heteroatom having no active hydrogen, or a 3 organic substituted silyl group, m is an integer of 1 or 2 And q is an integer of 0 or 1, and p + q is an integer of 2 or less, where, when general formula (6) is a modified conjugated diene copolymer (A), Polym is an aromatic vinyl Conjugated diene copolymer containing a compound-derived unit When 6) is a modified conjugated diene polymer (B), Polym is a conjugated diene polymer that does not contain a unit derived from an aromatic vinyl compound, and at least one terminal of Polym, which may be plural, is the above-mentioned This is a functional group represented by the general formula (1) .When there are a plurality of R34 and R35, they may be the same or different.

(In the general formula (7), A2 is a monovalent group having at least one functional group selected from the group consisting of a tertiary amine, pyridine, cyan and imine, and R41 and R42 are each independently, An alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, R43 is an alkylene group having 1 to 20 carbon atoms, r is an integer of 1 or 2, and s is an integer of 0 or 1. Here, when the general formula (7) is the modified conjugated diene copolymer (A), Polym is a conjugated diene copolymer containing a unit derived from an aromatic vinyl compound, and the general formula ( When 7) is a modified conjugated diene polymer (B), Polym is a conjugated diene polymer that does not contain a unit derived from an aromatic vinyl compound, and at least one terminal of Polym may be plural. General formula 1) it is a functional group represented by .R41, when R42 is plurally present, they may be each independently selected from the same.)

(In the general formula (8), R44 is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R45 is an alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms. Or an alkoxy group having 1 to 20 carbon atoms, and R46 is an alkylene group having 1 to 20 carbon atoms, and R47 and R48 are each independently hydrogen or a silyl group substituted with a hydrocarbon. Is an integer from 1 to 2, u is an integer from 0 to 1, v is an integer from 1 to 10. w is 3-tu when v is 1, and v is 2 or more. Here, when general formula (8) is a modified conjugated diene copolymer (A), Polym is a conjugated diene copolymer containing units derived from an aromatic vinyl compound. Yes, when the general formula (8) is a modified conjugated diene polymer (B), Pol m is a conjugated diene polymer containing no unit derived from an aromatic vinyl compound, and at least one terminal of Polym, which may be plural, is a functional group represented by the general formula (1) R44, When a plurality of R45 are present, they may be the same or different. A silyl group in which a conjugated diene compound and an aromatic vinyl compound are copolymerized in a hydrocarbon solvent using a lithium amide compound, and then substituted at the active terminal of the polymer with two or more alkoxy groups And a modified conjugated diene copolymer (A1) obtained by reacting a compound having one or more nitrogen atoms,
After polymerizing a conjugated diene compound in a hydrocarbon solvent using a lithium amide compound, a silyl group substituted with two or more alkoxy groups and one or more nitrogen atoms at the active terminal of the obtained polymer A modified conjugated diene polymer (B1) obtained by reacting a compound having
A modified conjugated diene polymer composition comprising: The compound having a silyl group substituted with two or more alkoxy groups and one or more nitrogen atoms is a compound represented by any one of the following general formulas (11) to (18). Modified conjugated diene polymer composition.

(In the general formula (11), R51 to R54 each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R58 and R59 each independently represent carbon. Represents an alkylene group of 1 to 20, m1 is an integer of 1 or 2, and n1 is an integer of 2 or 3. Here, when there are a plurality of R51 to R54, they are the same. May be different.)

(In the general formula (12), R61 to R64 each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R68 and R69 each independently represent carbon. Represents an alkylene group of 1 to 20, and when a plurality of R68, R69 and A61 are present, they may be the same or different, and m2 and n2 are each an integer of 0 to 3. p2 is an integer of 0 to 20, and when p2 is 2 or more, the plurality of repeating units represented by (R69-A61-R68) may be different from each other. And each of them may be the same or different, and A61 is a group represented by any one of the following general formulas (d), (e), and (f).)

(In the general formula (d), R70 and R71 are each independently an alkylene group having 1 to 20 carbon atoms, and together with two adjacent Ns, form a ring structure of five or more members.)

(In the general formula (e), R87 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms substituted by a hetero atom having no active hydrogen. And any one selected from the group consisting of three organic substituted silyl groups.)

(In the general formula (f), R90 is an alkylene group having 1 to 20 carbon atoms, and R95 and R96 are each independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. R1 is an integer of 0 to 3.)

(In the general formula (13), R101 and R102 each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R108 and R109 each independently represent carbon. Represents an alkylene group having 1 to 20 carbon atoms, and R112, R113, and R114 each independently contains Si, O, or N, and may be substituted with an organic group having no active hydrogen. I3 is an integer of 1 to 3. When a plurality of R101 and R102 are present, they may be the same or different.

(In the general formula (14), R201 and R202 are each independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R209 is an alkylene group having 1 to 20 carbon atoms. , R210, and R211 are each independently a divalent hydrocarbon group having 1 to 6 carbon atoms, and together with two adjacent Ns, form a ring structure of five or more members, and R215 has 1 to 20 carbon atoms. A hydrocarbon group having 1 to 20 carbon atoms substituted with a hetero atom having no active hydrogen, or a 3 organic substituted silyl group, m4 is an integer of 2 or 3. R201 and R202 are , When there are a plurality, they may be the same or different.)

(In the general formula (15), R301 and R302 are each independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R309 is an alkylene group having 1 to 20 carbon atoms. , R310 and R311 are each independently a divalent hydrocarbon group having 1 to 6 carbon atoms, and together with two adjacent Ns, form a ring structure of five or more members, and R315 and R316 each independently And a hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms substituted with a heteroatom having no active hydrogen, or a 3 organic substituted silyl group, and m5 is 2 or 3 (When there are a plurality of R301 and R302, they may be the same or different.)

(In the general formula (16), A400 is a monovalent group having at least one functional group selected from the group consisting of tertiary amine, pyridine, cyan, and imine, and R401 and R402 are each independently An alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, R408 is an alkylene group having 1 to 20 carbon atoms, m6 is an integer of 2 or 3. There are a plurality of R401 and R402. Sometimes they may be the same or different.)

(In the general formula (17), R501, R502 and R506 each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R508 represents an alkylene having 1 to 20 carbon atoms. R503, R504 and R505 are each independently an alkyl group or aryl group having 1 to 20 carbon atoms, or two of them are bonded to each other to form a ring together with the silicon atom to which they are bonded. M7 is an integer of 1 to 2, and f7 is an integer of 1 to 10. When a plurality of R501 to R505 and R508 are present, they may be the same or different. May be.)

(In the general formula (18), R601 and R602 each independently represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R608 represents an alkylene group having 1 to 20 carbon atoms. R603, R604 and R605 are each independently an alkyl group or aryl group having 1 to 20 carbon atoms, or two of them are bonded to each other to form a ring together with the silicon atom to which they are bonded. M8 is an integer of 1 to 2. R601 may be the same or different.   The silica-based inorganic filler is further contained in an amount of 0.5 to 300 parts by mass with respect to 100 parts by mass in total of the modified conjugated diene copolymer (A) and the modified conjugated diene polymer (B). The modified conjugated diene polymer composition according to any one of -4.   A modified conjugated diene polymer composition further comprising 75 parts by mass of a silica-based inorganic filler with respect to a total of 100 parts by mass of the modified conjugated diene copolymer (A) and the modified conjugated diene polymer (B). When the modified conjugated diene polymer composition was vulcanized, the difference in storage modulus (ΔG ′) measured at a strain of 0.1% and 10% at 50 ° C. and a frequency of 10 Hz was 0. The modified conjugated diene polymer composition according to any one of claims 1 to 4, which is 0.8 MPa or less.