JP6865622B2 - Method for Producing Modified Diene Polymer, Modified Diene Polymer, Rubber Composition and Tire - Google Patents

Description

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

In recent years, there has been an increasing demand for fuel efficiency of automobiles in connection with the movement of global carbon dioxide emission regulations accompanying the growing interest in environmental issues. In order to meet such demands, reduction of rolling resistance is also required for tire performance. Conventionally, as a method of reducing the rolling resistance of a tire, a method of optimizing the tire structure has also been studied, but the rubber composition applied to the tire has a low tan δ (hereinafter referred to as “low loss property”). It is currently practiced as a general method to use a material having excellent low heat generation.

As a method for obtaining such a rubber composition having low heat generation, it is conceivable to reduce the amount of a filler such as carbon black or silica, or to use carbon black having a large particle size. Deterioration of reinforcement, abrasion resistance, grip on wet roads, etc. is inevitable.

On the other hand, as a method for obtaining a rubber composition having low heat generation, many technical developments have been made to improve the dispersibility of the filler in the rubber composition. Among them, a method of modifying the polymerization active site of the conjugated diene polymer obtained by anionic polymerization using alkyllithium with a functional group capable of interacting with the filler is particularly effective.

For example, Patent Document 1 discloses a method in which carbon black is used as a filler and a modified conjugated diene-based polymer in which a polymerization active site is modified with a tin compound is used as a rubber component. Further, Patent Document 2 discloses a method in which carbon black is used as a filler and a modified conjugated diene-based polymer in which both ends of polymerization activity are modified with a tin compound is used as a rubber component.

However, when the modified conjugated diene polymer disclosed in Patent Documents 1 and 2 is used, the modified conjugated diene polymer is used in the rubber composition for fuel-efficient tires in which the amount of the filler and the softening agent is small. Although the effect of improving the dispersibility of the filler is large, in the rubber composition for general-purpose tires in which the amount of the filler and the softening agent is large, the effect of improving the dispersibility of the filler by the modified conjugated diene polymer is sufficiently exhibited. However, there are problems that the low loss property of the rubber composition, the breaking property and the abrasion resistance cannot be sufficiently improved.

Therefore, in Patent Document 3, a nitrogen-containing functional group is used as a rubber component for the purpose of improving the dispersibility of the filler and obtaining excellent low loss even when the amount of the filler or the softening agent is large. A rubber composition using one or more modified conjugated diene-based polymers is disclosed.

Japanese Unexamined Patent Publication No. 5-287121 Japanese Unexamined Patent Publication No. 6-49279 Japanese Unexamined Patent Publication No. 2005-298626

According to the rubber composition of Patent Document 3, it is possible to obtain a certain low loss property even when the amount of the filler or the softening agent is large. However, for the purpose of further reducing fuel consumption when used in tires, further improvement in low loss property is desired, and particularly when the rubber composition contains a large amount of reinforcing filler such as silica, reinforcing filling is performed. It has been desired to develop a technology capable of improving the dispersibility of the material and realizing excellent low loss.

Therefore, an object of the present invention is to obtain a modified diene polymer capable of obtaining a rubber composition having excellent low loss properties when used together with a reinforcing filler. The purpose is to provide a manufacturing method. Another object of the present invention is a modified diene polymer capable of realizing a rubber composition having excellent low loss property when used together with a reinforcing filler, a rubber composition having excellent low loss property, and a rubber composition having excellent low loss property. The purpose of the present invention is to provide tires with reduced rolling resistance.

The present inventors have conducted diligent research to achieve the above object. When a tetradin-based compound was used as a modifier for modifying the diene-based polymer containing 1,3-butadiene, the main chain of the diene-based polymer could be modified, and a reinforcing filler such as silica could be used. As a result of increasing the number of reaction sites, it was found that the dispersibility of the reinforcing filler can be improved.
Then, as a result of further diligent research, the present inventors made the main chain of the diene polymer efficient by mixing the diene polymer produced in advance with the tetrazine compound and then heating the mixture. It has been found that it can be specifically modified and excellent low loss property can be realized when it is used together with a reinforcing filler, and the present invention has been completed.

That is, the method for producing a modified diene polymer of the present invention includes a step of producing a diene polymer containing 1,3-butadiene and a step of producing the diene polymer.
A step of mixing the produced diene-based polymer with a tetrazine-based compound and then heating to modify the main chain of the diene-based polymer.
It is characterized by having.
With the above configuration, it is possible to obtain a modified diene-based polymer that can be used as a rubber composition having excellent low loss properties when used together with a reinforcing filler.

Further, in the method for producing a modified diene polymer of the present invention, it is preferable that the substituent in the tetrazine structure of the tetrazine compound has at least one element selected from N, O and F, and 3,6 More preferably, it is at least one selected from −di (2-pyridyl) -1,2,4,5-tetrazine and 3,6-di (4-pyridyl) -1,2,4,5-tetrazine. .. This is because the dispersibility of the reinforcing filler can be further improved, and the low loss property when used in the rubber composition can be further improved.

Further, in the method for producing a modified diene polymer of the present invention, when the molecular weight of the diene polymer is 100,000 to 2000000, the blending amount of the tetradin compound is based on 100 parts by mass of the diene polymer. , 0.01 to 2.5 parts by mass is preferable. This is because the dispersibility of the reinforcing filler can be further improved, and the low loss property when used in the rubber composition can be further improved.

Furthermore, in the method for producing a modified diene polymer of the present invention, the diene polymer preferably further contains an aromatic vinyl compound, and more preferably the aromatic vinyl compound is styrene. This is because the dispersibility of the reinforcing filler can be further improved, and the low loss property when used in the rubber composition can be further improved.

Further, in the method for producing a modified diene polymer of the present invention, heating of a mixture of the diene polymer and the tetrazine compound is preferably carried out as a drying step of the diene polymer. This is because the modification efficiency of the diene polymer can be increased.

The modified diene polymer of the present invention is characterized by being produced by the above-mentioned method for producing a modified diene polymer of the present invention.
This is because the above configuration makes it possible to realize a rubber composition having excellent low loss property when used together with a reinforcing filler.

The rubber composition of the present invention is characterized by containing the above-mentioned rubber component containing the modified diene polymer of the present invention and a reinforcing filler.
With the above configuration, the dispersibility of the reinforcing filler is high, and excellent low loss can be realized.

Further, in the rubber composition of the present invention, it is preferable that the reinforcing filler contains silica. This is because the dispersibility of the reinforcing filler becomes higher and better low loss property can be realized.

The tire of the present invention is characterized by using the rubber composition described above.
With the above configuration, excellent rolling resistance can be realized.

According to the present invention, a modified diene polymer capable of obtaining a modified diene polymer capable of producing a rubber composition excellent in low loss property when used together with a reinforcing filler. A manufacturing method can be provided. Further, according to the present invention, a modified diene polymer capable of realizing a rubber composition having excellent low loss property when used together with a reinforcing filler, a rubber composition having excellent low loss property, and a rubber composition having excellent low loss property. It is possible to provide a tire with reduced rolling resistance.

<Method for producing modified diene polymer>
Hereinafter, embodiments of the method for producing a modified diene polymer of the present invention will be described in detail.
The method for producing a modified diene polymer of the present invention includes a step of producing a diene polymer containing 1,3-butadiene and a step of producing the diene polymer.
A step of mixing the produced diene-based polymer with a tetrazine-based compound and then heating to modify the diene-based polymer.
It is characterized by having.
By using a tetrazine compound as a modifier for modifying the diene polymer containing 1,3-butadiene, the main chain of the diene polymer can be modified, and the main chain of the diene polymer can be modified with a reinforcing filler such as silica. As a result of increasing the number of reaction sites, it is possible to improve the dispersibility of the reinforcing filler. As a result, when the produced modified diene polymer is used together with the reinforcing filler to form a rubber composition, the low loss property of the rubber composition can be significantly improved.
Further, the main chain of the diene-based polymer can be efficiently denatured by mixing the produced diene-based polymer with the tetrazine-based compound and then heating the mixture.

(Diene polymer manufacturing process)
The method for producing a modified diene polymer of the present invention includes a step of producing a diene polymer containing 1,3-butadiene (hereinafter, may be referred to as a "diene polymer production step").

Here, in the diene polymer production step, a diene polymer containing 1,3-butadiene is obtained by a polymerization reaction. The polymerization method of the diene-based polymer containing 1,3-butadiene is not particularly limited, and a polymerization method generally used for 1,3-butadiene such as bulk polymerization, solution polymerization, and emulsion polymerization is adopted. be able to.
Examples of the solvent for solution polymerization and emulsification polymerization include saturated aliphatic hydrocarbons having 4 to 10 carbon atoms such as butene, pentane, hexane and heptane, and saturated alicyclic hydrocarbons having 5 to 20 carbon atoms such as cyclopentane and cyclohexane. Monoolefins such as hydrogen, 1-butene and 2-butene, aromatic hydrocarbons such as benzene, toluene and xylene, methylene chloride, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, 1,2-dichloroethane, chlorobenzene, Examples thereof include halogenated hydrocarbons such as bromobenzene and chlorotoluene. Among these, aliphatic hydrocarbons having 5 to 6 carbon atoms and alicyclic hydrocarbons are particularly preferable. These solvents may be used alone or in admixture of two or more. Moreover, 1,3-butadiene itself may be used as a polymerization solvent.

The molecular weight of the diene polymer is not particularly limited, but a peak molecular weight of 100,000 or more is preferable from the viewpoint of obtaining good fracture resistance and wear resistance, and is preferably 700,000 or less. However, it is more preferable in that good workability can be obtained in addition to good fracture resistance and wear resistance. Further, in order to achieve both high fracture resistance, abrasion resistance and workability, it is desirable that the peak molecular weight is 100,000 to 350,000. The peak molecular weight is defined as the polystyrene-equivalent peak molecular weight (Mp) measured by gel permeation chromatography (GPC).

Here, the diene-based polymer may contain 1,3-butadiene, and other configurations are not particularly limited. For example, the diene-based polymer may be a diene copolymer or a diene homopolymer.
Among them, it is preferable that the diene-based polymer is a homopolymer of a diene-based monomer or further contains an aromatic vinyl compound. Further, when the diene-based polymer further contains an aromatic vinyl compound, it is more preferable that the diene-based polymer is a copolymer of the diene-based monomer and the aromatic vinyl compound. This is because the low loss property, fracture property and wear resistance of the diene polymer can be improved.
From the same viewpoint, the diene-based polymer is a polymer (monopolymer) formed by polymerizing 60 to 100% by mass of a diene-based monomer and 0 to 40% by mass of an aromatic vinyl compound. Alternatively, it is particularly preferably a copolymer. Further, the proportion of the 1,3-butadiene monomer unit in the diene-based monomer is preferably 70% by mass or more.

The diene-based monomer contains 1,3-butadiene, but in addition, for example, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 2-phenyl-1,3-butadiene, and the like. Conjugated diene compounds such as 1,3-hexadiene can be included. These conjugated diene compounds may be used alone or in combination of two or more.

Further, as the aromatic vinyl compound as a monomer, styrene, α-methylstyrene, 1-vinylnaphthalene, 3-vinyltoluene, ethylvinylbenzene, divinylbenzene, 4-cyclohexylstyrene and 2,4,6- Examples thereof include trimethylstyrene, and among these, styrene is particularly preferable. These aromatic vinyl compounds may be used alone or in combination of two or more.
When styrene is contained as the aromatic vinyl compound, the amount of bound styrene is preferably 0 to 50%, more preferably 10 to 30%.

Further, the diene-based polymer has a cis-1,4 bond amount of preferably 94% or more, more preferably 96% or more, and particularly preferably 98% or more. When the amount of cis-1,4 bond of the diene polymer is less than 94%, the effect of the present invention tends to be difficult to be exhibited, and when it is within the above range, it is excellent due to the increase in stretch crystallinity. It is possible to exhibit crack resistance. The amount of cis-1,4 bond means the ratio of cis-1,4 bond in the butadiene compound unit in the butadiene polymer.

Further, in the diene-based polymer production step, the polymerization is not a conjugated system but has a structure in which the number of carbon atoms in the alkyl chain extended from an atom that radically cleaves at one point to become at least one radical is 5 to 10. Initiators can also be used.
Examples of the polymerization initiator include t-butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexano. More preferably, it is at least one selected from ate and t-hexylperoxy-2-ethylhexanoate, t-butylhydroperoxide and / or t-hexylperoxy-2-ethylhexanoate. Noate is more preferred.

(Diene polymer modification step)
The method for producing a modified diene polymer of the present invention comprises the diene polymer produced in the diene polymer production step following the diene polymer production step, and a tetrazine compound as a modifier. Is further provided with a step of modifying the diene-based polymer by heating after mixing the above (hereinafter, may be referred to as a “diene-based polymer modification step”).

By using the tetradine-based compound as a modifier, the tetradine-based compound modifies the main chain of the diene-based polymer, so that the number of reaction sites between the modified diene-based polymer and the reinforcing filler such as silica increases. As a result of being able to enhance the interaction with the reinforcing filler, it is possible to improve the dispersibility of the reinforcing filler.

式中、テトラジン系化合物の側鎖にあるＲ^１及びＲ^２は、それぞれ、置換又は無置換の炭素数１〜１１の炭化水素基を示す。 Here, the tetrazine-based compound is a compound having a tetrazine structure, and in the present invention, it is a compound having a structure of 1,2,4,5-tetrazine as represented by the following formula. is there.

^{In the formula, R 1} and R ^{2 in} the side chain of the tetrazine-based compound represent a substituted or unsubstituted hydrocarbon group having 1 to 11 carbon atoms, respectively.

Specific examples of the tetrazine-based compound include the following.

Further, as a specific example of the tetrazine-based compound,
1,2,4,5-Tetrazine,
3,6-bis (2-pyridyl) -1,2,4,5-tetrazine,
3,6-bis (3-pyridyl) -1,2,4,5-tetrazine,
3,6-bis (4-pyridyl) -1,2,4,5-tetrazine,
3,6-diphenyl-1,2,4,5-tetrazine,
3,6-dibenzyl-1,2,4,5-Tetrazine,
3,6-bis (2-furanyl) -1,2,4,5-tetrazine,
3-Methyl-6- (3-pyridyl) -1,2,4,5-tetrazine,
3,6-bis (3,5-dimethyl-1-pyrazolyl) -1,2,4,5-tetrazine,
3,6-bis (2-thienyl) -1,2,4,5-tetrazine,
3-Methyl-6- (2-pyridyl) -1,2,4,5-tetrazine,
3,6-bis (4-hydroxyphenyl) -1,2,4,5-tetrazine,
3,6-bis (3-hydroxyphenyl) -1,2,4,5-tetrazine,
3,6-bis (2-pyrimidinyl) -1,2,4,5-tetrazine,
3,6-bis (2-pyrazyl) -1,2,4,5-tetrazine and the like can also be mentioned.

Further, among the above-mentioned tetrazine-based compounds ^{, at least one of R 1} and R ² contains at least one element selected from N, O and F (the substituents in the tetrazine structure are N, O and F). It has at least one element selected from), more preferably contains at least N, further preferably a nitrogen-containing heterocycle, ^{and both R 1} and R ² are nitrogen-containing heterocycles. Is particularly preferred.
After the diene polymer is modified, the interaction between the diene polymer and silica can be increased, and more excellent low loss property can be realized.

From the same point of view, the tetrazine-based compound is
3,6-bis (2-pyridyl) -1,2,4,5-tetrazine (hereinafter, also referred to as "3,6-di (2-pyridyl) -1,2,4,5-tetrazine"),
3,6-bis (3-pyridyl) -1,2,4,5-tetrazine, (hereinafter also referred to as "3,6-di (3-pyridyl) -1,2,4,5-tetrazine")
3,6-bis (2-furanyl) -1,2,4,5-tetrazine, (hereinafter also referred to as "3,6-di (2-furanyl) -1,2,4,5-tetrazine")
3-Methyl-6- (3-pyridyl) -1,2,4,5-tetrazine, and
More preferably, it is at least one selected from 3-methyl-6- (2-pyridyl) -1,2,4,5-tetrazine.
Further, from the same viewpoint, the tetrazine compounds are 3,6-di (2-pyridyl) -1,2,4,5-tetrazine and 3,6-di (4-pyridyl) -1,2. , 4,5-Tetrazine, is particularly preferred.

The blending amount of the tetrazine-based compound is not particularly limited as long as it can modify the diene-based polymer. However, when the molecular weight of the diene-based polymer is 100,000 to 2000,000, the blending amount of the tetrazine-based compound is large from the viewpoint of enhancing the dispersibility of the reinforcing filler and realizing low loss at a higher level. , 0.01 to 2.5 parts by mass is preferable with respect to 100 parts by mass of the diene-based polymer. By setting the blending amount of the tetrazine-based compound to 0.01 parts by mass or more with respect to 100 parts by mass of the diene-based polymer, the diene-based polymer can be more reliably modified, 2.5. By setting the content to parts by mass or less, deterioration of workability and scorch resistance can be prevented.

Further, in the diene polymer modification step, heating is performed after mixing the diene polymer and the tetrazine compound. By this heating, the main chain of the diene polymer can be efficiently denatured. The heating is defined as "heating is performed after mixing the diene polymer and the tetrazine compound", but this is performed after quenching the polymerization reaction and mixing with the tetrazine compound. The mixture may be heated, or after quenching the polymerization reaction, the tetradine-based compound may be added in a heated state of the polymer, and heating may be started at the same time as mixing.

The temperature in the heating is not particularly limited as long as the diene polymer can be modified, but is 100 ° C. from the viewpoint that the main chain of the diene polymer can be modified more efficiently. Is preferable.
Further, the heating time is not particularly limited as long as the diene polymer can be modified.

Further, heating of the mixture of the diene-based polymer and the tetrazine-based compound is preferably carried out as a drying step of the diene-based polymer. This is because the drying step of the diene-based polymer is carried out at a high temperature, and therefore, the main chain of the diene-based polymer can be more efficiently modified by using the drying step. Further, in the reaction between the diene polymer and the tetrazine compound, the tetrazine compound can be uniformly mixed in the polymer by stirring and mixing the tetrazine compound in the polymer polymerization solution. As a result, there is an effect that the reaction efficiency is increased. Further, the heating immediately after the production of the polymer has an effect that the side reaction is small and the reaction efficiency is higher than the heating during the kneading.

Here, in the method for producing a modified diene polymer of the present invention, the main chain of the diene polymer can be modified by the tetradin compound, but another modifier is further added to form the diene polymer. The polymer can also be modified. The diene polymer is modified by the tetrazine compound to enhance the interaction with a reinforcing filler such as silica, but the modification with a tetrazine compound makes it difficult to obtain an interaction with the reinforcing filler (for example, carbon). By modifying it so that it interacts with other fillers (such as black) and other fillers (fillers other than reinforcing fillers), dispersibility is enhanced for many fillers, resulting in better low loss properties. Abrasion resistance can be achieved.

The mixing of the tetrazine-based compound is carried out in the diene-based polymer modification step after the diene-based polymer production step, but the timing of mixing the other modifiers is not particularly limited. The tetrazine-based compound may be mixed before, after, or at the same time.

The modifying agent other than the tetrazine-based compound can be appropriately selected depending on the type of modified functional group required.
For example, when the purpose is to further enhance the interaction of the modified diene polymer with silica, a modifying agent having at least one of the compounds represented by the following general formulas (I) to (X) can be mentioned. ..

前記一般（Ｉ）式中、Ｒ^１及びＲ^２は、それぞれ独立に炭素数１〜２０の一価の脂肪族炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基を示し、ａは０〜２の整数であり、ＯＲ^２が複数ある場合、複数のＯＲ^２は互いに同一でも異なっていても良く、また分子中には活性プロトンは含まれない。

In the general formula (I), R ¹ and R ² independently represent a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, respectively. a is an integer of 0 to 2, if the OR ² there is a plurality, the plurality of OR ² may be the same or different from each other, also in the molecule does not include active proton.

Here, specific examples of the compound represented by the general formula (I) (alkoxysilane compound) include, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, and tetra-n. -Butoxysilane, tetraisobutoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyl Triethoxysilane, ethyltripropoxysilane, ethyltriisopropoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltripropoxysilane, propyltriisopropoxysilane, butyltrimethoxysilane, butyltriethoxysilane, phenyltrimethoxysilane , Phenyltriethoxysilane, dimethoxydimethylsilane, methylphenyldimethoxysilane, dimethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, divinyldiethoxysilane, etc. Among these, tetraethoxysilane , Methyltriethoxysilane and dimethyldiethoxysilane are suitable. These may be used individually by 1 type and may be used in combination of 2 or more type.

前記一般式（ＩＩ）中、Ａ^１はエポキシ、イソシアネート、イミン、カルボン酸エステル、カルボン酸無水物、環状三級アミン、非環状三級アミン、ピリジン、シラザン及ジスルフィドからなる群より選択される少なくとも一種の官能基を有する一価の基であり、Ｒ^３は単結合又は二価の炭化水素基であり、Ｒ^４及びＲ^５は、それぞれ独立に炭素数１〜２０の一価の脂肪族炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であり、ｂは０〜２の整数であり、ＯＲ^５が複数ある場合、複数のＯＲ^５は互いに同一であっても異なっていても良く、また分子中には活性プロトンは含まれない。

In the general formula (II), A ¹ is an epoxy, isocyanate, imine, carboxylic acid ester, at least, a carboxylic acid anhydride, cyclic tertiary amines, acyclic tertiary amines, pyridine, are selected from the group consisting of silazane及disulfide It is a monovalent group having a kind of functional group, R ³ is a single-bonded or divalent hydrocarbon group, and R ⁴ and R ⁵ are independently monovalent aliphatic hydrocarbons having 1 to 20 carbon atoms. an aromatic hydrocarbon group of monovalent hydrocarbon group or a C6-18, b is an integer of 0 to 2, if the oR ⁵ there is a plurality, the plurality of oR ⁵ are be the same or different from each other Also, the molecule does not contain active protons.

Specific examples of the alkoxysilane compound represented by the general formula (II) include epoxy group-containing alkoxysilane compounds such as 2-glycidoxyethyltrimethoxysilane and 2-glycidoxyethyltriethoxysilane, (2). -Glysidoxyethyl) methyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, 2- (3,4-epoxy) Examples thereof include cyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane, and the like. Among these, 3-glycidoxypropyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane can be preferably used.

前記一般式（ＩＩＩ）中、ｎ１＋ｎ２＋ｎ３＋ｎ４＝４（但し、ｎ１、ｎ２、ｎ３及びｎ４は０〜４の整数であり、且つｎ１＋ｎ２＝1以上の整数）であり、Ａ¹は、飽和環状３級アミン化合物残基、不飽和環状３級アミン化合物残基、ケチミン残基、ニトリル基、（チオ）イソシアナート基（イソシアナート基又はチオイソシアナート基を示す。以下、同様。）、（チオ）エポキシ基、イソシアヌル酸トリヒドロカルビルエステル基、炭酸ジヒドロカルビルエステル基、ニトリル基、ピリジン基、（チオ）ケトン基、（チオ）アルデヒド基、アミド基、（チオ）カルボン酸エステル基、（チオ）カルボン酸エステルの金属塩、カルボン酸無水物残基、カルボン酸ハロゲン化合物残基、並びに、加水分解性基を有する第一若しくは第二アミノ基又はメルカプト基の中から選択される少なくとも１種の官能基であり、Ｒ²¹は、炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であり、ｎ１が2以上の場合には同一でも異なっていても良く、Ｒ²³は、炭素数1〜20の一価の脂肪族若しくは脂環式炭化水素基、炭素数６〜１８の一価の芳香族炭化水素基又はハロゲン原子（フッ素、塩素、臭素、ヨウ素）であり、ｎ３が２以上の場合には同一でも異なっていても良く、Ｒ²²は、炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であり、いずれも窒素原子及び／又はケイ素原子を含有していても良く、ｎ２が2以上の場合には、互いに同一若しくは異なっていても良く、或いは、一緒になって環を形成しており、Ｒ²⁴は、炭素数１〜２０の二価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の二価の芳香族炭化水素基であり、ｎ４が２以上の場合には同一でも異なっていても良い。
前記加水分解性基を有する第一若しくは第二アミノ基又は前記加水分解性基を有するメルカプト基における加水分解性基としては、トリメチルシリル基又はｔｅｒｔ−ブチルジメチルシリル基が好ましく、トリメチルシリル基が特に好ましい。
なお、本発明において、「炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基」とは、「炭素数１〜２０の一価の脂肪族炭化水素基若しくは炭素数３〜２０の一価の脂環式炭化水素基」をいう。二価の炭化水素基の場合も同様である。

In the general formula (III), n1 + n2 + n3 + n4 = 4 (where n1, n2, n3 and n4 are integers of 0 to 4 and n1 + n2 = 1 or more), and A ¹ is a saturated cyclic tertiary amine. Compound residue, unsaturated cyclic tertiary amine compound residue, ketimine residue, nitrile group, (thio) isocyanato group (indicates isocyanato group or thioisocyanate group; the same applies hereinafter), (thio) epoxy group. , Isocyanuric acid trihydrocarbyl ester group, dihydrocarbyl carbonate group, nitrile group, pyridine group, (thio) ketone group, (thio) aldehyde group, amide group, (thio) carboxylic acid ester group, (thio) carboxylic acid ester It is at least one functional group selected from a metal salt, a carboxylic acid anhydride residue, a carboxylic acid halogen compound residue, and a primary or secondary amino group or a mercapto group having a hydrolyzable group. R ²¹ is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and may be the same when n1 is 2 or more. ^{R 23} may be different, and R 23 is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or a halogen atom (fluorine, chlorine). , Bromine, iodine), and may be the same or different when n3 is 2 or more. R ²² is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or 6 carbon atoms. ~ 18 monovalent aromatic hydrocarbon groups, each of which may contain a nitrogen atom and / or a silicon atom, and when n2 is 2 or more, they may be the same or different from each other, or they may be different from each other. , Together to form a ring, R ²⁴ is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms. Yes, when n4 is 2 or more, it may be the same or different.
As the hydrolyzable group in the first or second amino group having the hydrolyzable group or the mercapto group having the hydrolyzable group, a trimethylsilyl group or a tert-butyldimethylsilyl group is preferable, and a trimethylsilyl group is particularly preferable.
In the present invention, the "monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms" means the "monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or 3 to 20 carbon atoms". It refers to a monovalent alicyclic hydrocarbon group. The same applies to the case of a divalent hydrocarbon group.

前記一般式（ＩＶ）中、ｐ１＋ｐ２＋ｐ３＝２（但し、ｐ１、ｐ２、ｐ３は０〜２の整数であり、且つｐ１＋ｐ２＝１以上の整数）であり、Ａ²は、ＮＲa（Ｒaは、一価の炭化水素基、加水分解性基又は含窒素有機基である。加水分解性基として、トリメチルシリル基又はｔｅｒｔ−ブチルジメチルシリル基が好ましく、トリメチルシリル基が特に好ましい。）、或いは、硫黄であり、Ｒ²⁵は、炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であり、ｐ１が２の場合には、互いに同一若しくは異なり、或いは、一緒になって環を形成しており、Ｒ²⁷は、炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基、炭素数６〜１８の一価の芳香族炭化水素基又はハロゲン原子（フッ素、塩素、臭素、ヨウ素）であり、Ｒ²⁶は、炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基、炭素数６〜１８の一価の芳香族炭化水素基又は含窒素有機基であり、いずれも窒素原子及び／又はケイ素原子を含有していても良く、ｐ２が２の場合には、互いに同一若しくは異なり、或いは、一緒になって環を形成しており、Ｒ²⁸は、炭素数１〜２０の二価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の二価の芳香族炭化水素基である。

In the general formula (IV), p1 + p2 + p3 = 2 (where p1, p2, p3 are integers of 0 to 2 and p1 + p2 = 1 or more), A ² is NRa (Ra is monovalent). Hydrocarbon group, hydrolyzable group or nitrogen-containing organic group. As the hydrolyzable group, a trimethylsilyl group or a tert-butyldimethylsilyl group is preferable, and a trimethylsilyl group is particularly preferable), or sulfur and R. ^{Reference numeral 25} denotes a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when p1 is 2, they are the same or the same as each other. Different or together to form a ring, R ²⁷ is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms and a monovalent aromatic hydrocarbon having 6 to 18 carbon atoms. It is a hydrogen group or a halogen atom (fluorine, chlorine, bromine, iodine), and R ²⁶ is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms and a monovalent fragrance having 6 to 18 carbon atoms. It is a group hydrocarbon group or a nitrogen-containing organic group, both of which may contain a nitrogen atom and / or a silicon atom, and when p2 is 2, they form a ring which is the same as, different from each other, or together. R ²⁸ is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.

前記一般式（Ｖ）中、ｑ１＋ｑ２＝３（但し、ｑ１は０〜２の整数であり、ｑ２は１〜３の整数である）であり、Ｒ³¹は炭素数１〜２０の二価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の二価の芳香族炭化水素基であり、Ｒ³²及びＲ³³はそれぞれ独立して加水分解性基、炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であり、Ｒ³⁴は炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であり、ｑ１が２の場合には同一でも異なっていても良く、Ｒ³⁵は炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であり、ｑ２が２以上の場合には同一でも異なっていても良い。

In the general formula (V), q1 + q2 = 3 (where q1 is an integer of 0 to 2 and q2 is an integer of 1 to 3), and R ³¹ is a divalent fat having 1 to 20 carbon atoms. It is a group or alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and R ³² and R ³³ are independently hydrolyzable groups and monovalent groups having 1 to 20 carbon atoms, respectively. It is an aliphatic or alicyclic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and R ³⁴ is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a carbon. It is a monovalent aromatic hydrocarbon group of numbers 6 to 18, and may be the same or different when q1 is 2, and R ³⁵ is a monovalent aliphatic or alicyclic hydrocarbon having 1 to 20 carbon atoms. It is a hydrogen group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when q2 is 2 or more, it may be the same or different.

前記一般式（ＶＩ）中、ｒ１＋ｒ２＝３（但し、ｒ１は１〜３の整数であり、ｒ２は０〜２の整数である）であり、Ｒ³⁶は炭素数１〜２０の二価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の二価の芳香族炭化水素基であり、Ｒ³⁷はジメチルアミノメチル基、ジメチルアミノエチル基、ジエチルアミノメチル基、ジエチルアミノエチル基、メチルシリル（メチル）アミノメチル基、メチルシリル（メチル）アミノエチル基、メチルシリル（エチル）アミノメチル基、メチルシリル（エチル）アミノエチル基、ジメチルシリルアミノメチル基、ジメチルシリルアミノエチル基、炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であり、ｒ１が２以上の場合には同一でも異なっていても良く、Ｒ³⁸は炭素数１〜２０のヒドロカルビルオキシ基、炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であり、ｒ２が２の場合には同一でも異なっていても良い。

In the general formula (VI), r1 + r2 = 3 (where r1 is an integer of 1 to 3 and r2 is an integer of 0 to 2), and R ³⁶ is a divalent fat having 1 to 20 carbon atoms. It is a group or alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and R ³⁷ is a dimethylaminomethyl group, a dimethylaminoethyl group, a diethylaminomethyl group, a diethylaminoethyl group, or a methylsilyl (methyl). ) Aminomethyl group, methylsilyl (methyl) aminoethyl group, methylsilyl (ethyl) aminomethyl group, methylsilyl (ethyl) aminoethyl group, dimethylsilylaminomethyl group, dimethylsilylaminoethyl group, monovalent with 1 to 20 carbon atoms It is an aliphatic or alicyclic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and may be the same or different when r1 is 2 or more, and R ³⁸ has 1 to 1 carbon atoms. It is a hydrocarbyloxy group of 20, a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and is the same when r2 is 2. But it can be different.

前記一般式（ＶＩＩ）中、ＴＭＳはトリメチルシリル基であり、Ｒ⁴⁰はトリメチルシリル基、炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であり、Ｒ⁴¹は炭素数１〜２０のヒドロカルビルオキシ基、炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であり、Ｒ⁴²は炭素数１〜２０の二価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の二価の芳香族炭化水素基である。

In the general formula (VII), TMS is a trimethylsilyl group, R ⁴⁰ is a trimethylsilyl group, a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic group having 6 to 18 carbon atoms. Group hydrocarbon groups, R ⁴¹ is a hydrocarbyloxy group having 1 to 20 carbon atoms, a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic group having 6 to 18 carbon atoms. It is a hydrocarbon group, and R ⁴² is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.

前記一般式（ＶＩＩＩ）中、ＴＭＳはトリメチルシリル基であり、Ｒ⁴³及びＲ⁴⁴はそれぞれ独立して炭素数１〜２０の二価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の二価の芳香族炭化水素基であり、Ｒ⁴⁵は炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であり、複数のＲ⁴⁵は、同一でも異なっていても良い。

In the general formula (VIII), TMS is a trimethylsilyl group, and R ⁴³ and R ⁴⁴ are independently divalent aliphatic or alicyclic hydrocarbon groups having 1 to 20 carbon atoms or 6 to 18 carbon atoms, respectively. It is a divalent aromatic hydrocarbon group, and R ⁴⁵ is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms. The plurality of R ^45s may be the same or different.

前記一般式（ＩＸ）中、ｒ１＋ｒ２＝３（但し、ｒ１は０〜２の整数であり、ｒ２は１〜３の整数である。）であり、ＴＭＳはトリメチルシリル基であり、Ｒ⁴⁶は炭素数１〜２０の二価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の二価の芳香族炭化水素基であり、Ｒ⁴⁷及びＲ⁴⁸はそれぞれ独立して炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であり、複数のＲ⁴⁷又はＲ⁴⁸は、同一でも異なっていても良い。

In the general formula (IX), r1 + r2 = 3 ( where, r1 is an integer of 0 to 2, r2 is an integer of 1-3.) Are, TMS is a trimethylsilyl group, R ⁴⁶ is the number of carbon atoms It is a divalent aliphatic or alicyclic hydrocarbon group of 1 to 20 or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and R ⁴⁷ and R ⁴⁸ are independently having 1 to 20 carbon atoms, respectively. It is a monovalent aliphatic or alicyclic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and a plurality of R ⁴⁷ or R ⁴⁸ may be the same or different.

前記一般式（Ｘ）中、Ｘはハロゲン原子であり、Ｒ⁴⁹は炭素数１〜２０の二価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の二価の芳香族炭化水素基であり、Ｒ⁵⁰及びＲ⁵¹はそれぞれ独立して、加水分解性基、炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であるか、或いは、Ｒ⁵⁰及びＲ⁵¹は結合して二価の有機基を形成しており、Ｒ⁵²及びＲ⁵³はそれぞれ独立してハロゲン原子、ヒドロカルビルオキシ基、炭素数１〜２０の一価の脂肪族若しくは脂環式炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基である。Ｒ⁵⁰及びＲ⁵¹としては、加水分解性基であることが好ましく、加水分解性基として、トリメチルシリル基又はｔｅｒｔ−ブチルジメチルシリル基が好ましく、トリメチルシリル基が特に好ましい。

In the general formula (X), X is a halogen atom, and R ⁴⁹ is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon having 6 to 18 carbon atoms. R ⁵⁰ and R ⁵¹ are independent groups, each of which is a hydrolyzable group, a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic group having 6 to 18 carbon atoms. It is a hydrocarbon group, or R ⁵⁰ and R ⁵¹ are bonded to form a divalent organic group, and R ⁵² and R ⁵³ are independently halogen atoms, hydrocarbyloxy groups, and 1 to 1 carbon atoms, respectively. It is a monovalent aliphatic or alicyclic hydrocarbon group of 20 or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms. The R ⁵⁰ and R ⁵¹ are preferably hydrolyzable groups, and as the hydrolyzable group, a trimethylsilyl group or a tert-butyldimethylsilyl group is preferable, and a trimethylsilyl group is particularly preferable.

The hydrocarbyloxysilane compounds represented by the general formulas (III) to (X) are preferably alkoxysilane compounds.
Further, among the compounds represented by the above formulas (I) to (X), tetraoxysilane, N, N-bis (trimethylsilyl) -3-aminopropyltriethoxysilane, N, N-bis (trimethylsilyl) -3. At least one selected from −aminopropylmethyldiethoxysilane, 3-dimethylaminopropyltriethoxysilane and 3-glycidoxypropyltriethoxysilane is particularly preferred.

In addition, when the purpose is to enhance the interaction between the modified diene polymer and carbon black, the following general formulas (XI), (XII-1), (XII-2), and (XIII) are used. Included are the denaturants shown.

_{R 'a SnX b ··· (XI} )
In the general formula (XI), R'independently has an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 to 20 carbon atoms. Selected from the group consisting of aralkyl groups; X is independently chlorine or bromine; a is 0 to 3, b is 1 to 4, but a + b = 4. The diene rubber modified with the tin-containing compound of formula (XI) has at least one tin-carbon bond.

Here, as R', specific examples include a methyl group, an ethyl group, an n-butyl group, a neofil group, a cyclohexyl group, an n-octyl group, a 2-ethylhexyl group and the like.
As the tin-containing compound of formula (XI), tin _{tetrachloride, R'SnCl 3, R '2 SnCl} 2, R' 3 SnCl , and the like are preferable, and tin tetrachloride is particularly preferred.

θ-C≡N ・ ・ ・ (XII-1)
θ-RC≡N ... (XII-2)
In the above formulas (I) and (II), θ represents a heterocyclic group. Further, it is preferable that θ is a heterocyclic group containing a nitrogen atom, a heterocyclic group containing an oxygen atom, a heterocyclic group containing a sulfur atom, a heterocyclic group containing two or more heteroatoms, and one or more cyano groups. It is preferably at least one heterocyclic group selected from the group consisting of heterocyclic groups containing. Further, it may be a heteroaromatic or heteroaromatic ring group such as thiophene, pyridine, furan, piperidine, dioxane, and further, a monocyclic, bicyclic, tricyclic, or polycyclic heterocyclic group. It may be.

Specifically, as such θ, for example, as a heterocyclic group containing a nitrogen atom, 2-pyridyl, 3-pyridyl, 4-pyridyl, pyrazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 3-pyridazinyl. , 4-pyridazinyl, N-methyl-2-pyrrolill, N-methyl-3-pyrrolill, N-methyl-2-imidazolyl, N-methyl-4-imidazolyl, N-methyl-5-imidazolyl, N-methyl-3 -Pyrazolyl, N-methyl-4-pyrazolyl, N-methyl-5-pyrazolyl, N-methyl-1,2,3-triazole-4-yl, N-methyl-1,2,3-triazole-5-yl , N-methyl-1,2,4-triazol-3-yl, N-methyl-1,2,4-triazol-5-yl, 1,2,4-triazine-3-yl, 1,2,4 -Triazine-5-yl, 1,2,4-triazine-6-yl, 1,3,5-triazinyl, N-methyl-2-pyrrolin-2-yl, N-methyl-2-pyrrolin-3-yl , N-Methyl-2-pyrrolin-4-yl, N-methyl-2-pyrrolin-5-yl, N-methyl-3-pyrrolin-2-yl, N-methyl-3-pyrrolin-3-yl, N -Methyl-2-imidazolin-2-yl, N-methyl-2-imidazolin-4-yl, N-methyl-2-imidazolin-5-yl, N-methyl-2-pyrazolin-3-yl, N-methyl -2-Pyrazoline-4-yl, N-methyl-2-pyrazolin-5-yl, 2-quinolyl, 3-quinolyl, 4-quinolyl, 1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, N-methylindole- 2-yl, N-methylindol-3-yl, N-methylisoindole-1-yl, N-methylisoindole-3-yl, 1-indridinyl, 2-indridinyl, 3-indridinyl, 1-phthalazinyl, 2 -Kinazolinyl, 4-quinazolinyl, 2-quinoxalinyl, 3-cinnolinyl, 4-cinnolinyl, 1-methylindazole-3-in, 1,5-naphthylidine-2-yl, 1,5-naphthylidine-3-yl, 1, 5-naphthylidine-4-yl, 1,8-naphthylidine-2-yl, 1,8-naphthylidine-3-yl, 1,8-naphthylidine-4-yl, 2-pteridinyl, 4-pteridinyl, 6-pteridinyl, 7-Pteridinyl, 1-methylbenzimidazol-2-yl, 6-phenanthridinyl, N-methyl-2-prinyl, N -Methyl-6-Prinyl, N-Methyl-8-Prinanth, N-Methyl-β-Carboline-1-yl, N-Methyl-β-Carboline-3-yl, N-Methyl-β-Carboline-4-yl , 9-Acridinyl, 1,7-Phenanthroline-2-yl, 1,7-Phenanthroline-3-yl, 1,7-Phenanthroline-4-yl, 1,10-Phenanthroline-2-yl, 1,10-Phenanthroline -3-yl, 1,10-phenanthroline-4-yl, 4,7-phenanthroline-1-yl, 4,7-phenanthroline-2-yl, 4,7-phenanthroline-3-yl, 1-phenazinyl, 2 -Phenanthrinyl, pyrrolidino, piperidino.

As heterocyclic groups containing an oxygen atom, 2-furyl, 3-frill, 2-benzo [b] frill, 3-benzo [b] frill, 1-isobenzo [b] frill, 3-isobenzo [b] frill, 2 -Naft [2,3-b] frills, 3-naphtho [2,3-b] frills can be mentioned.
As heterocyclic groups containing a sulfur atom, 2-thienyl, 3-thienyl, 2-benzo [b] thienyl, 3-benzo [b] thienyl, 1-isobenzo [b] thienyl, 3-isobenzo [b] thienyl, 2 -Naft [2,3-b] thienyl, 3-naphtho [2,3-b] thienyl can be mentioned.

As a heterocyclic group containing two or more heteroatoms, 2-oxazoline, 4-oxazolyl, 5-oxazolyl, 3-isooxazoline, 4-isoxazolyl, 5-isooxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3- Isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 1,2,3-oxadiazole-4-yl, 1,2,3-oxadiazole-5-yl, 1,3,4-oxadiazole-2- Il, 1,2,3-thiadiazole-4-yl, 1,2,3-thiadiazole-5-yl, 1,3,4-thiadiazole-2-yl, 2-oxazoline-2-yl, 2-oxazoline- 4-yl, 2-oxazoline-5-yl, 3-isooxazolinyl, 4-isooxazolinyl, isooxazolinyl, 2-thiazolin-2-yl, 2-thiazolin-4-yl, 2-thiazolin Examples thereof include -5-yl, 3-isothiazolinyl, 4-isothiazolinyl, 5-isothiazolinyl, 2-benzothiazolyl and morpholino.
Among these, θ is preferably a heterocyclic group containing a nitrogen atom, and particularly preferably 2-pyridyl, 3-pyridyl, and 4-pyridyl.

Specific examples of such a heterocyclic nitrile compound include 2-pyridinecarbonitrile, 3-pyridinecarbonitrile, 4-pyridinecarbonitrile, and pyrazinecarbo, as compounds having a heterocyclic group containing a nitrogen atom. Nitrile, 2-pyrimidine carbonitrile, 4-pyrimidine carbonitrile, 5-pyrimidine carbonitrile, 3-pyridazine carbonitrile, 4-pyridazine carbonitrile, N-methyl-2-pyrrol carbonitrile, N-methyl-3-pyrrole carbonitrile Nitrogen, N-methyl-2-imidazole carbonitrile, N-methyl-4-imidazole carbonitrile, N-methyl-5-imidazole carbonitrile, N-methyl-3-pyrazol carbonitrile, N-methyl-4-pyrazol carbonitrile Nitrigen, N-methyl-5-pyrazolcarbonitrile, N-methyl-1,2,3-triazole-4-carbonitrile, N-methyl-1,2,3-triazole-5-carbonitrile, N-methyl- 1,2,4-Triazole-3-carbonitrile, N-methyl-1,2,4-triazol-5-carbonitrile, 1,2,4-triazine-3-carbonitrile, 1,2,4-triazine -5-Carbonitrile, 1,2,4-Triazine-6-Carbonitrile, 1,3,5-Triazine Carbonitrile, N-Methyl-2-pyrrolin-2-carbonitrile, N-Methyl-2-pyrrolin- 3-Carbonitrile, N-Methyl-2-pyrrolin-4-carbonitrile, N-methyl-2-pyrrolin-5-carbonitrile, N-methyl-3-pyrrolin-2-carbonitrile, N-methyl-3- Pyrrolin-3-carbonitrile, N-methyl-2-imidazolin-2-carbonitrile, N-methyl-2-imidazolin-4-carbonitrile, N-methyl-2-imidazolin-5-carbonitrile, N-methyl- 2-Pyrazoline-3-carbonitrile, N-methyl-2-pyrazolin-4-carbonitrile, N-methyl-2-pyrazolin-5-carbonitrile, 2-quinoline carbonitrile, 3-quinoline carbonitrile, 4-quinoline Carbonitrile, 1-isoquinoline carbonitrile, 3-isoquinoline carbonitrile, 4-isoquinoline carbonitrile, N-methylindole-2-carbonitrile, N-methylindole-3-carbonitrile, N-methylisoindole-1-carbo Nitrogen, N-methylisoi Ndol-3-Carbonitrile, 1-Indolysin Carbonitrile, 2-Indoline Carbonitrile, 3-Indolydin Carbonitrile, 1-phthalazine Carbonitrile, 2-Kinazoline Carbonitrile, 4-Kinazoline Carbonitrile, 2-Kinoxaline Carbonitrile, 3-Synnoline Carbonitrile, 4-Synnoline Carbonitrile, 1-Methylindazole-3-Carbonitrile, 1,5-naphthylidine-2-Carbonitrile, 1,5-naphthylidine-3-Carbonitrile, 1, , 5-naphthylidine-4-carbonitrile, 1,8-naphthylidine-2-carbonitrile, 1,8-naphthylidine-3-carbonitrile, 1,8-naphthylidine-4-carbonitrile, 2-pteridine carbonitrile, 4 -Pteridinecarbonitrile, 6-pteridinecarbonitrile, 7-pteridinecarbonitrile, 1-methylbenzimidazol-2-carbonitrile, phenanthridin-6-carbonitrile, N-methyl-2-purincarbonitrile, N-methyl -6-Prinbonitrile, N-Methyl-8-Prinbonitrile, N-Methyl-β-Carboline-1-Carbonitrile, N-Methyl-β-Carboline-3-Carbonitrile, N-Methyl-β-Carboline -4-Carbonitrile, 9-acridine carbonitrile, 1,7-phenanthroline-2-carbonitrile, 1,7-phenanthroline-3-carbonitrile, 1,7-phenanthroline-4-carbonitrile, 1,10-phenanthroline -2-Carbonitrile, 1,10-Phenantroline-3-Carbonitrile, 1,10-Phenantroline-4-Carbonitrile, 4,7-Phenantroline-1-Carbonitrile, 4,7-Phenantroline-2-Carbonitrile, Examples thereof include 4,7-phenanthroline-3-carbonitrile, 1-phenazine carbonitrile, 2-phenazine carbonitrile, 1-pyrrolidin carbonitrile, and 1-piperidin carbonitrile.

Compounds having a heterocyclic group containing an oxygen atom include 2-fluoronitrile, 3-fluoronitrile, 2-benzo [b] flancarbonitrile, 3-benzo [b] flancarbonitrile, and isobenzo [b] furan-1-carbohydrate. Examples thereof include nitrile, isobenzo [b] furan-3-carbonitrile, naphtho [2,3-b] furan-2-carbonitrile, and naphtho [2,3-b] furan-3-carbonitrile.
Compounds having a heterocyclic group containing a sulfur atom include 2-thiophenecarbonitrile, 3-thiophenecarbonitrile, benzo [b] thiophene-2-carbonitrile, benzo [b] thiophene-3-carbonitrile, and isobenzo [b]. Examples thereof include thiophene-1-carbonitrile, isobenzo [b] thiophene-3-carbonitrile, naphtho [2,3-b] thiophene-2-carbonitrile, and naphtho [2,3-b] thiophene-3-carbonitrile. ..

Compounds having a heterocyclic group containing two or more heteroatoms include 2-oxazolecarbonitrile, 4-oxazolecarbonitrile, 5-oxazolecarbonitrile, 3-isoxazolecarbonitrile, 4-isooxazolecarbonitrile, and 5-iso. Oxazole carbonitrile, 2-thiazole carbonitrile, 4-thiazole carbonitrile, 5-thiazole carbonitrile, 3-isothiazole carbonitrile, 4-isothiazole carbonitrile, 5-isothiazole carbonitrile, 1,2,3-oxazole -4-Carbonitrile, 1,2,3-oxazole-5-Carbonitrile, 1,3,4-Oxazole-2-Carbonitrile, 1,2,3-Thiazole-4-Carbonitrile, 1,2,3 -Thiazol-5-Carbonitrile, 1,3,4-Thiazol-2-Carbonitrile, 2-Oxazoline-2-Carbonitrile, 2-Oxazoline-4-Carbonitrile, 2-Oxazoline-5-Carbonitrile, 3- Isooxazoline carbonitrile, 4-isooxazoline carbonitrile, 5-isooxazoline carbonitrile, 2-thiazolin-2-carbonitrile, 2-thiazolin-4-carbonitrile, 2-thiazolin-5-carbonitrile, 3-isothiazolin carbo Examples thereof include nitrile, 4-isothiazolin carbonitrile, 5-isothiazolin carbonitrile, benzothiazole-2-carbonitrile, and 4-morpholinocarbonitrile.

Compounds having two or more cyano groups include 2,3-pyridinedicarbonitrile, 2,4-pyridinedicarbonitrile, 2,5-pyridinedicarbonitrile, 2,6-pyridinedicarbonitrile, and 3,4-. Pyridin dicarbonitrile, 2,4-pyrimidine dicarbonitrile, 2,5-pyrimidine dicarbonitrile, 4,5-pyrimidine dicarbonitrile, 4,6-pyrimidine dicarbonitrile, 2,3-pyramidin dicarbonitrile, 2,5-Pyrazine dicarbonitrile, 2,6-Pyrazine dicarbonitrile, 2,3-Flange carbonitrile, 2,4-Flange carbonitrile, 2,5-Flange carbonitrile, 2,3-thiofendicarbonitrile , 2,4-thiofendicarbonitrile, 2,5-thiophenicarbonitrile, N-methyl-2,3-pyrroledicarbonitrile, N-methyl-2,4-pyrroledicarbonitrile, N-methyl-2 , 5-Pyrol dicarbonitrile, 1,3,5-triazine-2,4-dicarbonitrile, 1,2,4-triazine-3,5-dicarbonitrile, 3,2,4-triazine-3, 6-Dicarbonitrile, 2,3,4-pyridinetricarbonitrile, 2,3,5-pyridinetricarbonitrile, 2,3,6-pyridinetricarbonitrile, 2,4,5-pyridinetricarbonitrile, 2,4,6-pyridinetricarbonitrile, 3,4,5-pyridinetricarbonitrile, 2,4,5-pyrimidine tricarbonitrile, 2,4,6-pyrimidine tricarbonitrile, 4,5,6- Pyrimidine tricarbonitrile, pyrazinetricarbonitrile, 2,3,4-frantricarbonitrile, 2,3,5-frantricarbonitrile, 2,3,4-thiophenetricarbonitrile, 2,3,5-thiophene Tricarbonitrile, N-methyl-2,3,4-pyrroletricarbonitrile, N-methyl-2,3,5-pyrroletricarbonitrile, 1,3,5-triazine-2,4,6-tricarbohydrate Nitrile, 1,2,4-triazine-3,5,6-tricarbonitrile can be mentioned.
Among these, 2-cyanopyridine (2-pyridinecarbonitrile), 3-cyanopyridine (3-pyridinecarbonitrile), and 4-cyanopyridine (4-pyridincarbonitrile) are preferable.

（式中、各々のＲ^１は、独立して、１〜１２の炭素原子を有するアルキル、シクロアルキルまたはアラルキル基を示す。）

（式中、Ｒ_２は、３〜１６のメチレン基を有するアルキレン、置換アルキレン、オキシ−
またはＮ−アルキルアミノ−アルキレン基を示す。）］ (AM) Li (Q) y ... (XIII)
[In the formula, y is 0 or 0.5 to 3, Q is a solubilizing component selected from the group consisting of hydrocarbons, ethers, amines or mixtures thereof, and AM is a general formula. (XIII-1) or (XIII-2).

(In the formula, each R ¹ independently represents an alkyl, cycloalkyl or aralkyl group having 1 to 12 carbon atoms.)

(In the formula, R ₂ is an alkylene having a methylene group of 3 to 16, a substituted alkylene, and an oxy-.
Alternatively, it indicates an N-alkylamino-alkylene group. )]

In formula (XIII), (Q) is a solubilizing component and may be a hydrocarbon, ether, amine or a mixture thereof. The presence of this component (Q) makes the initiator soluble in the hydrocarbon solvent.
Further, the (Q) group includes dienyl or vinyl aromatic polymers or copolymers having a degree of polymerization consisting of 3 to about 300 polymerization units. The polymers include polybutadiene, polystyrene, polyisoprene and copolymers thereof.
Other examples of (Q) include polar ligands such as tetrahydrofuran (THF) and tetramethylethylenediamine (TMEDA).
The (AM) component represents an amino functional group, for example, by incorporating it into the starting site or head of the polymer, a polymer having at least one functional group at the end is synthesized.
When the soluble component (Q) is an ether or an amino compound, a solution of the functionalizing agent AM-H is prepared in the presence of (Q) in an anhydrous aprotic solvent such as cyclohexane, and then the solution is prepared. Initiators can be produced by adding an organic lithium compound in the same or similar solvent to this solution.
This organic lithium compound is composed of the general formula RLi (wherein R is an alkyl having 1 to about 20 carbon atoms, cycloalkyl, alkenyl, aryl and aralkyl, and 25 obtained from diolefins and vinylaryl monomers. It is represented by (selected from the group consisting of short chain length low molecular weight polymers) having the following units.
For example, typical alkyls include n-butyl, s-butyl, methyl, ethyl, isopropyl and the like. Further, cycloalkyl includes cyclohexyl and menthyl, and allyl and vinyl are preferable examples of alkenyl.
Further, the aryl and aralkyl groups include phenyl, benzyl, oligo (styryl) and the like, and the short chain length polymers include oligos produced by initiating the oligomerization of suitable monomers with organolithium (stylyl). Butazienyl), oligo (isoprenyl), oligo (styryl) and the like can be mentioned. The insitu method (the method described in JP-A-6-199921) is also preferably used. The organolithium compound is preferably n-butyllithium.

In the formula (XIII), substituted amino group represented by the formula (XIII-1) is, _{R 1} group in the formula is not particularly limited as long as it is an alkyl, cycloalkyl or aralkyl group having 1 to 12 carbon atoms However, preferred examples include methyl, ethyl, butyl, octyl, cyclohexyl, 3-phenyl-1-propyl and isobutyl. _{Each R 1 in} formula (XIII-1) may be the same or different.
Furthermore, in the formula (XIII), cyclic amino group represented by the formula (XIII-2) may, _{R 2} groups in the formula is a divalent alkylene having from 3 to 16 methylene groups, a substituted alkylene, oxy - Alternatively, there is no particular limitation as long as it is an N-alkylamino-alkylene group.
Here, the substituted alkylenes include alkylenes having one to eight substitutions. Suitable substituents are linear or branched alkyl, cycloalkyl, bicycloalkyl, aryl and aralkyl having 1 to about 12 carbon atoms. Preferred R2 groups include trimethylene, tetramethylene, hexamethylene, oxydiethylene, N-alkylazadiethylene, dodecamethylene, hexadecamethylene and the like.
In addition, there are many useful examples of cyclic amines including alkyl, cycloalkyl, aryl and aralkyl substituents of the cyclic and dicyclic amines, and but are not limited to 2- (2-ethylhexyl). ) Pyrrolidine; 3- (2-propyl) pyrrolidine; 3,5-bis (2-ethylhexyl) piperidine; 4-phenylpiperidin; 7-decyl-1-azacyclotridecane; 3,3-dimethyl-1-azacyclo Tetradecane; 4-dodecyl-1-azacyclooctane; 4- (2-phenylbutyl) -1-azacyclooctane; 3-ethyl-5-cyclohexyl-1-azacycloheptane; 4-hexyl-1-azacycloheptane 9-Isoamyl-1-azacycloheptane; 2-methyl-1-azacycloheptane-9-ene; 3-isobutyl-1-azacyclododecane; 2-methyl-7-t-butyl-1- Azacyclododecane; 5-nonyl-1-azacyclododecane; 8- (4'-methylphenyl) -5-pentyl-3-azabicyclo [5.4.0] undecane; 1-butyl-6-azabicyclo [3. 2.1] Octane; 8-ethyl-3-azabicyclo [3.2.1] Octane; 1-propyl-3-azabicyclo [3.2.2] nonane; 3- (t-butyl) -7-azabicyclo [ 4.3.0] Nonan; 1,5,5-trimethyl-3-azabicyclo [4.4.0] decane and the like.

Further, among the compounds represented by the above-mentioned formulas (XI), (XII-1), (XII-2), and (XIII), the denaturing agents are tin tetrachloride, 2-cyanopyridine, and hexamethyleneimine. It is particularly preferable to include at least one selected from the above.

Furthermore, the modification of the diene polymer includes the compounds represented by the above-mentioned general formulas (I) to (X) after modifying one end using an organic alkali metal compound as a polymerization initiator. The other end can also be denatured with a denaturing agent.

As the organic alkali metal compound used as the above-mentioned polymerization initiator, an organic lithium compound is preferable. The organic lithium compound is not particularly limited, but hydrocarbyl lithium or a lithium amide compound is preferably used. When hydrocarbyl lithium is used, it has a hydrocarbyl group at the polymerization initiation terminal and the other terminal is a polymerization active site. A modified diene-based rubber is obtained, and a hydrocarbyloxysilane compound containing a nitrogen atom and a silicon atom or a hydrocarbyloxysilane compound containing a silicon atom is reacted with the active terminal, which is a polymerization active site, to modify the compound.
Further, when the latter lithium amide compound is used, a modified diene rubber having a nitrogen-containing group at the polymerization initiation terminal and the other terminal being a polymerization active site can be obtained. Therefore, for example, hexamethylene is obtained at the polymerization initiation terminal. It is also possible to obtain a modified diene-based polymer to which imine is bonded and the alkoxysilane compound is bonded to the other end.

The hydrocarbyllithium as the polymerization initiator is preferably one having a hydrocarbyl group having 2 to 20 carbon atoms, for example, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-octyl. Lithium, n-decyllithium, phenyllithium, 2-naphthyllithium, 2-butylphenyllithium, 4-phenylbutyllithium, cyclohexyllithium, cycloventyllithium, reactive organisms of diisopropenylbenzene and butyllithium, etc. Of these, n-butyllithium is particularly preferable.
Further, examples of the lithium amide compound as the polymerization initiator include lithium hexamethyleneimide, lithium pyrrolidide, lithium piperidide, lithium heptamethyleneimide, lithium dodecamethyleneimide, lithium dimethylamide, lithium diethylamide and lithium dibutylamide. Lithium dipropylamide, lithium diheptylamide, lithium dihexylamide, lithium dioctylamide, lithiumdi-2-ethylhexylamide, lithium didecylamide, lithium-N-methylpyverazide, lithium ethylpropylamide, lithium ethylbutylamide, lithium ethylbenzylamide , Lithium methyl phenetyl amide and the like. Among these, cyclic lithium amides such as lithium hexamethyleneimide, lithium pyrrolidide, lithium piperidide, lithium heptamethyleneimide, and lithium dodecamethyleneimide are preferable from the viewpoint of the interaction effect with carbon black and the ability to initiate polymerization. In particular, lithium hexamethyleneimide and lithium pyrrolidide are suitable.
In addition, these lithium amide compounds can generally be prepared in advance from a secondary amine and a lithium compound for polymerization, but can also be prepared in a polymerization system (in-situ).

<Modified diene polymer>
The modified diene polymer of the present invention is characterized by being produced by the above-mentioned method for producing a modified diene polymer of the present invention.
The produced modified diene polymer of the present invention can improve the low loss property of the rubber composition when used together with a reinforcing filler.

<Rubber composition>
The rubber composition of the present invention is characterized by containing the above-mentioned rubber component containing the modified diene polymer of the present invention and a reinforcing filler.
By containing the modified diene polymer of the present invention as the rubber component, the dispersibility of the reinforcing filler is increased, and excellent low loss property can be realized.

(Rubber component)
The rubber composition of the present invention contains a rubber component containing the modified diene polymer of the present invention.
By containing the modified diene polymer of the present invention as a rubber component, a strong interaction with the reinforcing filler can be obtained.

Here, the rubber component can be composed of 100% of the modified diene polymer of the present invention, but a rubber other than the modified diene polymer of the present invention can be used as long as the object of the present invention is not impaired. It can also be contained.
The content of the modified diene polymer of the present invention in the rubber component is preferably 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 30% by mass or more.

The type of rubber constituting the rubber component is not particularly limited except that it contains the modified diene polymer of the present invention, and can be appropriately selected depending on the required performance. For example, diene such as natural rubber (NR), butadiene rubber (BR), isoprene rubber (IR), styrene butadiene rubber (SBR), styrene isoprene butadiene rubber (SIBR), chloroprene rubber (CR), and acrylonitrile butadiene rubber (NBR). Examples thereof include non-diene rubbers such as based rubbers, ethylene propylene diene rubbers (EPDM), ethylene propylene rubbers (EPM), and butyl rubbers (IIR). From these, one kind or two or more kinds of rubber can be appropriately selected and used.

Further, from the viewpoint of improving the wear resistance of the rubber composition, it is more preferable that the rubber component further contains natural rubber and / or isoprene rubber in addition to the modified diene polymer of the present invention. This is because the wear resistance of the rubber composition and other physical properties can be improved.
The content of the natural rubber and / or isoprene rubber is preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 70% by mass or more in the rubber component.

(Reinforcing filler)
The rubber composition of the present invention contains a reinforcing filler in addition to the rubber components described above.
As a result of the enhanced interaction of the reinforcing filler with the modified diene polymer in the rubber component, the dispersibility in the rubber composition is improved, and the low loss property of the rubber composition can be improved.

Here, the reinforcing filler may be any reinforcing filler usually used in the rubber field, and examples thereof include carbon black, silica, talc, clay, aluminum hydroxide, and titanium oxide.

Further, the reinforcing filler preferably contains at least silica among the above-mentioned reinforcing materials. The interaction with the diene polymer modified by the tetradiene compound becomes particularly high, and low loss property can be realized at a higher level. Further, the content of the silica in the reinforcing filler is preferably 30% by mass or more, and more preferably 35% by mass or more. This is because low loss can be achieved at a higher level.

The silica is not particularly limited. For example, wet silica, precipitated silica, colloidal silica, calcium silicate, aluminum silicate and the like can be mentioned.
Among the above, the silica is preferably wet silica or precipitated silica. This is because these silicas have high dispersibility and can further improve the low loss property and wear resistance of the rubber composition. Precipitated silica means that the reaction solution is allowed to react in a relatively high temperature, neutral to alkaline pH range at the initial stage of production to grow silica primary particles, and then controlled to the acidic side to aggregate the primary particles. It is the silica obtained as a result of making it.
Further, BET specific surface area of the wet silica is preferably a 40~350m ² / g, more preferably 80~300m ² / g. When the BET specific surface area of the wet silica is within the preferable range or the more preferable range, it is advantageous in that the rubber reinforcing property and the dispersibility in the rubber component can be compatible at a higher level. Specific examples of such commercially available wet silica products include Tosoh Silica Co., Ltd., trade names "Nipsil AQ" and "Nipsil KQ", Degussa Co., Ltd., and trade name "Ultra Jill VN3". Be done.

Further, from the viewpoint of achieving reinforcing properties at a higher level, it is more preferable that the reinforcing filler contains carbon black in addition to the silica.
The carbon black is also not particularly limited. For example, any hard carbon and soft carbon produced by the oil furnace method can be used. Among these, from the viewpoint of achieving better low loss resistance and wear resistance, it is preferable to use GPF, FEF, SRF, HAF, ISAF, IISAF, SAF grade carbon black, and further excellent wear resistance. From the viewpoint of realizing the properties, it is particularly preferable to use HAF, ISAF, IISAF, SAF grade carbon black.

(Other ingredients)
In addition, the rubber composition of the present invention can contain additives (other components) usually blended in the rubber composition to the extent that the effects of the invention are not impaired. For example, anti-aging agents, cross-linking accelerators, cross-linking agents, cross-linking accelerators, silane coupling agents, glycerin fatty acid esters, softeners, stearic acid, ozone deterioration inhibitors, surfactants commonly used in the rubber industry. Additives such as and the like can be appropriately blended.

As the anti-aging agent, known ones can be used and are not particularly limited. For example, a phenol-based anti-aging agent, an imidazole-based anti-aging agent, an amine-based anti-aging agent, and the like can be mentioned. These anti-aging agents may be used alone or in combination of two or more.

As the cross-linking accelerator, known ones can be used and are not particularly limited. For example, thiazole-based vulcanization accelerators such as 2-mercaptobenzothiazole and dibenzothiazil disulfide; Sulfenamide-based vulcanization accelerator; guanidine-based vulcanization accelerator such as diphenylguanidine; tetramethylthium disulfide, tetraethyl thiuram disulfide, tetrabutyl thiuram disulfide, tetradodecyl thiuram disulfide, tetraoctyl thiuram disulfide, tetrabenzyl thiuram disulfide, disulfide. Thiuram-based vulcanization accelerators such as pentamethylene thiuram tetrasulfide; dithiocarbamate-based vulcanization accelerators such as zinc dimethyldithiocarbamate; zinc dialkyldithiophosphate and the like can be mentioned.

The cross-linking agent is also not particularly limited. For example, sulfur, a bismaleimide compound and the like can be mentioned, and among them, sulfur is preferably used.
Regarding the types of the bismaleimide compound, for example, N, N'-o-phenylene bismaleimide, N, N'-m-phenylene bismaleimide, N, N'-p-phenylene bismaleimide, N, N'-( Illustrate 4,4'-diphenylmethane) bismaleimide, 2,2-bis- [4- (4-maleimidephenoxy) phenyl] propane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, and the like. Can be done.

Examples of the cross-linking promoting aid include zinc oxide (ZnO) and fatty acids. The fatty acid may be a saturated or unsaturated, linear or branched fatty acid, and the number of carbon atoms of the fatty acid is not particularly limited, but for example, a fatty acid having 1 to 30 carbon atoms, preferably 15 to 30 carbon atoms. More specifically, cyclohexanoic acid (cyclohexanecarboxylic acid), naphthenic acid such as alkylcyclopentane having a side chain; hexanoic acid, octanoic acid, decanoic acid (including branched carboxylic acid such as neodecanoic acid), dodecanoic acid, tetradecane Saturated fatty acids such as acids, hexadecanoic acid and octadecanoic acid (stearic acid); unsaturated fatty acids such as methacrylic acid, oleic acid, linoleic acid and linolenic acid; resin acids such as rosin, tall oil acid and avietic acid. These may be used alone or in combination of two or more. In the present invention, zinc oxide and stearic acid can be preferably used.

The method for producing the rubber composition of the present invention is not particularly limited. For example, it can be obtained by blending the rubber component, the reinforcing filler, and the other components by a known method and kneading them.

Regarding the silane coupling agent, for example, bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, bis (2-tri). Ethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercapto Ethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide, 2-tri Ethoxysilylethyl-N, N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilylpropylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylbenzolyltetrasulfide, 3-triethoxysilylpropylmethacrylate monosulfide, 3- Trimethoxysilylpropyl methacrylate monosulfide, bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyl dimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide, dimethoxymethylsilylpropylbenzothia Zolyltetrasulfide, 3-octanoylthiopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3 -Aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, 3-[ethoxybis (3,6,9,12,15) −Pentaoxaoctacosan-1-yloxy) Cyril] -1-Propylthiol (trade name “Si363” manufactured by Ebonic Degussa) and the like can be mentioned. In addition, these silane coupling agents may be used individually by 1 type, and may be used in combination of 2 or more type.

Further, when the rubber composition of the present invention contains silica as the reinforcing filler, it is preferable that the rubber composition further contains a glycerin fatty acid ester. This is because the workability of the rubber composition is improved, and the rolling resistance of the tire can be further reduced by applying the rubber composition to the tire.
The glycerin fatty acid ester is an ester of glycerin and two or more kinds of fatty acids. The glycerin fatty acid ester is a compound in which at least one of the three OH groups of glycerin and the COOH group of the fatty acid are ester-bonded.
Here, the glycerin fatty acid ester is a glycerin fatty acid diester (monoester component) in which one molecule of glycerin and one molecule of fatty acid are esterified, or one molecule of glycerin and two molecules of fatty acid are esterified. The diester component) may be a glycerin fatty acid triester (triester component) formed by esterifying one molecule of glycerin and three molecules of a fatty acid, or a mixture thereof, but a glycerin fatty acid monoester is preferable. When the glycerin fatty acid ester is a mixture of a glycerin fatty acid monoester, a glycerin fatty acid diester, and a glycerin fatty acid triester, the content of each ester can be measured by gel permeation chromatography (GPC). Further, the two fatty acids constituting the glycerin fatty acid diester and the three fatty acids constituting the glycerin fatty acid triester may be the same or different.
The two or more kinds of fatty acids (that is, the constituent fatty acids of the glycerin fatty acid ester) that are the raw materials of the glycerin fatty acid ester have 8 to 22 carbon atoms from the viewpoint of processability, low loss property, and breaking property of the rubber composition. A fatty acid is preferable, a fatty acid having 12 to 18 carbon atoms is more preferable, a fatty acid having 14 to 18 carbon atoms is further preferable, and a fatty acid having 16 carbon atoms and a fatty acid having 18 carbon atoms are further preferable. Further, among the two or more kinds of fatty acids that are the raw materials of the glycerin fatty acid ester, the most abundant fatty acid component and the second most abundant fatty acid component may be a fatty acid having 16 carbon atoms and the other fatty acid having 18 carbon atoms. More preferred.
When the glycerin fatty acid ester is an ester of glycerin, a fatty acid having 16 carbon atoms, and a fatty acid having 18 carbon atoms, the mass ratio of the fatty acid having 16 carbon atoms to the fatty acid having 18 carbon atoms (16 carbon atoms). (Fatty acid / fatty acid having 18 carbon atoms) is preferably in the range of 90/10 to 10/90, more preferably in the range of 80/20 to 20/80, and even more preferably in the range of 75/25 to 25/75. When the mass ratio of the fatty acid having 16 carbon atoms to the fatty acid having 18 carbon atoms is in this range, the processability, low loss property, and fracture property of the rubber composition can be further improved.

Further, the rubber composition of the present invention preferably further contains a softening agent from the viewpoint of realizing excellent low loss property and wear resistance. Examples of the softener include naphthenic base oils, paraffinic base oils, aroma base oils and the like. Here, the content of the softener is preferably 2 to 30 parts by mass with respect to 100 parts by mass of the rubber component. If the content of the softener exceeds 30 parts by mass with respect to 100 parts by mass of the rubber component, the softener may seep out to the surface of the rubber product or the wear resistance may decrease. In addition, since it interacts with the tetrazine moiety in the modified rubber component and shields it, the reactivity is lowered, and the low loss performance and the wear resistance may be lowered.
Further, among the softeners described above, it is preferable to use a naphthenic base oil or a paraffinic base oil, and it is most preferable to use a naphthenic base oil. This is because the aroma oil has a large amount of aromatic components, has a high affinity with the chemical which is an aromatic compound, and further inhibits the reaction with the polymer, which is not preferable. On the other hand, naphthenic base oils and paraffinic base oils have the effect of helping to diffuse and react in the polymer, and oils having a low pour point diffuse better into the polymer.
The classification of the naphthenic base oil, the paraffin-based base oil, and the aroma-based base oil is determined by the CA value, the CP value, and the CN value. For example, the naphthenic base oil is classified into TDAE, SRAE, RAE, Black Oil and the like. Further, what is classified as the paraffin-based base oil is spindle oil and paraffin oil.
Furthermore, a more preferable effect can be obtained with a mixed oil such as A / O Mix (Sankyo Yuka Kogyo Co., Ltd.), which is a mixture of the naphthenic base oil and the naphthenic asphalt.
The timing of blending these lubricating oils is not particularly limited, and for example, they may be oil-developed at the stage of manufacturing the rubber component, or may be added when the rubber composition is kneaded.

<Tire>
The tire of the present invention is characterized in that the rubber composition of the present invention described above is used. By including the rubber composition of the present invention as a tire material, rolling resistance can be reduced.
The tire of the present invention is not particularly limited except that the rubber composition of the present invention described above is used for any of the tire members, and can be produced according to a conventional method. As the gas to be filled in the tire, an inert gas such as nitrogen, argon or helium can be used in addition to normal or adjusted oxygen partial pressure.

Further, in the tire of the present invention, the rubber composition of the present invention described above is used for any of the tire members, and among the tire members, tread rubber, sidewall rubber, cord or fiber-coated rubber, bead filler or rubber chafer. It is preferable that it is used for tread rubber, and more preferably it is used for tread rubber. This is because when applied to these members, the benefits of the excellent low-loss effect of the rubber composition of the present invention can be fully enjoyed.

The type of tire of the present invention is not particularly limited, but is a passenger car tire, a studless tire, a run-flat tire, or a truck / bus tire from the viewpoint of more effectively reducing rolling resistance. Is preferable.

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

Modified or unmodified polymers A to D were produced according to the following procedure. The molecular properties of each polymer are shown in Table 1.

(Production of Modified Polymer A)
A cyclohexane solution of 1,3-butadiene and a cyclohexane solution of styrene were added to a dry, nitrogen-substituted 5 L pressure-resistant container so as to have 551 g of 1,3-butadiene and 129 g of styrene, and 2,2-ditetrahydrofuryl was added. After adding 0.48 g of propane and 0.34 g of n-butyllithium as a polymerization initiator, polymerization was carried out at 50 ° C. for 1.5 hours. The polymerization conversion rate at this time was almost 100%.
Then, 3 ml of an isopropanol 5 wt% solution of 2,6-di-t-butyl-p-cresol (BHT) was added to stop the reaction, and the obtained polymer cement was drum-dried to obtain the unmodified polymer A. Obtained.

(Production of Modified Polymer B)
A cyclohexane solution of 1,3-butadiene and a cyclohexane solution of styrene were added to a dry, nitrogen-substituted 5 L pressure-resistant container so as to have 551 g of 1,3-butadiene and 129 g of styrene, and 2,2-ditetrahydrofuryl was added. After adding 0.48 g of propane and 0.34 g of n-butyllithium as a polymerization initiator, polymerization was carried out at 50 ° C. for 1.5 hours. The polymerization conversion rate at this time was almost 100%.
The reaction was then stopped by adding 3 ml of a 5 wt% solution of 2,6-di-t-butyl-p-cresol (BHT) in isopropanol, followed by 3.71 g of 3,6-di (2-pyridyl)-. 1,2,4,5-Tetrazine was added and stirred. The obtained polymer cement was drum-dried to obtain a modified polymer B.

(Production of Modified Polymer C)
To a dry, nitrogen-substituted 5 L pressure resistant vessel was added 815 g of hexane and 1417 g of a 22.4 wt% hexane solution of 1,3-butadiene. 4.35 mL of 4.32 M methylaluminoxane toluene solution, 0.63 g of 22.4 wt% 1,3-butadiene hexane solution, 0.24 mL of 0.537 M neodymium versate cyclohexane solution, 1.0 M diisobutylaluminum A preformation catalyst was prepared by mixing 2.77 mL of a hexane solution of hydride and 0.52 mL of a hexane solution of 1.0 M diethylaluminum chloride. The catalyst was aged for 15 minutes and charged into the reactor. The temperature of the reactor jacket was then set to 65 ° C. Approximately 72 minutes after adding the catalyst, the polymerization mixture was cooled to room temperature and 15 ml of an isopropanol solution of 12 wt% 2,6-di-tert-butyl-4-methylphenol was added. The obtained polymer cement was drum-dried to obtain an unmodified polymer C.

(Production of Modified Polymer D)
To a dry, nitrogen-substituted 5 L pressure resistant vessel was added 815 g of hexane and 1417 g of a 22.4 wt% hexane solution of 1,3-butadiene. 4.35 mL of 4.32 M methylaluminoxane toluene solution, 0.63 g of 22.4 wt% 1,3-butadiene hexane solution, 0.24 mL of 0.537 M neodymium versate cyclohexane solution, 1.0 M diisobutylaluminum A preformation catalyst was prepared by mixing 2.77 mL of a hexane solution of hydride and 0.52 mL of a hexane solution of 1.0 M diethylaluminum chloride. The catalyst was aged for 15 minutes and charged into the reactor. The temperature of the reactor jacket was then set to 65 ° C. Approximately 72 minutes after adding the catalyst, the polymerization mixture was cooled to room temperature, 15 ml of an isopropanol solution of 12 wt% 2,6-di-tert-butyl-4-methylphenol was added, followed by 1.77 g of 3 , 6-Di (2-pyridyl) -1,2,4,5-tetrazine was added and stirred. The obtained polymer cement was drum-dried to obtain a modified polymer D.

<Examples 1 and 2 and Comparative Examples 1 and 2>
Using the above-mentioned modified polymers A to D, the rubber compositions having the formulation shown in Table 2 were prepared, and samples of Examples and Comparative Examples were obtained.
For each sample of Examples and Comparative Examples, (1) low loss property (tan δ) and (2) wear resistance were evaluated.

(1) Low loss (tan δ)
Each sample was vulcanized at 160 ° C. for 15 minutes to obtain vulcanized rubber. The vulcanized rubber obtained was measured for loss tangent (tan δ) using a spectrometer (manufactured by Ueshima Seisakusho Co., Ltd.) under the conditions of temperature 60 ° C., initial strain 2%, dynamic strain 1%, and frequency 52 Hz. did. The obtained value of tan δ is displayed as an index when the value of Comparative Example 1 is set to 100 for Comparative Example 1 and Example 1, and the value of Comparative Example 2 is used for Comparative Example 2 and Example 2. It was displayed as an index when it was set to 100. The results are shown in Table 2. The smaller the index value of low loss property, the better the low loss property.

(2) Abrasion resistance Each sample was vulcanized at 160 ° C. for 15 minutes to obtain vulcanized rubber. The obtained vulcanized rubber was subjected to a DIN wear test according to JIS-K6264-2: 2005 using a test piece cut out in a disk shape (diameter 16.2 mm × thickness 6 mm), and the amount of wear (mm). ³ ) was measured.
The obtained value of the amount of wear is the reciprocal of the value, and for Comparative Example 1 and Example 1, it is displayed as an index when the reciprocal value of Comparative Example 1 is set to 100, and for Comparative Example 2 and Example 2. , Displayed as an index when the reciprocal of Comparative Example 2 is 100. The results are shown in Table 2. The larger the index value of the amount of wear, the better the wear resistance.

* 1: "Nipsil AQ" manufactured by Tosoh Silica Co., Ltd.
* 2: Naphthenic oil "A / O MIX" manufactured by Sankyo Yuka Kogyo Co., Ltd.
* 3: "Diamond Black N234" manufactured by Mitsubishi Chemical Corporation
* 4: N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine * 5-1: Bis- [γ- (triethoxysilyl) -propyl] -tetrasulfide, manufactured by Evonik Degussa "Si69"
* 6: Diphenylguanidine, "Noxeller D" manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.
* 7: Benzothiazil disulfide, "Noxeller DM-P" manufactured by Ouchi Shinko Chemical Industry Co., Ltd.
* 8: N-t-Butyl-2-benzothiazyl sulfenamide, manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd. "Noxeller NS-P"

From the results in Table 2, the samples of Example 1 and Example 2 show superior results in terms of both low loss resistance and wear resistance as compared with the samples of Comparative Example 1 and Comparative Example 2, respectively. I understood.

According to the present invention, a modified diene polymer capable of obtaining a modified diene polymer capable of producing a rubber composition excellent in low loss property when used together with a reinforcing filler. A manufacturing method can be provided. Further, according to the present invention, a modified diene polymer capable of realizing a rubber composition having excellent low loss property when used together with a reinforcing filler, a rubber composition having excellent low loss property, and a rubber composition having excellent low loss property. It is possible to provide a tire with reduced rolling resistance.

Claims (6)

A process for producing a diene polymer containing 1,3-butadiene, and
The diene polymer produced and 3,6-bis (2-pyridyl) -1,2,4,5-tetrazine, 3,6-bis (3-pyridyl) -1,2,4,5- Tetrazine, 3,6-bis (2-furanyl) -1,2,4,5-tetrazine, 3-methyl-6- (3-pyridyl) -1,2,4,5-tetrazine and 3-methyl-6 -(2-Pyridyl) -1,2,4,5-Tetrazine-based compound is mixed with at least one tetrazine-based compound and then heated to modify the diene-based polymer.
A step of modifying the diene polymer with a denaturing agent having at least one of the compounds represented by the following general formulas (I) to (XIII).
A method for producing a modified diene-based polymer, which comprises the above.

(In the general formula (I), R ¹ and R ² independently represent a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, respectively. , a is an integer of 0 to 2, if the OR ² there is a plurality, the plurality of OR ² may be the same or different from each other, also in the molecule active proton is not included.)

(In the general formula (II), A ¹ is selected from the group consisting of epoxy, isocyanate, imine, carboxylic acid ester, carboxylic acid anhydride, cyclic tertiary amine, acyclic tertiary amine, pyridine, silazane and disulfide. It is a monovalent group having at least one functional group, R ³ is a single-bonded or divalent hydrocarbon group, and R ⁴ and R ⁵ are independently monovalent aliphatic groups having 1 to 20 carbon atoms, respectively. an aromatic hydrocarbon group of the hydrocarbon group or a monovalent C6-18, b is an integer of 0 to 2, if the oR ⁵ there is a plurality, the plurality of oR ⁵ being the same or different It may be present, and the molecule does not contain active protons.)

(In the general formula (III), n1 + n2 + n3 + n4 = 4 (where n1, n2, n3 and n4 are integers of 0 to 4 and n1 + n2 = 1 or more), and A ¹ is a saturated cyclic third class. Amine compound residue, unsaturated cyclic tertiary amine compound residue, ketimine residue, nitrile group, (thio) isocyanato group (indicates isocyanato group or thioisocyanate group; the same applies hereinafter), (thio) epoxy. Group, isocyanuric acid trihydrocarbyl ester group, dihydrocarbyl carbonate group, nitrile group, pyridine group, (thio) ketone group, (thio) aldehyde group, amide group, (thio) carboxylic acid ester group, (thio) carboxylic acid ester It is at least one functional group selected from the metal salt of the above, a carboxylic acid anhydride residue, a carboxylic acid halogen compound residue, and a primary or secondary amino group or a mercapto group having a hydrolyzable group. , R ²¹ is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and is the same when n1 is 2 or more. However, R ²³ may be a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or a halogen atom (fluorine, Chlorine, bromine, iodine), which may be the same or different when n3 is 2 or more, and R ²² is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or an alicyclic hydrocarbon group or a carbon number of carbon atoms. It is a monovalent aromatic hydrocarbon group of 6 to 18, both of which may contain a nitrogen atom and / or a silicon atom, and when n2 is 2 or more, they may be the same or different from each other. Alternatively, they form a ring together, and R ²⁴ is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms. When n4 is 2 or more, it may be the same or different.)

(In the general formula (IV), p1 + p2 + p3 = 2 (where p1, p2, p3 are integers of 0 to 2 and p1 + p2 = 1 or more), A ² is NRa (Ra is one). It is a valent hydrocarbon group, a hydrolyzable group or a nitrogen-containing organic group. As the hydrolyzable group, a trimethylsilyl group or a tert-butyldimethylsilyl group is preferable, and a trimethylsilyl group is particularly preferable), or sulfur. R ²⁵ is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when p1 is 2, they are the same as each other. Alternatively, they form a ring differently or together, and R ²⁷ is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms and a monovalent aromatic group having 6 to 18 carbon atoms. It is a hydrocarbon group or a halogen atom (fluorine, chlorine, bromine, iodine), and R ²⁶ is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms and a monovalent group having 6 to 18 carbon atoms. It is an aromatic hydrocarbon group or a nitrogen-containing organic group, both of which may contain a nitrogen atom and / or a silicon atom, and when p2 is 2, the rings are the same, different from each other, or together. R ²⁸ is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.)

(In the general formula (V), q1 + q2 = 3 (where q1 is an integer of 0 to 2 and q2 is an integer of 1 to 3), and R ³¹ is a divalent group having 1 to 20 carbon atoms. It is an aliphatic or alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and R ³² and R ³³ are independently hydrolyzable groups and monovalent groups having 1 to 20 carbon atoms, respectively. Is an aliphatic or alicyclic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and R ³⁴ is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms. It is a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and may be the same or different when q1 is 2, and R ³⁵ is a monovalent aliphatic or alicyclic group having 1 to 20 carbon atoms. It is a hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when q2 is 2 or more, it may be the same or different.)

(In the general formula (VI), r1 + r2 = 3 (where r1 is an integer of 1 to 3 and r2 is an integer of 0 to 2), and R ³⁶ is divalent with 1 to 20 carbon atoms. It is an aliphatic or alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and R ³⁷ is a dimethylaminomethyl group, a dimethylaminoethyl group, a diethylaminomethyl group, a diethylaminoethyl group, or a methylsilyl ( Methyl) aminomethyl group, methylsilyl (methyl) aminoethyl group, methylsilyl (ethyl) aminomethyl group, methylsilyl (ethyl) aminoethyl group, dimethylsilylaminomethyl group, dimethylsilylaminoethyl group, monovalent with 1 to 20 carbon atoms It is an aliphatic or alicyclic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and may be the same or different when r1 is 2 or more, and R ³⁸ has 1 carbon atom. It is a hydrocarbyloxy group of ~ 20, a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when r2 is 2. It may be the same or different.)

(In the general formula (VII), TMS is a trimethylsilyl group, R ⁴⁰ is a trimethylsilyl group, a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent group having 6 to 18 carbon atoms. It is an aromatic hydrocarbon group, and R ⁴¹ is a hydrocarbyloxy group having 1 to 20 carbon atoms, a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic group having 6 to 18 carbon atoms. It is a group hydrocarbon group, and R ⁴² is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.)

(In the general formula (VIII), TMS is a trimethylsilyl group, and R ⁴³ and R ⁴⁴ are independently divalent aliphatic or alicyclic hydrocarbon groups having 1 to 20 carbon atoms or 6 to 18 carbon atoms, respectively. R ⁴⁵ is a monovalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms. , Multiple R ^45s may be the same or different.)

(In the general formula (IX), r1 + r2 = 3 ( where, r1 is an integer of 0 to 2, r2 is an integer of 1 to 3.), TMS is a trimethylsilyl group, R ⁴⁶ is a carbon It is a divalent aliphatic or alicyclic hydrocarbon group having a number of 1 to 20, or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and R ⁴⁷ and R ⁴⁸ are independently having 1 to 20 carbon atoms, respectively. It is a monovalent aliphatic or alicyclic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and a plurality of R ⁴⁷ or R ⁴⁸ may be the same or different.)

(In the general formula (X), X is a halogen atom, and R ⁴⁹ is a divalent aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon having 6 to 18 carbon atoms. It is a hydrogen group, and R ⁵⁰ and R ⁵¹ are independently hydrolyzable groups, monovalent aliphatic or alicyclic hydrocarbon groups having 1 to 20 carbon atoms, or monovalent aromatic groups having 6 to 18 carbon atoms. It is a group hydrocarbon group, or R ⁵⁰ and R ⁵¹ are bonded to form a divalent organic group, and R ⁵² and R ⁵³ are independently halogen atoms, hydrocarbyloxy groups, and 1 carbon atoms, respectively. It is a monovalent aliphatic or alicyclic hydrocarbon group of ~ 20 or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms.)
_{R 'a SnX b ··· (XI} )
(In the above formula (XI), R'independently has an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 to 20 carbon atoms. Selected from the group consisting of aralkyl groups; X is independently chlorine or bromine; a is 0 to 3, b is 1 to 4, but a + b = 4. Tin of formula (XI). The diene rubber modified with the containing compound has at least one kind of tin-carbon bond.)
θ-C≡N ・ ・ ・ (XII-1)
θ-RC≡N ... (XII-2)
(In the formulas (XII-1) and (XII-2), θ represents a heterocyclic group.)
(AM) Li (Q) y ... (XIII)
(In the above formula (XIII), y is 0 or 0.5 to 3, Q is a solubilizing component selected from the group consisting of hydrocarbons, ethers, amines or mixtures thereof, and AM. Is the general formula (XIII-1) or (XIII-2).

(In the formula, each R ¹ independently represents an alkyl, cycloalkyl or aralkyl group having 1 to 12 carbon atoms.)

(In the formula, R ₂ is an alkylene having a methylene group of 3 to 16, a substituted alkylene, and an oxy-.
Alternatively, it indicates an N-alkylamino-alkylene group. ))) The tetrazine-based compound is selected from 3,6-di (2-pyridyl) -1,2,4,5-tetrazine and 3,6-di (4-pyridyl) -1,2,4,5-tetrazine. The method for producing a modified diene polymer according to claim 1, wherein the modified diene polymer is at least one kind of the polymer. When the peak molecular weight (Mp) of the diene-based polymer is 100,000 to 2000,000, the blending amount of the tetradin-based compound is 0.01 to 2.5 parts by mass with respect to 100 parts by mass of the diene-based polymer. The method for producing a modified diene polymer according to claim 1 or 2, wherein the modified diene polymer is produced. The method for producing a modified diene polymer according to any one of claims 1 to 3, wherein the diene polymer further contains an aromatic vinyl compound. The method for producing a modified diene polymer according to claim 4, wherein the aromatic vinyl compound is styrene. The modified diene system according to any one of claims 1 to 5, wherein the heating of the mixture of the diene-based polymer and the tetrazine-based compound is carried out as a step of drying the diene-based polymer. Method for producing polymer.