JP2008308517A - Rubber composition and tire - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a rubber composition having more improved low heat build-up, and capable of sufficiently maintaining the operability, and to provide a tire using the rubber composition. <P>SOLUTION: The rubber composition is obtained by compounding 10-130 pts.mass of hydrous silicic acid having 50-250 m<SP>2</SP>/g surface area measured by the adsorption of cetyltrimethylammonium bromide (CTAB), and satisfying the relation of the inequality (1): Y<5.00+0.47×X (wherein, Y is a percentage of a reduced mass when heated at 750°C for 3 hr; and X is a percentage of a reduced mass when heated at 105°C for 2 hr) with 100 pts.mass of a rubber component containing ≥10 mass% of a modified conjugated diene-based polymer having at least one or more kinds of functional groups, and further compounding 10-20 pts.mass of a silane coupling agent based on 100 pts.mass of the hydrous silicic acid. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a rubber composition and a tire using the rubber composition. More specifically, the present invention relates to a rubber composition excellent in low heat buildup while maintaining workability sufficiently, and a tire using the rubber composition.

  In recent years, there has been a growing interest in social demands for energy conservation and environmental issues. For this reason, there is a demand for lower fuel consumption of automobiles in connection with the movement of global carbon dioxide emission regulations. In order to meet such demands, reduction of rolling resistance is also demanded for tire performance. There are two methods for reducing the rolling resistance of the tire: a method by optimizing the tire structure, and a method using a rubber composition having low heat generation of the tire.

For example, as a method for obtaining a rubber composition having low exothermicity, a method using a specific silica as a filler to be used is known (see, for example, Patent Document 1). In addition, carbon black is used as a filler and the polymerization active terminal is modified with a tin compound (see, for example, Patent Document 2). Similarly, carbon black is used to introduce an amino group at the polymerization active terminal ( For example, see Patent Document 3).
However, it cannot be said that the dispersion of silica is sufficient with a simple silica dispersant alone, and further reduction in heat generation cannot be expected. In addition, a modified conjugated diene polymer introduced with a polymerization active terminal tends to cause an increase in ML _{1 + 4} , resulting in poor workability. It is a new problem.
JP 2001-131344 A Japanese Patent Publication No. 5-87530 JP 62-207342 A

  In view of the above problems, the present invention is to provide a rubber composition that can further improve low heat build-up and maintain sufficient workability, and a tire using the rubber composition.

The present inventors can disperse the rubber composition by blending a modified conjugated diene polymer having a specific functional group, hydrous silicic acid having an adsorption surface area within a specific range, and a silane coupling agent. The improved conjugated diene polymer and the filler are combined to improve the low heat buildup of the rubber composition, and the workability is sufficiently maintained, leading to the present invention. It is a thing.
That is, the present invention is characterized by the following configuration.

The adsorption surface area of cetyltrimethylammonium bromide (CTAB) is in the range of 50 to 250 m ² / g with respect to 100 parts by mass of the rubber component containing 10% by mass or more of the modified conjugated diene polymer having at least one kind of functional group. Yes, and Formula (1): Y <5.00 + 0.47 × X (Y in the formula is mass% decreased when heated at a temperature of 750 ° C. for 3 hours, and X is heated at a temperature of 105 ° C. for 2 hours) 10 to 130 parts by mass of hydrous silicic acid satisfying the relationship of) and 10 to 20 parts by mass of a silane coupling agent with respect to 100 parts by mass of the hydrous silicic acid. It is the rubber composition which becomes.

The modified conjugated diene polymer is preferably a copolymer of 1,3-butadiene and an aromatic vinyl compound, or a homopolymer of 1,3-butadiene.
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. .
The glass transition point (Tg) of the modified conjugated diene polymer is preferably 0 ° C. or lower.

The functional group of the modified conjugated diene polymer according to the present invention may be in the terminal and / or main chain or side chain of the polymerization initiator or the polymerization stopper of the modified conjugated diene polymer.
Further, 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. It is preferable.

  In the present invention, it is preferable to provide a tire using a member made of the rubber composition, particularly a tire in which the member is a tread member.

The rubber composition of the present invention maintains the M _{1 + 4} of the composition by blending the modified conjugated diene polymer and a filler that is a specific hydrosilicic acid, that is, maintains workability, and The low exothermic property (loss tangent: tan δ) of the composition becomes more excellent. And the tire which uses it can exhibit low rolling resistance further.

Embodiments of the present invention will be described below.
The rubber composition of the present invention contains 10% by mass or more of a modified conjugated diene polymer, and the adsorption surface area of cetyltrimethylammonium bromide (CTAB) is 50 to 250 m ^{2 with} respect to 100 parts by mass of the modified conjugated diene polymer. / G, and Formula (1): Y <5.00 + 0.47 × X (Y in the formula is a mass% decreased when heated at a temperature of 750 ° C. for 3 hours, and X is a temperature of 105 ° C.) 10 to 130 parts by mass of hydrous silicic acid satisfying the relationship of 2) and 10 to 20 parts by mass of silane coupling agent with respect to 100 parts by mass of hydrous silicic acid. Part.

<Modified conjugated diene polymer>
The modified conjugated diene polymer of the present invention has at least one functional group.
Further, 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. It is preferable.
The modified conjugated diene polymer can have its functional group at the terminal or main chain. In particular, in the case of a terminal functional group, the modified conjugated diene polymer can be formed by using a modification initiator or a modification terminator.
The rubber composition containing the modified conjugated diene polymer is improved in low heat build-up, but the deterioration of workability in the rubber composition is suppressed by blending the hydrous silicic acid described later.

The functional group containing nitrogen of the modified conjugated diene polymer according to the present invention includes a substituted or unsubstituted amino group, an amide residue, an isocyanate group, an imidazolyl group, an indolyl group, a nitrile group, a biridyl group, and a ketimine group. Preferably there is. 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 (I) or a cyclic amino group represented by the following formula (II).

ここで、Ｒ^１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、シクロへキシル基、及び３−フェニルプロピル基が好適に挙げられる。

Wherein, ^{R 1} is independently 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. Specifically, a methyl group, an ethyl group, a butyl group, an isobutyl group, an octyl group, a cyclohexyl group, and a 3-phenylpropyl group are preferable.

ここで、Ｒ^２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。
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 ² represents an alkylene group having 3 to 16 methylene groups, a substituted alkylene group, an oxyalkylene group or an N-alkylamino-alkylene group.
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.
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 method for producing a conjugated diene polymer by anionic polymerization using the 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, the conjugated diene compound alone Alternatively, a conjugated diene polymer can be produced by polymerizing a mixture of a conjugated diene compound and an aromatic vinyl 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 in 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 performed 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 an aromatic vinyl compound as a monomer, the content rate of the aromatic vinyl 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 a generated pressure, but it is usually preferred 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. Moreover, it is preferable to use what removed reaction-inhibiting substances, such as water, oxygen, a carbon dioxide, and a protic compound, as raw materials, such as a monomer used for superposition | polymerization, a polymerization initiator, and a solvent.

  On the other hand, when producing a conjugated diene polymer having an active terminal by coordination polymerization, it is preferable to use a rare earth metal compound as the polymerization initiator, and the following (a) component, (b) component, (c) component More preferably, these are used in combination.

  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 the 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 (a) components may be used individually by 1 type, or 2 or more types may be mixed and used for them.

The component (b) used for the coordination polymerization is selected from organoaluminum compounds. Specifically, as the organoaluminum compound, a trihydrocarbyl aluminum compound represented by the formula: R ⁹ ₃ Al, a hydrocarbyl aluminum hydride represented by the formula: R ⁹ ₂ AlH or R ⁹ AlH ₂ (in the formula, R ⁹ is 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, alkylaluminoxane, and the like. 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 together.

  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, complexes of zinc chloride with Lewis bases such as alcohol, magnesium chloride and Lewis such as alcohol. Examples thereof include a complex with a base, benzyl chloride, t-butyl chloride, benzyl bromide, t-butyl bromide, triphenylcarbonium tetrakis (pentafluorophenyl) borate and the like. These (c) components may be used individually by 1 type, or 2 or more types may be mixed and used for them.

  In addition to the components (a), (b), and (c), 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. 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 each said component can be set suitably, Usually, (a) component is 0.001-0.5 mmol per 100g of monomers. The molar ratio (b) component / (a) component is preferably 5 to 1000, and (c) component / (a) component is preferably 0.5 to 10.

  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, substituted and unsubstituted amino groups, amide residues, imidazolyl groups, indolyl groups, nitrile groups, pyridyl groups, ketimine groups and other functional groups containing nitrogen can be conjugated dienes. It can be introduced into the 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 ketone compound is eliminated to regenerate the active primary amine.

Moreover, as a silicon-containing compound that can be used as the modifier, a hydrocarbyloxysilane compound is preferable, and the following formula (III),
Alternatively, at least one hydrocarbyloxysilane compound selected from the group consisting of hydrocarbyloxysilane compounds represented by the formula: R ⁶ _p -Si- (OR ⁷ ) _4-p (IV) is more preferable.

In the formula, A ¹ is (thio) epoxy group, (thio) inocyanate group, (thio) ketone, (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 having at least one functional group selected from a group, a pyridine group, and a silazane group, or a disulfide group; R ³ and R ⁴ are each independently a monovalent group having 1 to 20 carbon atoms. An aliphatic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms; R ⁵ is a single bond or a divalent inert hydrocarbon group having 1 to 20 carbon atoms; Is an integer Ri; If OR ³ there are a plurality or different and a plurality of OR ³ in mutually identical; does not include active proton and onium salt is also in the molecule

Further, among the functional groups in A ^1, imine residue ketimine group, include aldimine residue, an amidine group, (thio) carboxylic acid ester groups, acrylate residues and methacrylates unsaturated carboxylic acid residues such as Includes 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 ³ and R ⁴ 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 ⁵ 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 (III) include, for example, (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 epoxy compounds in these compounds as thioepoxy groups Replacement There may be mentioned a was, among these, 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyl triethoxysilane are particularly preferred.

  Further, as the imine group-containing hydrocarbyloxysilane compound, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N- (1-methylethylidene) -3- (triethoxy Silyl) -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 triethoxy Trimethoxysilyl compounds corresponding to silyl compounds, methyldiethoxysilyl compounds, ethyldiethoxysilyl compounds, Examples thereof include tildimethoxysilyl compounds and ethyldimethoxysilyl compounds. Among these, N- (1-methylpropylidene) -3- (triethoxysilyl) -1-propanamine and N- (1,3 -Dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine is particularly preferred.

  Examples of the amidine partial structure-containing compound include 1- [3- (triethoxysilyl) propyl] -4,5-dihydroimidazole, 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 the silazane-containing alkoxysilane compound 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) aminoethyltrimethoxysilane N, N-bis (trimethylsilyl) aminoethyltriethoxysilane, N, N-bis (trimethylsilyl) aminoethylmethyldimethoxysilane, and N, N-bis (trimethylsilyl) aminoethylmethyldiethoxysilane And the like. Preferably, N, N-bis (trimethylsilyl) aminopropyltriethoxysilane, N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane, or 1-trimethylsilyl-2,2-dimethoxy-1-aza-2-sila Cyclopentane.

In the formula, R ⁶ and R ⁷ 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; It is 2 integer; if R ⁶ and oR ⁷ there are a plurality of each, or different in a plurality of R ⁶ and oR ⁷ on each mutually identical; in addition the molecule does not include active proton and an onium salt .

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

  The said hydrocarbyl oxysilane compound may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, the partial condensate of the said hydrocarbyl oxysilane compound can also be used.

  The modification reaction with the modifying agent is preferably performed 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 of polymerization initiators used for manufacture of a conjugated diene polymer, and the range of 0.5-1.5 mol is still more preferable. .

  The modified diene polymer preferably has a glass transition point (Tg) measured by a differential scanning calorimeter (DSC) of 0 ° C. or lower. If the glass transition point of the modified conjugated diene polymer exceeds 0 ° C., the low exothermic property and low temperature characteristics of the rubber composition tend to deteriorate.

The rubber composition of the present invention contains the above-described modified diene polymer as a rubber component. Here, the content of the modified diene polymer in the rubber component is 10% by mass or more. When the content of the modified conjugated diene polymer in the rubber component (A) is less than 10% by mass, the effect of improving the dispersibility of the filler and the like is small, and the workability of the rubber composition, low heat build-up, fracture characteristics, and Less effective to improve wear resistance. 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 rubber component (A) other than the modified diene polymer includes natural rubber (NR), unmodified styrene-butadiene copolymer (SBR), polybutadiene rubber ( BR), polyisoprene rubber (IR), butyl rubber (IIR), ethylene-propylene copolymer and the like can be used. Among these, natural rubber and polyisoprene rubber are preferable. These rubber components may be used alone or as a blend of two or more.

<Hydrosilicate>
The rubber composition of this invention mix | blends 10-130 mass parts of hydrous silicic acids with respect to 100 mass parts of modified conjugated diene polymers.
Hydrous silicic acid has an adsorption surface area of cetyltrimethylammonium bromide (hereinafter referred to as CTAB) in the range of 50 to 250 m ² / g and satisfies formula (1): Y <5.00 + 0.47 × X. It is characterized by being. Here, Y in the formula is a mass% decreased when heated at a temperature of 750 ° C. for 3 hours, and X is a mass% reduced when heated at a temperature of 105 ° C. for 2 hours.
In the hydrous silicic acid satisfying the mathematical formula (1), the amount of moisture adsorbed on the surface and the number of surface silanol groups are appropriately maintained, and by blending such hydrous silicic acid, the characteristics of the rubber composition are not deteriorated. In addition, the viscosity of the rubber composition when not vulcanized can be reduced, and the workability or processability of the rubber composition can be greatly improved. Therefore, by applying the rubber composition to a tire, particularly a tread of the tire, it is possible to achieve both further improvement of low heat generation and productivity in a factory.

The hydrous silicic acid used for the rubber composition of the present invention has a CTAB adsorption specific surface area of 50 to 250 m ² / g. In particular, it is preferable that it is 80-240 m < ² > / g. When the adsorption specific surface area of CTAB of the hydrous silicic acid used is less than 50 m ² / g, the storage elastic modulus of the rubber composition is lowered and the wear resistance cannot be ensured, and when it exceeds 250 m ² / g, The viscosity of the rubber composition at the time of unvulcanization increases and the processability deteriorates. Moreover, if it exists in the said range, the low exothermic property and destruction resistance of a rubber composition can be improved further.

Further, the hydrous silicic acid requires that the adsorption specific surface area of the CTAB and the heating reduction amounts X and Y ((%)) satisfy the relationship of the formula (1). When the hydrous silicic acid does not satisfy the relationship of the mathematical formula (1), the Mooney viscosity of the rubber composition increases, and the processability of the rubber composition tends to decrease.
In the formula (1), the mass decrease when heated at 105 ° C. for 2 hours is attributed to the desorption of moisture physically adsorbed on the hydrous silicic acid and the disappearance of the silanol groups of the hydrous silicic acid. And the hydrous silicic acid which satisfy | fills the relationship of Numerical formula (1) has few silanol groups, Therefore It is hard to aggregate than normal silica. In addition, hydrous silicic acid satisfying the relationship of formula (1) is optimal for the balance between surface silanol groups and adsorbed moisture to interact with the polar groups of the modified conjugated diene polymer. The dispersibility with respect to coalescence is high, and the low heat build-up and the fracture resistance of the rubber composition can be improved.

The hydrous silicic acid can be produced by adjusting various conditions when producing the hydrous silicic acid by a wet method, and as the hydrous silicic acid, a silicone-treated hydrophobic silica, heat-treated Silica or the like can also be used.
In the rubber composition of the present invention, the amount of the hydrous silicic acid is in the range of 10 to 130 affected areas with respect to 100 parts by mass of the modified conjugated diene polymer. If the amount of hydrous silicic acid is less than 10 parts by mass, the reinforcing property of the rubber composition may be insufficient. On the other hand, if it exceeds 130 parts by mass, the processability of the rubber composition will deteriorate.

<Silane coupling agent>
The silane coupling agent of the present invention is blended in order to improve the dispersibility of the hydrous silicic acid and the affinity with the modified conjugated diene polymer. In the range of. It is particularly preferably 5 to 10 parts by mass. If the blending amount of the silane coupling agent is less than 1 part by mass with respect to the hydrous silicic acid, the blending effect as a coupling agent is not sufficiently exhibited, and even if it is added in excess of 20 parts by mass, there is no difference in effect. .

  Examples of the silane coupling agent include vinyltriethoxysilane, vinyltrichlorosilane, γ-methacryloxypropyltrimethoxysilane, vinyltris (β-methoxy-ethoxy) silane, β- (3,4-epoxycyclohexyl) -ethyltri. Methoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, N- (β-aminoethyl) -γ -Aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, and γ-trimethoxysilyl Propyl di Examples thereof include tetrasulfides such as methylthiocarbamyl tetrasulfide, γ-trimethoxysilylpropylbenzothiazyl tetrasulfide, and bis [3- (triethoxysilyl) propyl] tetrasulfide.

  As the silane coupling agent, those having a chemical structure containing nitrogen and / or sulfur atoms are preferable from the viewpoint of affinity with butyl rubber, and as such a silane coupling agent, a known commercial product may be used. For example, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane Tetrasulfides such as methoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, bis [3- (triethoxysilyl) propyl] tetrasulfide, γ-trimethoxysilylpropylbenzothiazyltetrasulfide, etc. In particular, bis (3-triethoxysilylpropyl) Torasurufido [manufactured by Degussa "Si69"], .gamma.-mercaptopropyltrimethoxysilane [manufactured by Dow Corning Toray Co., Ltd. "SH6062"] can be suitably used. These may be used alone or in combination of two or more.

  The silane coupling agent may be added to the rubber composition by surface treatment of the inorganic filler with the silane coupling agent, and by adding this surface-treated silica, or by adding it during preparation of the rubber composition. Also good.

  In the rubber composition of the present invention, various chemicals usually used in the rubber industry, for example, vulcanizing agents, vulcanization accelerators, process oils, anti-aging agents, as long as the object of the present invention is not impaired. A scorch inhibitor, zinc white, stearic acid and the like can be contained. Examples of the vulcanizing agent include sulfur, and the amount thereof used is preferably 0.1 to 10.0 parts by mass, more preferably 1.0 to 5. 0 parts by mass. If the amount is less than 0.1 parts by mass, the fracture strength, wear resistance, and low heat build-up of the vulcanized rubber may be reduced. If the amount exceeds 10.0 parts by mass, rubber elasticity is lost. The vulcanization accelerator that can be used in the present invention is not particularly limited. For example, M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazyl). Sulfenamide) and other guanidine-based 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. Examples of the process oil that can be used in the rubber composition of the present invention include paraffinic, naphthenic, and aromatic oils. Aromatics are used for applications that emphasize tensile strength and wear resistance, and naphthenic or paraffinic systems are used for applications that emphasize hysteresis loss and low-temperature characteristics. The amount used is preferably 0 to 100 parts by mass with respect to 100 parts by mass of the rubber component, and if it exceeds 100 parts by mass, the tensile strength and low heat build-up of the vulcanized rubber tend to deteriorate.

The rubber composition of the present invention is obtained by kneading using a kneader such as a roll or an internal mixer. After molding, vulcanization is performed, and tire tread, under tread, carcass, sidewall, bead It can be used for applications such as anti-vibration rubber, belts, hoses, and other industrial products as well as tire member applications such as parts, but it is particularly preferably used as a rubber for tire treads.
The tire of the present invention is produced by an ordinary method using the rubber composition of the present invention. That is, if necessary, the rubber composition of the present invention containing various chemicals as described above is extruded into a tread member at an unvulcanized stage, and pasted and molded by a usual method on a tire molding machine. A green tire is formed. The green tire is heated and pressed in a vulcanizer to obtain a tire. The tire of the present invention thus obtained is excellent in low fuel consumption, fracture characteristics and wear resistance, and is excellent in productivity because the rubber composition has good processability.
The rubber composition and tire of the present invention are not limited to the above-described embodiments, and it is needless to say that various modifications can be made without departing from the gist of the present invention.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not restrict | limited at all by these Examples.
Various measurements in the examples were based on the following methods.
<Production of modified conjugated diene polymer>
A modified polymer was prepared as follows.
(Method for producing polymer A)
To 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, 0.2 mmol of ditetrahydrofurylpropane, and lithium hexylamide [(dihexylamine / lithium) = Adjusted in situ at 0.9 (mol ratio)] After 0.4 mmol was added, a polymerization reaction was carried out at 50 ° C. for 1.5 hours. The polymerization conversion rate at this time was almost 100%. Next, 0.5 mL of an isopropanol solution (BHT concentration: 5 mass%) of 2,6-di-t-butyl-p-cresol (BHT) is added to the polymerization reaction system to stop the polymerization reaction. The polymer A was obtained by drying according to the method.
The polymer A produced as described above has a bound styrene amount (aromatic vinyl compound amount) of 20% by mass, a butadiene part (conjugated diene compound part) has a vinyl bond amount of 58% by mass and a glass transition point (Tg). Was −38 ° C.

(Method for producing polymer B)
To 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, 0.2 mmol of ditetrahydrofurylpropane, and n-butyllithium (n-BuLi) 0. After adding 4 mmol, a polymerization reaction was performed 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. To obtain a polymer B.
The polymer B produced as described above has a bonded styrene content (aromatic vinyl compound content) of 20% by mass, a butadiene moiety (conjugated diene compound moiety) has a vinyl bond content of 59% by mass, and a glass transition point (Tg). Was −35 ° C.

(Method for producing 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.
Polymer C produced as described above has a bonded styrene content (aromatic vinyl compound content) of 20% by mass, a butadiene moiety (conjugated diene compound moiety) has a vinyl bond content of 58% by mass, and a glass transition point (Tg). Was −38 ° C.

(1) Number average molecular weight (Mn) and mass average molecular weight (Mw)
Gel permeation chromatography [GPC: Tosoh HLC-8020, column: Tosoh GMH-XL (two in series), detector: differential refractometer (RI)], based on monodisperse polystyrene, The number average molecular weight (Mn) and mass average molecular weight (Mw) in terms of polystyrene were determined. Table 1 shows the number average molecular weight of each polymer before the modification reaction and the weight average molecular weight after the modification reaction.

(2) Microstructure and amount of bound styrene The microstructure of the polymer was determined by an infrared method (Morero method), and the amount of bound styrene of the polymer was determined from the integral ratio of the 1H-NMR spectrum.

(3) Glass transition point Using a differential thermal analyzer (DSC) type 7 device manufactured by PerkinElmer, Inc., each polymer was cooled to -100 ° C and then heated at a rate of temperature increase of 10 ° C / min. The glass transition point of the polymer was measured.

<Production Example 1 of Hydrous Silicic Acid>
A 180 L jacketed stainless steel reaction vessel equipped with a stirrer was charged with 93 L of water and 0.6 L of sodium silicate aqueous solution (SiO ₂ 160 g / L, SiO ₂ / Na ₂ O molar ratio 3.3) and heated to 96 ° C. . The concentration of Na ₂ O in the resulting solution was 0.05 mol / L. While maintaining the temperature of this solution at 96 ° C., the same sodium silicate aqueous solution as described above was simultaneously added dropwise at 540 mL / min and sulfuric acid (18 mol / L) at a flow rate of 24 mL / min. The neutralization reaction was performed while adjusting the flow rate and maintaining the Na2O concentration in the reaction solution in the range of 0.00 to 0.01 mol / L. From the middle of the reaction, the reaction solution began to become cloudy, and the viscosity increased to a gel solution at 50 minutes.
Further, the addition was continued and the reaction was stopped in 75 minutes. The silica concentration in the resulting solution was 49 g / L. Subsequently, sulfuric acid similar to that described above was added to finish the acidification by setting the pH of the solution to 3 to obtain a silicic acid slurry. The obtained silicic acid slurry is filtered with a filter press and washed with water to obtain a wet cake. Then, the wet cake is made into a slurry using an emulsifier and dried with a spray dryer to obtain a wet method hydrous silicic acid A. Obtained.

<Evaluation of hydrous silicic acid>
The CTAB adsorption specific surface area, heat loss and loss on ignition of the hydrous silicic acid suitable for production as described above were evaluated by the following methods. For comparison, hydrous silicic acid “NipsilAQ” (trade name) manufactured by Tosoh Silica Co., Ltd. was also evaluated.

(4) Measurement of CTAB adsorption specific surface area It was carried out according to the method described in ASTM D3765-92. However, since the method described in ASTM D3765-92 is a method for measuring CTAB of carbon black, it is a method with some improvements.
That is, a cetyltrimethylammonium bromide (CTAB) standard solution was separately prepared without using IRB # 3 (83.0 m ² / g) which is a carbon black canonical crystal, whereby hydrous silicic acid OT (di-2) was prepared. -Sodium ethylhexylsulfosuccinate) was standardized, and the specific surface area was calculated from the amount of CTAB adsorbed with an adsorption cross-sectional area per molecule of CTAB on the hydrous silicate surface of 0.35 nm ² . This is because carbon black and hydrous silicic acid have different surfaces, and it is considered that there is a difference in CTAB adsorption even with the same surface area.

(5) Heat loss X and burning loss salt Y
Weigh the hydrous silicic acid sample. In the case of heat loss X, the sample is heated at 105 ° C. for 2 hours. In the case of ignition loss Y, the sample is heated at 750 ° C. for 3 hours, and then the weight of the sample is measured and heated. The difference from the previous sample mass was defined as mass reduction%.
Table 1 shows the evaluation of the produced hydrous silicic acid and the commercially available silica.

Next, the compounding prescription of following Table 3 and Table 4 was performed, and the rubber composition of an Example and a comparative example was prescribed. Further, the rubber composition was vulcanized or a tire was produced and evaluated using the rubber composition as a tread. The loss tangent (60 ° C. tan δ) and ML _{1 + 4} of the rubber composition were measured. The results are shown in Table 2.

(6) Loss tangent (60 ° C. tan δ)
Using a mechanical spectrometer manufactured by Rheometrics, tan δ at 60 ° C. was measured under conditions of a dynamic strain of 1.0% and a frequency (vibration) of 15 Hz.
In Tables 3 and 4, the values of Comparative Example 1 and Comparative Example 7 were each shown as an index, with the value being 100. The smaller the index value, the better.
Regarding the loss tangent (tan δ), the smaller the index value, the better the low exothermic property, while the storage modulus (G ′) indicates that the larger the index value, the higher the storage modulus. (7) ML _{1 + 4} (130 ° C)
The fluidity was evaluated by Mooney viscosity. The Mooney viscosity was measured at 130 ° C. using a Mooney viscometer manufactured by Shimadzu Corporation. The test method was performed according to JIS K6300, and ML _{1 + 4} (Mooney viscosity value after 1 minute preheating and after 4 minutes operation) was obtained. In Tables 3 and 4, the values of Comparative Example 1 and Comparative Example 7 were each shown as an index, with the value being 100. The smaller the index, the better the workability.

  * 2 in Tables 2 and 3: “Seast KH (N339) (trademark)” manufactured by Tokai Carbon Co., Ltd., * 3; Si75 manufactured by Degussa, * 4; N- (1,3-dimethylbutyl) -N ′ -Phenyl-p-phenylenediamine Ouchi Shinsei Chemical Industry Co., Ltd. Nocrack 6C, * 5; Diphenylguanidine Ouchi Shinsei Chemical Industry Co., Ltd. Noxeller D, * 6; Mercaptobenzothiazyl disulfide Ouchi Shinsei Chemical Industry ( Noxeller DM, * 6; Nt-butyl-2-benzothiazylsulfenamide Ouchi Shinsei Chemical Co., Ltd. Noxeller NS.

  The rubber composition of the present invention is excellent in low heat build-up, has good workability, and has industrial applicability that improves rolling resistance when used in a tire.

Claims (17)

The adsorption surface area of cetyltrimethylammonium bromide (CTAB) is in the range of 50 to 250 m ² / g with respect to 100 parts by mass of the rubber component containing 10% by mass or more of the modified conjugated diene polymer having at least one kind of functional group. Yes, and Formula (1): Y <5.00 + 0.47 × X (Y in the formula is mass% decreased when heated at a temperature of 750 ° C. for 3 hours, and X is heated at a temperature of 105 ° C. for 2 hours) 10 to 130 parts by mass of hydrous silicic acid satisfying the relationship of) and 10 to 20 parts by mass of a silane coupling agent with respect to 100 parts by mass of the hydrous silicic acid. A rubber composition.   The rubber composition according to claim 1, 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.   The rubber composition according to claim 2, 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 0 ° C. or lower.   The rubber composition according to claim 1, 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 5, wherein the organic alkali metal compound is a hydrocarbyl lithium compound or a lithium amide compound.   The functional group of the modified conjugated diene polymer is in the terminal and / or main chain or side chain of the polymerization initiator or polymerization stopper of the modified conjugated diene polymer. The rubber composition as described.   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. Item 8. The rubber composition according to any one of Items 1 to 7.   The functional group containing nitrogen is selected from the group consisting of an unsubstituted or substituted amino group, amide group, isocyanate group, imidazolyl group, indolyl group, nitrile group, pyridyl group, and ketimine group. 9. The rubber composition according to 8.   9. The rubber composition according to claim 8, wherein the functional group containing silicon is selected from the group consisting of an alkoxylyl 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, a carboxyl group, an epoxy group, a glycidoxy group, a glycidylamino group, a cyclic dithiane-derived functional group, an ester group, an aldehyde group, an alkoxy group, a ketone group, a thiocarboxyl group, The rubber composition according to claim 8, wherein the rubber composition is selected from the group consisting of a thioepoxy group, a thioglycidoxy group, a thioglycidylamino group, a thioester group, a thioaldehyde group, a thioalkoxy group, and a thioketone group.   The rubber composition according to claim 8, wherein the functional group containing a metal is a functional group containing an organic metal. The functional group containing nitrogen has the following formula (I):

(In the formula, each R ¹ 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). A group and the following formula (II):

Wherein R ² represents an alkylene group having 3 to 16 methylene groups, a substituted alkylene group, an oxyalkylene group or an N-alkylamino-alkylene group. The rubber composition according to claim 8, wherein The modified conjugated diene polymer has the following formula (III) at the active end of the conjugated diene polymer having an active end:

[In the formula, A ¹ is (thio) epoxy group, (thio) inocyanate group, (thio) ketone, (thio) aldehyde group, imine residue, amide residue, isocyanuric acid triester residue, (thio) carvone 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 having at least one functional group selected from a residue, a pyridine group, and a silazane group, or a disulfide group; R ³ and R ⁴ are each independently a monovalent group having 1 to 20 carbon atoms. An aliphatic hydrocarbon group or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms; R ⁵ is a single bond or a divalent inert hydrocarbon group having 1 to 20 carbon atoms; An integer of 3 There; If OR ³ there are a plurality, the plurality of OR ³ may be the same as or different from each other; and hydrocarbyloxysilane compounds in the molecule represented by is not included in the active proton and an onium salt] and the following formula (IV):
_{^{R 6 p -Si- (OR 7)}} 4-p ··· (IV)
[Wherein, R ⁶ and R ⁷ 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; If R ⁶ and oR ⁷ there are a plurality of each, or different in a plurality of R ⁶ and oR ⁷ on each mutually identical; be ~ 2 integer active proton and onium salt are included in addition molecular The rubber composition according to claim 7, wherein the rubber composition is obtained by reacting at least one selected from the group consisting of hydrocarbyloxysilane compounds represented by   The rubber composition according to any one of claims 1 to 14, wherein the rubber component contains the modified conjugated diene polymer and another diene rubber.   A tire using a member comprising the rubber composition according to any one of claims 1 to 15.   The tire according to claim 16, wherein the member is a tread member.