JP2008297358A - Rubber composition and tire using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a tire composition capable of enhancing the controllability and stability of a tire on a dry road surface without deteriorating rolling resistance, and to provide a tire that is excellent in controllability and stability on a dry road surface while keeping rolling resistance good using the rubber composition. <P>SOLUTION: The rubber composition comprises a blend of (A) 10 to 130 pts.mass of an inorganic filler containing silicic acid, for 100 pts.mass of a rubber component containing a modified conjugated diene polymer by 10 mass% or more, the modified conjugated diene polymer having at least one kind of functional group; (B) a silane coupling agent by 1 to 20 mass% for the inorganic filler (A); and (C) 0.5 to 10 pts.mass of a compound selected from specific esters and carboxylic acids. A tire where the rubber composition is used in a tire member such as a tread is also disclosed. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a rubber composition capable of improving steering stability without deteriorating rolling resistance of a tire and a tire using the rubber composition.

In recent years, there has been an increasing demand for fuel efficiency reduction of automobiles in connection with the global movement of regulation of carbon dioxide emissions due to increasing interest in environmental problems. In order to meet such demands, reduction of rolling resistance is also demanded for tire performance. Conventionally, as a technique for reducing the rolling resistance of a tire, a technique for optimizing the tire structure has been studied, but it is currently most important to use a rubber composition having a lower exothermic property as a rubber composition applied to the tire. This is done as a general method.
As a method of obtaining such a rubber composition having low exothermicity, a method of using silica as a filler to be used is known.
However, silica has a problem that the storage elastic modulus does not increase because the dispersibility of the filler is poor and vulcanization is delayed as compared with carbon black.

  In order to improve the above-mentioned drawbacks, Patent Document 1 discloses (A) natural rubber and / or diene synthetic rubber, (B) inorganic filler, and (C) reactive group A for rubber (A) in the same molecule. A compound having at least one and two or more adsorption groups B for the inorganic filler (B), (D) selected from maleic acid, fumaric acid, itaconic acid and sorbic acid as the reactive group A for the rubber (A) in the same molecule A rubber containing at least one compound selected from an acrylate ester or a methacrylic acid ester having a specific structure, or a compound having one or more groups A and amino groups each derived from an unsaturated carboxylic acid Compositions have been proposed. This improves the dispersibility of the inorganic filler and increases the storage elastic modulus of the vulcanized rubber composition without increasing the viscosity of the unvulcanized rubber and without impairing the processability, but reduces the rolling resistance. It was difficult to do.

By the way, in Patent Document 2 or 3, a rubber composition using a modified conjugated diene polymer in which an amino group is introduced at a polymerization active terminal as a rubber component and carbon black as a filler is proposed in order to reduce rolling resistance. In Patent Document 4 or 5, it is also proposed to blend silica with these modified conjugated diene polymers.
However, there is a problem that the storage elastic modulus of the vulcanized rubber composition is lowered.
Therefore, there is a new technology that can improve the driving stability on the dry road surface without deteriorating the rolling resistance of the tire by increasing the storage elastic modulus while maintaining the good loss tangent of the vulcanized rubber composition. It was requested.

JP 2003-176378 A JP-A-8-225604 JP-A-8-231658 JP-A-2005-232351 JP 2006-241358 A

  Accordingly, an object of the present invention is to provide a rubber composition capable of solving the above-described problems of the prior art and improving steering stability on a dry road surface of a tire without deteriorating rolling resistance. Another object of the present invention is to provide a tire using such a rubber composition, which maintains excellent rolling resistance and is excellent in driving stability on a dry road surface.

As a result of intensive studies to achieve the above object, the present inventor has found that in a rubber composition containing an inorganic filler containing silicic acid, a modified conjugated diene polymer having a specific functional group and a specific ester And the compound selected from carboxylic acids was found to achieve the above object, and the present invention was completed.
That is, the present invention provides 10 to 130 inorganic fillers (A) containing silicic acid with respect to 100 parts by mass of a rubber component containing 10% by mass or more of a modified conjugated diene polymer having at least one functional group. The mass part, the silane coupling agent (B) was selected from the group consisting of 1 to 20% by mass with respect to the inorganic filler (A) and the compounds represented by the following general formulas (I) to (III) It is a rubber composition formed by blending 0.5 to 10 parts by mass of at least one compound (C), and a tire applied to any of the tire members, particularly a tire applied to a tread.

［式中、Ａ¹、Ａ²及びＡ³はこれらのうち一つが式−（Ｒ¹Ｏ）_n−ＣＯ−ＣＲ²＝ＣＲ³−Ｒ⁴で表される基であり（ここでＲ¹は炭素数２〜４のアルキレン基、Ｒ²、Ｒ³及びＲ⁴はそれぞれ独立に水素原子又はメチル基、ｎはオキシアルキレン基の平均付加モル数を示す１〜３０の数である）、他は水素原子である。］

[Wherein, A ¹ , A ² and A ³ are groups in which one of them is represented by the formula — (R ¹ O) _n —CO—CR ² ═CR ³ —R ⁴ , where R ¹ is An alkylene group having 2 to 4 carbon atoms, R ² , R ³ and R ⁴ are each independently a hydrogen atom or a methyl group, n is a number from 1 to 30 indicating the average number of moles added of the oxyalkylene group), It is a hydrogen atom. ]

［式中、Ｒ⁵、Ｒ⁶及びＲ⁷はそれぞれ独立に炭素数２〜４のアルキレン基であり、ｍ１、ｍ２及びｍ３はそれぞれオキシアルキレン基の平均付加モル数を示す数で、ｍ１＋ｍ２＋ｍ３が０〜９０となる数である］

[Wherein R ⁵ , R ⁶ and R ⁷ are each independently an alkylene group having 2 to 4 carbon atoms, m1, m2 and m3 are numbers indicating the average number of added moles of the oxyalkylene group, and m1 + m2 + m3 is 0. It is a number that is ~ 90]

［式中、Ｒ⁸は、式−Ｒ⁹Ｏ−で示される基、式−（Ｒ¹⁰Ｏ）_S−で示される基、式−ＣＨ₂ＣＨ（ＯＨ）ＣＨ₂Ｏ−で示される基又は式−（Ｒ¹¹Ｏ−ＣＯ−Ｒ¹²−ＣＯＯ−）_t−Ｒ¹¹Ｏ−で示される基である。Ｒ⁹は炭素数２〜３６のアルキレン基，アルケニレン基又は２価の芳香族炭化水素基、Ｒ¹⁰は炭素数２〜４のアルキレン基、ｓはオキシアルキレン基の平均付加モル数を示す１〜６０の数、Ｒ¹¹は炭素数２〜１８のアルキレン基，アルケニレン基，２価の芳香族炭化水素基又は−（Ｒ¹³Ｏ）_uＲ¹³−（Ｒ¹³は炭素数２〜４のアルキレン基、ｕはオキシアルキレン基の平均付加モル数を示す１〜３０の数）、Ｒ¹²は炭素数２〜１８のアルキレン基，アルケニレン基又は２価の芳香族炭化水素基、ｔは平均値で１〜３０の数である。］

[Wherein R ⁸ represents a group represented by the formula —R ⁹ O—, a group represented by the formula — (R ¹⁰ O) _S —, a group represented by the formula —CH ₂ CH (OH) CH ₂ O—, or It is a group represented by the formula — (R ¹¹ O—CO—R ¹² —COO—) _t —R ¹¹ O—. R ⁹ represents an alkylene group having 2 to 36 carbon atoms, an alkenylene group or a divalent aromatic hydrocarbon group, R ¹⁰ represents an alkylene group having 2 to 4 carbon atoms, and s represents an average number of moles added of the oxyalkylene group. Number of 60, R ¹¹ is an alkylene group having 2 to 18 carbon atoms, alkenylene group, divalent aromatic hydrocarbon group or — (R ¹³ O) _u R ¹³ — (R ¹³ is an alkylene group having 2 to 4 carbon atoms) , U represents an average number of added moles of the oxyalkylene group of 1 to 30), R ¹² represents an alkylene group having 2 to 18 carbon atoms, an alkenylene group or a divalent aromatic hydrocarbon group, and t represents an average value of 1 A number of ~ 30. ]

  ADVANTAGE OF THE INVENTION According to this invention, the rubber composition which can improve the steering stability on the dry road surface of a tire can be provided, without deteriorating rolling resistance. Moreover, the tire which uses this rubber composition and is excellent in steering stability on a dry road surface, while maintaining favorable rolling resistance can be provided.

The present invention is described in detail below.
The present invention provides 10 to 130 parts by mass of an inorganic filler (A) containing silicic acid with respect to 100 parts by mass of a rubber component containing 10% by mass or more of a modified conjugated diene polymer having at least one functional group. 1 to 20% by mass of the silane coupling agent (B) with respect to the inorganic filler (A), and at least one selected from the group consisting of compounds represented by the following general formulas (I) to (III) It is a rubber composition obtained by blending 0.5 to 10 parts by mass of a compound (C) of a seed, and a tire in which it is applied to any of tire members, particularly a tire applied to a tread.
Here, general formula (I) refers to the following compounds.

式中、Ａ¹、Ａ²及びＡ³はこれらのうち一つが式−（Ｒ¹Ｏ）_n−ＣＯ−ＣＲ²＝ＣＲ³−Ｒ⁴で表される基であり（ここでＲ¹は炭素数２〜４のアルキレン基、Ｒ²、Ｒ³及びＲ⁴はそれぞれ独立に水素原子又はメチル基、ｎはオキシアルキレン基の平均付加モル数を示す１〜３０の数である）、他は水素原子である。

In the formula, A ¹ , A ² and A ³ are groups in which one of them is represented by the formula — (R ¹ O) _n —CO—CR ² ═CR ³ —R ⁴ (where R ¹ is carbon An alkylene group of 2 to 4, R ² , R ³ and R ⁴ are each independently a hydrogen atom or a methyl group, n is a number of 1 to 30 indicating the average number of added moles of an oxyalkylene group), and the others are hydrogen Is an atom.

Specific examples of the compound represented by the general formula (I) include trimellitic acid mono (2- (meth) acryloyloxyethyl) ester and trimellitic acid mono [2- (2- (meth) acryloyloxyethoxy). Ethyl] ester, trimellitic acid mono (ω- (meth) acryloyloxypolyoxyethylene (10)) ester, etc. trimellitic acid mono (ω- (meth) acryloyloxy POA (n)) ester (where (meth) Acryloyl represents methacryloyl or acryloyl, and POA (n) represents polyoxyethylene (hereinafter sometimes abbreviated as “POE”) or polyoxypropylene (hereinafter “POE”) in which 1 to 30 mol of oxyethylene or oxypropylene is added on average. May be abbreviated as “POP”).
Moreover, general formula (II) means the following compounds.

式中、Ｒ⁵、Ｒ⁶及びＲ⁷はそれぞれ独立に炭素数２〜４のアルキレン基であり、ｍ１、ｍ２及びｍ３はそれぞれオキシアルキレン基の平均付加モル数を示す数で、ｍ１＋ｍ２＋ｍ３が０〜９０となる数である。

In the formula, R ⁵ , R ⁶ and R ⁷ are each independently an alkylene group having 2 to 4 carbon atoms, m1, m2 and m3 are numbers indicating the average number of added moles of the oxyalkylene group, and m1 + m2 + m3 is 0 to 0. The number is 90.

Specific examples of the compound represented by the general formula (II) include POA (m) glycerin such as POE (8) glycerin trimaleate, POE (3) glycerin trimaleate, POP (10) glycerin trimaleate. Trimaleate (POA (m) represents polyoxyethylene or polyoxypropylene in which 0 to 90 mol of oxyethylene or oxypropylene is added on average).
Furthermore, general formula (III) refers to the following compounds.

式中、Ｒ⁸は、式−Ｒ⁹Ｏ−で示される基、式−（Ｒ¹⁰Ｏ）_S−で示される基、式−ＣＨ₂ＣＨ（ＯＨ）ＣＨ₂Ｏ−で示される基又は式−（Ｒ¹¹Ｏ−ＣＯ−Ｒ¹²−ＣＯＯ−）_t−Ｒ¹¹Ｏ−で示される基である。Ｒ⁹は炭素数２〜３６のアルキレン基，アルケニレン基又は２価の芳香族炭化水素基、Ｒ¹⁰は炭素数２〜４のアルキレン基、ｓはオキシアルキレン基の平均付加モル数を示す１〜６０の数、Ｒ¹¹は炭素数２〜１８のアルキレン基，アルケニレン基，２価の芳香族炭化水素基又は−（Ｒ¹³Ｏ）_uＲ¹³−（Ｒ¹³は炭素数２〜４のアルキレン基、ｕはオキシアルキレン基の平均付加モル数を示す１〜３０の数）、Ｒ¹²は炭素数２〜１８のアルキレン基，アルケニレン基又は２価の芳香族炭化水素基、ｔは平均値で１〜３０の数である。

In the formula, R ⁸ is a group represented by the formula —R ⁹ O—, a group represented by the formula — (R ¹⁰ O) _S —, a group represented by the formula —CH ₂ CH (OH) CH ₂ O—, or a formula — (R ¹¹ O—CO—R ¹² —COO—) _t —R ¹¹ O—. R ⁹ represents an alkylene group having 2 to 36 carbon atoms, an alkenylene group or a divalent aromatic hydrocarbon group, R ¹⁰ represents an alkylene group having 2 to 4 carbon atoms, and s represents an average number of moles added of the oxyalkylene group. Number of 60, R ¹¹ is an alkylene group having 2 to 18 carbon atoms, alkenylene group, divalent aromatic hydrocarbon group or — (R ¹³ O) _u R ¹³ — (R ¹³ is an alkylene group having 2 to 4 carbon atoms) , U represents an average number of added moles of the oxyalkylene group of 1 to 30), R ¹² represents an alkylene group having 2 to 18 carbon atoms, an alkenylene group or a divalent aromatic hydrocarbon group, and t represents an average value of 1 A number of ~ 30.

  Specific examples of the compound represented by the general formula (III) include dimaleates of alkylene diols such as glycerin dimaleate, 1,4-butanediol dimaleate, 1,6-hexanediol dimaleate, 1, 6-hexanediol difumarate and other alkylene diol difumarate, PEG200 dimaleate, polyoxyalkylene glycol dimaleate such as PEG600 dimaleate (herein, PEG200 and PEG600 are polyethylene glycol having an average molecular weight of 200 or 600, respectively), both Polybutylene maleate having a carboxyl group at the terminal, poly (PEG200) maleate having a carboxyl group at both terminals, such as a polycarboxylic acid type polyalkylene glycol / maleic polyester at both terminals, a carboxyl at both terminals Polybutylene adipate maleate having a dibutyl group, polyoxyalkylene glycol difumarate such as PEG600 difumarate, polybutylene fumarate having carboxyl groups at both ends, and poly (PEG200) fumarate having carboxyl groups at both ends Examples include acid type polyalkylene glycol / fumaric acid polyester.

The compound (C) preferably has a molecular weight of 250 or more, more preferably in the range of 250 to 5000, and particularly preferably in the range of 250 to 3000.
In addition, in this invention, a compound (C) may be used independently and may be used in combination of 2 or more type.
In the rubber composition of the present invention, it is necessary to add 0.5 to 10 parts by mass of the compound (C). If the amount is less than 0.5 parts by mass, the dispersion of the filler is not improved, and 10 parts by mass. This is because the dispersion of the filler is not further improved even if the content exceeds. From this viewpoint, 0.3 to 6 parts by mass is preferable, and 0.5 to 4 parts by mass is more preferable.

A modified conjugated diene polymer having at least one functional group (hereinafter simply referred to as “modified conjugated diene polymer”) contained in the rubber component (A) of the rubber composition of the present invention in an amount of 10% by mass or more. Is preferably a copolymer of 1,3-butadiene and an aromatic vinyl compound, or a homopolymer of 1,3-butadiene or isoprene. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, 1-vinylnaphthalene, 3-vinyltoluene, ethylvinylbenzene, divinylbenzene, 4-cyclohexylstyrene, 2,4,6-trimethylstyrene, and the like. Styrene is preferred.
The modified conjugated diene polymer preferably has a glass transition point (Tg) of 10 ° C. or lower. This is because if Tg is 10 ° C. or lower, the rolling resistance can be further reduced and the flexibility of the rubber composition at low temperatures can be increased.

The functional group of the modified conjugated diene polymer according to the present invention may be present in the terminal and / or main chain or side chain on the polymerization initiation side or polymerization termination side of the modified conjugated diene polymer.
The functional group of the modified conjugated diene polymer is a functional group selected from the group consisting of a functional group containing nitrogen, a functional group containing silicon, a functional group containing oxygen or sulfur, and a functional group containing a metal. Is preferred.

The functional group containing nitrogen of the modified conjugated diene polymer according to the present invention is a substituted or unsubstituted amino group, amide residue, isocyanate group, imidazolyl group, indolyl group, nitrile group, pyridyl group and ketimine group. It is preferable. Examples of the substituted or unsubstituted amino group include primary alkylamines, secondary alkylamines, cyclic amines, and amino groups derived from substituted or unsubstituted imines.
The substituted or unsubstituted amino group is more preferably a substituted amino group represented by the following formula (IV) or a cyclic amino group represented by the following formula (V).

ここで、Ｒ¹⁴は、それぞれ独立して炭素数１〜１２のアルキル基、炭素数３〜１２のシクロアルキル基又は炭素数７〜１２のアラルキル基である。具体的には、メチル基、エチル基、ブチル基、イソブチル基、オクチル基、シクロヘキシル基及び３-フェニルプロピル基等が好適に挙げられる。

Here, R < ¹⁴ > is respectively independently a C1-C12 alkyl group, a C3-C12 cycloalkyl group, or a C7-C12 aralkyl group. Specific examples include a methyl group, an ethyl group, a butyl group, an isobutyl group, an octyl group, a cyclohexyl group, and a 3-phenylpropyl group.

ここで、Ｒ¹⁵は、３〜１６のメチレン基を有するアルキレン基、置換アルキレン基、オキシアルキレン基又はＮ-アルキルアミノ-アルキレン基を示す。
また、Ｒ¹⁵として、具体的には、トリメチレン基、テトラメチレン基、ヘキサメチレン基、オキシジエチレン基、Ｎ-アルキルアザジエチレン基、ドデカメチレン基及びヘキサデカメチレン基等が好ましい。

Here, R ¹⁵ represents an alkylene group having 3 to 16 methylene groups, a substituted alkylene group, an oxyalkylene group or an N-alkylamino-alkylene group.
As R ¹⁵ , specifically, a trimethylene group, a tetramethylene group, a hexamethylene group, an oxydiethylene group, an N-alkylazadiethylene group, a dodecamethylene group, a hexadecamethylene group, and the like are preferable.

The functional group containing silicon of the modified conjugated diene polymer according to the present invention is preferably an organic silyl group or a siloxy group, and more specifically, an alkoxysilyl group, an alkylhalosilyl group, a siloxy group, A functional group selected from the group consisting of an alkylaminosilyl group and an alkoxyhalosilyl group is preferred. Moreover, it is preferable that it is a functional group which produces | generates a silanol group by hydrolysis as a functional group containing silicon.
And the functional group containing oxygen or sulfur of the modified conjugated diene polymer according to the present invention is a hydroxyl group, a carboxyl group, an epoxy group, a glycidoxy group, a diglycidylamino group, a cyclic dithian-derived functional group, an ester group, It is a functional group selected from the group consisting of an aldehyde group, an alkoxy group, a ketone group, a thiocarboxyl group, a thioepoxy group, a thioglycidoxy group, a thiodiglycidylamino group, a thioester group, a thioaldehyde group, a thioalkoxy group, and a thioketone group. Is preferred. The alkoxy group may be an alcohol-derived alkoxy group derived from benzophenone.
Furthermore, it is preferable that the functional group containing a metal of the modified conjugated diene polymer according to the present invention is a functional group containing an organic metal.

The modified conjugated diene polymer according to the present invention is preferably a polymer obtained by anionic polymerization using an organic alkali metal compound as a polymerization initiator, or a polymer obtained by coordination polymerization using a rare earth metal compound as a polymerization initiator.
As the organic alkali metal compound, it is preferable to use a hydrocarbyl lithium compound, a lithium amide compound, or a Group 1 metal alkoxide. Examples of the Group 1 metal of the Group 1 metal alkoxide include lithium, sodium, potassium, rubidium, and cesium. When a hydrocarbyl lithium compound is used as a polymerization initiator, a conjugated diene polymer having a hydrocarbyl group at the polymerization initiation terminal and the other terminal being a polymerization active site is obtained. On the other hand, when a lithium amide compound is used as the polymerization initiator, a conjugated diene polymer having a nitrogen-containing functional group at the polymerization initiation terminal and the other terminal being a polymerization active site is obtained. Without being modified with an agent, it can be used as a modified conjugated diene polymer in the present invention.
In addition, the usage-amount as a polymerization initiator of organolithium compounds, such as a hydrocarbyl lithium compound and a lithium amide compound, or a group 1 metal alkoxide has the preferable range of 0.2-20 mmol (mmol) per 100g of monomers.

  Examples of the hydrocarbyl lithium compound include ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-octyl lithium, n-decyl lithium, phenyl lithium, 2-naphthyl lithium, and 2-butylphenyl. Examples include lithium, 4-phenyl-butyllithium, cyclohexyllithium, cyclopentyllithium, reaction products of diisopropenylbenzene and butyllithium, and among these, ethyllithium, n-propyllithium, isopropyllithium, n-butyl Alkyl lithium such as lithium, sec-butyl lithium, tert-octyl lithium and n-decyl lithium is preferable, and n-butyl lithium is particularly preferable.

  On the other hand, the lithium amide compounds include lithium hexamethylene imide, lithium pyrrolidide, lithium piperidide, lithium heptamethylene imide, lithium dodecamethylene imide, lithium dimethylamide, lithium diethylamide, lithium dipropylamide, lithium dibutylamide, lithium Dihexylamide, lithium diheptylamide, lithium dioctylamide, lythym-2-ethylhexylamide, lithium didecylamide, lithium-N-methylpiperazide, lithium ethylpropylamide, lithium ethylbutyramide, lithium methylbutyramide, lithium ethylbenzylamide, Examples include lithium methylphenethylamide.

  The lithium amide compound is represented by the formula: Li-AM [wherein AM is a substituted amino group represented by the above formula (IV) or a cyclic amino group represented by the above formula (V)]. By using the lithium amide compound, at least one nitrogen-containing functional group selected from the group consisting of a substituted amino group represented by the formula (IV) and a cyclic amino group represented by the formula (V) was introduced. A modified conjugated diene polymer is obtained.

  The lithium amide compound may be preliminarily prepared from a secondary amine and a lithium compound and used for the polymerization reaction, but may be generated in a polymerization system. Here, examples of the secondary amine include dimethylamine, diethylamine, dibutylamine, dioctylamine, dicyclohexylamine, diisobutylamine and the like, as well as azacycloheptane (ie, hexamethyleneimine), 2- (2-ethylhexyl) pyrrolidine, 3 -(2-propyl) pyrrolidine, 3,5-bis (2-ethylhexyl) piperidine, 4-phenylpiperidine, 7-decyl-1-azacyclotridecane, 3,3-dimethyl-1-azacyclotetradecane, 4- Dodecyl-1-azacyclooctane, 4- (2-phenylbutyl) -1-azacyclooctane, 3-ethyl-5-cyclohexyl-1-azacycloheptane, 4-hexyl-1-azacycloheptane, 9-isoamyl -1-Azacycloheptadecane, 2-methyl-1-azacycloheptadec-9-ene, 3-isobutyl-1-azacyclododecane 2-Methyl-7-tert-butyl-1-azacyclododecane, 5-nonyl-1-azacyclododecane, 8- (4′-methylphenyl) -5-pentyl-3-azabicyclo [5.4.0] ] Undecane, 1-butyl-6-azabicyclo [3.2.1] octane, 8-ethyl-3-azabicyclo [3.2.1] octane, 1-propyl-3-azabicyclo [3.2.2] nonane And cyclic amines such as 3- (t-butyl) -7-azabicyclo [4.3.0] nonane and 1,5,5-trimethyl-3-azabicyclo [4.4.0] decane. On the other hand, as the lithium compound, the hydrocarbyl lithium compound can be used.

  The method for producing the modified conjugated diene polymer according to the present invention by anionic polymerization using the above organic alkali metal compound or the like as a polymerization initiator is not particularly limited. For example, in a hydrocarbon solvent inert to the polymerization reaction. A conjugated diene polymer can be produced by polymerizing a conjugated diene compound alone or a mixture of a conjugated diene compound and a vinyl aromatic compound. Here, as the hydrocarbon solvent inert to the polymerization reaction, propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, cyclohexane, propene, 1-butene, isobutene, 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 anionic polymerization may be performed in the presence of a randomizer. The randomizer can control the microstructure of the conjugated diene compound. For example, the randomizer can control the 1,2-bond content of a butadiene unit of a polymer using butadiene as a monomer, or can be styrene as a monomer. And butadiene units of a copolymer using butadiene are randomized.
Examples of the randomizer include dimethoxybenzene, tetrahydrofuran, dimethoxyethane, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, bistetrahydrofurylpropane, triethylamine, pyridine, N-methylmorpholine, N, N, N ′, N′-tetramethylethylenediamine, 1 , 2-dipiperidinoethane, potassium t-amylate, potassium t-butoxide, sodium t-amylate and the like. The amount of these randomizers used is preferably in the range of 0.01 to 100 molar equivalents per mole of the organic alkali metal compound as the polymerization initiator.

  The anionic polymerization may be carried out by any of solution polymerization, gas phase polymerization, and bulk polymerization. In the case of solution polymerization, the concentration of the monomer in the solution is preferably in the range of 5 to 50% by mass, A range of 10 to 30% by mass is more preferable. In addition, when using together a conjugated diene compound and a vinyl aromatic compound as a monomer, the content rate of the vinyl aromatic compound in a monomer mixture has the preferable range of 3-50 mass%, and 4-45 mass%. The range of is more preferable. Further, the polymerization mode is not particularly limited, and may be batch type or continuous type.

  The polymerization temperature of the anionic polymerization is preferably in the range of 0 to 150 ° C, more preferably in the range of 20 to 130 ° C. The polymerization can be carried out under generated pressure, but it is usually preferable to carry out the polymerization under a pressure sufficient to keep the monomer used in a substantially liquid phase. Here, when the polymerization reaction is carried out under a pressure higher than the generated pressure, it is preferable to pressurize the reaction system with an inert gas. In addition, it is preferable to use raw materials such as monomers, polymerization initiators, and solvents used for polymerization from which reaction inhibitors such as water, oxygen, carbon dioxide, and protic compounds have been removed in advance.

  On the other hand, when the modified conjugated diene polymer according to the present invention is produced by coordination polymerization using a rare earth metal compound as a polymerization initiator, the following (A) component, (B) component, and (C) component are used in combination: Is more preferable.

  The component (a) used for the coordination polymerization is selected from a rare earth metal compound, a complex compound of a rare earth metal compound and a Lewis base, and the like. Here, examples of rare earth metal compounds include rare earth element carboxylates, alkoxides, β-diketone complexes, phosphates and phosphites, and Lewis bases include acetylacetone, tetrahydrofuran, pyridine, N, N. -Dimethylformamide, thiophene, diphenyl ether, triethylamine, an organic phosphorus compound, monovalent or divalent alcohol, etc. are mentioned. As the rare earth element of the rare earth metal compound, lanthanum, neodymium, praseodymium, samarium and gadolinium are preferable, and among these, neodymium is particularly preferable. Specific examples of component (a) include neodymium tri-2-ethylhexanoate, complex compounds thereof with acetylacetone, neodymium trineodecanoate, complex compounds thereof with acetylacetone, neodymium tri-n-butoxide, and the like. It is done. These components (a) may be used alone or in combination of two or more.

The component (b) used in the coordination polymerization is selected from organoaluminum compounds. As the organoaluminum compound, specifically, a trihydrocarbyl aluminum compound represented by the formula: R ²² ₃ Al, a hydrocarbyl aluminum hydride represented by the formula: R ²² ₂ AlH or R ²² AlH ₂ (wherein R ²² are each independently a hydrocarbon group having 1 to 30 carbon atoms), hydrocarbylaluminoxane compounds having a hydrocarbon group having 1 to 30 carbon atoms, and the like. Specific examples of the organoaluminum compound include trialkylaluminum, dialkylaluminum hydride, alkylaluminum dihydride, and alkylaluminoxane. These compounds may be used alone or in combination of two or more. In addition, as (b) component, it is preferable to use aluminoxane and another organoaluminum compound in combination.

  The component (c) used in the coordination polymerization is a compound having a hydrolyzable halogen or a complex compound thereof with a Lewis base; an organic halide having a tertiary alkyl halide, benzyl halide or allyl halide; a non-coordinating anion And an ionic compound comprising a counter cation. Specific examples of the component (c) include alkylaluminum dichloride, dialkylaluminum chloride, silicon tetrachloride, tin tetrachloride, zinc chloride and Lewis base complexes such as alcohol, magnesium chloride and alcohol such as Lewis. Examples include complexes with bases, benzyl chloride, t-butyl chloride, benzyl bromide, t-butyl bromide, triphenylcarbonium tetrakis (pentafluorophenyl) borate and the like. These components (c) may be used alone or in combination of two or more.

  The polymerization initiator is preliminarily used by using the same conjugated diene compound and / or non-conjugated diene compound as the polymerization monomer, if necessary, in addition to the components (a), (b) and (c). May be prepared. Further, part or all of the component (a) or the component (c) may be supported on an inert solid. Although the usage-amount of said each component can be set suitably, (a) component is 0.001-0.5 millimoles (mmol) per 100g of monomers normally. In addition, (b) component / (b) component is preferably 5 to 1,000, and (c) component / (b) component is preferably 0.5 to 10 in molar ratio.

  The polymerization temperature in the coordination polymerization is preferably in the range of −80 to 150 ° C., and more preferably in the range of −20 to 120 ° C. Moreover, as a solvent used for coordination polymerization, a hydrocarbon solvent inert to the reaction exemplified in the above-mentioned anionic polymerization can be used, and the concentration of the monomer in the reaction solution is the same as in the case of anionic polymerization. . Furthermore, the reaction pressure in coordination polymerization is the same as that in the case of anionic polymerization, and it is desirable that the raw material used for the reaction substantially removes reaction inhibitors such as water, oxygen, carbon dioxide, and protic compounds.

  The method for producing the modified conjugated diene polymer according to the present invention includes a method in which the active terminal of the conjugated diene polymer having an active terminal produced as described above is modified with a modifier, and a lithium amide as described above. A method for modifying the terminal on the polymerization initiation side using a modifying group-containing polymerization initiator such as a compound, and modifying the active end of the conjugated diene polymer with a modifying agent (first-stage modification) and further modifying the modifying group and the modifying agent For example, a method of multistage modification in which a conjugated diene polymer is reacted, a method of grafting a modifier in the main chain or side chain of a conjugated diene polymer, and a method of copolymerizing with a functional group-containing monomer during polymerization of the conjugated diene polymer. It is done.

  In order to produce the modified conjugated diene polymer according to the present invention, when modifying the active end of the conjugated diene polymer having an active end produced as described above with a modifier, the modifier contains nitrogen. A compound, a silicon-containing compound, an oxygen or sulfur-containing compound, a tin-containing compound, or the like can be used.

Nitrogen-containing compounds that can be used as the modifier include bis (diethylamino) benzophenone, dimethylimidazolidinone, N-methylpyrrolidone, 4-dimethylaminobenzylideneaniline, and the like. By using these nitrogen-containing compounds as modifiers, functional groups containing nitrogen such as substituted and unsubstituted amino groups, amide residues, isocyanate groups, imidazolyl groups, indolyl groups, nitrile groups, pyridyl groups and ketimine groups can be obtained. It can introduce | transduce into a conjugated diene type polymer. A ketimine group, that is, an amino group having a ketimine structure (—N═CR ¹ R ² ) is a masked amino group, and does not exhibit the properties as a primary amine as it is. It is easily hydrolyzed and the active primary amine is regenerated by elimination of the ketone compound.

The silicon-containing compound that can be used as the modifier is preferably a hydrocarbyloxysilane compound, a hydrocarbyloxysilane compound represented by the following formula (VI) and a hydrocarbyloxysilane compound represented by the following formula (VII) More preferred is at least one hydrocarbyloxysilane compound selected from the group consisting of:
Hydrocarbyloxysilane compound represented by the following formula (VI):

ここで、Ａ⁴は(チオ)エポキシ基、(チオ)イソシアネート基、(チオ)ケトン基、(チオ)アルデヒド基、イミン残基、アミド残基、イソシアヌル酸トリエステル残基、(チオ)カルボン酸ヒドロカルビルエステル残基、(チオ)カルボン酸残基の金属塩、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、環状第２アミン残基、非環状第２アミン残基、ピリジン基及びシラザン基の中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あるいはジスルフィド基であり；Ｒ¹⁶及びＲ¹⁷は、それぞれ独立に炭素数１〜２０の一価の脂肪族炭化水素基又は炭素数６〜１８の一価の芳香族炭化水素基であり；Ｒ¹⁸は単結合又は炭素数１〜２０の二価の不活性炭化水素基であり；ｎは１〜３の整数であり；ＯＲ¹⁶が複数ある場合、複数のＯＲ¹⁶はたがいに同一でも異なっていてもよく；Ｒ¹⁷が複数ある場合、複数のＲ¹⁷はたがいに同一でも異なっていてもよく；また分子中には活性プロトン及びオニウム塩は含まれない。

Here, A ⁴ is (thio) epoxy group, (thio) isocyanate group, (thio) ketone group, (thio) aldehyde group, imine residue, amide residue, isocyanuric acid triester residue, (thio) carboxylic acid Hydrocarbyl ester residue, metal salt of (thio) carboxylic acid residue, carboxylic acid anhydride residue, carboxylic acid halide residue, carbonic acid dihydrocarbyl ester residue, cyclic secondary amine residue, acyclic secondary amine residue A monovalent group or disulfide group having at least one functional group selected from a group, a pyridine group and a silazane group; R ¹⁶ and R ¹⁷ are each independently a monovalent aliphatic group having 1 to 20 carbon atoms. A hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms; R ¹⁸ is a single bond or a divalent inert hydrocarbon group having 1 to 20 carbon atoms; It is an integer; OR ¹⁶ is double In some cases, a plurality of OR ¹⁶ may be the same as or different from each other; if R ¹⁷ is more or different and a plurality of R ¹⁷ is identical to each other; in addition the molecule active proton and an onium salt Is not included.

In the formula (VI), among the functional groups in A ⁴ , the imine residue includes a ketimine group, an aldimine residue, and an amidine group, and the (thio) carboxylic acid ester residue includes an acrylate residue, a methacrylate residue, etc. Of unsaturated carboxylic acid ester residues. Examples of the metal of the metal salt of the (thio) carboxylic acid residue include alkali metals, alkaline earth metals, Al, Sn, and Zn.

Examples of R ¹⁶ and R ¹⁷ 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, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group. , 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. Furthermore, 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 divalent inert hydrocarbon group having 1 to 20 carbon atoms in R ¹⁸ is preferably 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 the hydrocarbyloxysilane compound represented by the formula (VI) include (thio) epoxy group-containing hydrocarbyloxysilane compounds such as 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, ( 2-glycidoxyethyl) methyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, 2- (3,4- Epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane and the epoxy groups in these compounds as thioepoxy groups To give a replacement Among these, 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane are particularly preferable.

  Further, as imine-containing hydrocarbyloxysilane compounds, 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 their triethoxysilyl Trimethoxysilyl compounds, methyldiethoxysilyl compounds, ethyldiethoxysilyl compounds, methyldimethoxysilyl compounds, Examples thereof include N- (1-methylpropylidene) -3- (triethoxysilyl) -1-propanamine and N- (1,3-dimethylbutylidene). -3- (Triethoxysilyl) -1-propanamine is particularly preferred.

  The amidine partial structure-containing compound includes 1- [3- (triethoxysilyl) propyl] -4,5-dihydroimidazole and 1- [3- (trimethoxysilyl) propyl] -4,5-dihydroimidazole. N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole, N- (3-isopropoxysilylpropyl) -4,5-dihydroimidazole, N- (3-methyldiethoxysilylpropyl) -4 , 5-dihydroimidazole and the like. Among these, N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole is preferable.

  Furthermore, the following can be mentioned as another hydrocarbyl oxysilane compound. That is, examples of the carboxylic acid ester group-containing compound include 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, and 3-methacryloyloxypropyltriisosilane. Examples thereof include propoxysilane, and among these, 3-methacryloyloxypropyltrimethoxysilane is preferable.

  Examples of the isocyanate group-containing compound include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, and 3-isocyanatopropyltriisopropoxysilane. Of these, 3-isocyanatopropyltriethoxysilane is preferred.

  Furthermore, examples of the carboxylic acid anhydride-containing compound include 3-triethoxysilylpropyl succinic anhydride, 3-trimethoxysilylpropyl succinic anhydride, 3-methyldiethoxysilylpropyl succinic anhydride, and the like. Among these, 3-triethoxysilylpropyl succinic anhydride is preferable.

  Examples of silazane-containing alkoxysilane compounds include N, N-bis (trimethylsilyl) aminopropylmethyldimethoxysilane, 1-trimethylsilyl-2,2-dimethoxy-1-aza-2-silacyclopentane, N, N- Bis (trimethylsilyl) aminopropyltrimethoxysilane, N, N-bis (trimethylsilyl) aminopropyltriethoxysilane, N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane, N, N-bis (trimethylsilyl) aminoethyltri Methoxysilane, N, N-bis (trimethylsilyl) aminoethyltriethoxysilane, N, N-bis (trimethylsilyl) aminoethylmethyldimethoxysilane and N, N-bis (trimethylsilyl) aminoethylmethyldiethoxysilane N, N-bis (trimethylsilyl) aminopropyltriethoxysilane, N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane or 1-trimethylsilyl-2,2-dimethoxy- 1-aza-2-silacyclopentane.

Hydrocarbyloxysilane compound represented by the following formula (VII):
R ¹⁹ _p —Si— (OR ²⁰ ) _4-p (VII)
Here, R ¹⁹ and R ²⁰ are each independently a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms; An integer of 2; when there are multiple R ^{19 s} , multiple R ^19s may be the same or different; when there are multiple OR ^20s , the multiple OR ^20s may be the same or different; The molecule does not contain active protons and onium salts.

Examples of R ¹⁹ and R ²⁰ 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, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group. , 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. Furthermore, 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.

  Examples of the hydrocarbyloxysilane compound represented by the formula (VII) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, Tetra-sec-butoxysilane, tetra-tert-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, Butyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxy Silane, divinyl dimethoxysilane, divinyl diethoxy silane and the like, and among them, tetraethoxysilane is particularly preferred.

  The hydrocarbyloxysilane compounds represented by the above formulas (VI) and (VII) may be used alone or in combination of two or more. Moreover, the partial condensate of the said hydrocarbyl oxysilane compound can also be used.

  The modification reaction with the modifying agent is preferably carried out by a solution reaction, and the solution may contain a monomer used during polymerization. The reaction mode of the modification reaction is not particularly limited, and may be a batch type or a continuous type. Furthermore, the reaction temperature of the modification reaction is not particularly limited as long as the reaction proceeds, and the reaction temperature of the polymerization reaction may be employed as it is. In addition, the usage-amount of modifier | denaturant has the preferable range of 0.25-3.0 mol with respect to 1 mol (mol) of polymerization initiators used for manufacture of a conjugated diene polymer, 0.5-1.5 mol A range is more preferred.

In the rubber composition of the present invention, the rubber component is the modified conjugated diene polymer alone or contains 10% by mass or more of the modified conjugated diene polymer and another diene rubber.
The rubber component needs to contain the modified conjugated diene polymer in an amount of 10% by mass or more. If it is less than 10% by mass, the effect of improving the dispersibility of the reinforcing filler (A) is small, and the workability of the rubber composition is reduced. This is because the effect of improving the low heat build-up, fracture characteristics and wear resistance is small. In this respect, 20% by mass or more is preferable, and 30% by mass or more is more preferable.
In the rubber composition of the present invention, the diene rubber other than the modified conjugated diene polymer includes natural rubber (NR), unmodified styrene-butadiene copolymer (SBR), and polybutadiene rubber. (BR), polyisoprene rubber (IR), butyl rubber (IIR), ethylene-propylene-diene terpolymer (EPDM) and the like can be used, and among these, natural rubber and polyisoprene rubber are preferable. These rubber components may be used alone or as a blend of two or more.

Examples of the inorganic filler (A) containing silicic acid of the rubber composition of the present invention include silica, clay (Al ₂ O ₃ .2SiO ₂ ), kaolin (Al ₂ O ₃ .2SiO ₂ .2H ₂ O), pyro Fillite _{(Al 2 O 3 · 4SiO 2} · H 2 O), 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 ) Crystalline aluminosilicates containing hydrogen, alkali metals or alkaline earth metals that correct the charge, such as various zeolites.
Of these, silica is preferred. As silica, wet silica and dry silica are preferable, and wet silica is more preferable.

  An inorganic filler (A) needs to mix | blend 10-130 mass parts with respect to 100 mass parts of rubber components. If the amount is less than 10 parts by mass, the fracture characteristics and wear resistance of the rubber composition will be reduced. On the other hand, when it exceeds 130 parts by mass, the loss tangent of the rubber composition increases, and the rolling resistance of the tire increases. From these viewpoints, the content is preferably 15 to 120 parts by mass, and more preferably 20 to 110 parts by mass.

In the rubber composition of this invention, it is required to mix | blend 1-20 mass% of silane coupling agents (B) with respect to the inorganic filler (A) containing a silicic acid. As the silane coupling agent (B), any conventionally known silane coupling agent can be used, and in particular, the general formula (IX)
^{_{B 1 e B 2 3-e}} Si-X-S f -X-SiB 1 e B 2 3-e ··· (IX)
[ _Wherein B ¹ is C _c H _{2c + 1} O (c is an integer of 1 to 3) or a chlorine atom, B ² is an alkyl group having 1 to 3 carbon atoms, and X is a saturated or unsaturated group having 1 to 9 carbon atoms. A saturated alkylene group or an arylene group having 7 to 15 carbon atoms, e is an integer of 1 to 3, and f is an integer of 1 or more and may have a distribution. However, when e is 1, two B ² may be the same or different, and when e is 2 or 3, two or three B ¹ may be the same or different. . A compound represented by the general formula (X)
B ¹ _e B ² _3-e Si-XY (X)
[Wherein B ¹ , B ² , X, e are the same as described above, Y is a mercapto group, vinyl group, amino group, glycidoxy group or epoxy group], and general formula (XI)
B ¹ _e B ² _3-e Si—X—S _f —Z (XI)
[Wherein B ¹ , B ² , X, e and f are the same as above, Z is a benzothiazolyl group, N, N-dimethylthiocarbamoyl group or methacryloyl group, a saturated or unsaturated hydrocarbon having 1 to 15 carbon atoms. It is preferable to use at least one selected from the compounds represented by [Group].

Examples of the silane coupling agent represented by the general formula (IX) include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, and bis (3-methyldimethoxysilyl). Propyl) tetrasulfide, bis (3-triethoxysilylethyl) 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 Examples of silane coupling agents represented by general formula (X) such as 3-triethoxysilylethyl) trisulfide include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and vinyltriethoxysilane. , Vinyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane Examples of the silane coupling agent represented by the general formula (XI) include 3-trimethoxysilylpropyl-N, N-dimethylcarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide, 3- Trimethoxy silyl propyl methacryloyl mono sulfide, 3-triethoxysilylpropyl n- octyl disulfide, and the like, respectively.
In addition, 3-octanoylthiopropyltriethoxysilane (manufactured by General Electric Silicones, trademark: NXT silane) is also preferably used as a commercially available silane coupling agent.

  In this invention, a silane coupling agent (B) may be used independently and may be used in combination of 2 or more type. Moreover, content of a silane coupling agent (B) is chosen in the range of 1-20 mass% with respect to the inorganic filler (A) containing a silicic acid. If the content is less than 1% by mass, the effect of blending the silane coupling agent may not be sufficiently exhibited. On the other hand, if the content exceeds 20% by mass, the improvement of the effect is not seen for the amount, but rather the economy. Disadvantageous. Considering the blending effect and economy, the preferable content of this silane coupling agent (B) is in the range of 3 to 15% by mass.

  In the rubber composition of the present invention, in addition to the inorganic filler (A) containing silicic acid, other fillers such as carbon black, vulcanizing agents, vulcanization accelerators, zinc oxide, stearic acid, aging A compounding agent usually used in the rubber industry such as an inhibitor can be appropriately selected and blended within a range not impairing the object of the present invention. As these compounding agents, commercially available products can be suitably used. Moreover, the said rubber composition mix | blends the inorganic filler (A) containing the said silicic acid with the rubber component, and various compounding agents selected suitably, and uses a Banbury mixer, a roll, an intensive mixer, etc. After kneading, it can be produced by heating, extruding or the like.

  The tire of the present invention is characterized in that the rubber composition is applied to any of tire members. Here, in the tire of the present invention, it is particularly preferable to use the rubber composition of the present invention for the tread, and the tire using the rubber composition for the tread does not deteriorate the driving stability on the dry road surface. Low rolling resistance and excellent fuel efficiency. In addition, as gas with which the tire of the present invention is filled, normal or air with a changed oxygen partial pressure, or an inert gas such as nitrogen is exemplified. When the rubber composition of the present invention is used for a tread, for example, it is extruded on a tread member, and is pasted and molded by a usual method on a tire molding machine to form a raw tire. The green tire is heated and pressed in a vulcanizer to obtain a tire.

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.
In addition, the loss tangent (tan δ) and storage elastic modulus (G ′) of the rubber composition after vulcanization, the rolling resistance of the tire and the handling stability on the dry road surface, the micro of the unmodified and modified conjugated diene polymer, The structure, the amount of bound styrene, and the glass transition point (Tg) were evaluated by the following methods.

(1) Loss tangent (tan δ) and storage modulus (G ′)
Using a viscoelasticity measuring device (manufactured by Rheometrics), tan δ (60 ° C.) and storage elastic modulus (G ′) (60 ° C.) were measured at a temperature of 60 ° C., a strain of 5%, and a frequency of 15 Hz.
Tan δ (60 ° C.) was expressed as an index according to the following equation. The smaller the index value, the smaller the tan δ, the lower the rolling resistance, and the better the fuel efficiency.
Loss tangent index = (loss tangent of target rubber composition to be compared / loss tangent of rubber composition of Comparative Example 1, 2, 3 or 5) × 100
The storage elastic modulus (G ′) (60 ° C.) was expressed as an index according to the following formula. The larger the index value, the higher the storage elastic modulus and the better the steering stability on the dry road surface.
Storage elastic modulus (G ′) index = {Storage elastic modulus (G ′) of target rubber composition to be compared / Storage elastic modulus (G ′) of rubber composition of Comparative Example 1, 2, 3 or 5} × 100

(2) Tire rolling resistance After filling a pneumatic tire of tire size 185 / 70R14 with an internal pressure of 170 kPa, running on a large test drum at a speed of 80 km / h for a predetermined time while applying a load of 395 kg, The driving force of the drum was cut off, and each tire was allowed to travel inertially. The rolling resistance was obtained from the deceleration of the tire at this time, and the index of Comparative Example 1, 2, 3, or 5 was set to 100 and indicated by the following formula. . The larger the index, the lower the rolling resistance.
Test tire index = (rolling resistance of tire of Comparative Example 1, 2, 3 or 5 / rolling resistance of test tire to be compared) × 100

(3) Steering stability on dry road surface of tire Dry circuit course on tire size: 185 / 70R14, internal pressure: 180 kPa, load: driving performance when traveling in various driving modes under conditions equivalent to two passengers The braking performance, steering wheel response, and controllability during steering were comprehensively evaluated by the protest driver using the tires of Comparative Examples 1, 2, 3 or 5 as control tires based on the following evaluation criteria.
+1: When a protest driver feels better than a control tire.
+2: When a protest driver feels better than a control tire.
+3: When a driver feels better than a control tire so that a skilled driver can understand.
+4: When a driver feels better than a control tire.
-1: When the protest driver feels that it is so subtle as compared to the control tire.
-2: When the protest driver feels that it is worse than the control tire.
-3: When the driver feels that it is bad enough to be understood by a skilled driver among general drivers compared to the control tire.
-4: When it feels worse than a control tire to the extent that a general driver can understand.

(4) Microstructure and bound styrene content The microstructure of each conjugated diene polymer is determined by the infrared method (Morero method), and the bound styrene content of each conjugated diene polymer is determined from the integration ratio of the ¹ H-NMR spectrum. It was.
(5) Glass transition point Using a differential thermal analyzer (DSC) 7 type apparatus manufactured by PerkinElmer, Inc., each conjugated diene polymer was cooled to -100 ° C and then heated at a rate of 10 ° C / min. Then, the glass transition point of each polymer was measured.

Production Example 1 (Production of Polymer A)
In an 800 mL pressure-resistant glass container that has been dried and purged with nitrogen, 300 g of cyclohexane, 40 g of 1,3-butadiene, 10 g of styrene, and 2 mmol of tetrahydrofuran are added, and lithium piperidylamide [(piperidine / lithium) = 0.9 (molar ratio) Prepared in situ] After adding 0.4 mmol, a polymerization reaction was carried out at 50 ° C. for 1.5 hours. The polymerization conversion rate at this time was almost 100%. Thereafter, 0.5 mL of an isopropanol solution (BHT concentration: 5% by mass) of 2,6-di-t-butyl-p-cresol (BHT) was added to the polymerization reaction system to stop the polymerization reaction, and further according to a conventional method. The polymer A was obtained by drying.
When the obtained polymer A was analyzed by the above method, the amount of bound styrene (aromatic vinyl compound amount) was 20% by mass, the vinyl bond amount of the butadiene portion (conjugated diene compound portion) was 58% by mass, and glass The transition point (Tg) was -38 ° C.

Production Example 2 (Production of Polymer B)
In a dry, nitrogen-substituted 800 mL pressure-resistant glass container, add 300 g of cyclohexane, 40 g of 1,3-butadiene, 10 g of styrene, 0.2 mmol of ditetrahydrofurylpropane, and further add 0.4 mmol of n-butyllithium (n-BuLi). After the addition, a polymerization reaction was carried out at 50 ° C. for 1.5 hours. The polymerization conversion rate at this time was almost 100%. Next, 0.43 mmol of 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine (manufactured by Shin-Etsu Chemical Co., Ltd.) is quickly added as a modifier to the polymerization reaction system, and further at 50 ° C. Denaturation reaction was performed for 30 minutes. Thereafter, 0.5 mL of an isopropanol solution (BHT concentration: 5% by mass) of 2,6-di-t-butyl-p-cresol (BHT) was added to the polymerization reaction system to stop the polymerization reaction, and further according to a conventional method. Polymer B was obtained.
When the obtained polymer B was analyzed by the above method, the amount of bound styrene (aromatic vinyl compound) was 20% by mass, the amount of vinyl bond in the butadiene part (conjugated diene compound part) was 59% by mass, and glass The transition point (Tg) was -35 ° C.

Production Example 3 (Production of Polymer C)
A polymer C was obtained in the same manner as in Production Example 2 except that N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole (manufactured by Gelest) was used as the modifier.
When the obtained polymer C was analyzed by the above method, the amount of bonded styrene (aromatic vinyl compound) was 20% by mass, the amount of vinyl bond in the butadiene portion (conjugated diene compound portion) was 58%, and the glass transition The point (Tg) was -38 ° C.

Example 1 and Comparative Example 1
Two types of rubber compositions were prepared by kneading with a Banbury mixer with the formulation shown in Table 1. A vulcanized rubber sample was prepared from these two rubber compositions under the conditions of a vulcanization temperature of 165 ° C. and a vulcanization time of 15 minutes, and the loss tangent (tan δ) and storage elastic modulus (G ′) of the vulcanized rubber composition were determined. It was measured. The results are shown in Table 1.
Next, two types of pneumatic tires of tire size 185 / 70R14 using these two types of rubber compositions as a tread having a single-layer structure were prepared, and rolling resistance and steering stability on a dry road surface were evaluated according to the evaluation methods described above. Sex was measured. The results are shown in Table 1.

＊１： ＪＳＲ（株）製、ＢＲ０１
＊２： アロマティックオイル、富士興産（株）製、商標「アロマックス＃３」
＊３： 東ソー・シリカ（株）製、商標「ニプシルＡＱ」
＊４： 三菱化学（株）製、商標「ダイアブラック Ｎ３３９」
＊５： ビス(３-トリエトキシシリルプロピル)テトラスルフィド、デグサ社製シランカップリング剤、商標「Ｓｉ６９」
＊６： ＰＯＥ（１０）は、オキシエチレンが１０モル付加したポリオキシエチレンを示す。
＊７：Ｎ−(１,３-ジメチルブチル)−Ｎ’−フェニル−ｐ−フェニレンジアミン、精工化学（株）製、商標「オゾノン６Ｃ」
＊８： Ｎ−ｔ−ブチル−２−ベンゾチアゾリルスルフェンアミド、大内新興化学工業（株）製、商標「ノクセラーＮＳ・Ｆ」
＊９： Ｎ−シクロヘキシル−２−ベンゾチアゾリルスルフェンアミド、大内新興化学工業（株）製、商標「ノクセラーＣＺ」

* 1: BR01 manufactured by JSR Corporation
* 2: Aromatic oil, manufactured by Fuji Kosan Co., Ltd., trademark “Aromax # 3”
* 3: Trademark “Nipsil AQ” manufactured by Tosoh Silica Co., Ltd.
* 4: Trademark “Dia Black N339” manufactured by Mitsubishi Chemical Corporation
* 5: Bis (3-triethoxysilylpropyl) tetrasulfide, Degussa silane coupling agent, trademark “Si69”
* 6: POE (10) represents polyoxyethylene added with 10 mol of oxyethylene.
* 7: N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine, manufactured by Seiko Chemical Co., Ltd., trademark “Ozonon 6C”
* 8: Nt-butyl-2-benzothiazolylsulfenamide, manufactured by Ouchi Shinsei Chemical Co., Ltd., trademark “Noxeller NS • F”
* 9: N-cyclohexyl-2-benzothiazolylsulfenamide, manufactured by Ouchi Shinsei Chemical Co., Ltd., trademark “Noxeller CZ”

Example 2 and Comparative Example 2
Two kinds of rubber compositions were prepared by kneading with a Banbury mixer with the formulation shown in Table 2. A vulcanized rubber sample was prepared from these two rubber compositions under the conditions of a vulcanization temperature of 165 ° C. and a vulcanization time of 15 minutes, and the loss tangent (tan δ) and storage elastic modulus (G ′) of the vulcanized rubber composition were determined. It was measured. The results are shown in Table 2.
Next, two types of pneumatic tires of tire size 185 / 70R14 using these two types of rubber compositions as a tread having a single-layer structure were prepared, and rolling resistance and steering stability on a dry road surface were evaluated according to the evaluation methods described above. Sex was measured. The results are shown in Table 2.

＊１： ＪＳＲ（株）製、ＩＲ２２００
＊２： 東ソー・シリカ（株）製、 商標「ニプシルＡＱ」
＊３： 三菱化学（株）製、 商標「ダイアブラック Ｎ３３９」
＊４： ビス(３-トリエトキシシリルプロピル)テトラスルフィド、デグサ社製シランカップリング剤、 商標「Ｓｉ６９」
＊５： 一般式（III）で表される化合物において、Ｒ⁸が式−（Ｒ¹¹Ｏ−ＣＯ−Ｒ¹²−ＣＯＯ−）_t−Ｒ¹¹Ｏ−で示される基であって、Ｒ¹¹が式−（Ｒ¹³Ｏ）_u−Ｒ¹³−で示される基、Ｒ¹³がエチレン基、ｕが３．５、Ｒ¹²が−ＣＨ＝ＣＨ−、ｔが４の化合物である。
＊６： Ｎ−(１,３-ジメチルブチル)−Ｎ’−フェニル−ｐ−フェニレンジアミン、精工化学（株）製、商標「オゾノン６Ｃ」
＊７： ジフェニルグアニジン、大内新興化学工業（株）製、商標「ノクセラーＤ」
＊８： メルカプトベンゾチアジルジスルフィド、大内新興化学工業（株）製、商標「ノクセラーＤＭ」
＊９： Ｎ−ｔ−ブチル−２−ベンゾチアゾリルスルフェンアミド、大内新興化学工業（株）製、商標「ノクセラーＮＳ」

* 1: IR2200, manufactured by JSR Corporation
* 2: Trademark “Nipsil AQ”, manufactured by Tosoh Silica Corporation
* 3: Trademark “Dia Black N339” manufactured by Mitsubishi Chemical Corporation
* 4: Bis (3-triethoxysilylpropyl) tetrasulfide, a silane coupling agent manufactured by Degussa, trademark “Si69”
* 5: In the compound represented by the general formula (III), R ⁸ is a group represented by the formula — (R ¹¹ O—CO—R ¹² —COO—) _t —R ¹¹ O—, and R ¹¹ is A group represented by the formula — (R ¹³ O) _u —R ¹³ —, R ¹³ is an ethylene group, u is 3.5, R ¹² is —CH═CH—, and t is 4.
* 6: N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine, manufactured by Seiko Chemical Co., Ltd., trademark “Ozonon 6C”
* 7: Diphenylguanidine, manufactured by Ouchi Shinsei Chemical Co., Ltd., trademark “Noxeller D”
* 8: Mercaptobenzothiazyl disulfide, manufactured by Ouchi Shinsei Chemical Co., Ltd., trademark “Noxeller DM”
* 9: Nt-Butyl-2-benzothiazolylsulfenamide, manufactured by Ouchi Shinsei Chemical Co., Ltd., trademark “Noxeller NS”

Example 3 and Comparative Examples 3-4
Three types of rubber compositions were prepared by kneading with a Banbury mixer with the formulation shown in Table 3. Vulcanized rubber samples were prepared from these three rubber compositions under the conditions of a vulcanization temperature of 165 ° C. and a vulcanization time of 15 minutes, and the loss tangent (tan δ) and storage elastic modulus (G ′) of the vulcanized rubber composition were determined. It was measured. The results are shown in Table 3.
Next, two types of pneumatic tires of tire size 185 / 70R14 using each of these three types of rubber compositions as a tread having a single-layer structure were prepared, and rolling resistance and steering stability on a dry road surface were evaluated according to the evaluation methods described above. Sex was measured. The results are shown in Table 3.

＊１： 東ソー・シリカ（株）製、商標「ニプシルＡＱ」
＊２： 三菱化学（株）製、商標「ダイアブラック Ｎ３３９」
＊３： ビス(３-トリエトキシシリルプロピル)テトラスルフィド、デグサ社製シランカップリング剤、 商標「Ｓｉ６９」
＊４：一般式（III）で表される化合物において、Ｒ⁸は式−（Ｒ¹¹Ｏ−ＣＯ−Ｒ¹²−ＣＯＯ−）_t−Ｒ¹¹Ｏ−で示される基であって、Ｒ¹¹がブチレン基、Ｒ¹²が−ＣＨ＝ＣＨ−、ｔが４の化合物である。
＊５： アロマティックオイル、富士興産（株）製、商標「アロマックス＃３」
＊６：Ｎ−(１,３-ジメチルブチル)−Ｎ’−フェニル−ｐ−フェニレンジアミン、精工化学（株）製、商標「オゾノン６Ｃ」
＊７： ジフェニルグアニジン、大内新興化学工業（株）製、商標：ノクセラーＤ
＊８： メルカプトベンゾチアジルジスルフィド、大内新興化学工業（株）製、商標：ノクセラーＤＭ
＊９： Ｎ−ｔ−ブチル−２−ベンゾチアゾリルスルフェンアミド、大内新興化学工業（株）製、商標「ノクセラーＮＳ・Ｆ」

* 1: Trademark “Nipsil AQ” manufactured by Tosoh Silica Co., Ltd.
* 2: Trademark “Dia Black N339” manufactured by Mitsubishi Chemical Corporation
* 3: Bis (3-triethoxysilylpropyl) tetrasulfide, silane coupling agent manufactured by Degussa, trademark “Si69”
* 4: In formula (III) compound represented by, R ⁸ has the formula - a ^{(R 11 O-CO-R} 12 -COO-) t -R 11 O- a group represented, R ¹¹ is A butylene group, R ¹² is —CH═CH—, and t is 4.
* 5: Aromatic oil, manufactured by Fuji Kosan Co., Ltd., trademark “Aromax # 3”
* 6: N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine, manufactured by Seiko Chemical Co., Ltd., trademark “Ozonon 6C”
* 7: Diphenylguanidine, manufactured by Ouchi Shinsei Chemical Co., Ltd., Trademark: Noxeller D
* 8: Mercaptobenzothiazyl disulfide, manufactured by Ouchi Shinsei Chemical Co., Ltd., Trademark: Noxeller DM
* 9: Nt-butyl-2-benzothiazolylsulfenamide, manufactured by Ouchi Shinsei Chemical Co., Ltd., trademark “Noxeller NS • F”

Examples 4 to 5 and Comparative Example 5
Three types of rubber compositions were prepared by kneading with a Banbury mixer with the formulation shown in Table 4. Vulcanized rubber samples were prepared from these three rubber compositions under the conditions of a vulcanization temperature of 165 ° C. and a vulcanization time of 15 minutes, and the loss tangent (tan δ) and storage elastic modulus (G ′) of the vulcanized rubber composition were determined. It was measured. The results are shown in Table 4.
Next, two types of pneumatic tires of tire size 185 / 70R14 using these two types of rubber compositions as a tread having a single-layer structure were prepared, and rolling resistance and steering stability on a dry road surface were evaluated according to the evaluation methods described above. Sex was measured. The results are shown in Table 4.

＊１： ランクセス（株）製 溶液重合ＳＢＲ、商標「Ｂｕｎａ ＶＳＬ ５０２５−１」
＊２： 東ソー・シリカ（株）製、 商標「ニプシルＫＱ」
＊３〜＊９は、表２と同じである。

* 1: Solution polymerization SBR manufactured by LANXESS, Inc., trademark “Buna VSL 5025-1”
* 2: Trademark “Nipsil KQ” manufactured by Tosoh Silica Co., Ltd.
* 3 to * 9 are the same as in Table 2.

As is clear from Tables 1 to 4, the rubber composition of Example 1 had the same loss tangent and higher storage elastic modulus than the rubber composition of Comparative Example 1. And the rubber composition of Example 2 had a low loss tangent and a high storage elastic modulus compared with the rubber composition of Comparative Example 2. Further, the rubber composition of Example 3 had the same loss tangent and significantly higher storage elastic modulus than the rubber composition of Comparative Example 3. And compared with the rubber composition of Comparative Example 4, the loss tangent was low. Furthermore, the rubber compositions of Examples 4 and 5 had a lower loss tangent and a higher storage elastic modulus than the rubber composition of Comparative Example 5.
Further, the pneumatic tire of Example 1 is compared with the pneumatic tire of Comparative Example 1, the pneumatic tire of Example 2 is further compared with the pneumatic tire of Comparative Example 2, and the pneumatic tire of Example 3 is further compared. Compared with the pneumatic tire of Comparative Example 3, the pneumatic tires of Examples 4 and 5 have a rolling resistance equal to or higher than that of the pneumatic tire of Comparative Example 5 and dry. The handling stability on the road has been greatly improved.
On the other hand, the pneumatic tire of Example 3 had better rolling resistance than the pneumatic tire of Comparative Example 4.

  The rubber composition of the present invention is used for various pneumatic tires for passenger cars, small trucks, light passenger cars, light trucks and large vehicles (for trucks, buses, construction vehicles, etc.), particularly pneumatic radial tires. It is suitably used as a tread member or a side wall member.

Claims (20)

10 to 130 parts by mass of an inorganic filler (A) containing silicic acid with respect to 100 parts by mass of a rubber component containing 10% by mass or more of a modified conjugated diene polymer having at least one functional group, silane coupling 1 to 20% by mass of the agent (B) with respect to the inorganic filler (A) and at least one compound selected from the group consisting of compounds represented by the following general formulas (I) to (III) ( A rubber composition comprising 0.5 to 10 parts by mass of C).

[Wherein, A ¹ , A ² and A ³ are groups in which one of them is represented by the formula — (R ¹ O) _n —CO—CR ² ═CR ³ —R ⁴ , where R ¹ is An alkylene group having 2 to 4 carbon atoms, R ² , R ³ and R ⁴ are each independently a hydrogen atom or a methyl group, n is a number from 1 to 30 indicating the average number of moles added of the oxyalkylene group), It is a hydrogen atom. ]

[Wherein R ⁵ , R ⁶ and R ⁷ are each independently an alkylene group having 2 to 4 carbon atoms, m1, m2 and m3 are numbers indicating the average number of added moles of the oxyalkylene group, and m1 + m2 + m3 is 0. It is a number that is ~ 90]

[Wherein R ⁸ represents a group represented by the formula —R ⁹ O—, a group represented by the formula — (R ¹⁰ O) _S —, a group represented by the formula —CH ₂ CH (OH) CH ₂ O—, or It is a group represented by the formula — (R ¹¹ O—CO—R ¹² —COO—) _t —R ¹¹ O—. R ⁹ represents an alkylene group having 2 to 36 carbon atoms, an alkenylene group or a divalent aromatic hydrocarbon group, R ¹⁰ represents an alkylene group having 2 to 4 carbon atoms, and s represents an average number of moles added of the oxyalkylene group. Number of 60, R ¹¹ is an alkylene group having 2 to 18 carbon atoms, alkenylene group, divalent aromatic hydrocarbon group or — (R ¹³ O) _u R ¹³ — (R ¹³ is an alkylene group having 2 to 4 carbon atoms) , U represents an average number of added moles of the oxyalkylene group of 1 to 30), R ¹² represents an alkylene group having 2 to 18 carbon atoms, an alkenylene group or a divalent aromatic hydrocarbon group, and t represents an average value of 1 A number of ~ 30. ]   The rubber composition according to claim 1, wherein the inorganic filler (A) containing silicic acid is silica.   The rubber composition according to claim 1 or 2, wherein the modified conjugated diene polymer is a copolymer of 1,3-butadiene and an aromatic vinyl compound, or a homopolymer of 1,3-butadiene or isoprene. .   The rubber composition according to claim 3, wherein the aromatic vinyl compound is styrene.   The rubber composition according to claim 1, wherein the modified conjugated diene polymer has a glass transition point (Tg) of 10 ° C. or less.   The functional group of the modified conjugated diene polymer is in the terminal and / or main chain or side chain on the polymerization initiation side or polymerization termination side of the modified conjugated diene polymer. The rubber composition as described.   The rubber composition according to any one of claims 1 to 6, wherein the modified conjugated diene polymer is polymerized using an organic alkali metal compound or a rare earth metal compound.   The rubber composition according to claim 7, wherein the organic alkali metal compound is a hydrocarbyl lithium compound, a lithium amide compound, or a Group 1 metal alkoxide.   The rubber composition according to claim 8, wherein the Group 1 metal is lithium, sodium, potassium, rubidium, or cesium.   The functional group of the modified conjugated diene polymer is a functional group selected from the group consisting of a functional group containing nitrogen, a functional group containing silicon, a functional group containing oxygen or sulfur, and a functional group containing a metal. The rubber composition in any one of 1-9.   The functional group containing nitrogen is a functional group selected from the group consisting of a substituted or unsubstituted amino group, an amide residue, an isocyanate group, an imidazolyl group, an indolyl group, a nitrile group, a pyridyl group, and a ketimine group. 10. The rubber composition according to 10.   The rubber composition according to claim 10, wherein the silicon-containing functional group is a functional group that generates a silanol group by hydrolysis.   The rubber composition according to claim 10, wherein the silicon-containing functional group is a functional group selected from the group consisting of an alkoxysilyl group, an alkylhalosilyl group, a siloxy group, an alkylaminosilyl group, and an alkoxyhalosilyl group.   The functional group containing oxygen or sulfur is a hydroxyl group, carboxyl group, epoxy group, glycidoxy group, diglycidylamino group, cyclic dithiane-derived functional group, ester group, aldehyde group, alkoxy group, ketone group, thiocarboxyl group The rubber composition according to claim 10, which is a functional group selected from the group consisting of thioepoxy group, thioglycidoxy group, thiodiglycidylamino group, thioester group, thioaldehyde group, thioalkoxy group, and thioketone group.   The rubber composition according to claim 10, wherein the functional group containing a metal is a functional group containing an organic metal. The functional group containing nitrogen has the following formula (IV):

[In the formula, each R ¹⁴ independently represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms] And the following formula (V):

[Wherein R ¹⁵ represents an alkylene group having 3 to 16 methylene groups, a substituted alkylene group, an oxyalkylene group or an N-alkylamino-alkylene group], and is selected from the group consisting of cyclic amino groups The rubber composition according to claim 10. The modified conjugated diene polymer has the following formula (VI) at the active end of the conjugated diene polymer having an active end:

[In the formula, A ⁴ represents (thio) epoxy group, (thio) isocyanate group, (thio) ketone group, (thio) aldehyde group, imine residue, amide residue, isocyanuric acid triester residue, (thio) carboxyl Acid hydrocarbyl ester residue, metal salt of (thio) carboxylic acid residue, carboxylic anhydride residue, carboxylic acid halide residue, carbonic acid dihydrocarbyl ester residue, cyclic secondary amine residue, acyclic secondary amine A monovalent group or disulfide group having at least one functional group selected from a residue, a pyridine group, and a silazane group; R ¹⁶ and R ¹⁷ are each independently a monovalent fatty acid having 1 to 20 carbon atoms; An aromatic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms; R ¹⁸ is a single bond or a divalent inert hydrocarbon group having 1 to 20 carbon atoms; It is an integer; OR ¹⁶ is double In some cases, a plurality of OR ¹⁶ may be the same as or different from each other; if R ¹⁷ is more or different and a plurality of R ¹⁷ is identical to each other; in addition the molecule active proton and an onium salt Is not included] and a hydrocarbyloxysilane compound represented by the following formula (VII):
R ¹⁹ _p —Si— (OR ²⁰ ) _4-p (VII)
[Wherein, R ¹⁹ and R ²⁰ each independently represents a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms; be ~ 2 integer; if R ¹⁹ is plural, R ¹⁹ may be the same as or different from each other; when the OR ²⁰ there are a plurality, the plurality of OR ²⁰ may be the same as or different from each other And wherein the molecule is free of active protons and onium salts], and obtained by reacting at least one selected from the group consisting of hydrocarbyloxysilane compounds represented by The rubber composition as described.   The rubber composition according to any one of claims 1 to 17, wherein the rubber component contains the modified conjugated diene polymer and another diene rubber.   A tire using a member containing the rubber composition according to claim 1.   The tire according to claim 19, wherein the member is a tread.