JP2011088988A - Tire - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a tire enhancing the on-ice performance without impairing the driveability on a dry road surface and wet road surface and reducing rolling resistance. <P>SOLUTION: This tire is characterized by using a rubber composition comprising: 100 pts.mass of a rubber matrix containing at least one type of diene-based rubber selected from a group consisting of a natural rubber, a polyisoprene rubber, and a polybutadiene rubber and a high molecular weight-modified conjugate diene-based polymer having a weight average molecular weight before modification of more than 15×10<SP>4</SP>and 200×10<SP>4</SP>or less; 0.5 pt.mass or more and less than 100 pts.mass of a hydrogenated resin; 5 to 50 pts.mass of a low molecular weight-modified conjugate diene-based polymer having a weight average molecular weight before modification of 2×10<SP>3</SP>to 15×10<SP>4</SP>; and 20 to 200 pts.mass of a reinforcing filler. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a tire, and more particularly to a tire with improved performance on ice and reduced rolling resistance without impairing steering stability on dry and wet road surfaces.

  Conventionally, as a tire used in winter, the glass transition point (Tg) is lowered in order to improve the performance on ice, and the temperature is low (here, the low temperature is a temperature during running on ice, about -20 to 0 ° C). In many cases, the elastic modulus is set low. However, since the elastic modulus at high temperatures tends to decrease when the elastic modulus at low temperature is generally lowered, the conventional winter tire has a driving stability performance on a dry road surface (hereinafter referred to as “dry steering stability performance”). Low driving stability on wet roads (hereinafter referred to as “wet handling stability”) is not sufficient. Furthermore, the heat generation and rolling resistance (RR) are high, which is sufficient for the market demand to reduce rolling resistance. There was a problem that was not able to cope with.

  On the other hand, in Patent Document 1, a rubber composition is obtained by blending a foaming agent with a rubber matrix and having a specific range of bubble ratios after vulcanization and dynamic elastic moduli at 0 ° C. and 60 ° C. Winter tires (studless tires) that have been used as tire tread rubber and modified conjugated diene polymers as the rubber matrix of the rubber composition have been proposed. The rolling resistance is reduced.

JP 2004-238619A

  However, although the winter tire disclosed in Patent Document 1 has improved on-ice performance and reduced rolling resistance compared to conventional tires, recently, further improvement on on-ice performance with respect to the tire, There is a need for reduction in rolling resistance, and there is still room for improvement.

  Accordingly, an object of the present invention is to provide a tire that solves the above-described problems of the prior art, improves performance on ice, and reduces rolling resistance without impairing steering stability on dry and wet road surfaces. .

  As a result of intensive studies to achieve the above object, the present inventors have formulated a specific diene rubber, in particular, a high molecular weight modified conjugated diene polymer, a low molecular weight modified conjugated diene polymer, and a hydrogenated resin. Thus, the present inventors have found that the performance on ice can be improved and the rolling resistance can be reduced without impairing the handling stability on the dry road surface and the wet road surface, and the present invention has been completed.

The tire according to the present invention has at least one diene rubber selected from the group consisting of natural rubber, polyisoprene rubber and polybutadiene rubber, and a weight average molecular weight before modification exceeding 15 × 10 ⁴ and not more than 200 × 10 ⁴ For 100 parts by mass of a rubber matrix containing a high molecular weight modified conjugated diene polymer, the hydrogenated resin is 0.5 parts by mass or more and less than 100 parts by mass, and the weight average molecular weight before modification is 2 × 10 ³ to 15 ×. A rubber composition comprising 5 to 50 parts by mass of a low molecular weight modified conjugated diene polymer of 10 ⁴ and 20 to 200 parts by mass of a reinforcing filler is used.

  In such a tire, more preferably, the bonded aromatic vinyl content (X) (%) of the low molecular weight modified conjugated diene polymer and the vinyl bond content (Y) (%) of the conjugated diene moiety are X + ( Y / 2) <25 is satisfied.

Preferably, the low molecular weight modified conjugated diene polymer contains at least one functional group selected from the group consisting of a tin-containing functional group, a silicon-containing functional group, and a nitrogen-containing functional group.
More preferably, the low molecular weight modified conjugated diene polymer is a low molecular weight modified polybutadiene and / or a low molecular weight modified polyisoprene.

Also preferably, the high molecular weight modified conjugated diene polymer contains at least one functional group selected from the group consisting of a tin-containing functional group, a silicon-containing functional group, and a nitrogen-containing functional group.
More preferably, the high molecular weight modified conjugated diene polymer is a modified polybutadiene rubber and / or modified polyisoprene rubber.

  Preferably, the reinforcing filler is carbon black and / or silica.

  By the way, the rubber matrix is preferably composed of 10 to 95% by mass of a high molecular weight modified conjugated diene polymer and 90 to 5% by mass of the diene rubber.

  More preferably, it further contains 3 to 30 parts by mass of fine particles having an average major axis of 5 to 1000 μm with respect to 100 parts by mass of the rubber matrix.

And preferably, the silicon-containing functional group is derived from a dialkoxysilane compound or a trialkoxysilane compound.
The tire according to any one of claims 1 to 10, wherein the nitrogen-containing functional group preferably has a primary amino group.

［式中、Ｒ^１及びＲ^３はそれぞれ独立して−ＯＲ、−ＯＨ又は炭素数１〜２０のアルキル基であり、Ｒ^２は炭素数１〜２０のアルキレン基であり、Ｒは硫黄原子、酸素原子、窒素原子及び／又はハロゲン原子を有していても良い炭素数１〜２０のヒドロカルビル基である］、又は下記一般式（化２）：

［式中、Ｒ^４及びＲ^６はそれぞれ独立して−ＯＲ、−ＯＨ又は炭素数１〜２０のアルキル基であり、Ｒ^５及びＲ^７はそれぞれ独立して炭素数１〜２０のアルキレン基であり、Ｒは硫黄原子、酸素原子、窒素原子及び／又はハロゲン原子を有していても良い炭素数１〜２０のヒドロカルビル基であり、ＭはＳｉ、Ｔｉ、Ｓｎ、Ｂｉ、Ｚｒ又はＡｌであり、Ｒ^８は−ＯＨ、炭素数１〜３０のヒドロカルビル基、炭素数２〜３０のヒドロカルビルカルボキシル基、炭素数５〜２０の１，３−ジカルボニル含有基、炭素数１〜２０のヒドロカルビルオキシ基、並びに炭素数１〜２０のヒドロカルビル基及び／又は炭素数１〜２０のヒドロカルビルオキシ基で三置換されたシロキシ基からなる群から選ばれる基であり、複数のＲ^８は同一でも異なっていても良く、ｋは｛（Ｍの価数）−２｝であり、ｎは０又は１である］で表わされることが好ましい。 By the way, the low molecular weight modified conjugated diene polymer and / or the high molecular weight modified conjugated diene polymer is represented by the following general formula (Formula 1):

[Wherein, R ¹ and R ³ are each independently —OR, —OH or an alkyl group having 1 to 20 carbon atoms, R ² is an alkylene group having 1 to 20 carbon atoms, R is a sulfur atom, It is a C1-C20 hydrocarbyl group optionally having an oxygen atom, a nitrogen atom and / or a halogen atom], or the following general formula (Formula 2):

[Wherein, R ⁴ and R ⁶ are each independently —OR, —OH or an alkyl group having 1 to 20 carbon atoms, and R ⁵ and R ⁷ are each independently an alkylene group having 1 to 20 carbon atoms. R is a C 1-20 hydrocarbyl group optionally having a sulfur atom, an oxygen atom, a nitrogen atom and / or a halogen atom, and M is Si, Ti, Sn, Bi, Zr or Al. , R ⁸ is —OH, a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyl carboxyl group having 2 to 30 carbon atoms, a 1,3-dicarbonyl-containing group having 5 to 20 carbon atoms, or a hydrocarbyloxy group having 1 to 20 carbon atoms. , and a group selected from the group consisting of siloxy group that is tri-substituted with hydrocarbyloxy group of hydrocarbyl and / or 1 to 20 carbon atoms having 1 to 20 carbon atoms, more R ⁸ are different and the same May have, k is the {(valence of M) -2}, n is preferably represented by a 0 or 1].

  Preferably, the low molecular weight modified conjugated diene polymer and / or the high molecular weight modified conjugated diene polymer has a C—N bond at the polymerization initiation terminal of the polymer.

Preferably, the difference in SP value between the rubber matrix and the hydrogenated resin is 1.5 or less.
Here, the SP value of the rubber matrix and (hydrogenated) resin can be calculated according to the Fedors method.

Preferably, the hydrogenated resin is a resin obtained by hydrogenating a petroleum resin or a natural resin.
More preferably, the hydrogenated resin is a hydrogenated terpene resin obtained by hydrogenating a terpene resin, and the softening point of the hydrogenated terpene resin is 80 to 180 ° C.

  Preferably, the total content of natural rubber, polyisoprene rubber and polybutadiene rubber in the rubber matrix is 50% by mass or more.

  Preferably, the rubber composition is used for a tread.

  More preferably, the rubber composition has 5 to 50% by volume of air bubbles in the rubber matrix after vulcanization.

  According to the present invention, a specific amount of a hydrogenated resin, a low molecular weight modified conjugated diene polymer before modification, and a reinforcing filler are blended with a specific rubber matrix and used for a tread member of a tire. Thus, it is possible to provide a tire capable of improving the performance on ice and reducing the rolling resistance without impairing the handling stability on the dry road surface and the wet road surface.

The present invention is described in detail below.
The tire of the present invention has at least one diene rubber selected from the group consisting of natural rubber, polyisoprene rubber and polybutadiene rubber, and has a weight average molecular weight of more than 15 × 10 ⁴ and not more than 200 × 10 ⁴ before modification. 0.5 parts by mass or more and less than 100 parts by mass of a hydrogenated resin with respect to 100 parts by mass of a rubber matrix containing a high molecular weight modified conjugated diene polymer, and the weight average molecular weight before modification is 2 × 10 ³ to 15 × 10 ⁴ , 5 to 50 parts by mass of a low molecular weight modified conjugated diene polymer and 20 to 200 parts by mass of a reinforcing filler are used, which is necessary. Depending on, other compounding agents can be contained.

Here, to limit the weight average molecular weight prior to modification of high molecular weight modified conjugated diene polymer 15 × 10 ⁴ to exceed 200 × 10 ⁴ or less, the wear resistance and fracture If it is 15 × 10 ⁴ or less This is because the characteristics deteriorate, and when it exceeds 200 × 10 ⁴ , the workability of the rubber composition decreases. From these viewpoints, the weight average molecular weight of the high molecular weight modified conjugated diene polymer before modification is preferably 20 × 10 ^{4 to} 150 × 10 ⁴ , and more preferably 20 × 10 ^{4 to} 120 × 10 ^4. .

Further, the weight average molecular weight before modification of the low molecular weight modified conjugated diene polymer is limited to 2 × 10 ³ to 15 × 10 ⁴ when it is less than 2 × 10 ³ and dynamic shear storage elasticity at high temperature. This is because the rate G ′ decreases and the dynamic loss tangent tan δ increases, and if it exceeds 15 × 10 ⁴ , workability decreases. From these viewpoints, the weight average molecular weight of the low molecular weight modified conjugated diene polymer before modification is preferably 5 × 10 ^{3 to} 12 × 10 ⁴ .

  The reason why the blending amount of the low molecular weight modified conjugated diene polymer is limited to 5 to 50 parts by mass is that if it is less than 5 parts by mass, the on-ice performance and wet performance of the tire cannot be improved. This is because the wear resistance and fracture resistance are reduced. From these viewpoints, the blending amount of the low molecular weight modified conjugated diene polymer is preferably 5 to 40 parts by mass, and more preferably 5 to 30 parts by mass.

  The compounding amount of the reinforcing filler is limited to 5 to 200 parts by mass. When the reinforcing filler is less than 5 parts by mass, the interaction between the high molecular weight modified conjugated diene polymer and the reinforcing filler is limited. This is because the rolling resistance of the tire is remarkably increased when the reinforcing filler exceeds 200 parts by mass. From these viewpoints, the compounding amount of the reinforcing filler is preferably 20 to 120 parts by mass, and more preferably 30 to 100 parts by mass.

  And generally, by blending the resin, tan δ (loss tangent) near 0 ° C. can be improved and wet grip performance can be improved, but tan δ other than near 0 ° C. also increases at the same time, for example, Tan δ around 50 ° C. also increases. Here, tan δ around 50 ° C. is considered as one index of tire rolling resistance. Generally, by using a rubber composition having a high tan δ around 50 ° C. as a tread member, the tire rolling resistance increases. End up.

On the other hand, since the SP value decreases when the resin is hydrogenated, the difference in SP value between the hydrogenated resin and the rubber matrix such as natural rubber, polyisoprene rubber, and polybutadiene rubber is higher than that of the unhydrogenated resin. Small. Therefore, the hydrogenated resin is highly compatible with natural rubber, polyisoprene rubber, polybutadiene rubber, and the like. As a result, when a hydrogenated resin is blended, the peak of tan δ becomes sharp, tan δ near 0 ° C. rises specifically, and tan δ other than near 0 ° C. does not rise so much, so a rubber composition blended with a hydrogenated resin By using for the tread member of a tire, it becomes possible to improve wet grip performance, without deteriorating other performances, such as rolling resistance.
In particular, a combination of natural rubber or polyisoprene rubber and a hydrogenated resin is preferable.

  In addition, when the compounding amount of the hydrogenated resin is less than 0.5 parts by mass with respect to 100 parts by mass of the rubber matrix, the effect of improving tan δ at 0 ° C. is small, so the wet grip performance of the tire is sufficiently improved. On the other hand, at 100 parts by mass or more, the solubility of the hydrogenated resin in the rubber matrix is exceeded, so the improvement in tan δ at 0 ° C. is small and the tan δ at 50 ° C. is high. is there. From these viewpoints, the compounding amount of the hydrogenated resin is preferably in the range of 1 to 50 parts by mass with respect to 100 parts by mass of the rubber matrix.

  The rubber matrix of the rubber composition used for the tire of the present invention contains at least one diene rubber selected from the group consisting of natural rubber (NR), polyisoprene rubber (IR) and polybutadiene rubber (BR), and is necessary. Depending on the above, other synthetic rubbers may be included. Examples of other synthetic rubbers include styrene-butadiene copolymer rubber (SBR), ethylene-propylene-diene rubber (EPDM), butadiene-isoprene copolymer rubber, styrene- Examples include isoprene copolymer rubber, styrene-isoprene-butadiene rubber, chloroprene rubber (CR), butyl rubber (IIR), halogenated butyl rubber, and acrylonitrile-butadiene rubber (NBR). These rubber matrices may be used alone or in a blend of two or more.

  Note that styrene-butadiene copolymer rubber (SBR) often used in rubber compositions for treads is not as small as natural rubber, polyisoprene rubber and polybutadiene rubber because the difference in SP value from hydrogenated resin is not as small. In the rubber composition in which the matrix is mainly composed of SBR, the compounding effect of the hydrogenated resin is small. Therefore, the rubber composition used in the tire of the present invention preferably has a total content of natural rubber, polyisoprene rubber and polybutadiene rubber in the rubber matrix of 50% by mass or more.

  The hydrogenated resin used in the rubber composition used in the tire of the present invention is obtained by hydrogenating a resin, preferably a resin obtained by hydrogenating a petroleum resin or a natural resin. Here, the hydrogenation of the resin can be performed by a known method, and a commercially available hydrogenated resin can also be used in the present invention.

  The petroleum resin used as the raw material for the hydrogenated resin is, for example, a cracked oil containing unsaturated hydrocarbons such as olefins and diolefins by-produced together with petrochemical basic raw materials such as ethylene and propylene by thermal decomposition of naphtha of petrochemical industry. It is obtained by polymerizing a fraction with a Friedel-Crafts catalyst as a mixture. The petroleum resin is obtained by (co) polymerizing an aliphatic petroleum resin obtained by (co) polymerization of a C5 fraction obtained by thermal decomposition of naphtha, or a C9 fraction obtained by thermal decomposition of naphtha. Aromatic petroleum resins, copolymer petroleum resins obtained by copolymerizing the C5 fraction and C9 fraction, alicyclic compound petroleum resins such as dicyclopentadiene, styrene, substituted styrene, styrene and other Examples thereof include styrene resins such as copolymers with monomers.

  Examples of the natural resin that is a raw material for the hydrogenated resin include terpene resins such as α-pinene-based, β-pinene-based, and dipentene-based resins, aromatic modified terpene resins, and terpene phenol resins.

  As the hydrogenated resin, specifically, Idemitsu Kosan Imabe S100 (trade name, softening point 100 ° C.), Idemitsu Kosan Imabu S110 (trade name, softening point 110 ° C.), Idemitsu Kosan Imabu Y100 (trade name, Imabu Y135 (trade name, softening point 135 ° C.), Idemitsu Kosan Imabu P90 (trade name, softening point 90 ° C.), Idemitsu Kosan Imabu P100 (trade name, softening point 100 ° C.) Imabe P125 (trade name, softening point 125 ° C), Idemitsu Kosan Imabe P140 (trade name, softening point 140 ° C), Alcon P70 (trade name, softening point 70 ° C), Arakawa Chemical Co., Ltd., Arakawa Chemical Co., Ltd. Alcon P90 (trade name, softening point 90 ° C), Alcon P100 (trade name, softening point 100 ° C), Arakawa Chemical Co., Ltd. Alcon P11 (Trade name, softening point 115 ° C.), Arakawa Chemical Alcon P125 (trade name, softening point 125 ° C.), Arakawa Chemical Alcon P140 (trade name, softening point 140 ° C.), Arakawa Chemical Alcon SP10 Name, softening point 100 ° C.), Alcon M90 (trade name, softening point 90 ° C.), Arakawa Chemical Co., Ltd., Alcon M100 (trade name, softening point 100 ° C.), Arakawa Chemical Alcon M115 (trade name, Alcon M135 (trade name, softening point 135 ° C) manufactured by Arakawa Chemical Co., Ltd. Alcon SM10 (trade name, softening point 100 ° C) manufactured by Arakawa Chemical Co., Ltd., KR1840 (trade name, softening point 100 manufactured by Arakawa Chemical Co., Ltd.) ℃), KR1842 manufactured by Arakawa Chemical Co., Ltd. (trade name, softening point 120 ° C.), Marukaretsu H505 manufactured by Maruzen Petrochemical (trade name, softening point 105 ° C.), Marukaretsu manufactured by Maruzen Petrochemical 90 (trade name, softening point 90 ° C.), Maruzetsu 700F (trade name, softening point 95 ° C.) by Maruzen Petrochemical, Marukaretsu H925 (trade name, softening point 123 ° C.) by Maruzen Petrochemical, Marukaretsu H970 by Maruzen Petrochemical ( (Trade name, softening point 175 ° C.), Yashara Chemical Clearon P105 (trade name, softening point 105 ° C.), Yashara Chemical Clearon P115 (trade name, softening point 115 ° C.), Yashara Chemical Clearon P125 (trade name, softening point 125 ° C.) Yasuhara Chemical Clearon P135 (trade name, softening point 135 ° C), Yasuhara Chemical Clearon P150 (trade name, softening point 152 ° C), Yasuhara Chemical Clearon M105 (trade name, softening point 105 ° C), Yasuhara Chemical Clearon M115 (trade name) , Softening point 115 ° C) Clearon K100 made by Hara Chemical (trade name, softening point 100 ° C.), Clearon K110 made by Yashara Chemical (trade name, softening point 110 ° C.), Clearon K4100 made by Yashara Chemical (trade name, softening point 100 ° C.), Clearon K 4090 made by Yashara Chemical (trade name) , Softening point 90 ° C.). These hydrogenated resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  In the rubber composition used in the tire of the present invention, the hydrogenated resin is more preferably a hydrogenated terpene resin obtained by hydrogenating a terpene resin, particularly preferably a hydrogenated terpene resin having a softening point of 80 to 180 ° C. . Since the hydrogenated terpene resin originally hydrogenates a terpene resin having a low SP value, the SP value is particularly low. Therefore, the hydrogenated terpene resin has a particularly small difference in SP value from a rubber matrix such as natural rubber, polyisoprene rubber and polybutadiene rubber, and the effect of the present invention is remarkably exhibited. When a hydrogenated terpene resin having a softening point of less than 80 ° C. is used, steering stability tends to deteriorate. On the other hand, when a softened point exceeds 180 ° C., when a hydrogenated terpene resin is used, The effect of improving tan δ is small, and tan δ at 50 ° C. becomes high.

  In the rubber composition used for the tire of the present invention, the difference in SP value between the rubber matrix and the hydrogenated resin is preferably 1.5 or less. When the difference in SP value between the rubber matrix and the hydrogenated resin is 1.5 or less, the compatibility between the rubber matrix and the hydrogenated resin is particularly good, so that the effects of the present invention are remarkably exhibited, such as rolling resistance. The wet grip performance can be greatly improved without deteriorating other performance.

  The rubber composition used in the tire of the present invention has a bonded aromatic vinyl content (X) (%) of the low molecular weight modified conjugated diene polymer and a vinyl bond content (Y) (%) of the conjugated diene. It is preferable to satisfy X + (Y / 2) <25. If {X + (Y / 2)} is less than 25, the performance on ice is improved.

In the rubber composition used in the tire of the present invention, the low molecular weight modified conjugated diene polymer is at least one functional group selected from the group consisting of a tin-containing functional group, a silicon-containing functional group, and a nitrogen-containing functional group. It is preferable to contain.
The high molecular weight modified conjugated diene polymer preferably contains at least one functional group selected from the group consisting of a tin-containing functional group, a silicon-containing functional group, and a nitrogen-containing functional group.
This is because these functional groups are rich in reactivity with the reinforcing filler and improve the reinforcing property of the rubber composition.
In particular, a tin-containing functional group is preferable because it is highly reactive with carbon black, a silicon-containing functional group is preferable because it is highly reactive with silica, and a nitrogen-containing functional group is highly reactive with both carbon black and silica. Therefore, it is preferable.

  Examples of tin-containing functional groups include tin halide compound residues, such as triphenyltin chloride, tributyltin chloride, triisopropyltin chloride, trihexyltin chloride, trioctyltin chloride, diphenyltin dichloride, dibutyltin dichloride, dihexyltin. Preference is given to residues which are produced by leaving one or more chlorine atoms from a tin chloride compound selected from the group consisting of dichloride, dioctyltin dichloride, phenyltin trichloride, butyltin trichloride, octyltin trichloride and tin tetrachloride.

Examples of the silicon-containing functional group include a residue formed by leaving one or more of —OR ^{3 of the} hydrocarbyloxysilane compound represented by the following general formula (1) and its partial condensate.

式中、Ａは、イソシアネート基、チオイソシアネート基、イミン残基、アミド基、第一級アミノ基、第一級アミンのオニウム塩残基、環状第二級アミノ基、環状第二級アミンのオニウム塩残基、非環状第二級アミノ基及び非環状第二級アミンのオニウム塩残基、イソシアヌル酸トリエステル残基、環状第三級アミノ基、非環状第三級アミノ基、ニトリル基、ピリジン残基、環状第三級アミンのオニウム塩残基、非環状第三級アミンのオニウム塩残基、エポキシ基、チオエポキシ基、ケトン基、チオケトン基、アルデヒド基、チオアルデヒド基、カルボン酸エステル残基、チオカルボン酸エステル残基、カルボン酸無水物残基、カルボン酸ハロゲン化物残基、炭酸ジヒドロカルビルエステル残基、スルフィド基、マルチスルフィド基、ヒドロキシ基、チオール基、アリル又はベンジルＳｎ結合を有する基、スルフォニル基及びスルフィニル基から選ばれる少なくとも一種の官能基を有する一価の基、Ｒ^１は単結合又は二価の不活性炭化水素基、Ｒ^２及びＲ^３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、ｍは０〜２の整数であり、ＯＲ^３が複数ある場合、複数のＯＲ^３は同一でも異なっていてもよい。上記の内、第一級アミノ基は変性反応終了後までアルキルシリル基（例えば、メチルシリル基やエチルシリル基）等により保護されていることが好ましい。

In the formula, A is an isocyanate group, thioisocyanate group, imine residue, amide group, primary amino group, onium salt residue of primary amine, cyclic secondary amino group, onium of cyclic secondary amine Salt residue, acyclic secondary amino group and onium salt residue of acyclic secondary amine, isocyanuric acid triester residue, cyclic tertiary amino group, acyclic tertiary amino group, nitrile group, pyridine Residues, onium salt residues of cyclic tertiary amines, onium salt residues of acyclic tertiary amines, epoxy groups, thioepoxy groups, ketone groups, thioketone groups, aldehyde groups, thioaldehyde groups, carboxylic acid ester residues Thiocarboxylic acid ester residue, carboxylic acid anhydride residue, carboxylic acid halide residue, carbonic acid dihydrocarbyl ester residue, sulfide group, multisulfide group, hydroxyl group Group, a thiol group, an allyl or a group having a benzyl Sn bond, monovalent group having at least one functional group selected from a sulfonyl group and sulfinyl group, R ¹ is a single bond or a divalent inactive hydrocarbon radical, R ² and R ³ each 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, and m is an integer of 0 to 2. If the OR ³ there are a plurality, the plurality of OR ³ may be the same or different. Of the above, the primary amino group is preferably protected by an alkylsilyl group (for example, a methylsilyl group or an ethylsilyl group) or the like until after the modification reaction.

Preferred examples of the divalent inert hydrocarbon group in R ¹ include an alkylene group having 1 to 20 carbon atoms. The alkylene group may be linear, branched, or cyclic, but a linear one is particularly preferable. Examples of the linear alkylene group include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, a decamethylene group, and a dodecamethylene group.

Examples of R ² and R ³ include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an aralkyl group having 7 to 18 carbon atoms. Here, the alkyl group and alkenyl group may be linear, branched, or cyclic, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, Isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, decyl, dodecyl, cyclopentyl, cyclohexyl, vinyl, propenyl, allyl, hexenyl, octenyl, cyclo A pentenyl group, a cyclohexenyl group, etc. are mentioned.
The aryl group may have a substituent such as a lower alkyl group on the aromatic ring, and examples thereof include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. Further, the aralkyl group may have a substituent such as a lower alkyl group on the aromatic ring, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.

The silicon-containing functional group is preferably derived from a dialkoxysilane compound or a trialkoxysilane compound.
Here, the two alkoxy groups of the dialkoxysilane compound are each independently an alkoxy group having 1 to 20 carbon atoms which may have a substituent. Similarly, the three alkoxy groups of the trialkoxysilane compound are each independently an alkoxy group having 1 to 20 carbon atoms which may have a substituent.

As the nitrogen-containing functional group, A is an isocyanate group among the residues formed by leaving one or more of —OR ^{3 of the} hydrocarbyloxysilane compound represented by the general formula (1) and its partial condensate. Thioisocyanate group, imine residue, amide group, primary amino group, primary amine onium salt residue, cyclic secondary amino group, cyclic secondary amine onium salt residue, acyclic secondary Primary amino group and onium salt residue of acyclic secondary amine, isocyanuric acid triester residue, cyclic tertiary amino group, acyclic tertiary amino group, nitrile group, pyridine residue, cyclic tertiary amine And a nitrogen-containing hydrocarbyloxysilane compound residue which is an onium salt residue of an acyclic tertiary amine.

  Of the nitrogen-containing hydrocarbyloxysilane compounds represented by the general formula (1), N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1- Propanamine, N- (1-methylethylidene) -3- (triethoxysilyl) -1-propanamine, N-ethylidene-3- (triethoxysilyl) -1-propanamine, N- (1-methylpropylidene) ) -3- (Triethoxysilyl) -1-propanamine, N- (4-N, N-dimethylaminobenzylidene) -3- (triethoxysilyl) -1-propanamine, N- (cyclohexylidene)- 3- (Triethoxysilyl) -1-propanamine and trimethoxysilyl corresponding to these triethoxysilyl compounds Preferred examples include compounds, methyldiethoxysilyl compounds, ethyldiethoxysilyl compounds, methyldimethoxysilyl compounds, and ethyldimethoxysilyl compounds. Among these, N- (1-methylpropylidene) -3- (Triethoxysilyl) -1-propanamine and N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine are preferred.

  Other imine residue (amidine group) -containing compounds include 1- [3- (triethoxysilyl) propyl] -4,5-dihydroimidazole, 1- [3- (trimethoxysilyl) propyl] -4. , 5-dihydroimidazole, 3- [10- (triethoxysilyl) decyl] -4-oxazoline and the like, among which 3- (1-hexamethyleneimino) propyl (triethoxy) silane, (1-Hexamethyleneimino) methyl (trimethoxy) silane, 1- [3- (triethoxysilyl) propyl] -4,5-dihydroimidazole and 1- [3- (trimethoxysilyl) propyl] -4,5- A preferred example is dihydroimidazole. N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole, N- (3-isopropoxysilylpropyl) -4,5-dihydroimidazole, N- (3-methyldiethoxysilylpropyl)- 4,5-dihydroimidazole and the like can be mentioned, among which N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole is preferable.

  Among the nitrogen-containing hydrocarbyloxysilane compounds represented by the general formula (1), the isocyanate group-containing compounds include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and 3-isocyanatopropyl. Examples thereof include methyldiethoxysilane and 3-isocyanatopropyltriisopropoxysilane. Among these, 3-isocyanatopropyltriethoxysilane is preferable.

  Among the nitrogen-containing hydrocarbyloxysilane compounds represented by the general formula (1), examples of the cyclic tertiary amino group-containing compound include 3- (1-hexamethyleneimino) propyl (triethoxy) silane, 3- (1-hexa Methyleneimino) propyl (trimethoxy) silane, (1-hexamethyleneimino) methyl (trimethoxy) silane, (1-hexamethyleneimino) methyl (triethoxy) silane, 2- (1-hexamethyleneimino) ethyl (triethoxy) silane, 2- (1-hexamethyleneimino) ethyl (trimethoxy) silane, 3- (1-pyrrolidinyl) propyl (triethoxy) silane, 3- (1-pyrrolidinyl) propyl (trimethoxy) silane, 3- (1-heptamethyleneimino) Propyl (triethoxy) silane, 3- (1- Heptamethyleneimino) propyl (triethoxy) silane, 3- (1-hexamethyleneimino) propyl (diethoxy) methylsilane, 3- (1-hexamethyleneimino) can be preferably exemplified propyl (diethoxy) ethylsilane. Particularly preferred are 3- (1-hexamethyleneimino) propyl (triethoxy) silane and (1-hexamethyleneimino) methyl (trimethoxy) silane. Furthermore, examples of other hydrocarbyloxysilane compounds include 2- (trimethoxysilylethyl) pyridine, 2- (triethoxysilylethyl) pyridine, 4-ethylpyridine and the like.

Among the nitrogen-containing hydrocarbyloxysilane compounds represented by the general formula (1), 3-dimethylaminopropyl (triethoxy) silane, 3-dimethylaminopropyl (trimethoxy) are used as the acyclic tertiary amino group-containing hydrocarbyloxysilane compounds. Silane, 3-diethylaminopropyl (triethoxy) silane, 3-diethylaminopropyl (trimethoxy) silane, 2-dimethylaminoethyl (triethoxy) silane, 2-dimethylaminoethyl (trimethoxy) silane, 3-dimethylaminopropyl (diethoxy) methylsilane, Examples include 3-dibutylaminopropyl (triethoxy) silane, among which 3-diethylaminopropyl (triethoxy) silane and 3-dimethylaminopropyl (trieth). Shi) silane are preferred.
Further, examples of the nitrogen-containing hydrocarbyloxysilane compound represented by the general formula (1) include 2- (trimethoxysilylethyl) pyridine, 2- (triethoxysilylethyl) pyridine, 2-cyanoethyltriethoxysilane and the like. It is done.

式中、Ｒ^４及びＲ^６は夫々独立に−ＯＲ、−ＯＨ又は炭素数１〜２０のアルキル基であり、Ｒ^５は炭素数１〜２０のアルキレン基であり、Ｒは硫黄原子、酸素原子、窒素原子及び／又はハロゲン原子を有していても良い炭素数１〜２０のヒドロカルビル基である。

ここで、Ｒ^７及びＲ^９は夫々独立に−ＯＲ、−ＯＨ又は炭素数１〜２０のアルキル基であり、Ｒ^８及びＲ^１０は夫々独立に炭素数１〜２０のアルキレン基であり、Ｒは硫黄原子、酸素原子、窒素原子及び／又はハロゲン原子を有していても良い炭素数１〜２０のヒドロカルビル基であり、ＭはＳｉ、Ｔｉ、Ｓｎ、Ｂｉ、Ｚｒ又はＡｌであり、Ｒ^１１は−ＯＨ、炭素数１〜３０のヒドロカルビル基、炭素数２〜３０のヒドロカルビルカルボキシル基、炭素数５〜２０の１，３−ジカルボニル含有基、炭素数１〜２０のヒドロカルビルオキシ基、並びに炭素数１〜２０のヒドロカルビル基及び／又は炭素数１〜２０のヒドロカルビルオキシ基で三置換されたシロキシ基からなる群から選ばれる基であり、複数のＲ^１１は同一でも異なっていても良く、ｋは｛（Ｍの価数）−２｝であり、ｎは０又は１の整数である］
なお、上記一般式（２）及び（３）の−（Ｐｏｌｙｍｅｒ）は共役ジエン重合体のポリマー鎖である。 As the nitrogen-containing functional group, among the residues formed by leaving one or more of —OR ^{3 of the} hydrocarbyloxysilane compound represented by the general formula (1) and the partial condensate thereof, the following general formula ( The monovalent functional group represented by 2) or the divalent functional group represented by the following general formula (3) is particularly preferred. This is because the primary amino group of the general formula (2) or the general formula (3) particularly improves the reinforcing properties of both carbon black and silica.

In the formula, R ⁴ and R ⁶ are each independently —OR, —OH or an alkyl group having 1 to 20 carbon atoms, R ⁵ is an alkylene group having 1 to 20 carbon atoms, and R is a sulfur atom or an oxygen atom. And a hydrocarbyl group having 1 to 20 carbon atoms which may have a nitrogen atom and / or a halogen atom.

Here, R ⁷ and R ⁹ are each independently —OR, —OH or an alkyl group having 1 to 20 carbon atoms; R ⁸ and R ¹⁰ are each independently an alkylene group having 1 to 20 carbon atoms; Is a hydrocarbyl group having 1 to 20 carbon atoms which may have a sulfur atom, an oxygen atom, a nitrogen atom and / or a halogen atom, M is Si, Ti, Sn, Bi, Zr or Al, and R ¹¹ Is —OH, a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyl carboxyl group having 2 to 30 carbon atoms, a 1,3-dicarbonyl-containing group having 5 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms, and carbon a group selected from the group consisting of trisubstituted siloxy groups 1-20 hydrocarbyl group and / or a hydrocarbyloxy group having 1 to 20 carbon atoms, the R ¹¹ s are identical or different Well, k is the {(valence of M) -2}, n is an integer of 0 or 1]
In the above general formulas (2) and (3),-(Polymer) is a polymer chain of a conjugated diene polymer.

As -OR of R ⁴ , R ⁶ , R ⁷ and R ^{9 in} the general formulas (2) and (3), methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec -Butoxy group, tert-butoxy group, pentyloxy group, allyloxy group, phenoxy group, benzyloxy group and the like, and these functional groups have a sulfur atom, an oxygen atom, a nitrogen atom and / or a halogen atom. May be. The sulfur atom may be contained in R as, for example, —SH, —S _X — (X is an integer of 1 to 5), or an epithio group. The oxygen atom may be contained in R as —OH, —O—, an epoxy group, an acyl group, or a carboxyl group. The nitrogen atom is an amino group (primary amino group, secondary amino group, or acyclic or cyclic tertiary amino group), imino group, amidine group, isocyanate group, N-hydroxy group, N-oxide group, It may be contained in R as a nitrile group, an imine residue, or a cyano group.

^Further, R ^4, the alkyl group of R 6, carbon atoms ^{R 7} and ^{R 9} 1 to 20, a methyl group, an ethyl group, a propyl group, an isopropyl group, n- butyl group, isobutyl group, sec- butyl group, Examples thereof include a tert-butyl group, a pentyl group, a hexyl group, and an octyl group.
The halogen atom which may be contained in R may be any of fluorine, chlorine, bromine and iodine, but chlorine or bromine is preferred.

Examples of the alkylene group having 1 to 20 carbon atoms of R ⁵ , R ⁸ and R ¹⁰ include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1, 4-diyl group, butane-1,3-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, Nonane-1,9-diyl group, decane-1,10-diyl group and the like can be mentioned.

In general, R ⁷ and R ⁹ are the same, and R ⁸ and R ¹⁰ are the same. This is because the divalent functional group represented by the above general formula (3) is formed by condensing two polymer chains having the same monovalent functional group represented by the above general formula (2).

  The primary amino group of the general formula (2) or (3) is formed by an alkylsilyl group (for example, a methylsilyl group or an ethylsilyl group) until the end of the modification reaction, as in the case of the general formula (1). It is preferably protected.

  A residue from which lithium is released from a lithium amide compound described later as an initiator for anionic polymerization is also preferable as the nitrogen-containing functional group contained in the high molecular weight modified conjugated diene polymer or the low molecular weight modified conjugated diene polymer.

Further, among the at least one functional group selected from the group consisting of a tin-containing functional group, a silicon-containing functional group, and a nitrogen-containing functional group contained in the high molecular weight modified conjugated diene polymer, the above general formula (2) The monovalent functional group represented or the divalent functional group represented by the general formula (3) is preferable.
On the other hand, among the at least one functional group selected from the group consisting of a tin-containing functional group, a silicon-containing functional group, and a nitrogen-containing functional group contained in the low molecular weight modified conjugated diene polymer, the above general formula (2) It may be a monovalent functional group represented or a functional group other than the divalent functional group represented by the general formula (3).
Since the monovalent functional group represented by the general formula (2) or the divalent functional group represented by the general formula (3) has high reactivity with the reinforcing filler, a high molecular weight modified conjugated diene polymer. This is because the rubber composition further improves the reinforcing property due to the reaction between the reinforcing filler and the reinforcing filler, and further improves the dry steering stability performance, wear resistance and fracture resistance.

  The nitrogen-containing functional group or the functional group containing a nitrogen atom and a silicon atom preferably has an amino group, and more preferably has a primary amino group.

In the rubber composition used in the tire of the present invention, the low molecular weight modified conjugated diene polymer is preferably low molecular weight modified polybutadiene and / or low molecular weight modified polyisoprene, and particularly preferably modified polybutadiene.
The high molecular weight modified conjugated diene polymer is preferably a high molecular weight modified polybutadiene rubber and / or a modified polyisoprene rubber, and particularly preferably a high molecular weight modified polybutadiene rubber. This is because the glass transition point (Tg) of the low molecular weight modified conjugated diene polymer and the high molecular weight modified conjugated diene polymer is lowered to improve the performance on ice.

  Examples of the conjugated diene monomer used in the low molecular weight modified conjugated diene polymer and the high molecular weight modified conjugated diene polymer include 1,3-butadiene, isoprene, 1,3-pentadiene, and 2,3-dimethyl-1. , 3-butadiene, 2-phenyl-1,3-butadiene, 1,3-hexadiene and the like. These may be used alone or in combination of two or more, and among these, 1,3-butadiene is particularly preferable.

  Examples of the aromatic vinyl monomer used in the low molecular weight modified conjugated diene polymer and the high molecular weight modified conjugated diene polymer include styrene, α-methylstyrene, 1-vinylnaphthalene, 3-vinyltoluene, and ethyl. Examples thereof include vinylbenzene, divinylbenzene, 4-cyclohexylstyrene, 2,4,6-trimethylstyrene and the like. These may be used alone or in combination of two or more, but among these, styrene is particularly preferred.

The polymerization reaction system for obtaining the low molecular weight modified conjugated diene polymer and the high molecular weight modified conjugated diene polymer used in the rubber composition used in the tire of the present invention will be described.
In order to introduce a tin-containing functional group, a silicon-containing functional group, or a nitrogen-containing functional group into the active terminal of the conjugated diene polymer by reacting the active terminal of the conjugated diene polymer with the modifier, The coalescence is preferably such that at least 10% of the polymer chains have living or pseudo-living properties. Examples of such a polymerization reaction having a living property include anionic polymerization and coordination anionic polymerization, and anionic polymerization is preferable in that a wide range of modification is possible.

  As the alkali metal compound used as the initiator for the anionic polymerization described above, a lithium compound is preferable. The lithium compound is not particularly limited, but hydrocarbyl lithium and lithium amide compounds are preferably used. When the former hydrocarbyl lithium is used, it has a hydrocarbyl group at the polymerization initiation terminal and the other terminal is a polymerization active site. A conjugated diene polymer is obtained. When the latter lithium amide compound is used, a conjugated diene polymer having a nitrogen-containing group at the polymerization initiation terminal, that is, having a CN bond and the other terminal being a polymerization active site is obtained. .

  As the hydrocarbyl lithium, those having a hydrocarbyl group having 2 to 20 carbon atoms are preferable, for example, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-octyl lithium, n-decyl. Examples include lithium, phenyllithium, 2-naphthyllithium, 2-butylphenyllithium, 4-phenylbutyllithium, cyclohexyllithium, cyclobenthyllithium, and reactive organisms of diisopropenylbenzene and butyllithium. Of these, n-butyllithium is particularly preferable.

  On the other hand, as the lithium amide compound, for example, lithium hexamethylene imide, lithium pyrrolidide, lithium piperidide, lithium heptamethylene imide, lithium dodecamethylene imide, lithium dimethyl amide, lithium diethyl amide, lithium dibutyl amide, lithium dipropyl amide, lithium Diheptylamide, lithium dihexylamide, lithium dioctylamide, lithium di-2-ethylhexylamide, lithium didecylamide, lithium-N-methylpiverazide, lithium ethylpropylamide, lithium ethylbutyramide, lithium ethylbenzylamide, lithium methylphenethylamide, etc. Is mentioned. Among these, in view of the interaction effect on carbon black and the ability to initiate polymerization, cyclic lithium amides such as lithium hexamethylene imide, lithium pyrrolidide, lithium piperidide, lithium heptamethylene imide, and lithium dodecamethylene imide are preferable, In particular, lithium hexamethylene imide and lithium pyrrolidide are suitable.

  In general, these lithium amide compounds prepared from secondary amines and lithium compounds can be used for polymerization, but can also be prepared in the polymerization system (in-situ). The amount of the polymerization initiator used is preferably selected in the range of 0.2 to 20 mmol per 100 g of monomer.

A method for producing a conjugated diene polymer by anionic polymerization using the lithium compound as a polymerization initiator is not particularly limited, and a conventionally known method can be used.
Specifically, in an organic solvent inert to the reaction, for example, a hydrocarbon solvent such as an aliphatic, alicyclic, or aromatic hydrocarbon compound, a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl are used. The monomer is anionically polymerized with the lithium compound as a polymerization initiator in the presence of a randomizer to be used, if desired, to obtain a conjugated diene polymer having a target active end.
In addition, when a lithium compound is used as a polymerization initiator, not only a conjugated diene polymer having an active terminal but also a conjugated compound having an active terminal compared to the case of using a catalyst containing a lanthanum series rare earth element compound described above. A diene-aromatic vinyl copolymer can also be obtained efficiently.

  The hydrocarbon solvent is preferably one having 3 to 8 carbon atoms, such as propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, cyclohexane, propene, 1-butene, isobutene and trans-2. -Butene, cis-2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, benzene, toluene, xylene, ethylbenzene and the like. These may be used alone or in combination of two or more.

  The monomer concentration in the solvent is preferably 5 to 50% by mass, more preferably 10 to 30% by mass. When copolymerization is performed using a conjugated diene monomer and an aromatic vinyl monomer, the content of the aromatic vinyl monomer in the charged monomer mixture is preferably in the range of 55% by mass or less.

  The randomizer used as desired is the control of the microstructure of the conjugated diene polymer, such as the vinyl bond in the butadiene polymer, the vinyl bond in the butadiene moiety in the butadiene-styrene copolymer, and the increase in the vinyl bond in the isoprene polymer. Or a compound having an action of controlling the composition distribution of monomer units in a conjugated diene-aromatic vinyl copolymer, for example, randomizing butadiene units or styrene units in a butadiene-styrene copolymer. The randomizer is not particularly limited, and any one of known compounds generally used as a conventional randomizer can be appropriately selected and used.

  Specific examples of the randomizer include dimethoxybenzene, tetrahydrofuran, dimethoxyethane, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, oxolanyl propane oligomers [especially those containing 2,2-bis (2-tetrahydrofuryl) -propane, etc.], Examples thereof include ethers such as triethylamine, pyridine, N-methylmorpholine, N, N, N ′, N′-tetramethylethylenediamine, 1,2-dipiperidinoethane, and tertiary amines. Further, potassium salts such as potassium t-amylate and potassium t-butoxide, and sodium salts such as sodium t-amylate can also be used.

  One of these randomizers may be used alone, or two or more thereof may be used in combination. The amount used is preferably selected in the range of 0.01 to 1000 molar equivalents per mole of the lithium compound.

  The temperature in this polymerization reaction is preferably selected in the range of 0 to 150 ° C, more preferably 20 to 130 ° C. The polymerization reaction can be carried out under generated pressure, but it is usually desirable to operate at a pressure sufficient to keep the monomer in a substantially liquid phase. That is, the pressure depends on the particular material being polymerized, the polymerization medium used and the polymerization temperature, but higher pressures can be used if desired, such pressure being a gas that is inert with respect to the polymerization reaction. Can be obtained by an appropriate method such as pressurizing.

In the above-mentioned anionic polymerization, all raw materials involved in the polymerization, such as a polymerization initiator, a solvent, and a monomer, should be used after removing reaction-inhibiting substances such as water, oxygen, carbon dioxide, and protic compounds. desirable.
The polymerization reaction may be performed either batchwise or continuously.
In this way, a conjugated diene polymer having an active end is obtained.

  In the present invention, the conjugated diene polymer having an active terminal obtained as described above is incorporated with the above-described modifier capable of introducing a tin-containing functional group, a silicon-containing functional group and a nitrogen-containing functional group. The stoichiometric amount or an excess thereof is preferably added to the active end of the diene polymer and reacted with the active end bonded to the polymer. The modification reaction may be performed under the same temperature and pressure conditions as the polymerization reaction.

  The amount of the above-mentioned modifier used is usually 0.2 to 10 equivalents, preferably 0.5 to 5.0 equivalents, based on a functional group capable of undergoing a modification reaction, per 1 g atomic equivalent of lithium atom. If the amount is less than 2 equivalents, the rebound resilience and low heat build-up effect of the vulcanized rubber is inferior. On the other hand, if the amount exceeds 10 equivalents, unreacted substances increase and odor is generated, the vulcanization speed is increased, The effects of rebound resilience and low heat build-up are reduced, which is not preferable.

  The modified conjugated diene polymer represented by the general formula (2) is reacted with a hydrocarbyloxysilane compound having a protected primary amino group at the active terminal of the conjugated diene polymer obtained by anionic polymerization or coordination polymerization. The first-stage modification reaction is performed, and then the protecting group of the nitrogen atom protected by steam stripping or the like is eliminated.

  The modified conjugated diene polymer represented by the general formula (3) is a hydrocarbyloxysilane compound having a primary amino group protected at the active terminal of a conjugated diene polymer obtained by anionic polymerization or coordination polymerization. After the first-stage modification reaction, the second-stage modification reaction is further performed using a specific condensation accelerator, and then the protecting group of the nitrogen atom protected by steam stripping or the like is removed. .

Examples of the hydrocarbyloxysilane compound having a protected primary amino group include N, N-bis (trimethylsilyl) aminopropylmethyldimethoxysilane, 1-trimethylsilyl-2,2-dimethoxy-1-aza-2-sila. Cyclopentane, N, N-bis (trimethylsilyl) aminopropyltrimethoxysilane, N, N-bis (trimethylsilyl) aminopropyltriethoxysilane, N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane, N, N- Bis (trimethylsilyl) aminoethyltrimethoxysilane, N, N-bis (trimethylsilyl) aminoethyltriethoxysilane, N, N-bis (trimethylsilyl) aminoethylmethyldimethoxysilane or N, N-bis (trimethylsilyl) aminoe It can be preferably exemplified a methyl diethoxy silane. Particularly preferably, N, N-bis (trimethylsilyl) aminopropylmethyldimethoxysilane, N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane or 1-trimethylsilyl-2,2-dimethoxy-1-aza-2-sila Mention may be made of cyclopentane.
The said hydrocarbyl oxysilane compound may be used individually by 1 type, and may be used in combination of 2 or more type.

  In the second stage modification reaction for producing the modified conjugated diene polymer represented by the general formula (3) according to the tire of the present invention, the hydrocarbyloxysilane compound residue introduced into the active site of the conjugated diene polymer It is preferable to perform group condensation or condensation with the unreacted hydrocarbyloxysilane compound in the presence of a condensation accelerator. As the condensation accelerator, a combination of a metal compound of Si, Ti, Sn, Bi, Zr or Al and water can be used.

Among the condensation accelerators, the metal compound includes a divalent tin compound represented by the following general formula (4), a tetravalent tin compound represented by the following general formula (5), and the following general formula (6). ) Is preferred.
Sn (OCOR ¹² ) ₂ (4)
Here, R ¹² is an alkyl group having 2 to 19 carbon atoms.
R ¹³ _x SnA ¹ _y B ¹ _4- yx (5)
Here, R ¹³ is an aliphatic hydrocarbon group having 1 to 30 carbon atoms, x is an integer of 1 to 3, y is 1 or 2, A ¹ is a hydrocarbyl carboxyl group having 2 to 30 carbon atoms, and 5 to 20 carbon atoms. Selected from a 1,3-dicarbonyl-containing group, a C 3-20 hydrocarbyloxy group, and a C 1-20 hydrocarbyl group and / or a siloxy group trisubstituted with a C 1-20 hydrocarbyloxy group. Group B ¹ is a hydroxy group or halogen.
A ² _z TiB ² _4-z (6)
Here, A ² is a group selected from a C 3-20 alkoxy group, a C 1-20 alkyl group and / or a siloxy group trisubstituted with a C 1-20 alkoxy group, and B ² is carbon. 1,3-dicarbonyl-containing group of formula 5-20, z is 2 or 4.

  More specifically, as the above condensation accelerator, divalent tin dicarboxylic acid {particularly, bis (hydrocarbylcarboxylic acid) salt} or tetravalent dihydrocarbyltin dicarboxylic acid salt {bis (hydrocarbylcarboxylic acid) } Salt), bis (β-diketonate), alkoxy halide, monocarboxylate hydroxide, alkoxy (trihydrocarbylsiloxide), alkoxy (dihydrocarbylalkoxysiloxide), bis (trihydrocarbylsiloxide), bis ( Dihydrocarbylalkoxysiloxide) and the like can be preferably used. The hydrocarbyl group bonded to tin preferably has 4 or more carbon atoms, and particularly preferably has 4 to 8 carbon atoms.

  Examples of the titanium compound include tetravalent titanium tetraalkoxide, dialkoxybis (β-diketonate), tetrakis (trihydrocarbyl oxide), and tetrakis (trihydrocarbyl oxide) is particularly preferably used.

Examples of the bismuth compound include bismuth carboxylates {particularly hydrocarbyl carboxylates}, and examples of the zirconium compound include zirconium alkoxides and zirconium carboxylates {particularly hydrocarbyl carboxylates}. be able to.
Examples of the aluminum compound include aluminum alkoxides and aluminum carboxylates {particularly hydrocarbyl carboxylates}. Examples of the silicon compounds include silicon alkoxides and silicon carboxylates {particularly hydrocarbyls. Carboxylate}.

  Specific examples of the titanium compound include tetrakis (2-ethyl-1,3-hexanediolato) titanium, tetrakis (2-methyl-1,3-hexanediolato) titanium, tetrakis (2-propyl-1, 3-hexanediolato) titanium, tetrakis (2-butyl-1,3-hexanediolato) titanium, tetrakis (1,3-hexanediolato) titanium, tetrakis (1,3-pentanediolato) titanium, tetrakis ( 2-methyl-1,3-pentanediolato) titanium, tetrakis (2-ethyl-1,3-pentanediolato) titanium, tetrakis (2-propyl-1,3-pentanediolato) titanium, tetrakis (2- Butyl-1,3-pentanediolato) titanium, tetrakis (1,3-heptanediolato) titanium, tetrakis (2-methyl-) , 3-Heptanediolato) titanium, tetrakis (2-ethyl-1,3-heptanediolato) titanium, tetrakis (2-propyl-1,3-heptanediolato) titanium, tetrakis (2-butyl-1,3-heptanediolato) titanium, tetrakis (2-ethylhexoxy) titanium, tetramethoxy titanium, tetraethoxy titanium, tetra-n-propoxy titanium, tetraisopropoxy titanium, tetra-n-butoxy titanium, tetra-n-butoxy titanium oligomer, tetraisobutoxy titanium, tetra-sec -Butoxytitanium, tetra-tert-butoxytitanium, bis (oleate) bis (2-ethylhexanoate) titanium, titanium dipropoxybis (triethanolamate), titanium dibutoxybis (triethanolamate) , Titanium tributoxy systemate, titanium tripropoxy systemate, titanium tripropoxyacetylacetonate, titanium dipropoxybis (acetylacetonate), titanium tripropoxy (ethylacetoacetate), titaniumpropoxyacetylacetonatebis (ethylacetoacetate) , Titanium tributoxyacetylacetonate, titanium dibutoxybis (acetylacetonate), titanium tributoxyethylacetoacetate, titaniumbutoxyacetylacetonatebis (ethylacetoacetate), titanium tetrakis (acetylacetonate), titanium diacetylacetonatebis (Ethyl acetoacetate), bis (2-ethylhexanoate) titanium oxide, bis (laurate) titanium oxide, bis (naphth Tenate) titanium oxide, bis (stearate) titanium oxide, bis (oleate) titanium oxide, bis (linoleate) titanium oxide, tetrakis (2-ethylhexanoate) titanium, tetrakis (laurate) titanium, tetrakis (naphthenate) titanium, Tetrakis (stearate) titanium, Tetrakis (oleate) titanium, Tetrakis (linoleate) titanium, Titanium di-n-butoxide (bis-2,4-pentandionate), Titanium oxide bis (stearate), Titanium oxide bis (tetramethyl) Heptane dionate), titanium oxide bis (pentanedionate), titanium tetra (lactate) and the like. Among these, tetrakis (2-ethyl-1,3-hexanediolato) titanium, tetrakis (2-ethylhexoxy) titanium, and titanium di-n-butoxide (bis-2,4-pentanedionate) are preferable.

As the tin compound, specifically, stannous 2-ethylhexanoate {[CH ₃ (CH ₂ ) ₃ CH (C ₂ H ₅ ) CO ₂ ] ₂ Sn (divalent)}, octanoic acid Stannous, stannous neodecanoate, stannous isooctanoate, stannous isodecanoate, 2,2-dimethyldecanoic acid, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctanoate, dimethyltin dilaurate, etc. It is done.
Examples of bismuth compounds include tris (2-ethylhexanoate) bismuth, tris (laurate) bismuth, tris (naphthenate) bismuth, tris (stearate) bismuth, tris (oleate) bismuth, tris (linoleate) bismuth and the like. Can do.

  Specific examples of the zirconium compound include tetraethoxyzirconium, tetran-propoxyzirconium, tetraisopropoxyzirconium, tetran-butoxyzirconium, tetrasec-butoxyzirconium, tetratert-butoxyzirconium, and tetra (2-ethylhexyl). Zirconium, zirconium tributoxy systemate, zirconium tributoxyacetylacetonate, zirconium dibutoxybis (acetylacetonate), zirconium tributoxyethylacetoacetate, zirconiumbutoxyacetylacetonatebis (ethylacetoacetate), zirconium tetrakis (acetylacetonate) ), Zirconium diacetylacetonate bis (ethyl acetoacetate), bis (2 Ethylhexanoate) zirconium oxide, bis (laurate) zirconium oxide, bis (naphthenate) zirconium oxide, bis (stearate) zirconium oxide, bis (oleate) zirconium oxide, bis (linoleate) zirconium oxide, tetrakis (2-ethylhexa) Noate) zirconium, tetrakis (laurate) zirconium, tetrakis (naphthenate) zirconium, tetrakis (stearate) zirconium, tetrakis (oleate) zirconium, tetrakis (linoleate) zirconium and the like.

  Specific examples of the aluminum compound include triethoxyaluminum, tri-n-propoxyaluminum, tri-i-propoxyaluminum, tri-n-ptoxyaluminum, trisec-butoxyaluminum, tritert-butoxyaluminum, tri (2- Ethylhexyl) aluminum, aluminum dibutoxy systemate, aluminum dibutoxyacetylacetonate, aluminum butoxybis (acetylacetonate), aluminum dibutoxyethylacetoacetate, aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), tris (2-ethylhexanoate) aluminum, tris (laurate) aluminum, tris (naphthenate) aluminum, tris ( Teareto) aluminum, tris (oleate) aluminum, can be mentioned tris (linolate) aluminum and the like.

  Water is preferably used in the form of a solution such as a simple substance or alcohol, or a dispersed micelle in a hydrocarbon solvent, and if necessary, in the reaction system such as adsorbed water on the solid surface or hydrated water of hydrate. Water that is potentially contained in a compound capable of releasing water can also be used effectively. Accordingly, it is also preferable to use a compound that can easily release water, such as a solid having adsorbed water or a hydrate, in combination with the condensation accelerator.

The condensation accelerator and water may be added separately to the reaction system or mixed immediately before use as a mixture, but long-term storage of the mixture is not preferable because it causes decomposition of the metal compound.
In addition, water may be charged into the reaction system as a solution of an organic solvent compatible with water such as alcohol, or water is directly injected and dispersed in the hydrocarbon solution using various chemical engineering techniques. You may let them. Water may be added by steam stripping or the like after completion of the second stage modification reaction.
The amount of the condensation accelerator used is preferably selected so that the molar ratio of the metal of the metal compound and the proton source to the total amount of hydrocarbyloxysilyl bonds present in the system is 0.1 or more.
The number of moles of the condensation accelerator metal and water effective for the reaction is preferably 0.1 or more as a molar ratio to the total amount of hydrocarbyloxysilyl groups present in the reaction system. The upper limit varies depending on the purpose and reaction conditions, but 0.5 to 3 molar equivalents of effective water may be present with respect to the amount of hydrocarbyloxysilyl groups bonded to the polymer active site before the condensation treatment. preferable.

The second-stage modification reaction using the condensation accelerator is preferably performed at a temperature of 20 ° C. or higher, and more preferably in the range of 30 to 120 ° C. The reaction time is 0.5 minutes to 10 hours, preferably 0.5 minutes to 5 hours, more preferably about 0.5 to 120 minutes, and further preferably 3 to 60 minutes.
In addition, the pressure of the reaction system at the time of the second stage modification reaction is usually 0.01 to 20 MPa, preferably 0.05 to 10 MPa.

In the present invention, in this modification reaction, if desired, a known anti-aging agent or a short stop agent for the purpose of terminating the polymerization reaction, and a step after introducing a hydrocarbyloxysilane compound residue into the active site of the polymer. , Can be added. Further, after completion of the modification reaction, a condensation inhibitor such as a higher carboxylic acid ester of a polyhydric alcohol may be added to the reaction system.
After the modification treatment in this way, a conventionally known post-treatment such as desolvation such as steam stripping can be performed to obtain the desired modified polymer.

  The deprotection treatment that removes the protecting group of the protected nitrogen atom after the completion of the first-stage modification reaction or after the completion of the second-stage modification reaction to form a primary amino group is performed by desorption using steam such as steam stripping as described above. In addition to the solvent treatment, the protecting group on the primary amino group can be removed by various methods as necessary at any stage from the completion of the first-stage modification reaction or the stage of the second-stage modification reaction to the solvent removal to the dried polymer. By converting to a free primary amino group by hydrolysis, a protected primary amino group derived from the hydrocarbyloxysilane compound can be deprotected.

The modified conjugated diene polymer according to the present invention is obtained, for example, as follows.
N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane is used as the hydrocarbyloxysilane compound, and among the condensation accelerators, a divalent Sn bis (hydrocarbylcarboxylic acid) salt is used as the metal compound. If the protecting group of the nitrogen atom protected by steam stripping or the like is removed after completion of the step modification reaction, a modified conjugated diene polymer having a primary amino group represented by the following formula (7) is obtained.

Next, a polymerization catalyst system for coordination anion polymerization will be described. As a polymerization catalyst system for coordination anionic polymerization, a catalyst containing a lanthanum series rare earth element compound in an organic solvent is used.
As a catalyst containing a lanthanum series rare earth element compound,
(A) component: a rare earth element-containing compound having an atomic number of 57 to 71 in the periodic table, or a reaction product of these compounds with a Lewis base,
(B) component: The following general formula (8):
AlR ¹⁴ R ¹⁵ R ¹⁶ (8)
(Wherein R ¹⁴ and R ¹⁵ are the same or different and are a hydrocarbyl group having 1 to 10 carbon atoms or a hydrogen atom, and R ¹⁶ is a hydrocarbyl group having 1 to 10 carbon atoms, provided that R ¹⁶ is the above R ¹⁴ or And may be the same as or different from R ¹⁵ ), and component (C): at least one of a complex compound of a Lewis acid, a metal halide and a Lewis base, and an organic compound containing an active halogen It is preferred to polymerize the conjugated diene monomer with a catalyst system comprising:

  In the present invention, in addition to the above components (A) to (C), an organoaluminum oxy compound, so-called aluminoxane is added as a component (D) in addition to the above components (A) to (C). preferable. Here, it is more preferable that the catalyst system is preliminarily prepared in the presence of the component (A), the component (B), the component (C), the component (D) and the conjugated diene monomer.

  In the present invention, the component (A) of the catalyst system containing a lanthanum series rare earth element compound is a compound containing a rare earth element having an atomic number of 57 to 71 in the periodic table, or a reaction product of these compounds with a Lewis base. . Here, among the rare earth elements having atomic numbers 57 to 71, neodymium, praseodymium, cerium, lanthanum, gadolinium, samarium, or a mixture thereof is preferable, and neodymium is particularly preferable.

The rare earth element-containing compound is preferably a salt that is soluble in a hydrocarbon solvent, and specifically includes carboxylates, alkoxides, β-diketone complexes, phosphates, and phosphites of the rare earth elements. Of these, carboxylates and phosphates are preferable, and carboxylates are particularly preferable.
Here, examples of the hydrocarbon solvent include saturated aliphatic hydrocarbons having 4 to 10 carbon atoms such as butane, pentane, hexane and heptane, saturated alicyclic hydrocarbons having 5 to 20 carbon atoms such as cyclopentane and cyclohexane, -Monoolefins such as butene, 2-butene, aromatic hydrocarbons such as benzene, toluene, xylene, methylene chloride, chloroform, trichloroethylene, perchloroethylene, 1,2-dichloroethane, chlorobenzene, bromobenzene, chlorotoluene, etc. A halogenated hydrocarbon is mentioned.

As the rare earth element carboxylate, the following general formula (9):
(R ¹⁷ —CO ₂ ) ₃ M ¹ (9)
(Wherein R ¹⁷ is a hydrocarbyl group having 1 to 20 carbon atoms, and M ¹ is a rare earth element having atomic numbers 57 to 71 in the periodic table). Here, R ¹⁷ may be saturated or unsaturated, is preferably an alkyl group or an alkenyl group, and may be linear, branched or cyclic. The carboxyl group is bonded to a primary, secondary or tertiary carbon atom. Specific examples of the carboxylate include octanoic acid, 2-ethylhexanoic acid, oleic acid, neodecanoic acid, stearic acid, benzoic acid, naphthenic acid, versatic acid [trade names of Shell Chemical Co., Ltd. , A carboxylic acid in which a carboxyl group is bonded to a tertiary carbon atom] and the like. Among these, salts of 2-ethylhexanoic acid, neodecanoic acid, naphthenic acid, and versatic acid are preferable.

As the alkoxide of the rare earth element, the following general formula (10):
(R ¹⁸ O) ₃ M ² (10)
(Wherein, R ¹⁸ is a hydrocarbyl group having 1 to 20 carbon atoms, and M ² is a rare earth element having an atomic number of 57 to 71 in the periodic table). Examples of the alkoxy group represented by R ¹⁸ O include 2-ethyl-hexyloxy group, oleyloxy group, stearyloxy group, phenoxy group, and benzyloxy group. Among these, 2-ethyl-hexyloxy group and benzyloxy group are preferable.

  Examples of the rare earth element β-diketone complex include the rare earth element acetylacetone complex, benzoylacetone complex, propionitrileacetone complex, valerylacetone complex, and ethylacetylacetone complex. Among these, an acetylacetone complex and an ethylacetylacetone complex are preferable.

  Examples of the rare earth element phosphate and phosphite include the rare earth element, bis (2-ethylhexyl) phosphate, bis (1-methylheptyl phosphate), bis (p-nonylphenyl) phosphate, phosphorus Acid bis (polyethylene glycol-p-nonylphenyl), phosphoric acid (1-methylheptyl) (2-ethylhexyl), phosphoric acid (2-ethylhexyl) (p-nonylphenyl), 2-ethylhexylphosphonic acid mono-2-ethylhexyl 2-ethylhexylphosphonic acid mono-p-nonylphenyl, bis (2-ethylhexyl) phosphinic acid, bis (1-methylheptyl) phosphinic acid, bis (p-nonylphenyl) phosphinic acid, (1-methylheptyl) (2 -Ethylhexyl) phosphinic acid, (2-ethylhexyl) (p-nonylphenyl) phosphine Among these, the rare earth elements, bis (2-ethylhexyl) phosphate, bis (1-methylheptyl) phosphate, mono-2-ethylhexyl 2-ethylhexylphosphonate, bis A salt with (2-ethylhexyl) phosphinic acid is preferred.

  Among the rare earth element-containing compounds, neodymium phosphate and neodymium carboxylate are more preferable, and in particular, neodymium branch such as neodymium 2-ethylhexanoate, neodymium neodecanoate, neodymium versatate, etc. Carboxylate is most preferred.

  The component (A) may be a reaction product of the rare earth element-containing compound and a Lewis base. The reaction product has improved solubility of the rare earth element-containing compound in the solvent due to the Lewis base, and can be stably stored for a long period of time. In order to easily solubilize the rare earth element-containing compound in a solvent and to store stably for a long period of time, the Lewis base is used in a proportion of 0 to 30 mol, preferably 1 to 10 mol, per mol of rare earth element. Or as a mixture of the two or as a product obtained by reacting both in advance. Here, examples of the Lewis base include acetylacetone, tetrahydrofuran, pyridine, N, N-dimethylformamide, thiophene, diphenyl ether, triethylamine, an organic phosphorus compound, and a monovalent or divalent alcohol.

  The rare earth element-containing compound as the component (A) described above or a reaction product of these compounds and a Lewis base can be used alone or in combination of two or more.

  In the present invention, the organoaluminum compound represented by the general formula (7), which is the component (B) of the catalyst system used for the polymerization of the terminal active polymer, includes trimethylaluminum, triethylaluminum, tri-n-propylaluminum, Triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum; diethylaluminum hydride, di-n-propyl hydride Aluminum, di-n-butylaluminum hydride, diisobutylaluminum hydride, dihexylaluminum hydride, diisohexylaluminum hydride, dioctylaluminum hydride, dihydride Seo octyl aluminum, ethyl aluminum dihydride, n- propyl aluminum dihydride, include isobutyl aluminum dihydride and the like, among these, triethylaluminum, triisobutylaluminum, hydrogenated diethylaluminum, hydrogenated diisobutylaluminum are preferred. The organoaluminum compound as the component (B) described above can be used alone or in combination of two or more.

  In the present invention, the component (C) of the catalyst system used for the polymerization of the terminal active polymer is at least selected from the group consisting of a Lewis acid, a complex compound of a metal halide and a Lewis base, and an organic compound containing an active halogen. It is a kind of halogen compound.

The Lewis acid has Lewis acidity and is soluble in hydrocarbons. Specifically, methyl aluminum dibromide, methyl aluminum dichloride, ethyl aluminum dibromide, ethyl aluminum dichloride, butyl aluminum dibromide, butyl aluminum dichloride, dimethyl aluminum bromide, dimethyl aluminum chloride, diethyl bromide Aluminum, diethylaluminum chloride, dibutylaluminum bromide, dibutylaluminum chloride, methylaluminum sesquibromide, methylaluminum sesquichloride, ethylaluminum sesquibromide, ethylaluminum sesquichloride, dibutyltin dichloride, aluminum tribromide, antimony trichloride, Examples include antimony pentachloride, phosphorus trichloride, phosphorus pentachloride, tin tetrachloride, and silicon tetrachloride. Among these, diethylaluminum chloride, sesquiethylaluminum chloride, ethylaluminum dichloride, diethylaluminum bromide, ethylaluminum sesquibromide, and ethylaluminum dibromide are preferable.
Alternatively, a reaction product of an alkylaluminum and a halogen such as a reaction product of triethylaluminum and bromine can be used.

  The metal halide constituting the complex compound of the above metal halide and Lewis base includes beryllium chloride, beryllium bromide, beryllium iodide, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, iodine. Calcium chloride, barium chloride, barium bromide, barium iodide, zinc chloride, zinc bromide, zinc iodide, cadmium chloride, cadmium bromide, cadmium iodide, mercury chloride, mercury bromide, mercury iodide, manganese chloride, Manganese bromide, manganese iodide, rhenium chloride, rhenium bromide, rhenium iodide, copper chloride, copper iodide, silver chloride, silver bromide, silver iodide, gold chloride, gold iodide, gold bromide, etc. Of these, magnesium chloride, calcium chloride, barium chloride, manganese chloride, zinc chloride, and copper chloride are preferred. , Magnesium chloride, manganese chloride, zinc chlorides, copper chloride being particularly preferred.

  Moreover, as a Lewis base which comprises the complex compound of the said metal halide and a Lewis base, a phosphorus compound, a carbonyl compound, a nitrogen compound, an ether compound, alcohol, etc. are preferable. Specifically, tributyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, triethylphosphine, tributylphosphine, triphenylphosphine, diethylphosphinoethane, diphenylphosphinoethane, acetylacetone, benzoylacetone , Propionitrile acetone, valeryl acetone, ethyl acetylacetone, methyl acetoacetate, ethyl acetoacetate, phenyl acetoacetate, dimethyl malonate, diethyl malonate, diphenyl malonate, acetic acid, octanoic acid, 2-ethyl-hexanoic acid, olein Acid, stearic acid, benzoic acid, naphthenic acid, versatic acid, triethylamine, N, N-dimethylacetamide, tetrahydrofuran, diphenyl ether, 2-ethyl-hexyl alcohol Examples include oleyl alcohol, stearyl alcohol, phenol, benzyl alcohol, 1-decanol, and lauryl alcohol. Among these, tri-2-ethylhexyl phosphate, tricresyl phosphate, acetylacetone, 2-ethylhexanoic acid, versatic acid, 2 -Ethylhexyl alcohol, 1-decanol and lauryl alcohol are preferred.

The Lewis base is usually reacted at a ratio of 0.01 to 30 mol, preferably 0.5 to 10 mol, per 1 mol of the metal halide. When the reaction product with the Lewis base is used, the metal remaining in the polymer can be reduced.
Examples of the organic compound containing the active halogen include benzyl chloride.

  Examples of the aluminoxane as component (D) include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, chloroaluminoxane, and the like. By adding aluminoxane as the component (D), the molecular weight distribution becomes sharp and the activity as a catalyst is improved.

The amount or composition ratio of each component of the catalyst system used in the present invention is appropriately selected according to its purpose or necessity. Of these, the component (A) is preferably used in an amount of 0.00001 to 1.0 mmol, and more preferably 0.0001 to 0.5 mmol, relative to 100 g of 1,3-butadiene. When the amount of component (A) used is within the above range, excellent polymerization activity can be obtained, and the need for a deashing step is eliminated.
Moreover, the ratio of (A) component and (B) component is molar ratio, and (A) component: (B) component is usually 1: 1-1: 700, Preferably it is 1: 3-1: 500.
Furthermore, the ratio of the halogen in the component (A) and the component (C) is a molar ratio, usually 1: 0.1 to 1:30, preferably 1: 0.2 to 1:15, more preferably 1: 2.0 to 1: 5.0.
Moreover, the ratio of the aluminum and (A) component in (D) component is molar ratio, and is 1: 1-700: 1 normally, Preferably it is 3: 1-500: 1. By making the amount of these catalysts within the range of the component ratio, it is preferable because it acts as a highly active catalyst and there is no need for a step of removing the catalyst residue.
In addition to the above components (A) to (C), the polymerization reaction may be carried out in the presence of hydrogen gas for the purpose of adjusting the molecular weight of the polymer.

  As a catalyst component, in addition to the component (A), the component (B), the component (C), and the component (D) used as necessary, a conjugated diene monomer such as 1,3-butadiene may be used as necessary. A small amount, specifically, a ratio of 0 to 1000 mol per 1 mol of the compound of component (A) may be used. A conjugated diene monomer such as 1,3-butadiene as a catalyst component is not essential, but when used in combination, there is an advantage that the catalytic activity is further improved.

In the production of the catalyst, for example, the components (A) to (C) are dissolved in a solvent, and a conjugated diene monomer such as 1,3-butadiene is reacted as necessary.
In that case, the addition order of each component is not specifically limited, Furthermore, you may add an aluminoxane as (D) component. From the viewpoint of improving the polymerization activity and shortening the polymerization initiation induction period, it is preferable that these components are mixed in advance, reacted, and aged.

Here, the aging temperature is about 0 to 100 ° C, and preferably 20 to 80 ° C. When the temperature is less than 0 ° C, aging is not sufficiently performed, and when the temperature exceeds 100 ° C, the catalytic activity may be reduced or the molecular weight distribution may be broadened.
The aging time is not particularly limited, and can be aged by bringing it into contact with the line before adding to the polymerization reaction tank. Usually, 0.5 minutes or more is sufficient, and stable for several days.

In the production of the conjugated diene (co) polymer having terminal activity, a conjugated diene monomer alone or a conjugated diene monomer is used in an organic solvent using a catalyst system containing the lanthanum series rare earth element-containing compound. It can be obtained by solution polymerization of other conjugated diene monomers. Here, an inert organic solvent is used as the polymerization solvent. Examples of the inert organic solvent include saturated aliphatic hydrocarbons having 4 to 10 carbon atoms such as butane, pentane, hexane and heptane, saturated alicyclic hydrocarbons having 5 to 20 carbon atoms such as cyclopentane and cyclohexane, 1- Monoolefins such as butene and 2-butene, aromatic hydrocarbons such as benzene, toluene and xylene, methylene chloride, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, 1,2-dichloroethane, chlorobenzene, bromobenzene, chloro And halogenated hydrocarbons such as toluene.
Among these, C5-C6 aliphatic hydrocarbon and alicyclic hydrocarbon are particularly preferable. These solvents may be used alone or in a combination of two or more.
The monomer concentration in the solvent used for this coordinated anionic polymerization is preferably 5 to 50% by mass, more preferably 10 to 30% by mass.

  In the present invention, the temperature in the coordination anionic polymerization reaction is preferably selected in the range of -80 to 150 ° C, more preferably -20 to 120 ° C. The polymerization reaction can be carried out under generated pressure, but it is usually desirable to operate at a pressure sufficient to keep the monomer in a substantially liquid phase. That is, the pressure depends on the particular material being polymerized, the polymerization medium used and the polymerization temperature, but higher pressures can be used if desired, such pressure being a gas that is inert with respect to the polymerization reaction. Can be obtained by an appropriate method such as pressurizing.

  In the case of modifying the active end of the conjugated diene (co) polymer having an active end obtained by the coordinated anionic polymerization reaction, the hydrocarbyloxysilane compound is reacted in advance in the above-described pre-modification reaction step, followed by hydrolysis. And (i) an organic silane compound and the conjugated diene (co) polymer are bonded to each other by performing an addition or substitution reaction on the active site in the vicinity of the characteristic group. A modification reaction may be caused by reacting an organosilane compound having a functional group that promotes the reaction between the silanol group and the reinforcing filler or (ii) a functional group that promotes the reaction between the silanol group and the reinforcing filler. From the viewpoint of smoothly proceeding.

In the above-mentioned anionic polymerization and coordination anionic polymerization, all the raw materials involved in the polymerization such as polymerization initiator, solvent, monomer and the like have removed reaction inhibitors such as water, oxygen, carbon dioxide, and protic compounds. It is desirable to use one.
The polymerization reaction may be carried out either batchwise or continuously.
Thus, a conjugated diene (co) polymer having an active end is obtained.

In the modified conjugated diene polymer according to the present invention, the cis-1,4 bond content of the conjugated diene moiety is preferably 30% or more. This is because if it is less than 30%, the low temperature characteristics of the rubber composition deteriorate, and the performance on ice of the tire deteriorates.
The cis-1,4 bond content and the vinyl bond content are measured by the infrared method (Morello method).

The modified conjugated diene polymer according to the present invention preferably has a number average molecular weight (Mn) of 100,000 to 500,000, and more preferably 150,000 to 300,000. Moreover, it is preferable that molecular weight distribution (Mw / Mn) is 1-3, and it is more preferable that it is 1.1-2.7. By setting the number average molecular weight of the modified conjugated diene polymer within the above range, the elastic modulus of the vulcanizate is decreased and the increase in hysteresis loss is suppressed, and the excellent low rolling resistance of the tire of the present invention is obtained. Excellent kneading workability of the rubber composition containing the diene polymer can be obtained. In addition, by making the molecular weight distribution of the modified conjugated diene polymer within the above range, even if the modified conjugated diene polymer is blended with the rubber composition, the workability of the rubber composition is not lowered and kneading is easy. Thus, the physical properties of the rubber composition can be sufficiently improved.
Here, the number average molecular weight (Mn) and the molecular weight distribution were measured by GPC [manufactured by Tosoh Corporation, HLC-8020] using a refractometer as a detector, and were shown in terms of polystyrene using monodisperse polystyrene as a standard. The column is GMHXL [manufactured by Tosoh] and the eluent is tetrahydrofuran.

  The rubber composition according to the tire of the present invention preferably contains 5 to 200 parts by mass of filler, more preferably 20 to 120 parts by mass, and still more preferably 30 to 100 parts by mass with respect to 100 parts by mass of the rubber matrix. . When the filler is less than 5 parts by mass, the interaction described later between the modified conjugated diene polymer represented by the general formula (2) or the general formula (3) and the filler cannot be enjoyed, and the filler This is because if the material exceeds 200 parts by mass, the rolling resistance of the tire is remarkably increased.

In the present invention, the filler is preferably carbon black and / or an inorganic filler, and the inorganic filler is preferably silica.
Further, since the modified conjugated diene polymer reacts favorably with both carbon black and silica, the dispersibility of both carbon black and silica is improved, and the dynamic loss tangent tan δ at 60 ° C. of the tread rubber composition is improved. Since it becomes remarkably small, the rolling resistance of the tire of the present invention is further reduced.

The carbon black used as the reinforcing filler preferably has a nitrogen adsorption specific surface area (measured according to N ₂ SA, JIS K 6217-2: 2001) of 70 to 200 m ² / g. Examples of the carbon black in this range include SAF-HS, SAF, ISAF-HS, ISAF, ISAF-LS, N285, N339, HAF-HS, HAF, and HAF-LS. The carbon black nitrogen adsorption specific surface area is particularly preferably from 85 to 180 m ² / g.

Any commercially available silica can be used as the reinforcing filler, and wet silica, dry silica, and colloidal silica are particularly preferable, and wet silica is particularly preferable. Silica has a BET specific surface area (measured in accordance with ISO 5794/1) of preferably 100 m ² / g or more, more preferably 150 m ² / g or more, and particularly preferably 170 m ² / g or more. Examples of such silica include Tosoh Silica Co., Ltd., trade name “Nipsil AQ” (BET specific surface area = 190 m ² / g), “Nipsil KQ”, Degussa Co., Ltd., trade name “Ultra Gil VN3” (BET specific surface area = 175 m). ² / g) can be used.

In addition to the reinforcing filler, the following inorganic filler may be blended if desired. For example, alumina (Al ₂ O ₃ ), alumina hydrate (Al ₂ O ₃ .H ₂ O), aluminum hydroxide [Al (OH) ₃ ], aluminum carbonate [Al ₂ (CO ₃ ) ₂ ], water magnesium oxide [Mg _(OH) 2], magnesium oxide (MgO), magnesium carbonate (MgCO _3), talc _{(3MgO · 4SiO 2 · H 2} O), attapulgite _{(5MgO · 8SiO 2 · 9H 2} O), titanium white ( TiO ₂ ), titanium black (TiO _2n-1 ), calcium oxide (CaO), calcium hydroxide [Ca (OH) ₂ ], aluminum magnesium oxide (MgO · Al ₂ O ₃ ), clay (Al ₂ O ₃ · 2SiO) _2), kaolin _{(Al 2 O 3 · 2SiO 2} · 2H 2 O), pyrophyllite _{(Al 2 O 3 · 4SiO 2} · H 2 ), Bentonite _{(Al 2 O 3 · 4SiO 2} · 2H 2 O), aluminum silicate _{(Al 2 SiO 5, Al 4} · 3SiO 4 · 5H 2 O etc.), magnesium silicate _{(Mg 2} SiO 4, MgSiO ₃ etc. ), Calcium silicate (Ca ₂ · SiO ₄ etc.), aluminum calcium silicate (Al ₂ O ₃ · CaO · 2SiO ₂ etc.), magnesium calcium silicate (CaMgSiO ₄ ), calcium carbonate (CaCO ₃ ), zirconium oxide ( ZrO ₂ ), zirconium hydroxide [ZrO (OH) ₂ .nH ₂ O], zirconium carbonate [Zr (CO ₃ ) ₂ ], crystalline aluminosilicate, and the like.

  When silica is blended in the rubber composition used in the tire of the present invention, it is preferable that 1 to 20% by mass of a silane coupling agent is blended with respect to silica. Examples of the silane coupling agent include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (3-methyldimethoxysilylpropyl) tetrasulfide, and bis (3-triethoxy Silylethyl) tetrasulfide, bis (3-triethoxysilylpropyl) disulfide, bis (3-trimethoxysilylpropyl) disulfide, bis (3-methyldimethoxysilylpropyl) disulfide, bis (3-triethoxysilylethyl) disulfide, Bis (3-triethoxysilylpropyl) trisulfide, bis (3-trimethoxysilylpropyl) trisulfide, bis (3-methyldimethoxysilylpropyl) trisulfide, bis (3-triethoxysilylene) Le) sulfur-containing alkoxysilane compounds such trisulfide and the like.

  The rubber matrix of the rubber composition used in the tire of the present invention preferably comprises 10 to 95% by mass of a high molecular weight modified conjugated diene polymer and 90 to 5% by mass of a diene rubber, and the high molecular weight modified conjugated diene type. More preferably, the polymer consists of 10 to 90% by mass and diene rubber 90 to 10% by mass. The reason why the modified conjugated diene polymer is 10% by mass or more in the rubber matrix is to achieve the effects of on-ice performance and low rolling resistance.

The high molecular weight modified conjugated diene polymer represented by the general formula (2) or the general formula (3) preferably reacts with both carbon black and silica. When combined with natural rubber, silica is more likely to be present in the natural rubber, and the high molecular weight modified conjugated diene polymer causes more silica in the high molecular weight modified conjugated diene polymer. Since the dynamic storage elastic modulus E ′ at −20 ° C. of the tread rubber composition is remarkably reduced, the flexibility of the tread at −20 ° C. is increased and the performance on ice is further improved.
Moreover, since the high molecular weight modified conjugated diene polymer having the functional group represented by the general formula (2) or the general formula (3) at the molecular chain end reacts suitably with both carbon black and silica, Since the dispersibility of both black and silica is improved and the dynamic storage elastic modulus E ′ of the tread rubber composition at 30 ° C. is increased, the dry steering stability performance of the tire of the present invention is improved.
In view of the above, the rubber matrix is more preferably a combination of the modified conjugated diene polymer and natural rubber (modified conjugated diene polymer 10 to 95% by mass and natural rubber 90 to 5% by mass). A combination of carbon black and silica (10 to 90% by mass of carbon black and 90 to 10% by mass of silica, more preferably 20 to 80% by mass of carbon black and 80 to 20% by mass of silica) is further preferable as a filler.

The rubber composition used in the tire of the present invention is a short fiber made of a thermoplastic resin, and the rubber composition is heated until the temperature of the rubber composition reaches the maximum vulcanization temperature when vulcanized. Short fibers characterized by melting or softening in the matrix may be contained. Here, the compounding quantity of this short fiber is 0.2-10 mass parts with respect to 100 mass parts of said rubber matrices, Preferably it is 0.5-5 mass parts. The maximum vulcanization temperature means the maximum temperature reached by the rubber composition during vulcanization. For example, in the case of mold vulcanization, it means the maximum temperature that the rubber composition reaches from the time when the rubber composition enters the mold until the rubber composition exits the mold and cools. The maximum vulcanization temperature can be measured, for example, by embedding a thermocouple in the rubber composition.
When the rubber composition according to the tire of the present invention contains the short fiber, after vulcanization, there are long bubbles in the tread, the long bubbles are exposed on the surface due to wear of the tread, and the hole portion is formed. It is formed and functions as a drainage channel for efficient drainage. Here, the hole portion may be any one of a hole shape, a hollow shape, and a groove shape. Moreover, since the surface of the hole part of the tread is covered with a solidified protective layer of melted or softened short fibers, it is excellent in water channel shape retention, water channel edge wear, water channel retention during load input, and the like. As thickness of a protective layer, 0.5-50 micrometers is preferable.

  The material of the short fiber is not particularly limited as long as it is a thermoplastic resin having the thermal characteristics, and can be appropriately selected according to the purpose. Preferred examples of the short fibers having the thermal characteristics include short fibers made of a crystalline polymer having a melting point lower than the maximum vulcanization temperature. The short fiber made of the crystalline polymer will be described as an example. The larger the difference between the melting point of the short fiber and the maximum vulcanization temperature of the rubber composition, the faster the vulcanization of the rubber composition. The short fibers melt. On the other hand, when the melting point of the short fiber is too close to the maximum vulcanization temperature of the rubber composition, the short fiber does not melt quickly at the initial stage of vulcanization, and the short fiber melts at the end of vulcanization. At the end of vulcanization, the air present in the short fibers diffuses and is dispersed or taken into the vulcanized rubber composition, and a sufficient amount of air is retained in the melted short fibers. Not. On the other hand, if the melting point of the short fiber is too low, the short fiber is melted by heat at the time of kneading the rubber composition, poor dispersion due to fusion of the short fibers at the kneading stage, and short fiber at the kneading stage. Is disadvantageous in that it is divided into a plurality of lengths, and short fibers are dissolved in the rubber composition and dispersed microscopically.

  The upper limit of the melting point (or softening point) of the short fiber is not particularly limited, but is preferably selected in consideration of the above points. Generally, it is higher than the maximum vulcanization temperature of the rubber composition. It is preferably lower by 10 ° C. or higher, and more preferably lower by 20 ° C. or higher. The industrial vulcanization temperature of the rubber composition is generally about 190 ° C. at the maximum. For example, when the maximum vulcanization temperature is set to 190 ° C., the melting point of the short fiber is Is usually selected within a range of 190 ° C. or lower, preferably 180 ° C. or lower, and more preferably 170 ° C. or lower. On the other hand, considering the kneading of the rubber composition, the melting point (or softening point) of the short fibers is preferably 5 ° C. or more, more preferably 10 ° C. or more, and more preferably 20 ° C. with respect to the maximum temperature during kneading. The above is particularly preferable. Assuming that the maximum temperature in kneading the rubber composition is, for example, 95 ° C., the melting point of the short fibers is preferably 100 ° C. or higher, more preferably 105 ° C. or higher, and particularly preferably 115 ° C. or higher. The melting point of the short fibers can be measured using a known melting point measuring device or the like. For example, the melting peak temperature measured using a DSC measuring device can be used as the melting point.

  The short fiber may be formed from the above-described crystalline polymer, may be formed from an amorphous polymer, or may be formed from a crystalline polymer and an amorphous polymer. However, in the present invention, it is preferably formed from an organic material containing a crystalline polymer from the viewpoint that the viscosity change occurs suddenly at a certain temperature due to the phase transition and viscosity control is easy. More preferably, it is formed only from a functional polymer.

  Examples of the crystalline polymer include polyethylene (PE), polypropylene (PP), polybutylene, polybutylene succinate, polyethylene succinate, syndiotactic-1,2-polybutadiene (SPB), polyvinyl alcohol (PVA), Single-composition polymers such as polyvinyl chloride (PVC), those having a melting point controlled to an appropriate range by copolymerization, blending, or the like can be used, and those having additives added thereto can also be used. These may be used individually by 1 type and may use 2 or more types together. Among these crystalline polymers, polyolefins and polyolefin copolymers are preferable, polyethylene (PE) and polypropylene (PP) are more preferable in terms of general availability and availability, polyethylene (PE) in terms of low melting point and easy handling. Is particularly preferred.

  Examples of the non-crystalline polymer include polymethyl methacrylate (PMMA), acrylonitrile / butadiene / styrene copolymer (ABS), polystyrene (PS), polyacrylonitrile, copolymers thereof, and blends thereof. Etc. These may be used individually by 1 type and may use 2 or more types together. The crystalline polymer and the amorphous polymer may be used in combination.

  There is no restriction | limiting in particular as the fineness of the said short fiber, Although it can select suitably according to the objective, 1-1100 dTex is preferable and 2-900 dTex is more preferable from a viewpoint of improving the said performance on ice and snow. The average diameter (D) of the short fibers is not particularly limited and may be appropriately selected depending on the intended purpose. In the vulcanized rubber obtained by vulcanizing a rubber composition containing the short fibers In addition, in order to efficiently form a long bubble that can function as a micro drainage groove to be described later, 0.03 to 0.3 mm is preferable, and 0.06 to 0.25 mm is more preferable. If the average diameter (D) is less than 0.03 mm, it is difficult to form a long cylindrical foaming groove, and it is not preferable in that many yarn breaks occur during the production of the short fibers, and 0.3 mm is preferable. When it exceeds, the average diameter (diameter) of the said short fiber will become large, and the number of cylindrical foaming grooves will decrease in the same compounding quantity, and there exists a tendency for drainage efficiency to worsen.

The rubber composition used in the tire of the present invention is preferably 3 to 30 parts by mass, more preferably 3 to 30 parts by mass of fine particles having an average major axis of 5 to 1000 μm, preferably 5 to 500 μm, based on 100 parts by mass of the rubber matrix. -15 mass parts may be included.
This fine particle (1) scratches the road surface on ice on the tread surface, and (2) the fine particle is detached from the tread, and a hole is formed in the surface layer part of the tread (tread surface and its vicinity). It forms and drains the melted water from the ice on the ice. The average major axis of the fine particles refers to the average maximum diameter.
Here, the average major axis of the fine particles is preferably 5 μm or more because the performance on ice is further improved due to the scratch effect, and the average major axis of the fine particles is preferably 1000 μm or less because of wear resistance. This is because the fracture resistance is further improved.
Further, it is preferable to contain 3 parts by mass or more of fine particles because the performance on ice is further improved, and it is preferable to contain 15 parts by mass or less of fine particles to improve wear resistance and fracture resistance. Because.
The average major axis is obtained by randomly selecting 100 fine particles with an electron microscope, measuring each major axis, and averaging the 100 major axes measured.

  Further, the fine particles preferably have an aspect ratio of 1.1 or more, and preferably have corners. More preferably, the aspect ratio is 1.2 or more, and further preferably 1.3 or more. Here, the presence of a corner means that the entire surface is not a spherical surface or a smooth curved surface. Fine particles having corners can be used from the beginning for the fine particles of the present invention, but even if the fine particles are spherical, they can be used with the corners existing on the surface of the fine particles, and more Corners can be present.

  The fine particles blended in the rubber composition used in the tire of the present invention are not limited to those described above, and may be any fine particles that are present after vulcanization without being softened by vulcanization of the tire. As the fine particles, fine particles having a Mohs hardness of 2 or more are preferable. For example, gypsum fine particles, calcite fine particles, fluorite fine particles, feldspar fine particles, quartz fine particles, olivine fine particles, iron fine particles, eggshell powder, zirconium oxide fine particles, calcium carbonate Plant fine particles, silica fine particles, wollastonite fine particles, alkali feldspar fine particles, natural silicon oxide fine particles, inorganic fine particles such as porous natural glass (for example, Mohs hardness 5) fine particles, walnut shells and other seed shells and fruit nuclei Fine particles, organic cured fine particles such as (meth) acrylic cured resin fine particles, epoxy cured resin fine particles, zinc oxide whiskers (for example, Panatetra (tetrapot-shaped zinc oxide) manufactured by Matsushita Amtech Co., Ltd.), stars from Okinawa Prefecture Sand, glass fiber, aluminum whisker, polyester fiber, nylon fiber, polyvinyl Examples thereof include short fibers that do not soften or melt at the vulcanization temperature of tires such as Lumar fibers and aromatic polyamide fibers, expanded graphite, thermally expanded microcapsules, and shirasu balloons. More preferably, silica glass having a Mohs hardness of 5 or more ( Examples include Mohs hardness 6.5), quartz (Mohs hardness 7.0), and fused alumina (Mohs hardness 9.0). Among these, alumina (aluminum oxide) such as single crystal alumina and polycrystalline alumina, silica glass, and the like are particularly preferable because they are inexpensive and can be used easily.

The above expanded graphite is a powder substance having an average major axis of 30 to 600 μm, preferably 100 to 350 μm as a particle size including a substance that is vaporized by heat between layers of graphite particles, and expands by heat during vulcanization. It is preferable that it becomes a graphite expanded body (Expanded Graphite).
Expanded graphite has a structure in which sheets formed of carbon atoms overlap each other and contain a vaporizable interlayer material between the layers. For example, the interlayer material is vaporized and expanded by heating to form a graphite expanded body. Since the material is hard before the expansion treatment, quality deterioration due to mixing hardly occurs, and since it expands irreversibly at a constant temperature, it is possible to easily form a foreign substance with a space inside the rubber matrix by vulcanizing the tire. . The tread part of a tire using such rubber has moderate surface irregularities when worn like other fine particles, and improves the frictional force on ice by efficiently removing the water film on the contact surface between ice and the tire. Move to.

  As the expanded graphite having an expansion start temperature of 190 ° C. or lower, for example, “Graph Guard 160-50” or “Graph Guard 160-80” manufactured by UCAR Graphtech of the United States is commercially available from Sakai Industries. . Expanded graphite refers to an unexpanded product immediately after acid treatment in terms of term, but may also refer to an already expanded product after heat treatment. The expanded graphite blended as a rubber composition in the present invention is an unexpanded product before heat treatment.

  The thermal expansion microcapsules described above are powder particles in which a liquid or solid that is vaporized, decomposed, or chemically reacted by heat to generate a gas is encapsulated in a thermoplastic resin, and have a temperature equal to or higher than the expansion start temperature, usually 140. It expands when heated at a temperature of ˜190 ° C., and a gas is contained in the outer shell made of the thermoplastic resin, and the average major axis of the thermoplastic resin particles is preferably 5 to 300 μm before expansion, More preferably, the average major axis is 10 to 200 μm.

  As such heat-expandable thermoplastic resin particles, for example, the product name “Expancel 091DU-80” or “Expancel 092DU-120” is currently available from EXPANCEL, Sweden, or from Matsumoto Yushi. The name “Matsumoto Microsphere F-85” or “Matsumoto Microsphere F-100” is available.

  As described above, it is preferable that the fine particles are detached from the tread to form a hole in the tread surface layer portion (tread surface and its vicinity). For this purpose, the fine particles are bonded to the tread rubber composition by vulcanization. It is desirable that the vulcanized adhesive strength is low.

  When the fine particles are blended with the rubber composition according to the present invention or when the fine particles are not blended, the fine particle-containing organic fibers may be blended. Here, the fine particle-containing organic fiber is preferably blended in an amount of 0.1 to 30 parts by weight, more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the rubber matrix, and 0.3 to 15 parts by weight. More preferably, it is partially blended. Moreover, it is preferable that the average fiber diameter of fine particle containing organic fiber is 10-1000 micrometers. This fine particle-containing organic fiber melts or softens in the matrix of the rubber composition until the temperature of the rubber composition reaches the maximum vulcanization temperature when the tire is vulcanized. It consists of the same material as the short fibers that sometimes melt or soften. The method for measuring the average fiber diameter of the fine particle-containing organic fibers is the same as the method for measuring the average long diameter of the fine particles.

  Further, fine particles are contained in the above-mentioned short fibers that melt or soften in the matrix of the rubber composition until the temperature of the rubber composition reaches the maximum vulcanization temperature at the time of vulcanization of the tire. You may mix | blend as a fiber. The structure and material of the short fiber that melts or softens when the tire is vulcanized are as described above. The blending amount of the fine particle-containing short fibers is preferably 3 to 20 parts by mass, and more preferably 3 to 15 parts by mass with respect to 100 parts by mass of the rubber matrix of the rubber composition used in the tire of the present invention.

  Further, the rubber composition used in the tire of the present invention includes, in addition to the rubber matrix, hydrogenated resin, and reinforcing filler, compounding agents commonly used in the rubber industry, such as softeners and anti-aging agents. , Coupling agents, vulcanization accelerators, vulcanization accelerators, vulcanizing agents, process oils, anti-aging agents, anti-scorching agents, zinc white, stearic acid, thermosetting resins, thermoplastic resins, etc. It can select suitably in the range which does not injure the objective of invention, and can mix | blend within the range of a normal compounding quantity. As these compounding agents, commercially available products can be suitably used. The rubber composition used in the tire of the present invention is obtained by blending a rubber matrix with a hydrogenated resin and various compounding agents appropriately selected as necessary, kneading, heating, extruding, and the like. Can be manufactured.

The rubber composition used in the tire of the present invention may further contain 1 to 50 parts by mass of a softening agent with respect to 100 parts by mass of the rubber matrix as desired. It is because processability is improved by blending the softener.
In addition, when blending both the low molecular weight modified conjugated diene polymer and the softener, the total blended amount of the low molecular weight modified conjugated diene polymer and the softener is 100 parts by weight of the rubber matrix. It is preferable that it is 6-60 mass parts. This is because workability is improved when the amount is 6 parts by mass or more, and wear resistance and fracture resistance are improved when the amount is 60 parts by mass or less. From these viewpoints, the total amount of the low molecular weight modified conjugated diene polymer and the softening agent is preferably 6 to 55 parts by mass, and more preferably 6 to 50 parts by mass.

  In the rubber composition used in the tire of the present invention, as a softener that is optionally blended, the pour point is low (for example, about pour point −10 to −60 ° C., preferably pour point −20 to −60 ° C., More preferably, the pour point is −30 to −60 ° C.) Process oil such as naphthenic process oil and paraffinic process oil, or dibutyl phthalate, di- (2-ethylhexyl) phthalate, butyl benzyl phthalate, di-n- Examples thereof include plasticizers such as octyl phthalate.

  The rubber composition used in the tire of the present invention is preferably sulfur crosslinkable, and sulfur is suitably used as a vulcanizing agent. The amount used is preferably 0.1 to 10 parts by mass of sulfur (total amount of sulfur and sulfur donors) with respect to 100 parts by mass of the rubber matrix. This is because within this range, the necessary elastic modulus and strength of the vulcanized rubber composition can be ensured and fuel efficiency can be obtained. In this respect, it is more preferable to blend 0.5 to 7 parts by mass of the sulfur content.

  The vulcanization accelerator that can be used in the present invention is not particularly limited, and examples thereof include M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), and CZ (N-cyclohexyl-2-benzothiazyl). Sulfenamide) and other guanidine vulcanization accelerators such as DPG (diphenylguanidine) can be used, and the amount used is 0.1-5. 0 mass part is preferable, More preferably, it is 0.2-3.0 mass part.

  Further, examples of the anti-aging agent that can be used in the rubber composition used in the tire of the present invention include 3C (N-isopropyl-N′-phenyl-p-phenylenediamine, 6C [N- (1,3-dimethylbutyl)]. -N'-phenyl-p-phenylenediamine], AW (6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline), high-temperature condensate of diphenylamine and acetone, and the like. The amount is preferably 0.1 to 6.0 parts by mass, more preferably 0.3 to 5.0 parts by mass, with respect to 100 parts by mass of the rubber matrix.

  Examples of the plasticizer that can be used in the rubber composition according to the tire of the present invention include phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, di- (2-ethylhexyl) phthalate, and di-n-octyl phthalate. Etc. are used. The amount of use is preferably 0 to 50 parts by mass, more preferably 0 to 30 parts by mass with respect to 100 parts by mass of the rubber matrix. If it is 50 mass parts or less, it can suppress that the tensile strength of vulcanized rubber and low heat generating property (low fuel consumption property) deteriorate.

In the rubber composition used for the tire of the present invention, 1 to 15 parts by mass of a foaming agent is preferably blended with 100 parts by mass of the rubber matrix.
Examples of the foaming agent include azodicarbonamide (ADCA), dinitrosopentamethylenetetramine (DPT), dinitrosopentastyrenetetramine, benzenesulfonyl hydrazide derivatives, p, p′-oxybisbenzenesulfonylhydrazide (OBSH), carbon dioxide. Ammonium bicarbonate generated, sodium bicarbonate, ammonium carbonate, nitrososulfonylazo compound generating nitrogen, N, N′-dimethyl-N, N′-dinitrosophthalamide, toluenesulfonyl hydrazide, p-toluenesulfonyl semicarbazide, p , P′-oxybisbenzenesulfonyl semicarbazide and the like. Among these foaming agents, azodicarbonamide (ADCA) and dinitrosopentamethylenetetramine (DPT) are preferable from the viewpoint of production processability. Moreover, these foaming agents may be used individually by 1 type, and may use 2 or more types together.

The tire tread of the present invention preferably has 5 to 50% by volume of air bubbles in the rubber matrix. The bubble rate (Vs) can be calculated by the following equation.
Vs = (ρ ₀ / ρ ₁ −1) × 100 (%)
(Wherein, [rho ₁ represents the density of the rubber composition after vulcanization ^{(g / cm 3), ρ} 0 represents the density of the solid phase portion in the rubber composition after vulcanization (g / cm ^3). )
The density of the rubber composition after vulcanization and the density of the solid phase part in the rubber composition after vulcanization are calculated from the mass in ethanol and the mass in air. Further, the bubble ratio (Vs) can be appropriately changed depending on the type and amount of the foaming agent and foaming aid described later.
The reason why the bubble rate is preferably 5% by volume or more is that the effect of improving the performance on ice is higher, and that the bubble rate is preferably 50% by volume or less is preferable for fracture resistance and wear resistance. It is because it improves more. From these viewpoints, the bubble ratio is more preferably 10 to 35% by volume, and further preferably 15 to 30% by volume.

  There is no restriction | limiting in particular as a form of the said foaming agent, According to the objective, it can select suitably from particulate form, liquid form, etc. The form of the foaming agent can be observed using, for example, a microscope. Moreover, the average particle diameter of a particulate foaming agent can be measured using a Coulter counter etc., for example.

  The foaming agent is preferably used in combination with urea, zinc stearate, zinc benzenesulfinate, zinc white or the like as a foaming aid. These may be used individually by 1 type and may use 2 or more types together. By using a foaming aid in combination, the foaming reaction can be promoted to increase the degree of completion of the reaction, and unnecessary deterioration can be suppressed over time.

  The rubber composition used for the tire of the present invention is obtained by kneading using a kneader such as a Banbury mixer, roll, internal mixer, etc., according to the above compounding prescription, after extrusion molding, on a tire molding machine. After forming by a normal method and forming a green tire, vulcanization is performed to form a tire tread.

The tire of the present invention is characterized by using the tire rubber composition described above for a tread member. The tire of the present invention can be produced by forming a green tire using the above rubber composition as a tread member and vulcanizing the green tire according to a conventional method. In addition, since the tire rubber composition described above is used for the tread member of the tire of the present invention, the tire of the present invention has sufficiently secured other performance such as rolling resistance, and a wet grip. The performance is particularly good.
Moreover, as gas with which the tire of the present invention is filled, an inert gas such as nitrogen, argon, helium, etc. can be used in addition to normal or air having an adjusted oxygen partial pressure.

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

<Weight average molecular weight (Mw) before modification>
It measured using GPC [The Tosoh make, HLC-8020] using the refractometer as a detector, and showed it by polystyrene conversion which used the monodisperse polystyrene as a standard. The column is GMHXL [manufactured by Tosoh] and the eluent is tetrahydrofuran.

Production Example 1: Production of High Molecular Weight Modified Conjugated Diene Polymer A In a pressure-resistant glass container having an internal volume of about 900 mL that has been dried and purged with nitrogen, 283 g of cyclohexane, 100 g of 1,3-butadiene monomer, 2,2-ditetrahydrofuryl 0.015 mmol of propane was injected as a cyclohexane solution, 0.50 mmol of n-butyllithium (BuLi) was added thereto, and then polymerization was performed in a 50 ° C. warm water bath equipped with a stirrer for 4.5 hours. The polymerization conversion was almost 100%. To this polymerization system, 0.50 mmol of tin tetrachloride was added as a cyclohexane solution and stirred at 50 ° C. for 30 minutes. Thereafter, 0.5 mL of an isopropanol 5% solution of 2,6-di-t-butyl-p-cresol (BHT) was added to stop the reaction, followed by drying according to a conventional method, whereby a high molecular weight modified conjugated diene system. Polymer A was obtained. The obtained high molecular weight modified conjugated diene polymer A had a vinyl bond content of 20% and a weight average molecular weight (Mw) before modification of 300 × 10 ³ .

Production Example 2 Production of High Molecular Weight Modified Conjugated Diene Polymer B High molecular weight modified conjugated diene heavy polymer was prepared in the same manner as Production Example 1 except that tin tetrachloride in Production Example 1 was changed to equimolar tetraethoxysilane. Combined B was obtained. The obtained high molecular weight modified conjugated diene polymer B had a vinyl bond content of 20% and a weight average molecular weight (Mw) before modification of 300 × 10 ³ .

Production Example 3 Production of High Molecular Weight Modified Conjugated Diene Polymer C Production Example 1 except that tin tetrachloride of Production Example 1 was changed to equimolar N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane. Similarly, a high molecular weight modified conjugated diene polymer C was obtained. The obtained high molecular weight modified conjugated diene polymer C had a vinyl bond content of 20% and a weight average molecular weight (Mw) before modification of 300 × 10 ³ .

Production Example 4: Production of high molecular weight modified conjugated diene polymer D In a pressure-resistant glass container having an internal volume of about 900 mL which has been dried and purged with nitrogen, 283 g of cyclohexane, 100 g of 1,3-butadiene monomer, 2,2-ditetrahydrofuryl 0.015 mmol of propane was injected as a cyclohexane solution, 0.50 mmol of lithium hexamethyleneimide (HMILi) was added thereto, and then polymerization was performed in a 50 ° C. warm water bath equipped with a stirrer for 4.5 hours. The polymerization conversion rate was almost 100%. Thereafter, 0.5 mL of a 5 mass% isopropanol solution of 2,6-di-tert-butyl-p-cresol (BHT) was added to stop the reaction, followed by drying according to a conventional method. Diene polymer D was obtained. The obtained high molecular weight modified conjugated diene polymer D had a vinyl bond content of 20% and a weight average molecular weight (Mw) before modification of 300 × 10 ³ .

Production Example 5 Production of High Molecular Weight Modified Conjugated Diene Polymer E A nitrogen-substituted 5 liter autoclave was charged with 2.4 kg of cyclohexane and 300 g of 1,3-butadiene under nitrogen. As a catalyst component, a solution of neodymium versatate (0.09 mmol) in cyclohexane, methylaluminoxane (MAO: PMAO manufactured by Tosoh Akzo) (1.8 mmol) in toluene, diisobutylaluminum hydride (DIBAH: manufactured by Kanto Chemical) ( 5.0 mmol) and a solution of diethylaluminum chloride (0.18 mmol) in toluene and 1,3-butadiene (4.5 mmol) were aged at 50 ° C. for 30 minutes and polymerized at 80 ° C. for 60 minutes. . The reaction conversion of 1,3-butadiene was almost 100%. Further, after adding 0.55 mmol of N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine as an unmodified modifier, a modification reaction was performed for another 30 minutes. Thereafter, a methanol solution containing 1.5 g of 2,4-tert-butyl-p-cresol was added to terminate the polymerization, followed by drying according to a conventional method, whereby a high molecular weight modified conjugated diene polymer E Got. The obtained high molecular weight modified conjugated diene polymer E had a vinyl bond content of 3% and a weight average molecular weight (Mw) before modification of 300 × 10 ³ .

Production Example 6 Production of High Molecular Weight Modified Conjugated Diene Polymer F In a pressure-resistant glass container having an internal volume of about 900 mL which was dried and purged with nitrogen, 283 g of cyclohexane, 100 g of 1,3-butadiene monomer, 2,2-ditetrahydrofuryl 0.015 mmol of propane was injected as a cyclohexane solution, 0.50 mmol of n-butyllithium (BuLi) was added thereto, and then polymerization was performed in a 50 ° C. warm water bath equipped with a stirrer for 4.5 hours. The polymerization conversion rate was almost 100%. To this polymerization system, 0.50 mmol of 3- [N, N-methyl (trimethylsilyl) amino] propyldimethylethoxysilane was added as a cyclohexane solution and stirred at 50 ° C. for 30 minutes. Thereafter, 0.5 mL of a 5 mass% isopropanol solution of 2,6-di-tert-butyl-p-cresol (BHT) was added to stop the reaction, followed by drying according to a conventional method. A diene polymer (modified polybutadiene) F was obtained.

Production Example 7 Production of High Molecular Weight Modified Conjugated Diene Polymer G In Production Example 7, 0.50 mmol of 3- [N, N-methyl (trimethylsilyl) amino] propyldimethylethoxysilane was added to 3-glycidoxypropyltrimethoxysilane. A high molecular weight modified conjugated diene polymer (modified polybutadiene) G was obtained in the same manner as in Production Example 7 except that the amount was changed to 0.50 mmol.

Production Example 8 Production of High Molecular Weight Modified Conjugated Diene Polymer H In Production Example 7, 0.50 mmol of 3- [N, N-methyl (trimethylsilyl) amino] propyldimethylethoxysilane was added to N- (1,3-dimethylbutyrate). A high molecular weight modified conjugated diene polymer (modified polybutadiene) H was obtained in the same manner as in Production Example 7 except that the amount was changed to 0.50 mmol of (redene) -3- (triethoxysilyl) -1-propanamine.

Production Example 9 Production of High Molecular Weight Modified Conjugated Diene Polymer I In Production Example 7, 0.50 mmol of 3- [N, N-methyl (trimethylsilyl) amino] propyldimethylethoxysilane was added to N- [3- (triethoxysilyl). ) Propyl] -4,5-dihydroimidazole A high molecular weight modified conjugated diene polymer (modified polybutadiene) I was obtained in the same manner as in Production Example 7, except that the amount was changed to 0.50 mmol.

Production Example 10 Production of Low Molecular Weight Modified Conjugated Diene Polymer In a pressure-resistant glass container having an internal volume of about 900 mL which has been dried and purged with nitrogen, 283 g of cyclohexane, 25 g of 1,3-butadiene monomer, 2,2-ditetrahydrofurylpropane 0.015 mmol was injected as a cyclohexane solution, 0.50 mmol of n-butyllithium (BuLi) was added thereto, and then polymerization was performed in a 50 ° C. warm water bath equipped with a stirrer for 4.5 hours. The polymerization conversion was almost 100%. To this polymerization system, 0.50 mmol of tin tetrachloride was added as a cyclohexane solution and stirred at 50 ° C. for 30 minutes. Thereafter, the reaction was stopped by adding 0.5 mL of a 5% solution of 2,6-di-t-butyl-p-cresol (BHT) in 5% isopropanol, followed by drying according to a conventional method, thereby reducing the low molecular weight modified conjugated diene system. A polymer was obtained. The resulting low molecular weight modified conjugated diene polymer had a vinyl bond content of 20% and a weight average molecular weight (Mw) before modification of 80 × 10 ³ .

1) Styrene-butadiene copolymer rubber: # 1500, manufactured by JSR Co., Ltd.
2) Carbon black: ISAF {N2SA (m ² / g) = 115 (m ² / g)}, manufactured by Asahi Carbon Co., Ltd., trade name “Asahi # 80” 190 m ² / g)
3) Silica: Tosoh Silica, trade name “Nipsil AQ” (BET specific surface area = 190 m ² / g)
4) Silane coupling agent: bis (3-triethoxysilylpropyl) tetrasulfide, manufactured by Degussa, trade name “Si69”
6) Anti-aging agent IPPD: N-phenyl-N′-isopropylphenyl-p-phenylenediamine, manufactured by Seiko Chemical Co., Ltd., “Ozonon 3C”
7) Vulcanization accelerator MBTS: Dibenzothiazyl disulfide, manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., trade name “Noxeller DM”
8) Vulcanization accelerator CBS: N-cyclohexyl-2-benzothiazylsulfenamide, manufactured by Ouchi Shinsei Chemical Co., Ltd., trade name “Noxeller CZ”
9) Foaming agent: {dinitrosopentamethylenetetramine (DPT)} / urea} = 1/1 mixture 10) Fine particles: alumina powder, average major axis 60 μm, Showa Denko K.K., trade name “Standard Alumina A- 12 "
10) Fine particles: Alumina powder, average major axis 60 μm, manufactured by Showa Denko KK, trade name “Standard Alumina A-12”
11) TEOS: Tetraethoxysilane 12) Modifier: N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane 12) HMI: hexamethyleneimine {lithium hexamethyleneimide (HMILi) was used as an initiator. }
13) S340: N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, manufactured by Chisso Corporation, trade name “Syraace S340”
14) Resin A: Terpene resin, YS resin PX1000 (manufactured by Yasuhara Chemical, softening point 100 ° C.)
15) Resin B: Hydrogenated terpene resin, Clearon P105 (manufactured by Yasuhara Chemical, softening point 105 ° C.)
16) Resin C: Hydrogenated C9 resin, Alcon M100 (Arakawa Chemical Industries, softening point 100 ° C.)
17) Resin D: Hydrogenated terpene resin, Clearon M105 (manufactured by Yasuhara Chemical, softening point 105 ° C.)
18) Resin E: Hydrogenated terpene resin, Clearon P125 (manufactured by Yasuhara Chemical, softening point 125 ° C.)
19) Resin F: Hydrogenated C9 resin, Alcon P100 (Arakawa Chemical Industries, softening point 100 ° C.)
20) Resin G: Hydrogenated terpene resin, Clearon P150 (manufactured by Yasuhara Chemical, softening point 152 ° C.)
21) Resin H: Hydrogenated terpene resin, Clearon K4100 (manufactured by Yasuhara Chemical, softening point 100 ° C.)

According to the formulation shown in Table 1, a rubber composition for tires was prepared by kneading and compounding using a Banbury mixer. After vulcanizing the obtained rubber composition for tires at 145 ° C. for 33 minutes, a pneumatic tire having a size of 195 / 65R15 (tread: one-layer structure) was prototyped using the rubber composition as a tread rubber. The on-ice performance, wet handling stability, dry handling stability and rolling resistance performance were measured according to the following methods. The results are shown in Table 2.
In addition, the numerical value of Table 1 is shown by a mass part.

<Performance on ice>
A slab sheet having a length of 40 mm, a width of 5 mm, and a thickness of 2 mm in the longitudinal direction of the tire was cut out from the tire tread in a plane parallel to the ground contact surface having a depth of 1 mm from the groove bottom, and used as a sample. About this sample, using a spectrometer manufactured by Ueshima Seisakusho Co., Ltd., a storage elastic modulus under conditions of a distance between chucks of 10 mm, an initial strain of 200 micrometers (microns), a dynamic strain of 1%, a frequency of 52 Hz, and a measurement temperature of −20 ° C. (E ′) was measured. The performance on ice of the comparative example tire was set to 100, and the index was expressed by the following formula. The larger the index value, the better the performance on ice.
Performance on ice (index) = {E ′ of comparative tire (−20 ° C.) / E ′ of test tire (−20 ° C.)} × 100

<Wet handling stability>
The loss tangent (tan δ) was measured with the same spectrometer and measurement conditions as the performance on ice except that a sample similar to the performance on ice was used and the measurement temperature was 0 ° C. The wet handling stability performance of the comparative example tire was set to 100, and the index was expressed by the following formula. The larger the index value, the better the wet steering stability performance.
Wet steering stability performance (index) = {tan δ of test tire (0 ° C.) / Tan δ of comparative example tire (0 ° C.)} × 100

<Dry maneuvering stability>
The storage elastic modulus (E ′) was measured by using the same sample as the on-ice performance and using the same spectrometer and measurement conditions as the on-ice performance except that the measurement temperature was 30 ° C. The wet handling stability performance of the comparative example tire was set to 100, and the index was expressed by the following formula. The larger the index value, the better the wet steering stability performance.
Dry steering stability performance (index) = {E ′ of test tire (30 ° C.) / E ′ of comparative tire (30 ° C.)} × 100

<Rolling resistance performance>
According to JIS K6394, tan δ at 0 ° C. and 50 ° C. was measured, and with respect to Example tires 1 to 24, the resistance value of the comparative example tire was taken as 100 and indicated as an index. Regarding tan δ at 0 ° C., the larger the index value, the better the wet grip property, and regarding tan δ at 50 ° C., the smaller the index value, the smaller the rolling resistance.

  As is clear from Table 2, the Example tires 1 to 24 dramatically improved the performance on ice, the wet steering stability performance, the dry steering stability performance, and the rolling resistance performance as compared with the comparative tire.

  The tire of the present invention is suitably used as a winter tire for passenger cars, light vehicles, light trucks and trucks and buses, particularly as a studless tire.

Claims (20)

At least one diene rubber selected from the group consisting of natural rubber, polyisoprene rubber and polybutadiene rubber, and a high molecular weight modified conjugated diene system having a weight average molecular weight of more than 15 × 10 ⁴ and not more than 200 × 10 ⁴ before modification Low molecular weight modification in which a hydrogenated resin is 0.5 parts by mass or more and less than 100 parts by mass and a weight average molecular weight before modification is 2 × 10 ³ to 15 × 10 ⁴ with respect to 100 parts by mass of a rubber matrix containing a polymer. A tire comprising a rubber composition containing 5 to 50 parts by mass of a conjugated diene polymer and 20 to 200 parts by mass of a reinforcing filler.   The bonded aromatic vinyl content (X) (%) of the low molecular weight modified conjugated diene polymer and the vinyl bond content (Y) (%) of the conjugated diene moiety satisfy X + (Y / 2) <25. The tire according to claim 1.   The low molecular weight modified conjugated diene-based polymer contains at least one functional group selected from the group consisting of a tin-containing functional group, a silicon-containing functional group, and a nitrogen-containing functional group. Tire described in.   The tire according to any one of claims 1 to 3, wherein the low molecular weight modified conjugated diene polymer is low molecular weight modified polybutadiene and / or low molecular weight modified polyisoprene.   The high molecular weight modified conjugated diene polymer contains at least one functional group selected from the group consisting of a tin-containing functional group, a silicon-containing functional group, and a nitrogen-containing functional group. The tire according to any one of the above.   The tire according to any one of claims 1 to 5, wherein the high molecular weight modified conjugated diene polymer is a high molecular weight modified polybutadiene rubber and / or a high molecular weight modified polyisoprene rubber.   The tire according to any one of claims 1 to 6, wherein the reinforcing filler is carbon black and / or silica.   The tire according to any one of claims 1 to 7, wherein the rubber matrix comprises 10 to 95% by mass of a high molecular weight modified conjugated diene polymer and 90 to 5% by mass of the diene rubber.   Furthermore, 3-30 mass parts of microparticles | fine-particles with an average major axis 5-1000 micrometers are included with respect to 100 mass parts of said rubber matrices, The tire in any one of Claims 1-8 characterized by the above-mentioned.   The tire according to any one of claims 1 to 9, wherein the silicon-containing functional group is derived from a dialkoxysilane compound or a trialkoxysilane compound.   The tire according to any one of claims 1 to 10, wherein the nitrogen-containing functional group has a primary amino group. The low molecular weight modified conjugated diene polymer and / or the high molecular weight modified conjugated diene polymer is represented by the following general formula (1):

[Wherein, R ¹ and R ³ are each independently —OR, —OH or an alkyl group having 1 to 20 carbon atoms, R ² is an alkylene group having 1 to 20 carbon atoms, R is a sulfur atom, It is a C1-C20 hydrocarbyl group optionally having an oxygen atom, a nitrogen atom and / or a halogen atom], or the following general formula (2):

[Wherein, R ⁴ and R ⁶ are each independently —OR, —OH or an alkyl group having 1 to 20 carbon atoms, and R ⁵ and R ⁷ are each independently an alkylene group having 1 to 20 carbon atoms. R is a C 1-20 hydrocarbyl group optionally having a sulfur atom, an oxygen atom, a nitrogen atom and / or a halogen atom, and M is Si, Ti, Sn, Bi, Zr or Al. , R ⁸ is —OH, a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyl carboxyl group having 2 to 30 carbon atoms, a 1,3-dicarbonyl-containing group having 5 to 20 carbon atoms, or a hydrocarbyloxy group having 1 to 20 carbon atoms. , and a group selected from the group consisting of siloxy group that is tri-substituted with hydrocarbyloxy group of hydrocarbyl and / or 1 to 20 carbon atoms having 1 to 20 carbon atoms, more R ⁸ are different and the same May have, k is the {(valence of M) -2}, tire according to any one of claims 1 to 11 n is characterized by represented by a 0 or 1].   The low molecular weight modified conjugated diene polymer and / or the high molecular weight modified conjugated diene polymer has a CN bond at a polymerization initiation terminal of the polymer. Tires.   The tire according to any one of claims 1 to 13, wherein a difference in SP value between the rubber matrix and the hydrogenated resin is 1.5 or less.   The tire according to any one of claims 1 to 14, wherein the hydrogenated resin is a resin obtained by hydrogenating a petroleum resin or a natural resin.   The tire according to any one of claims 1 to 15, wherein the hydrogenated resin is a hydrogenated terpene resin obtained by hydrogenating a terpene resin.   The tire according to any one of claims 1 to 16, wherein the hydrogenated terpene resin has a softening point of 80 to 180 ° C.   The tire according to any one of claims 1 to 17, wherein the total content of natural rubber, polyisoprene rubber and polybutadiene rubber in the rubber matrix is 50 mass% or more.   The tire according to any one of claims 1 to 18, wherein the rubber composition is used for a tread.   The tire according to any one of claims 1 to 19, wherein the rubber composition has 5 to 50% by volume of air bubbles in the rubber matrix after vulcanization.