JP2010189613A - Tire - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a superior tire having a following performance, in which a rubber composition is used for tread, wherein the rubber composition contains a modified conjugated diene-based polymer excellent in the interaction of a rubber component and silica being a filler and a silane coupling agent having a specified structure, and is thereby improved in the dispersion of silica into the rubber component and in the low heat build-up property and the wear resistance. <P>SOLUTION: The rubber composition includes: (A) a rubber component containing 10 pts.mass or more of a modified conjugated diene-based polymer, obtained by reacting a modifier represented by general formula (1) with an active terminal of a conjugated diene-based polymer with an organometallic active terminal having nucleophilic reactivity; (B) silica in an amount of 20-150 pts.mass to 100 pts.mass of the rubber component; and (C) at least one kind of silane coupling agent having a specified structure in an amount of 1-25 mass% to the silica being the (B)-component. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a tire, and more particularly, a rubber component of silica by containing a modified conjugated diene polymer excellent in interaction between a rubber component and silica as a filler and a silane coupling agent having a specific structure. The present invention relates to a tire having the above-described performance using a rubber composition improved in dispersion therein and improved in low heat buildup and wear resistance in a tread.

Conventionally, carbon black is frequently used as a reinforcing filler for rubber. This is because carbon black can provide high reinforcement and excellent wear resistance compared to other fillers. On the other hand, in response to social demands for energy conservation in recent years, when reducing the heat generation of rubber for tires for the purpose of saving fuel consumption of automobiles, the amount of carbon black is reduced or the use of carbon black with a large particle size is used. However, in any case, it is known that reinforcement, wear resistance, and grip performance on wet road surfaces are inevitably lowered.
On the other hand, wet silica is known as a filler that achieves both low heat generation and grip on wet road surfaces (see, for example, Patent Documents 1 to 4). This wet silica is a silanol that is a surface functional group. Particles tend to agglomerate due to hydrogen bonding of the group, and the dispersion into the rubber becomes poor, so the wear resistance is not lowered. To improve the dispersion of the silica in the rubber, the kneading time is lengthened. There is a need.

  In order to improve these drawbacks, silane coupling agents have been developed (see Patent Documents 5 to 7). However, the combination of silica and silane coupling agent alone is still insufficient to achieve both high exothermic properties and high wear resistance. Therefore, further study is necessary to satisfy the required performance of the market.

JP-A-6-248116 JP-A-7-70369 JP-A-8-245838 JP-A-3-252431 WO2004 / 000930 brochure JP 2006-169538 A Special table 2004-525230 gazette

  The present invention relates to a tire, and more specifically, includes a modified conjugated diene polymer excellent in interaction between a rubber component and silica as a filler, and a silane coupling agent having a specific structure, and has low heat buildup and resistance. An object of the present invention is to provide an excellent tire having the above-described performance using a rubber composition with improved wear characteristics, particularly in a tread.

The inventors include a rubber composition containing a specific amount of a conjugated diene rubber modified with a modifier having a specific structure as a rubber component and silica as a filler and a silane coupling agent having a specific structure. In particular, it has been found that a tire used for a tread can achieve the above-mentioned purpose. The present invention has been completed based on such findings.
That is, the present invention
[1] (A) The conjugated diene polymer having an organometallic active terminal having nucleophilic reactivity has the following general formula (1)

Wherein A ¹ is a hydrocarbyloxy group having 2 or more carbon atoms, A ² is a hydrolyzable functional group, R ¹ is a hydrocarbon group, R ² is a divalent hydrocarbon group, and X is a saturated cyclic tertiary group. Among amine compound residues, unsaturated cyclic tertiary amine compound residues, ketimine residues, nitrile groups, (thio) isocyanate groups, (thio) epoxy groups, and secondary amino groups having removable functional groups At least one functional group selected is shown. A ¹ and A ² may be the same or different. ] (B) 20-150 parts by mass of silica with respect to 100 parts by mass of the rubber component containing 10 parts by mass or more of the modified conjugated diene polymerization obtained by reacting the modifier represented by And (C) containing at least one silane coupling agent represented by the following general formulas (2) to (6) in a proportion of 1 to 25% by mass with respect to the silica of the component (B). A tire using the rubber composition,

[Wherein R ³ represents —Cl, —Br, R ⁸ O—, R ⁸ C (═O) O—, R ⁸ R ⁹ C═NO—, R ⁸ R ⁸ N— or — (OSiR ⁸ R ^{9 _{) m (OSiR 7 R 8 R}} 9) ( provided that, R ⁸ and R ⁹ is a hydrocarbon group of each independently a hydrogen atom or a C1-18 monovalent.), R ⁴ is R ^3, a hydrogen An atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms, R ⁵ is R ³ , R ⁴ or — [O (R ¹⁰ O) _a ] _0.5 — group (where R ¹⁰ is alkylene having 1 to 18 carbon atoms) Group, a is an integer of 1 to 4), R ⁶ is a divalent hydrocarbon group having 1 to 18 carbon atoms, R ⁷ is a monovalent hydrocarbon group having 1 to 18 carbon atoms, x, y and z are numbers satisfying the relationship of x + y + 2z = 3, 0 ≦ x ≦ 3, 0 ≦ y ≦ 2, and 0 ≦ z ≦ 1. ]

[Wherein R ¹¹ is or straight chain having 1 to 20 carbon atoms, branched or cyclic alkyl group, G is independently an alkanediyl group or an alkenediyl group having 1 to 9 carbon atoms, Z ^a are each independently a group capable of binding with two silicon _{atoms, [- 0-] 0.5, [} - 0-G-] is a group selected from _0.5, or _{[-O-G-O-] 0.5} , Z ^b is a group that can independently bond to two silicon atoms, and is a functional group represented by [—O—G—O—] _0.5 , and Z ^c is independently —Cl, —Br , —OR ¹² , R ¹² C (═O) O—, R ¹² R ¹³ C═NO—, R ¹² R ¹³ N—, R ¹² —, HO—G—O—. R and G coincide with the above notation. m, n, u, v, and w are independently 1 ≦ m ≦ 20, 0 ≦ n ≦ 20, 0 ≦ u ≦ 3, 0 ≦ v ≦ 2, 0 ≦ w ≦ 1, and 1 / 2u + v + 2w = 2 or 3.
When there are a plurality of A parts, each of Z ^a _u , Z ^b _v and Z ^c _w in the plurality of A parts may be the same or different. When there are a plurality of B parts, Z ^a _u in the plurality of B parts , Z ^b _v and Z ^c _w may be the same or different. ]

[Wherein R ¹⁴ and R ¹⁵ are each a hydrocarbon group having 1 to 4 carbon atoms, R ¹⁶ is a divalent hydrocarbon group having 1 to 15 carbon atoms, q is an integer of 0 to 2, and r is 1 as an average value. Less than 4 and R ¹⁷ is (a): (S—R ¹⁸ —S), (b): (R ¹⁹ —S _d —R ²⁰ ) and (c): (R ²¹ —S _g —R ²² —S). _h— R ²³ ), wherein R ^{18 to} R ²³ are linear or branched divalent hydrocarbon groups having 1 to 20 carbon atoms and divalent aromatic groups. A divalent organic group containing a hetero group other than a group group or sulfur and oxygen, wherein R ^{18 to} R ²³ may be the same or different, and d, g and h are each an average value of 1 or more and less than 4 is there. ]

[Wherein R ²⁴ is a methyl group or an ethyl group, R ²⁵ is a methoxy group, is an ethoxy group or —O— (Y—O) _m —X, and Y is branched or unbranched, saturated. other or not saturated, divalent hydrocarbon group, X is C ₁ -C ₉ - alkyl group, m is 1 to 40, R ²⁶ is methyl group, ethyl group or R ²⁵ , R ²⁷ is a branched or unbranched, saturated or unsaturated, aliphatic, aromatic or aliphatic / aromatic mixed divalent C ₁ -C ₁₂ hydrocarbon group. ]

[Wherein R ²⁸ may be the same or different, each linear or branched alkyl group having 1 to 4 carbon atoms and linear or branched alkoxy having 2 to 8 carbon atoms. Represents a monovalent hydrocarbon group selected from the group consisting of alkyl groups, R ²⁹ and R ³⁰ may be the same or different, each linear or branched alkyl group having 1 to 6 carbon atoms; And a monovalent hydrocarbon group selected from the group consisting of a phenyl group and t is an integer or fraction in the range of 3-5. ]
[2] In the modifier represented by the general formula (1), A ¹ is a hydrocarbyloxy group having 2 to 18 carbon atoms, A ² is a hydrocarbyloxy group having 1 to 18 carbon atoms or a halogen atom, and R ¹ is a carbon number. A tire using the rubber composition according to the above [1], wherein 1 to 18 hydrocarbon groups, R ² is a divalent hydrocarbon group having 1 to 20 carbon atoms,
[3] A tire using the rubber composition according to the above [1] or [2], wherein A ² is a hydrocarbyloxy group having 1 to 18 carbon atoms in the modifier represented by the general formula (1).
[4] A tire using the rubber composition according to the above [2] or [3], wherein R ² in the general formula (1) is an alkanediyl group having 2 to 10 carbon atoms.
[5] A tire using the rubber composition according to any one of the above [2] to [4], wherein A ¹ in the general formula (1) is an ethoxy group,
[6] A tire using the rubber composition according to any one of the above [2] to [5], wherein R ¹ in the general formula (1) is a methyl group,
[7] Any one of the above [2] to [6], wherein, in general formula (1), the unsaturated cyclic tertiary amine compound residue in X is an imidazole residue, dihydroimidazole residue, oxazole residue or pyridyl group A tire using the rubber composition of
[8] X in the general formula (1) represents a ketimine residue, a saturated cyclic tertiary amine compound residue, an imidazole residue, a dihydroimidazole residue, a pyridyl group, a nitrile group, an isocyanate group, and a removable functional group. A tire using the rubber composition according to the above [7], which is a monovalent group having at least one nitrogen-containing functional group selected from secondary amino groups having
[9] The nitrogen-containing functional group is at least one selected from a saturated cyclic tertiary amine compound residue, a ketimine residue, an imidazole residue, a dihydroimidazole residue, and a secondary amino group having a detachable functional group. A tire using the rubber composition of [8] above, which is a seed,
[10] A conjugated diene polymer having an organometallic active terminal having nucleophilic reactivity is an organic alkali metal compound containing C-Li or N-Li as a polymerization initiator, and a conjugated diene compound alone or a conjugated diene compound A tire using the rubber composition according to any one of the above [1] to [9], which is obtained by anionic polymerization of an aromatic vinyl compound;
[11] A tire using the rubber composition according to the above [10], wherein the conjugated diene compound is at least one selected from 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene.
[12] A tire using the rubber composition according to the above [10] or [11], wherein the aromatic vinyl compound is styrene,
[13] A tire using the rubber composition according to the above [1], wherein the functional group capable of binding to silica of the component (C) is an alkoxysilane group,
[14] The component (C) represented by the general formula (3) is represented by the chemical formula (7),

Chemical formula (8), and

Chemical formula (9)

[In the formula, each L is independently an alkanediyl or alkenediyl group having 1 to 9 carbon atoms. A tire using the rubber composition of [1] above, which is a silane coupling agent represented by
[15] A tire using the rubber composition according to the above [1], wherein r in the general formula (4) is 1.
[16] The rubber composition according to the above [1], wherein g, d, and h in (a), (b), and (c) in R ¹⁷ of the general formula (4) are 2 or more and 3 or less as an average value. Used tires,
[17] The above, wherein R ¹⁷ in the general formula (4) is (c): R ²¹ —S _d —R ²² —S _h —R ²³ , and R ²¹ , R ²² and R ²³ are hexylene groups. A tire using the rubber composition of [1],
[18] A tire using the above [1] rubber composition, wherein the component (C) in the general formula (5) contains the oligomerized or polymerized organosilane of the general formula (5),
[19] The component (C) in the general formula (5) is dimethylethoxysilylpropyl mercaptan, methyldiethoxysilylpropyl mercaptan, diethylethoxysilylpropyl mercaptan, ethyldiethoxysilylpropyl mercaptan, dimethylmethoxysilylpropyl mercaptan, methyldimethoxy. A tire using the rubber composition according to the above [1], which is silylpropyl mercaptan, diethylmethoxysilylpropyl mercaptan and ethyldimethoxysilylpropyl mercaptan;
[20] In the general formula (6), R ¹ is selected from the group consisting of methyl, ethyl, n-propyl and isopropyl groups, and R ² and R ³ are methyl, ethyl, n-propyl, isopropyl, n-butyl, a tire using the rubber composition according to the above [1], selected from the group consisting of n-hexyl and phenyl groups,
[21] The component (C) in the general formula (6) is represented by the following general formula (10),

[Wherein t represents a range of 3 to 5. A tire using the rubber composition according to the above [20], which is bis-monoethoxydimethylsilylpropyl tetrasulfide (MESPT) represented by
[22] A tire using the rubber composition according to any one of the above [1] to [21], wherein the amount of silica relative to the total amount of filler is 20% by mass or more by mass ratio,
[23] Carbon black is contained as a reinforcing filler in an amount of 10 parts by mass or more based on 100 parts by mass of the rubber component, and the total amount of carbon black and silica is in the range of 40 to 160 parts by mass. A tire using the rubber composition according to any one of [24], and [24] a tire using any one of the rubber compositions [1] to [23] as a tread member,
Is to provide.

  According to the present invention, in a silica-containing rubber composition used for a tire, as a modifier, a bifunctional hydrocarbyl having two hydrocarbyloxy groups directly bonded to a silicon atom and having a specific functional group in the same molecule A modified conjugated diene polymer obtained by using an oxysilane derivative is contained in a rubber component in an amount of 10 parts by mass or more, and a silane coupling agent having a specific structure is added at a ratio of 1 to 25% by mass with respect to silica. By including it, it is possible to provide a tire having the above-described performance using a rubber composition excellent in low heat buildup and wear resistance, which exhibits excellent interaction with silica and has a high balance between both performances, and is excellent in wear resistance. .

First, the conjugated diene polymer used in the rubber composition relating to the tire of the present invention will be described.
[(A) Modified Conjugated Diene Polymer]
The (A) modified conjugated diene polymer used in the rubber composition relating to the tire of the present invention has, as a modifier, an active terminal of the conjugated diene polymer having an organometallic active terminal having nucleophilic reactivity. It can be obtained by reacting the silane compound represented by the general formula (1) and / or a partial condensate thereof to carry out a modification reaction.

(Conjugated diene polymer having active terminal)
The conjugated diene polymer having an organometallic active terminal having nucleophilic reactivity used in the present invention is obtained by copolymerizing a diene monomer alone or with another monomer, and a method for producing the same. Is not particularly limited, and any of solution polymerization method, gas phase polymerization method, and bulk polymerization method can be used, but the solution polymerization method is particularly preferable. Moreover, any of a batch type and a continuous type may be sufficient as the superposition | polymerization form.
The active site metal present in the molecule of the conjugated diene polymer is preferably one selected from alkali metals and alkaline earth metals, preferably alkali metals, and particularly preferably lithium metal.

In the solution polymerization method, for example, an organic alkali metal compound, particularly a lithium compound is used as a polymerization initiator, and a conjugated diene compound alone or a conjugated diene compound and an aromatic vinyl compound are anionically polymerized to produce a target polymer. Can do.
Furthermore, it is also effective to mix a halogen-containing monomer and activate the halogen atom in the polymer with an organometallic compound. For example, it is also effective to lithiate the bromine moiety of a copolymer containing an isobutylene unit, a paramethylstyrene unit and a parabromomethylstyrene unit to form an active site.

Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-hexadiene, and the like. Is mentioned. These may be used alone or in combination of two or more, and among these, 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene are particularly preferred.
Examples of the aromatic vinyl compound used for copolymerization with these conjugated diene compounds include styrene, α-methylstyrene, 1-vinylnaphthalene, 3-vinyltoluene, ethylvinylbenzene, divinylbenzene, and 4-cyclohexane. Examples include xyl styrene and 2,4,6-trimethyl styrene. These may be used alone or in combination of two or more, and among these, styrene is particularly preferable.

Furthermore, when copolymerization is carried out using a conjugated diene compound and an aromatic vinyl compound as monomers, the use of 1,3-butadiene and styrene, respectively, is practical, such as the availability of the monomers, and The anionic polymerization characteristics are particularly suitable because of excellent living characteristics.
Moreover, when the solution polymerization method is used, the monomer concentration in the solvent is preferably 5 to 50% by mass, more preferably 10 to 30% by mass. In addition, when copolymerizing using a conjugated diene compound and an aromatic vinyl compound, the content of the aromatic vinyl compound in the charged monomer mixture is preferably in the range of 0 to 55% by mass.

  The lithium compound of the polymerization initiator is not particularly limited, but hydrocarbyl lithium and lithium amide compounds are preferably used. When the former hydrocarbyl lithium is used, it has a hydrocarbyl group at the polymerization initiation terminal and the other terminal. A conjugated diene polymer having a polymerization active site is obtained. When the latter lithium amide compound is used, a conjugated diene polymer having a nitrogen-containing group at the polymerization initiation terminal and the other terminal being a polymerization active site is obtained.

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

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

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

A method for producing a conjugated diene polymer by anionic polymerization using the lithium compound as a polymerization initiator is not particularly limited, and a conventionally known method can be used.
Specifically, in an organic solvent inert to the reaction, for example, a hydrocarbon solvent such as an aliphatic, alicyclic or aromatic hydrocarbon compound, the conjugated diene compound or the conjugated diene compound and the aromatic vinyl compound are The desired conjugated diene polymer can be obtained by anionic polymerization in the presence of the randomizer used, if desired, using a lithium compound as a polymerization initiator.

  The hydrocarbon solvent is preferably one having 3 to 8 carbon atoms, such as propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, cyclohexane, propene, 1-butene, isobutene, 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 randomizer used as desired is a control of the microstructure of the conjugated diene polymer, such as an increase in 1,2 bonds in the butadiene portion in the butadiene-styrene copolymer, an increase in 3,4 bonds in the isoprene polymer, or the like. It is a compound having an action of controlling the composition distribution of monomer units in a conjugated diene compound-aromatic vinyl compound copolymer, for example, randomizing butadiene units and styrene units in a butadiene-styrene copolymer. The randomizer is not particularly limited, and any one of known compounds generally used as a conventional randomizer can be appropriately selected and used. Specifically, dimethoxybenzene, tetrahydrofuran, dimethoxyethane, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, 2,2-bis (2-tetrahydrofuryl) -propane, triethylamine, pyridine, N-methylmorpholine, N, N, N ′, Examples thereof include ethers such as N′-tetramethylethylenediamine and 1,2-dipiperidinoethane, and tertiary amines. Further, potassium salts such as potassium tert-amylate and potassium tert-butoxide, and sodium salts such as sodium tert-amylate can also be used.

  These randomizers may be used individually by 1 type, and may be used in combination of 2 or more type. The amount used is preferably selected in the range of 0.01 to 1000 molar equivalents per mole of the lithium compound.

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

In this polymerization, it is desirable that all raw materials involved in the polymerization, such as a polymerization initiator, a solvent, and a monomer, are obtained by removing reaction inhibitors such as water, oxygen, carbon dioxide, and protic compounds.
It is preferable that the glass transition temperature (Tg) calculated | required by the differential thermal analysis method of the conjugated diene type polymer obtained is -95 degreeC--15 degreeC. By setting the glass transition temperature within the above range, it is possible to obtain a conjugated diene polymer that can suppress the increase in viscosity and can be easily handled.

(Modifier)
In the method for producing the (A) modified conjugated diene polymer used in the present invention, the active terminal of the conjugated diene polymer having an organometallic active terminal having nucleophilic reactivity obtained as described above is added. As a modifier, the general formula (1)

The silane compound represented by these and / or its partial condensate are made to react.
In the general formula (1), A ¹ represents a hydrocarbyloxy group having 2 or more carbon atoms, A ² represents a hydrolyzable functional group, R ¹ represents a hydrocarbon group, R ² represents a divalent hydrocarbon group, and X represents , A saturated cyclic tertiary amine compound residue, an unsaturated cyclic tertiary amine compound residue, a ketimine residue, a nitrile group, a (thio) isocyanate group, a (thio) epoxy group, and a secondary having a detachable functional group At least one functional group selected from amino groups is shown. A ¹ and A ² may be the same or different.
Specifically, A ¹ is a hydrocarbyloxy group having 2 to 18 carbon atoms (also referred to as a hydrocarbyloxy group), R ¹ is a hydrocarbon group having 1 to 18 carbon atoms, and R ² is a carbon number. Examples thereof include 1 to 20 divalent hydrocarbon groups.

Examples of the hydrocarbyloxy group having 2 to 18 carbon atoms represented by A ¹ include an alkoxy group having 2 to 18 carbon atoms or an alkenyloxy group, an aryloxy group having 6 to 18 carbon atoms, and an aralkyloxy group having 7 to 18 carbon atoms. Among them, an alkoxy group having 2 to 10 carbon atoms is preferable from the viewpoint of having good reactivity. The alkyl group constituting the alkoxy group may be linear, branched or cyclic. Examples of such alkoxy groups include ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, various pentoxy groups, various hexoxy groups, and various heptoxy groups. , Various octoxy groups, various decyloxy groups, cyclopetyloxy groups, cyclohexyloxy groups, and the like. Among these, from the viewpoint of reactivity, an alkoxy group having 2 to 6 carbon atoms is preferable, and an ethoxy group is particularly preferable.
When A ¹ is a methoxy group, condensation between the modified sites is likely to occur, and as a result, the introduced modified group cannot sufficiently exhibit the interaction with the filler, and the object of the present invention is hardly achieved.
A ² includes a hydrocarbyloxy group having 1 to 18 carbon atoms or a halogen atom, and a hydrocarbyloxy group having 1 to 18 carbon atoms is preferable.
A ¹ and A ² may be the same or different.

Examples of the hydrocarbon group having 1 to 18 carbon atoms represented by R ¹ include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and 7 to 7 carbon atoms. Among these, an alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable, from the viewpoint of the reactivity and performance of the modifier. The alkyl 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 group, tert. -A butyl group, various pentyl groups, various hexyl groups, various octyl groups, various decyl groups, a cyclopentyl group, a cyclohexyl group, etc. can be mentioned. Among these, from the viewpoint of the reactivity and performance of the modifier, an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group is particularly preferable.
The divalent hydrocarbon group having 1 to 20 carbon atoms represented by R ² is preferably an alkanediyl group having 1 to 20 carbon atoms, and an alkanediyl group having 2 to 10 carbon atoms from the viewpoint of the performance of the modifier. Are more preferable, and an alkanediyl group having 2 to 6 carbon atoms is more preferable.
The alkanediyl group having 2 to 6 carbon atoms may be linear or branched. For example, ethylene group, 1,3-propanediyl group, 1,2-propanediyl group, various butanediyl groups, various types Examples thereof include a pentanediyl group and various hexanediyl groups, and among these, linear ones such as ethylene group, 1,3-propanediyl group, 1,4-butanediyl group, 1,5-pentanediyl group 1,6-hexanediyl group and the like, and 1,3-propanediyl group is particularly preferable.

Examples of the saturated cyclic tertiary amine compound residue in X include a hexamethyleneimino group, a pyrrolidinyl group, a piperidinyl group, a heptamethyleneimino group, and a dodecamethyleneimino group. Examples of the compound residue include an imidazole residue, a dihydroimidazole residue, an oxazole residue, and a pyridyl group.
X includes a ketimine residue, a saturated cyclic tertiary amine compound residue, an imidazole residue, a dihydroimidazole residue, a pyridyl group, a nitrile group, an isocyanate group, and a detachable functional group from the viewpoint of performance. It is preferably a monovalent group having at least one nitrogen-containing functional group selected from secondary amino groups, saturated cyclic tertiary amine compound residue, ketimine residue, imidazole residue, dihydroimidazole residue and It is more preferably a monovalent group having at least one selected from secondary amino groups having a detachable functional group.
Among the functional groups in the monovalent group represented by X, examples of the protected secondary amino group that can be deprotected include N- (trimethylsilyl) amino group. The (thio) isocyanate group is a —NCO group or a —NCS group.
Examples of the monovalent group containing a (thio) epoxy group include a glycidoxy group, a 3,4-epoxycyclohexyl group, and those obtained by replacing the epoxy ring in these groups with a thioepoxy ring.

The modifier used in the present invention is a bifunctional hydrocarbyloxysilane compound and / or a partial condensate thereof as described above. Here, the partial condensate means a product in which a part (not all) of the SiOR groups of the hydrocarbyloxysilane compound are bonded by SiOSi by condensation.
Further, when the modifier used in the present invention is a monofunctional hydrocarbyloxysilane compound having one hydrocarbyloxy group directly bonded to a silicon atom, the hydrocarbyloxy group is consumed by the modification reaction, and an inorganic filler such as silica. Since the modifying group that interacts with is not introduced, the object of the present invention cannot be achieved.
On the other hand, in the case of a trifunctional hydrocarbyloxysilane compound having three hydrocarbyloxy groups directly bonded to a silicon atom, a conjugated diene polymer having a plurality of active ends reacts with one molecule of the modifier, whereby Highly efficient introduction of modified ends per molecule cannot be achieved.
In the modification reaction in the present invention, the conjugated diene polymer having an active end to be used is preferably one in which at least 10% of the polymer chains have a living property.

  As the bifunctional hydrocarbyloxysilane compound represented by the general formula (1), for example, when X has a ketimine residue, as a specific example, N- (1,3-dimethylbutylidene) -3- [diethoxy ( Methyl) silyl] -1-propanamine, N- (1-methylethylidene) -3- [diethoxy (methyl) silyl] -1-propanamine, N-ethylidene-3- [diethoxy (methyl) silyl] -1- Propanamine, N- [1-methylpropylidene) -3- [diethoxy (methyl) silyl] -1-propanamine, N- (4-N, N-dimethylaminobenzylidene) -3- [diethoxy (methyl) silyl ] 1-propanamine, N- (cyclohexylidene) -3- [diethoxy (methyl) silyl] -1-propanamine and their diethoxy (methyl) E) Diethoxy (ethyl) silyl compound, dipropoxy (methyl) silyl compound, dipropoxy (ethyl) silyl compound, etc. corresponding to the silyl compound can be mentioned, among these, N- (1,3-dimethylbutylidene) -[Diethoxy (methyl) silyl] -1-propanamine and N- (1,3-dimethylbutylidene)-[dipropoxy (methyl) silyl] -1-propanamine are preferred.

  As the bifunctional hydrocarbyloxysilane compound represented by the general formula (1), for example, when X has an imidazole residue or a dihydroimidazole residue, as a specific example, 1- [3- [diethoxy (methyl) silyl] Propyl] -imidazole, 1- [3- [diethoxy (ethyl) silyl] propyl] -imidazole, 1- [3- [dipropoxy (methyl) silyl] propyl] -imidazole, 1- [3- [dipropoxy (ethyl) silyl] ] Propyl] -imidazole, 1- [3- [diethoxy (methyl) silyl] propyl] -4,5-dihydroimidazole, 1- [3- [diethoxy (ethyl) silyl] propyl] -4,5-dihydroimidazole, 1- [3- [Dipropoxy (methyl) silyl] propyl] -4,5-dihydroimidazo And 1- [3- [dipropoxy (ethyl) silyl] propyl] -4,5-dihydroimidazole, among which 1- [3- [diethoxy (methyl) silyl] propyl]- Imidazole, 1- [3- [dipropoxy (methyl) silyl] propyl] -imidazole, 1- [3- [diethoxy (methyl) silyl] propyl] -4,5-dihydroimidazole and 1- [3- [dipropoxy (methyl) ) Silyl] propyl] -4,5-dihydroimidazole is preferred.

  As the bifunctional hydrocarbyloxysilane compound represented by the general formula (1), for example, when X has a pyridyl group or a nitrile group, as a specific example, 2- [2- [diethoxy (methyl) silyl] ethyl] -Pyridine, 2- [2- [dipropoxy (methyl) silyl] ethyl] -pyridine, 2- [3- [diethoxy (methyl) silyl] propyl] -pyridine, 2- [3- [diethoxy (ethyl) silyl] propyl ] -Pyridine, 2- [3- [dipropoxy (methyl) silyl] propyl] -pyridine, 2- [3- [dipropoxy (ethyl) silyl] propyl] -pyridine, 4- [2- [diethoxy (methyl) silyl] Ethyl] -pyridine, 4- [2- [dipropoxy (methyl) silyl] ethyl] -pyridine, 4- [3- [diethoxy (methyl) Ryl] propyl] -pyridine, 4- [3- [diethoxy (ethyl) silyl] propyl] -pyridine, 4- [3- [dipropoxy (methyl) silyl] propyl] -pyridine, 4- [3- [dipropoxy (ethyl) ) Pyridine compounds such as silyl] propyl] -pyridine, 1-cyano-3- [diethoxy (methyl) silyl] -propane, 1-cyano-3- [diethoxy (ethyl) silyl] -propane, 1-cyano-3- And cyano compounds such as [dipropoxy (methyl) silyl] -propane and 1-cyano-3- [dipropoxy (ethyl) silyl] -propane. Among these, 2- [3- [diethoxy (methyl) silyl] propyl] -pyridine, 2- [3- [dipropoxy (methyl) silyl] propyl] -pyridine, 4- [3- [diethoxy (methyl) silyl ] Propyl] -pyridine, 4- [3- [dipropoxy (methyl) silyl] propyl] -pyridine, 1-cyano-3- [diethoxy (methyl) silyl] -propane and 1-cyano-3- [dipropoxy (methyl) Silyl] -propane is preferred.

As the bifunctional hydrocarbyloxysilane compound represented by the general formula (1), for example, when X has a (thio) isocyanate group or an oxazole residue, as a specific example, 1-isocyanate 3- [diethoxy (methyl ) Silyl] -propane, 1-isocyanate 3- [diethoxy (ethyl) silyl] -propane, 1-isocyanate 3- [dipropoxy (methyl) silyl] -propane, 1-isocyanate 3- [dipropoxy (ethyl) silyl ] Isocyanate compounds such as propane, thioisocyanate compounds in which the isocyanate in the above isocyanate compounds is replaced by thioisocyanate, 4- [3- [diethoxy (methyl) silyl] propyl] -oxazole, 4- [3- [Diethoxy (ethyl) silyl] propyl] -o Sasol, 4- [3- [dipropoxy (methyl) silyl] propyl] - oxazole, 4- [3- [dipropoxy (ethyl) silyl] propyl] - such as oxazole compounds such as oxazole and the like. Among these, 1-isocyanate 3- [diethoxy (methyl) silyl] -propane, 1-isocyanate 3- [dipropoxy (methyl) silyl] -propane, 4- [3- [diethoxy (methyl) silyl] propyl ] -Oxazole and 4- [3- [dipropoxy (methyl) silyl] propyl] -oxazole are preferred.
In the present invention, the oxazole residue also includes an isoxazole residue.

  As the bifunctional hydrocarbyloxysilane compound represented by the general formula (1), for example, when X has a (thio) epoxy group, as a specific example, 1-glycidoxy-3- [diethoxy (methyl) silyl] -propane 1-glycidoxy-3- [diethoxy (ethyl) silyl] -propane, 1-glycidoxy-3- [dipropoxy (methyl) silyl] -propane, 1-glycidoxy-3- [dipropoxy (ethyl) silyl] -propane, 1 -(3,4-epoxycyclohexyl) -3- [diethoxy (methyl) silyl] -propane, 1- (3,4-epoxycyclohexyl) -3- [diethoxy (ethyl) silyl] -propane, 1- (3 4-epoxycyclohexyl) -3- [dipropoxy (methyl) silyl] -propane, 1- (3,4-e Carboxymethyl-cyclohexyl) -3- [dipropoxy (ethyl) silyl] - epoxy compounds such as propane, and thioepoxy compound is replaced with thioepoxy group an epoxy group in the epoxy compound, and the like. Among these, 1-glycidoxy-3- [diethoxy (methyl) silyl] -propane, 1-glycidoxy-3- [dipropoxy (methyl) silyl] -propane, 1- (3,4-epoxycyclohexyl) -3- [Diethoxy (methyl) silyl] -propane and 1- (3,4-epoxycyclohexyl) -3- [dipropoxy (methyl) silyl] -propane are preferred.

In the present invention, the bifunctional hydrocarbyloxysilane compound represented by the general formula (1) and / or a part thereof reacted with the active end of a conjugated diene polymer having an organometallic active end having nucleophilic reactivity One modifier may be used alone, or two or more modifiers may be used in combination.
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. .

(Condensation accelerator)
In the present invention, in order to accelerate the condensation reaction involving the bifunctional hydrocarbyloxysilane compound used as the modifier, the condensation reaction is performed in the presence of a condensation accelerator as necessary. May be.
As the condensation accelerator, a compound of an element belonging to at least one of Group 4, Group 13, Group 14 and Group 15 of the periodic table is used.
As the condensation accelerator, at least one selected from a titanium compound, a tin compound, a zirconium compound, a bismuth compound, and an aluminum compound is preferably used, and more preferably, the alkoxide or carboxyl of each of the above elements. Acid salt and acetylacetonate complex salt, more preferably titanium alkoxide, titanium carboxylate, tin carboxylate, bismuth carboxylate, zirconium alkoxide, zirconium carboxylate, aluminum alkoxide and It is an aluminum carboxylate.

  As the condensation accelerator comprising a titanium compound, tetrakis (2-ethyl-1,3-hexanediolato) titanium, tetrakis (2-methyl-1,3-hexanediolato) titanium, tetrakis (2-propyl-1, 3-hexanediolato) titanium, tetrakis (2-butyl-1,3-hexanediolato) titanium, tetrakis (1,3-hexanediolato) titanium, tetrakis (1,3-pentanediolato) titanium, tetrakis ( 2-methyl-1,3-pentanediolato) titanium, tetrakis (2-ethyl-1,3-pentanediolato) titanium, tetrakis (2-propyl-1,3-pentanediolato) titanium, tetrakis (2- Butyl-1,3-pentanediolato) titanium, tetrakis (1,3-heptanediolato) titanium, tetrakis (2-methyl) -1,3-heptanediolato) titanium, tetrakis (2-ethyl-1,3-heptanediolato) titanium, tetrakis (2-propyl-1,3-heptanediolato) titanium, tetrakis (2-butyl-1,3-heptanediolato) titanium , Tetrakis (2-ethylhexoxy) titanium, tetramethoxy titanium, tetraethoxy titanium, tetra-n-propoxy titanium, tetraisopropoxy titanium, tetra-n-butoxy titanium, tetra-n-butoxy titanium oligomer, tetraisobutoxy titanium, tetra -Sec-butoxytitanium, tetra-tert-butoxytitanium, bis (oleate) bis (2-ethylhexanoate) titanium, titanium dipropoxybis (triethanolamate), titanium dibutoxybis (triethanolaminine) G), titanium tributoxy systemate, titanium tripropoxy systemate, titanium tripropoxyacetylacetonate, titanium dipropoxybis (acetylacetonate), titanium tripropoxy (ethylacetoacetate), titaniumpropoxyacetylacetonatebis (ethylacetate) Acetate), titanium tributoxyacetylacetonate, titanium dibutoxybis (acetylacetonate), titanium tributoxyethylacetoacetate, titaniumbutoxyacetylacetonatebis (ethylacetoacetate), titanium tetrakis (acetylacetonate), titanium diacetylacetate Bis (ethyl acetoacetate), bis (2-ethylhexanoate) titanium oxide, bis (laurate) titanium oxide, bis ( Naphthenate) titanium oxide, bis (stearate) titanium oxide, bis (oleate) titanium oxide, bis (linoleate) titanium oxide, tetrakis (2-ethylhexanoate) titanium, tetrakis (laurate) titanium, tetrakis (naphthenate) titanium, Tetrakis (stearate) titanium, Tetrakis (oleate) titanium, Tetrakis (linoleate) titanium, Titanium di-n-butoxide (bis-2,4-pentanedionate), Titanium oxide bis (tetramethylheptanedionate), Titanium oxide bis (Pentandionate), titanium tetra (lactate), and the like. Among these, tetrakis (2-ethyl-1,3-hexanediolato) titanium, tetrakis (2-ethylhexoxy) titanium, and titanium di-n-butoxide (bis-2,4-pentanedionate) are preferable.

As the condensation accelerator composed of a tin compound, for example, divalent tin carboxylate and tetravalent dihydrocarbyltin dicarboxylate can be preferably exemplified, and bis (2-ethylhexanoic acid) tin is particularly preferable. It is.
Examples of the condensation accelerator composed of a bismuth compound include tris (2-ethylhexanoate) bismuth, tris (laurate) bismuth, tris (naphthenate) bismuth, tris (stearate) bismuth, tris (oleate) bismuth, tris ( Linoleate) bismuth. Of these, tris (2-ethylhexanoate) is preferred.

  Examples of the condensation accelerator composed of a zirconium compound include tetraethoxyzirconium, tetran-propoxyzirconium, tetraisopropoxyzirconium, tetran-butoxyzirconium, tetrasec-butoxyzirconium, tetratert-butoxyzirconium, tetra (2-ethylhexoxy). Zirconium, zirconium tributoxy systemate, zirconium tributoxyacetylacetonate, zirconium dibutoxybis (acetylacetonate), zirconium tributoxyethylacetoacetate, zirconiumbutoxyacetylacetonatebis (ethylacetoacetate), zirconium tetrakis (acetylacetonate) ), Zirconium diacetylacetonate bis (ethylacetoacetate) Bis (2-ethylhexanoate) zirconium oxide, bis (laurate) zirconium oxide, bis (naphthenate) zirconium oxide, bis (stearate) zirconium oxide, bis (oleate) zirconium oxide, bis (linoleate) zirconium oxide, tetrakis ( 2-ethylhexanoate) zirconium, tetrakis (laurate) zirconium, tetrakis (naphthenate) zirconium, tetrakis (stearate) zirconium, tetrakis (oleate) zirconium, tetrakis (linoleate) zirconium and the like. Among these, tetra n-propoxyzirconium, bis (2-ethylhexanoate) zirconium oxide, bis (oleate) zirconium oxide, and zirconium tetrakis (acetylacetonate) are preferable.

Examples of the condensation accelerator composed of an aluminum compound include triethoxyaluminum, tri-n-propoxyaluminum, triisopropoxyaluminum, tri-n-butoxyaluminum, trisec-butoxyaluminum, tritert-butoxyaluminum, tri (2-ethylhexoxy) Aluminum, aluminum dibutoxy systemate, aluminum dibutoxyacetylacetonate, aluminum butoxybis (acetylacetonate), aluminum dibutoxyethylacetoacetate, aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), tris (2 -Ethylhexanoate) aluminum, tris (laurate) aluminum, tris (naphthenate) aluminum Tris (stearate) aluminum, tris (oleate) aluminum, and tris (linolate) aluminum.
Among these, triisopropoxyaluminum, trisec-butoxyaluminum, tris (2-ethylhexanoate) aluminum, tris (stearate) aluminum, and aluminum tris (acetylacetonate) are preferable.

The amount of the condensation accelerator used is preferably such that the number of moles of the compound is 0.1 to 10 as the molar ratio to the total amount of hydrocarbyloxy groups bonded to silicon atoms present in the reaction system. .5 to 5 is particularly preferable. By setting the use amount of the condensation accelerator within the above range, the condensation reaction proceeds efficiently.
The addition time of the condensation accelerator is usually 5 minutes to 5 hours after the start of the modification reaction, preferably 15 minutes to 1 hour after the start of the modification reaction.

The condensation reaction in the present invention is preferably performed in the presence of water, and the temperature during the condensation reaction is preferably 85 to 180 ° C, more preferably 100 to 170 ° C, and particularly preferably 110 to 150 ° C.
By setting the temperature during the condensation reaction within the above range, the condensation reaction can be progressed and completed efficiently, and the deterioration of the quality due to the aging reaction of the polymer due to changes over time of the resulting modified conjugated diene polymer is suppressed. Can do.

The condensation reaction time is usually about 5 minutes to 10 hours, preferably about 15 minutes to 5 hours. By setting the condensation reaction time within the above range, the condensation reaction can be completed smoothly.
The pressure of the reaction system during the condensation reaction is usually 0.01 to 20 MPa, preferably 0.05 to 10 MPa.
There is no restriction | limiting in particular about the form of a condensation reaction, You may carry out by a continuous type using apparatuses, such as a batch type reactor and a multistage continuous type reactor. Moreover, you may perform this condensation reaction and a desolvent simultaneously.
When a difunctional hydrocarbyloxysilane compound having a protected secondary amino group is used as a modifier, the silyl protecting group in the protected amino group is converted to a free imino group by hydrolysis. Can do. By removing this solvent, a dried polymer having a secondary amino group is obtained. In addition, the deprotection treatment of the protected secondary amino group derived from the modifier can be performed as necessary in any stage from the stage including the condensation treatment to the solvent removal to the dry polymer.

The modified conjugated diene polymer used in the rubber composition in the present invention 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 Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the modified conjugated diene polymer used in the rubber composition in the present invention is preferably 10 to 150, more preferably _{15 to} 100. By setting the Mooney viscosity value within the above range, a rubber composition having excellent kneading workability and mechanical properties after vulcanization can be obtained.

[(B) Silica]
Next, the component (B) silica will be described.
In the rubber composition in the present invention, silica is used as an essential component of the filler. The silica is not particularly limited, and can be arbitrarily selected from those conventionally used as reinforcing fillers for rubber. Examples of the silica include wet silica (hydrous silicic acid) and dry silica (anhydrous silicic acid). Among them, the improvement effect of fracture characteristics and the combined effect of wet grip property and low rolling resistance are most remarkable. Wet silica is preferred.
The wet silica preferably has a nitrogen adsorption specific surface area (N ₂ SA) according to the BET method of 140 to 280 m ² / g from the viewpoints of balance of reinforcement, workability, wet grip properties, and wear resistance, It is more preferable that it is 170-250 m < ² > / g. Suitable wet silica includes, for example, AQ, VN3, LP, NA, etc. manufactured by Tosoh Silica Co., Ltd., Ultrazil VN3 (N ₂ SA: 210 m ² / g) manufactured by Degussa.

(Other fillers)
Among the fillers, carbon black and / or inorganic fillers other than silica are used as fillers other than silica, and carbon black is preferred. Examples of carbon black include FEF, GPF, SRF, HAF, N339, IISAF, ISAF, and SAF. Nitrogen adsorption specific surface area of the carbon black _{(N 2 SA, JIS K 6217-2} : conforms to 2001) is preferably from 20~160m ² / g, more preferably 70~160m ² / g. Further, preferably dibutyl phthalate oil absorption: a (DBP, JIS K 6217-4 compliant to 2001) of carbon black 80~170cm ³ / 100g. By using these carbon blacks, the effect of improving various physical properties, particularly fracture characteristics, is increased. Preferred carbon blacks are HAF, N339, IISAF, ISAF and SAF.

Examples of inorganic fillers other than silica include compounds represented by the following general formula (11).
mM ¹ · xSiOy · zH ₂ O (11)
(In the formula, M ¹ represents a metal selected from the group consisting of aluminum, magnesium, titanium, calcium, and zirconium, an oxide or hydroxide of these metals, and a hydrate thereof, or carbonic acid of these metals. And m, x, y, and z are each an integer of 1 to 5, an integer of 0 to 10, an integer of 2 to 5, and an integer of 0 to 10. In the case where x and z are both 0, the inorganic compound is at least one metal, metal oxide or metal hydroxide selected from aluminum, magnesium, titanium, calcium and zirconium.)

Examples of the inorganic filler represented by the above formula include alumina (Al ₂ O ₃ ) such as γ-alumina and α-alumina, alumina monohydrate such as boehmite and diaspore (Al ₂ O ₃ .H ₂ O), gibbsite. Aluminum hydroxide [Al (OH) ₃ ], aluminum carbonate [Al ₂ (CO ₃ ) ₂ ], magnesium hydroxide [Mg (OH) ₂ ], magnesium oxide (MgO), magnesium carbonate (MgCO ₃₎ ), Talc (3MgO · 4SiO ₂ · H ₂ O), attapulgite (5MgO · 8SiO ₂ · 9H ₂ O), titanium white (TiO ₂ ), titanium black (TiO _2n-1 ), calcium oxide (CaO), hydroxide calcium [Ca (OH) _2], magnesium aluminum oxide _{(MgO · Al 2 O 3)} , clay _{(Al 2 O 3 · 2SiO 2} ), kaolin (Al ₂ O ₃ 2SiO ₂ · 2H ₂ O), pyrophyllite _{(Al 2 O 3 · 4SiO 2} · H 2 O), bentonite _{(Al 2 O 3 · 4SiO 2} · 2H 2 O), aluminum silicate (Al ₂ SiO _5, Al ₄ · 3SiO ₄ · 5H ₂ O), 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 ), magnesium calcium silicate (CaMgSiO ₄ ), calcium carbonate (CaCO ₃ ), zirconium oxide (ZrO ₂ ), zirconium hydroxide [ZrO (OH) ₂ .nH ₂ O], zirconium carbonate [Zr (CO ₃ ) ₂ ], crystalline aluminosilicates containing hydrogen, alkali metals or alkaline earth metals that correct the charge, such as various zeolites, can be used. Moreover, it is preferable that M ¹ in the general formula (10) is at least one selected from aluminum metal, aluminum oxide or hydroxide, hydrates thereof, and aluminum carbonate.
These inorganic compounds represented by the above formulas may be used alone or in combination of two or more.

[(C) Silane coupling agent]
In the rubber composition according to the present invention, as the component (C), a silane coupling agent containing at least an element or a functional group capable of binding to the inorganic filler and a protected mercapto group is used. By having a protected mercapto group, it is possible to prevent the occurrence of initial vulcanization (scorch) during processing prior to the vulcanization process, so that the processability is good and can be combined with an inorganic filler. Since it has an element or a functional group, the dispersibility of an inorganic filler becomes favorable. Among these, as the functional group that can be bonded to the inorganic filler, an alkoxysilane group is preferable because the above effect is excellent.

<Silane coupling agent represented by general formula (2)>
As the silane coupling agent represented by the general formula (2),

[Wherein R ³ represents —Cl, —Br, R ⁸ O—, R ⁸ C (═O) O—, R ⁸ R ⁹ C═NO—, R ⁸ R ⁸ N— or — (OSiR ⁸ R ^{9 _{) m (OSiR 7 R 8 R}} 9) ( provided that, R ⁸ and R ⁹ is a hydrocarbon group of each independently a hydrogen atom or a C1-18 monovalent.), R ⁴ is R ^3, a hydrogen An atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms, R ⁵ is R ³ , R ⁴ or — [O (R ¹⁰ O) _a ] _0.5 — group (where R ¹⁰ is alkylene having 1 to 18 carbon atoms) Group, a is an integer of 1 to 4), R ⁶ is a divalent hydrocarbon group having 1 to 18 carbon atoms, R ⁷ is a monovalent hydrocarbon group having 1 to 18 carbon atoms, x, y and z are numbers satisfying the relationship of x + y + 2z = 3, 0 ≦ x ≦ 3, 0 ≦ y ≦ 2, and 0 ≦ z ≦ 1. The silane coupling agent represented by this is used.
In the general formula (2), examples of the monovalent hydrocarbon group having 1 to 18 carbon atoms include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, and an aryl group having 6 to 18 carbon atoms. And an aralkyl group having 7 to 18 carbon atoms. Here, the alkyl group and alkenyl group may be linear, branched or cyclic, and the aryl group and aralkyl group have a substituent such as a lower alkyl group on the aromatic ring. Also good. Specific examples of these monovalent hydrocarbon groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl groups. , Pentyl group, hexyl group, octyl group, decyl group, dodecyl group, cyclopentyl group, cyclohexyl group, vinyl group, propenyl group, allyl group, hexenyl group, octenyl group, cyclopentenyl group, cyclohexenyl group, etc. .

In the general formula (2), the alkylene group having 1 to 18 carbon atoms represented by R ¹⁰ may be linear, branched or cyclic, and is particularly preferably linear. is there. 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 divalent hydrocarbon group having 1 to 18 carbon atoms represented by R ⁶ include an alkylene group having 1 to 18 carbon atoms, an alkenylene group having 2 to 18 carbon atoms, and a cycloalkylene having 5 to 18 carbon atoms. Groups, cycloalkylalkylene groups having 6 to 18 carbon atoms, arylene groups having 6 to 18 carbon atoms, and aralkylene groups having 7 to 18 carbon atoms. The alkylene group and alkenylene group may be linear or branched, and the cycloalkylene group, cycloalkylalkylene group, arylene group, and aralkylene group may have a substituent such as a lower alkyl group on the ring. You may have.
R ⁶ is preferably an alkylene group having 1 to 6 carbon atoms, particularly preferably a linear alkylene group such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group or a hexamethylene group. it can.

Examples of the silane coupling agent represented by the general formula (2) include 3-hexanoylthiopropyltriethoxysilane, 3-octanoylthiopropyltriethoxysilane, 3-decanoylthiopropyltriethoxysilane, 3 -Lauroylthiopropyltriethoxysilane, 2-hexanoylthioethyltriethoxysilane, 2-octanoylthioethyltriethoxysilane, 2-decanoylthioethyltriethoxysilane, 2-lauroylthioethyltriethoxysilane, 3-hexa Noylthiopropyltrimethoxysilane, 3-octanoylthiopropyltrimethoxysilane, 3-decanoylthiopropyltrimethoxysilane, 3-lauroylthiopropyltrimethoxysilane, 2-hexanoylthioethyltrimethoxysilane, 2- Kuta Neu Lucio ethyltrimethoxysilane, 2- deca Neu thio ethyltrimethoxysilane, and the like of 2-lauroyl thio ethyltrimethoxysilane.
In the rubber composition according to the present invention, by using such a silane coupling agent as the component (C), it is excellent in workability at the time of rubber processing, and also has good wet braking performance and wear resistance. Tires can be given.

<Silane coupling agent represented by general formula (3)>
In the rubber composition according to the present invention, as the component (C), the general formula (3)

[Wherein R ¹¹ is or straight chain having 1 to 20 carbon atoms, branched or cyclic alkyl group, G is independently an alkanediyl group or an alkenediyl group having 1 to 9 carbon atoms, Z ^a are each independently a group capable of binding with two silicon _{atoms, [- 0-] 0. 5,} [- 0-G-] is a group selected from _0.5, or [-O-G-O-] _0.5 , Z ^b each independently represents a group capable of bonding to two silicon atoms, and is a functional group represented by [—O—G—O—] _0.5 , and Z ^c each independently represents —Cl, A functional group represented by —Br, —OR ¹² , R ¹² C (═O) O—, R ¹² R ¹³ C═NO—, R ¹² R ¹³ N—, R ¹² —, HO—G—O—; Yes, R and G agree with the above notation. m, n, u, v, and w are independently 1 ≦ m ≦ 20, 0 ≦ n ≦ 20, 0 ≦ u ≦ 3, 0 ≦ v ≦ 2, 0 ≦ w ≦ 1, and 1 / 2u + v + 2w = 2 or 3.
When there are a plurality of A parts, each of Z ^a _u , Z ^b _v and Z ^c _w in the plurality of A parts may be the same or different. When there are a plurality of B parts, Z ^a _u in the plurality of B parts , Z ^b _v and Z ^c _w may be the same or different. The silane coupling agent represented by these is used.

  As the silane coupling agent obtained by the general formula (3), the following chemical formula (7),

Chemical formula (8), and

Chemical formula (9),

[In formula, L is respectively independently a C1-C9 alkanediyl group or alkenediyl group. ] Can be mentioned.

Examples of the silane coupling agent represented by the chemical formula (7) include “NXT Low-V Silane” manufactured by Momentive Performance Materials.
Moreover, as a silane coupling agent represented by Chemical formula (8), the trademark "NXT Ultra Low-V Silane" made by Momentive Performance Materials is mentioned.
Furthermore, examples of the silane coupling agent represented by the chemical formula (9) include “NXT _- Z” manufactured by Momentive Performance Materials.
Since the silane coupling agent obtained by the chemical formulas (8) and (9) has a large number of alkyl carbons in the alkoxysilane, the generation of volatile compounds VOC (especially alcohol) is small, and this is especially preferable in the working environment. The silane coupling agent is more preferable because it has low exothermic properties.
In the present invention, the silane coupling agent of component (C) may be used alone or in combination of two or more. Moreover, the compounding quantity is selected in 2-25 mass% with respect to the silica in the filler of the said (B) component. If the blending amount of the silane coupling agent is within the above range, the effects of the present invention are sufficiently exhibited. A preferable blending amount is in the range of 5 to 15% by mass.
Moreover, the content of the silane coupling agent in the rubber composition is preferably in the range of 1 to 3% by mass from the viewpoint of the effect of the present invention.
In addition, since the mercapto group is protected in the silane coupling agent, it is necessary to perform deprotection to couple the polymer, so that a proton donor represented by DPG (diphenylguanidine) or the like is used as a deprotecting agent. It is preferable to mix in the final kneading step. The amount used is preferably from 0.1 to 5.0 parts by weight, more preferably from 0.2 to 3.0 parts by weight, per 100 parts by weight of the rubber component.

<Silane coupling agent represented by general formula (4)>
In the rubber composition according to the present invention, as the component (C), the general formula (4)

[Wherein R ¹⁴ and R ¹⁵ are each a hydrocarbon group having 1 to 4 carbon atoms, R ¹⁶ is a divalent hydrocarbon group having 1 to 15 carbon atoms, q is an integer of 0 to 2, and r is 1 as an average value. Less than 4 and R ¹⁷ is (a): (S—R ¹⁸ —S), (b): (R ¹⁹ —S _d —R ²⁰ ) and (c): (R ²¹ —S _g —R ²² —S). _h— R ²³ ), wherein R ^{18 to} R ²³ are linear or branched divalent hydrocarbon groups having 1 to 20 carbon atoms and divalent aromatic groups. A divalent organic group containing a hetero group other than a group group or sulfur and oxygen, wherein R ^{18 to} R ²³ may be the same or different, and d, g and h are each an average value of 1 or more and less than 4 is there. The silane coupling agent represented by this is used.

The component (C) silane coupling agent used in the present invention has a sulfur-containing compound represented by an average composition formula (4) having an organooxysilyl group at both ends of the molecule and a sulfide or polysulfide at the center of the molecule. Silane compound.
In this general formula, R ¹⁴ and R ¹⁵ are each a hydrocarbon group having 1 to 4 carbon atoms, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i- Examples thereof include a butyl group, a t-butyl group, a vinyl group, an allyl group, and an isopropenyl group. R ¹ and R ² may be the same or different. R ¹⁶ is a divalent hydrocarbon group having 1 to 15 carbon atoms. For example, methylene group, ethylene group, propylene group, n-butylene group, i-butylene group, hexylene group, decylene group, phenylene Group, methylphenylethylene group and the like. q represents an integer of 0 to 2, and m is 1 or more and less than 4 as an average value. r may have an average value within this range, and may be a mixture of a plurality of sulfur-containing silane compounds having different r. From the viewpoint of the effect of the present invention described later, r is preferably 1 or more and less than 2 as an average value, and more preferably r is 1.
R ^{17 in the} general formula (4) is the following (a): (S—R ¹⁸ —S), (b): (R ¹⁹ —S _d —R ²⁰ ) and (c): (R ²¹ —S _g — R ²² —S _h —R ²³ ). From the viewpoint of the effect of the present invention, R ¹⁷ is preferably (c): (R ²¹ —S _g —R ²² —S _h —R ²³ ).

Here, R ^{18 to} R ²³ are linear or branched divalent hydrocarbon groups having 1 to 20 carbon atoms, divalent aromatic groups, or divalent organic groups containing hetero elements other than sulfur and oxygen. For example, methylene group, ethylene group, propylene group, n-butylene group, i-butylene group, hexylene group, decylene group, phenylene group, methylphenylethylene group, etc. and nitrogen which is a hetero element other than sulfur and oxygen And groups having phosphorus introduced therein. R ^{18 to} R ²³ in R ¹⁷ (any one of the functional groups represented by (a) to (c)) of the general formula (4) may be the same or different. From the viewpoint of the effect of the present invention and production cost, R ^{18 to} R ²³ in R ⁴ (any one of the functional groups represented by (a) to (c)) of the general formula (4) are hexylene groups. Preferably there is.
R ¹⁷ must contain a sulfur atom, and d, g, and h are 1 or more and less than 4 on average. From the viewpoint of the effect of the present invention to be described later, d, g, and h are each preferably an average value of 2 or more and less than 4, and more preferably 2 or more and 3 or less.

  As a silane coupling agent, a sulfur-containing silane compound having a specific structure having an organooxysilyl group at both ends of the molecule and a sulfide or polysulfide at the center of the molecule is blended at a ratio of 1 to 25% by mass with respect to silica. Thus, a rubber composition having a high dispersibility of silica, and when used as a tread member of a tire, a tire having high wear resistance, low rolling resistance, and improved braking performance on a wet road surface can be obtained. it can.

<Silane coupling agent represented by general formula (5)>
In the rubber composition according to the present invention, as the component (C), the general formula (5)

[Wherein R ²⁴ is a methyl group or an ethyl group, R ²⁵ is a methoxy group, is an ethoxy group or —O— (Y—O) _m —X, and Y is branched or unbranched, saturated. other or not saturated, divalent hydrocarbon group, X is C ₁ -C ₉ - alkyl group, m is 1 to 40, R ²⁶ is methyl group, ethyl group or R ²⁵ , R ²⁷ is a branched or unbranched, saturated or unsaturated, aliphatic, aromatic or aliphatic / aromatic mixed divalent C ₁ -C ₁₂ hydrocarbon group. The silane coupling agent represented by this is used.

When used as a rubber composition, R ²⁴ is a methyl group or an ethyl group, R ²⁵ is represented by —O— (Y—O) _m —X, and Y is branched or unbranched, saturated or saturated. A divalent hydrocarbon group, preferably CH ₂ , CH ₂ CH ₂ , CH ₂ CH (CH ₃ ) or CH (CH ₃ ) CH ₂ .
X is a C1 to C9 alkyl group, preferably methyl or ethyl, m is 1 to 40, preferably 2 to 30, more preferably 3 to 25, 4 to 20, particularly preferably 10 to 20 preferable. R ²⁶ is methyl, ethyl, methoxy, ethoxy or R ²⁵ and R ²⁷ is branched or unbranched, saturated or unsaturated, aliphatic, aromatic or aliphatic / aromatic mixed And an organosilane represented by a divalent C _{1 to} C ₁₂ -hydrocarbon group.
Preferred examples of R ²⁷ include CH ₂ , CH ₂ CH ₂ , CH ₂ CH ₂ CH ₂ , CH ₂ CH ₂ CH ₂ CH ₂ , CH (CH ₃ ), CH ₂ CH (CH ₃ ), CH (CH ₃ ). _{CH 2, C (CH 3)} 2, CH (C 2 H 5), CH 2 CH 2 CH (CH 3) or _{CH 2 CH (CH 3) CH} 2 can be mentioned.

As a compound represented by the general formula (5), dimethylethoxysilylpropyl mercaptan, methyldiethoxysilylpropyl mercaptan, diethylethoxysilylpropyl mercaptan, ethyldiethoxysilylpropyl mercaptan, dimethylmethoxysilylpropyl mercaptan, methyldimethoxysilylpropyl mercaptan, diethyl methoxysilylpropyl mercaptan, ethyl dimethoxy silyl propyl _{mercaptan, (CH 3 O) (CH} 3) 2 Si- (CH 2) 2 CH (CH 3) -SH or _{(C 2 H 3 O) (} CH 3) 2 Si _{- (CH 2) 2 CH (} CH 3) can be mentioned -SH. As a commercial item, the product name "Si363" by Degussa company can be mentioned. By using the silane coupling agent, it is possible to obtain a rubber composition in which the low exothermic property and wear resistance of the vulcanizate are improved.

<Silane coupling agent represented by general formula (6)>
In the rubber composition according to the present invention, as the component (C), the general formula (6)

[Wherein R ²⁸ may be the same or different, each linear or branched alkyl group having 1 to 4 carbon atoms and linear or branched alkoxy having 2 to 8 carbon atoms. Represents a monovalent hydrocarbon group selected from the group consisting of alkyl groups, R ²⁹ and R ³⁰ may be the same or different, each linear or branched alkyl group having 1 to 6 carbon atoms; And a monovalent hydrocarbon group selected from the group consisting of a phenyl group and t is an integer or fraction in the range of 3-5. The silane coupling agent represented by this is used.
Conventionally used polysulfurized alkoxysilanes such as bis- (alkoxysilylalkyl) polysulfides, especially bis-3-triethoxysilylpropyltetrasulfide [(C ₂ H ₅ O) ₃ Si ( CH ₂ ) ₃ S ₂ ] ₂ (sometimes abbreviated as TESPT) manufactured by Degussa and trade name [Si69].
However, these elastomer compositions mainly composed of silica and TESPT have a substantially very low vulcanization rate as compared with conventional compositions filled with carbon black, and require vulcanization for a long time. However, the silane coupling agent represented by the general formula (6) can achieve a curing time substantially equivalent to the curing time of the conventional composition mainly composed of carbon black. Among them, the following general formula (10),

[Bis-monoethoxydimethylsilylpropyl tetrasulfide] (MESPT may be omitted) represented by [wherein t represents a range of 3 to 5] is particularly preferable.
Here, t is in the range of 3-5, preferably in the range of 3.5-4.5.
Compared to the case where conventional TESPT is used by using a combination of the MESPT and a modified diene polymer as a rubber component, the rubber has improved wear resistance and low rolling resistance (low fuel consumption). The tire of the present invention excellent in wear resistance and fuel efficiency using the composition and the rubber composition in a tread can be obtained.
Moreover, as a preferable silane coupling agent represented by General formula (6), following General formula (12),

及び下記一般式（１３）

And the following general formula (13)

等をあげることができる。

Etc.

[Rubber composition]
The rubber composition according to the present invention comprises (B) 20 to 150 parts by mass of silica and (C) described above with respect to 100 parts by mass of the rubber component containing 10 parts by mass or more of the above-mentioned (A) modified conjugated diene polymer. A silane coupling agent is contained at a ratio of 1 to 25% by mass with respect to silica of the component (B).
(Rubber component)
The rubber composition used in the present invention needs to contain at least 10 parts by mass of the (A) modified conjugated diene polymer as a rubber component. A more preferable content of the modified conjugated diene polymer in the rubber component is 30 parts by mass or more, and particularly 40 parts by mass or more is preferable. By setting the modified conjugated diene polymer in the rubber component to 10 parts by mass or more, a rubber composition having desired physical properties can be obtained.
This modified conjugated diene polymer may be used alone or in combination of two or more. Other rubber components used in combination with the modified conjugated diene polymer include natural rubber, synthetic isoprene rubber, butadiene rubber, styrene-butadiene rubber, ethylene-α-olefin copolymer rubber, ethylene-α-olefin-diene. Preferably, it contains 90-0 parts by mass of at least one selected from copolymer rubber, chlorobrene rubber, halogenated butyl rubber, and a copolymer of styrene having a halogenated methyl group and isobutylene, and 70-0 parts by mass It is more preferable that it contains, and it is especially preferable that 60-0 mass part is included.

(Filler)
The rubber composition used in the present invention needs to contain 20 to 150 parts by mass of (B) silica as a filler with respect to 100 parts by mass of the rubber component. Preferably, it is 20-120 mass parts, More preferably, it is 40-110 mass parts. By making the compounding quantity of the silica into the above-mentioned range, it is possible to suppress the deterioration of workability and obtain excellent low rolling resistance.
Moreover, as a compounding quantity of a silica, the ratio of the silica with respect to the total amount of fillers has preferable 20 mass% or more. More preferably, it is 30 mass% or more. By setting the blending ratio, reduction of rolling resistance can be ensured.

Furthermore, the rubber composition used in the present invention preferably contains carbon black as a filler. The total amount of carbon black is preferably 10 parts by mass or more with respect to 100 parts by mass of the rubber component, and the total amount of carbon black and silica is 40 from the viewpoint of reinforcing effect and the effect of improving various physical properties thereby. -160 mass parts is preferable. By setting the amounts of carbon black and silica in the above ranges, the factory workability such as kneading workability is excellent, and desired fracture characteristics and abrasion resistance can be obtained as a rubber composition.
The details of the component (A), the component (B) and the component (C) are as described above.

  In the rubber composition used in the present invention, a modified polymer in which a functional group having a high affinity for silica is introduced into a molecular active site is used as a rubber component. , It can be reduced more than usual. The blending amount of the preferred silane coupling agent varies depending on the kind of the silane coupling agent, but is preferably selected in the range of 1 to 25% by mass with respect to silica. If this amount is less than 1% by mass, the effect as a coupling agent is hardly exhibited, and if it exceeds 25% by mass, the rubber component may be gelled. From the viewpoints of the effect as a coupling agent and the prevention of gelation, the preferred amount of the silane coupling agent is in the range of 1 to 20% by mass, more preferably 5 to 15% by mass.

(Preparation and use of rubber composition)
The method for preparing the rubber composition used in the present invention is not particularly limited, and the rubber component can be added and mixed using an ordinary kneader, such as a Banbury mixer, roll, intensive mixer, or the like.
In the rubber composition used in the present invention, various chemicals usually used in the rubber industry, for example, a vulcanizing agent, a vulcanization accelerator, a process oil, an aging, are used as long as the purpose of the present invention is not impaired. An inhibitor, a scorch inhibitor, zinc white, stearic acid and the like can be contained.
The rubber composition used for the tire of the present invention is obtained by kneading using a kneader such as an open kneader such as a roll or a closed kneader such as a Banbury mixer, and is added after the molding process. It can be applied to various rubber products. For example, it can be used for tire applications such as tire treads, under treads, carcass, sidewalls, side reinforcing rubbers, and bead parts (particularly bead fillers), but in particular, low heat generation and excellent wear resistance, low fuel consumption It is suitably used as a tread rubber for automobile tires, large tires, and high performance tires.

[tire]
The tire of the present invention is characterized in that the rubber composition described above is used for a tire member. As the tire member, a tread, a base tread, a sidewall, a side reinforcing rubber, and a bead filler can be preferably exemplified, and the rubber composition described above can be used for any of these, particularly for a tread. preferable.
A tire using the rubber composition of the present invention as a tread has low rolling resistance and excellent fuel efficiency and wear resistance. 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.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to the following Example at all.
In addition, the tire (tire size) which used for the tread the microstructure (bonded vinyl content, bound styrene content) of modified and unmodified styrene-butadiene rubber (solution SBR), and the rubber composition obtained with each compounding composition shown in Table 1 : 195 / 65R15) rolling resistance (low RR) and wear resistance were measured and evaluated by the following methods.

(1) Microstructure of modified solution SBR (1) -1. Bound vinyl content of the conjugated diene moiety (% of total diene moiety)
Obtained by 270 MHz ¹ H-NMR.
(1) -2. Bonded styrene content of modified SBR (% by weight in polymer)
Obtained by 270 MHz ¹ H-NMR.

(2) Tire performance (2) -1. Rolling resistance (RR)
Using a rotating drum having an outer diameter of 1707.6 mm and a width of 350 mm having a steel plane, measurement was performed by a coasting method by rotating at a speed of 80 km / h under the action of a load of 4500 N (460 kg). The measured values were indexed with the value of Comparative Example 1 as 100. The larger this value, the better the rolling resistance (low fuel consumption).
(2) -2. Abrasion resistance Tire size: 195 / 65R15 tires are used on actual paved roads for 20,000 kilometers, and the remaining grooves are measured, and the distance traveled for 1mm of tread wear is compared. The index is shown with 1 being 100. It shows that abrasion resistance is so favorable that an index | exponent is large.

Synthesis Example 1 Synthesis of modifier A A N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine 1 mol / kg in a dry, nitrogen-substituted 300 ml pressure-resistant glass container A 1 mol / liter diethyl ether solution of methyllithium was added dropwise so as to be equimolar with this solution, and stirred well to obtain N- (1,3-dimethylbutyrate as the modifier A. A denaturing agent solution (A) of (redene) -3- [diethoxy (methyl) silyl] -1-propanamine was prepared.

Synthesis Example 2 Synthesis of Modifier B In Synthesis Example 1, instead of N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, 1- (3-triethoxysilylpropyl) The modifier solution B of 1- [3- [diethoxy (methyl) silyl] propyl] -imidazole was prepared as the modifier B in the same manner as in Synthesis Example 1 except that) -imidazole was used.

Production Example 1
<Production of SBR having active terminal>
Add 1,3-butadiene in cyclohexane and styrene in cyclohexane to a dry, nitrogen-substituted 800 mL pressure-resistant glass container so that 1,3-butadiene 60 g and styrene 15 g are added, and 2,2-ditetrahydrofuryl is added. After adding 0.70 mmol of propane and further adding 0.70 mmol of n-butyllithium (BuLi), a polymerization reaction was performed in a hot water bath at 50 ° C. for 1.5 hours. The polymerization conversion rate at this time was almost 100%.
<Modification reaction process>
Next, the modifier A was added in an amount such that the modifying agent A was equimolar with respect to lithium (Li), and the modification reaction was further performed at 50 ° C. for 30 minutes.
<Post-polymerization treatment>
Next, an isopropanol solution of 2,6-di-tert-butyl-p-cresol (BHT) was added to the polymerization reaction system to stop the polymerization reaction. Thereafter, steam was blown to lower the solvent partial pressure (steam stripping) to remove the solvent, followed by vacuum drying to obtain modified SBR A. The resulting modified SBR A had a bound styrene content of 21% by weight and a bound vinyl content of the butadiene portion of 55%.

Production Example 2
In Production Example 1, modified SBR B was obtained in the same manner as in Production Example 1 except that the modifier B was used instead of the modifier A. The resulting modified SBR B had a bound styrene content of 20% by weight and a bound vinyl content of the butadiene portion of 55%.

Unmodified SBR
Unmodified SBR used as a control was SBR obtained by performing post-polymerization treatment without modifying SBR obtained by the production of SBR having an active terminal in Production Example 1.

Synthesis example 1 of silane coupling agent represented by general formula (4)
In a 0.5 liter separable flask equipped with a nitrogen gas inlet tube, a thermometer, a Dimroth condenser and a dropping funnel, ethanol 80 g, anhydrous sodium sulfide 5.46 g (0.07 mol), sulfur 2.24 g (0. 07 mol), and the temperature was raised to 80 ° C. While this solution was stirred, 33.7 g (0.14 mol) of propyltriethoxysilane chloride ((CH ₃ CH ₂ O) ₃ Si— (CH ₂ ) ₃ —Cl) and 1,6-dichlorohexane (ClCH _{2 - (CH 2) 4 -CH 2} Cl) 10.8g (0.07 mol) was slowly added dropwise. After completion of dropping, stirring was continued at 80 ° C. for 10 hours. After completion of the stirring, the mixture was cooled and the formed salt was filtered off, and then ethanol as a solvent was distilled under reduced pressure.
The obtained solution was subjected to infrared absorption spectrum analysis (IR analysis), ¹ H nuclear magnetic resonance spectrum analysis ( ¹ H-NMR analysis), and supercritical chromatography analysis. As a result, an average composition formula (CH ₃ CH ₂ O) ₃ it was confirmed that the _{Si- (CH 2) 3 -S-} S- (CH 2) 6 -S-S- (CH 2) 3 -Si (OCH 2 CH 3) the compound represented by _3. That is, in the average composition formula (4), R ¹ is an ethyl group, R ³ is an n-propyl group, R ⁴ is S— (CH ₂ ) ₆ —S (general formula (a), and R ⁵ is ( CH ₂ ) ₆ ), p = 0 and m = 1. The purity of this product in gel permeation chromatographic analysis (GPC analysis) was 82.5%.

Examples 1-10 and Comparative Examples 1-5
Each rubber composition of Examples 1-10 and Comparative Examples 1-5 was prepared according to the compounding prescription shown in Table 1.
Using each rubber composition as a tread, a tire was prototyped (tire size: 195 / 65R15), and rolling resistance (low fuel consumption) and body wear were measured. The measurement results are shown in Table 1.

「注」
＊１．ＳＢＲ１７１２［ＪＳＲ社製］ゴム成分１００質量部に対して３７．５質量部の油で油展。油分１８．７５質量部含む
＊２．無変性ＳＢＲ：製造実施例１のＳＢＲを変性すること無しに重合後処理を行ったＳＢＲを用いた。
＊３．変性ＳＢＲ Ａ：変性剤としてケイ素原子に直接結合するヒドロカルビルオキシ基を２つ有する「Ｎ−（１，３−ジメチルブチリデン）−３−［ジエトキシ（メチル）シリル］−１−プロパンアミン」を用いた.
＊４．変性ＳＢＲ Ｂ：変性剤としてケイ素原子に直接結合するヒドロカルビルオキシ基を２つ有する「１−［３−［ジエトキシ（メチル）シリル］プロピル］−イミダゾール」を用いた。
＊５．カーボンブラック：シーストＫＨ（Ｎ３３９）［東海カーボン社製］
＊６．シリカ：ニプシールＡＱ［東・ソーシリカ社製］
＊７．シランカップリング剤：「Ｓｉ６９」［Ｄｅｇｕｓｓａ社製］
＊８．ＮＴＸシラン：Ｇｅｎｅｒａｌ Ｅｌｅｃｔｒｉｃ社製、商品名「ＮＸＴシラン」、化学名：３−オクタノイルチオプロピルトリエトキシシラン
＊９．ＮＸＴ Ｚシラン：Ｍｏｍｅｎｔｉｖｅ Ｐｅｒｆｏｒｍａｎｃｅ Ｍａｔｅｒｉａｌｓ社製、商標、「ＮＸＴ_-Ｚ」
＊１０．シランカップリング剤：「Ｓｉ３６３」［Ｄｅｇｕｓｓａ社製］
＊１１．一般式（４）で表されるシランカップリング剤の合成例１で得られたものを用いた。
＊１２．モノアルキルジエトキシシラン：化学名：ビス−モノエトキシジメチルシリルプロピルテトラスルフィド
＊１３．老化防止剤６Ｃ：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
＊１３．加硫促進剤ＤＰＧ：ジフェニルガニジン
＊１４．加硫促進剤ＣＺ：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
＊１５．加硫促進剤ＤＭ：ジベンゾチアジルジスルフィド

"note"
* 1. SBR1712 [manufactured by JSR] Oil-extended with 37.5 parts by mass of oil with respect to 100 parts by mass of the rubber component. Contains 18.75 parts by mass of oil. * 2. Unmodified SBR: SBR subjected to post-polymerization treatment without modifying SBR of Production Example 1 was used.
* 3. Modified SBR A: “N- (1,3-dimethylbutylidene) -3- [diethoxy (methyl) silyl] -1-propanamine” having two hydrocarbyloxy groups directly bonded to silicon atoms is used as a modifier. It was.
* 4. Modified SBR B: “1- [3- [diethoxy (methyl) silyl] propyl] -imidazole” having two hydrocarbyloxy groups directly bonded to a silicon atom was used as a modifier.
* 5. Carbon black: Seast KH (N339) [Tokai Carbon Co., Ltd.]
* 6. Silica: Nipseal AQ [East / So silica company]
* 7. Silane coupling agent: “Si69” [manufactured by Degussa]
* 8. NTX silane: manufactured by General Electric, trade name “NXT silane”, chemical name: 3-octanoylthiopropyltriethoxysilane * 9. NXT Z Silane: Momentive Performance Materials, trademark, “NXT _- Z”
* 10. Silane coupling agent: “Si363” [manufactured by Degussa]
* 11. The silane coupling agent represented by the general formula (4) obtained in Synthesis Example 1 was used.
* 12. Monoalkyldiethoxysilane: Chemical name: Bis-monoethoxydimethylsilylpropyl tetrasulfide * 13. Anti-aging agent 6C: N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine * 13. Vulcanization accelerator DPG: Diphenylganidine * 14. Vulcanization accelerator CZ: N-cyclohexyl-2-benzothiazolylsulfenamide * 15. Vulcanization accelerator DM: Dibenzothiazyl disulfide

The following can be seen from Table 1.
Examples 1 to 10 in which a specific amount of (A) component modified diene polymer, (B) silica and (C) silane coupling agents represented by general formulas (2) to (6) are combined are comparative examples. Compared to 1 to 5, excellent results in both fuel efficiency and wear resistance are obtained.
In particular, the combination of the component (A), the component (B), and NXT silane, NXT Z silane and the silane obtained in Synthesis Example 1 represented by the general formula (4) as a silane coupling agent is low fuel consumption. It can be seen that both the wear resistance and the wear resistance are improved in a well-balanced manner.

According to the present invention, in a silica-containing rubber composition, a bifunctional hydrocarbyloxysilane derivative having two hydrocarbyloxy groups directly bonded to a silicon atom and having a specific functional group in the same molecule is used as a modifier. Silica by containing 10 parts by mass or more of the modified conjugated diene polymer obtained by using the rubber component and further containing a silane coupling agent having a specific structure in a proportion of 1 to 25% by mass with respect to silica. Thus, it is possible to provide a tire having the above-described performance using a rubber composition excellent in low heat generation and wear resistance, in which both performances are highly balanced and both performances are highly balanced.

Claims (24)

(A) A conjugated diene polymer having an organometallic active terminal having nucleophilic reactivity has the following general formula (1)

Wherein A ¹ is a hydrocarbyloxy group having 2 or more carbon atoms, A ² is a hydrolyzable functional group, R ¹ is a hydrocarbon group, R ² is a divalent hydrocarbon group, and X is a saturated cyclic tertiary group. Among amine compound residues, unsaturated cyclic tertiary amine compound residues, ketimine residues, nitrile groups, (thio) isocyanate groups, (thio) epoxy groups, and secondary amino groups having removable functional groups At least one functional group selected is shown. A ¹ and A ² may be the same or different. The rubber component containing 10 parts by mass or more of the modified conjugated diene polymer obtained by reacting the modifier represented by formula (B) and 20 to 150 parts by mass of silica with respect to 100 parts by mass of the rubber component And (C) at least one silane coupling agent represented by the following general formulas (2) to (6) is contained in a proportion of 1 to 25% by mass with respect to the silica of the component (B). A tire using a rubber composition characterized by the above.

[Wherein R ³ represents —Cl, —Br, R ⁸ O—, R ⁸ C (═O) O—, R ⁸ R ⁹ C═NO—, R ⁸ R ⁸ N— or — (OSiR ⁸ R ^{9 _{) m (OSiR 7 R 8 R}} 9) ( provided that, R ⁸ and R ⁹ is a hydrocarbon group of each independently a hydrogen atom or a C1-18 monovalent.), R ⁴ is R ^3, a hydrogen An atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms, R ⁵ is R ³ , R ⁴ or — [O (R ¹⁰ O) _a ] _0.5 — group (where R ¹⁰ is alkylene having 1 to 18 carbon atoms) Group, a is an integer of 1 to 4), R ⁶ is a divalent hydrocarbon group having 1 to 18 carbon atoms, R ⁷ is a monovalent hydrocarbon group having 1 to 18 carbon atoms, x, y and z are numbers satisfying the relationship of x + y + 2z = 3, 0 ≦ x ≦ 3, 0 ≦ y ≦ 2, and 0 ≦ z ≦ 1. ]

[Wherein R ¹¹ is or straight chain having 1 to 20 carbon atoms, branched or cyclic alkyl group, G is independently an alkanediyl group or an alkenediyl group having 1 to 9 carbon atoms, Z ^a are each independently a group capable of binding with two silicon _{atoms, [- 0-] 0. 5,} [- 0-G-] is a group selected from _0.5, or [-O-G-O-] _0.5 , Z ^b each independently represents a group capable of bonding to two silicon atoms, and is a functional group represented by [—O—G—O—] _0.5 , and Z ^c each independently represents —Cl, A functional group represented by —Br, —OR ¹² , R ¹² C (═O) O—, R ¹² R ¹³ C═NO—, R ¹² R ¹³ N—, R ¹² —, HO—G—O—; Yes, R and G agree with the above notation. m, n, u, v, and w are independently 1 ≦ m ≦ 20, 0 ≦ n ≦ 20, 0 ≦ u ≦ 3, 0 ≦ v ≦ 2, 0 ≦ w ≦ 1, and 1 / 2u + v + 2w = 2 or 3.
When there are a plurality of A parts, each of Z ^a _u , Z ^b _v and Z ^c _w in the plurality of A parts may be the same or different. When there are a plurality of B parts, Z ^a _u in the plurality of B parts , Z ^b _v and Z ^c _w may be the same or different. ]

[Wherein R ¹⁴ and R ¹⁵ are each a hydrocarbon group having 1 to 4 carbon atoms, R ¹⁶ is a divalent hydrocarbon group having 1 to 15 carbon atoms, q is an integer of 0 to 2, and r is 1 as an average value. Less than 4 and R ¹⁷ is (a): (S—R ¹⁸ —S), (b): (R ¹⁹ —S _d —R ²⁰ ) and (c): (R ²¹ —S _g —R ²² —S). _h— R ²³ ), wherein R ^{18 to} R ²³ are linear or branched divalent hydrocarbon groups having 1 to 20 carbon atoms and divalent aromatic groups. A divalent organic group containing a hetero group other than a group group or sulfur and oxygen, wherein R ^{18 to} R ²³ may be the same or different, and d, g and h are each an average value of 1 or more and less than 4 is there. ]

[Wherein R ²⁴ is a methyl group or an ethyl group, R ²⁵ is a methoxy group, is an ethoxy group or —O— (Y—O) _m —X, and Y is branched or unbranched, saturated. other or not saturated, divalent hydrocarbon group, X is C ₁ -C ₉ - alkyl group, m is 1 to 40, R ²⁶ is methyl group, ethyl group or R ²⁵ , R ²⁷ is a branched or unbranched, saturated or unsaturated, aliphatic, aromatic or aliphatic / aromatic mixed divalent C ₁ -C ₁₂ hydrocarbon group. ]

[Wherein R ²⁸ may be the same or different, each linear or branched alkyl group having 1 to 4 carbon atoms and linear or branched alkoxy having 2 to 8 carbon atoms. Represents a monovalent hydrocarbon group selected from the group consisting of alkyl groups, R ²⁹ and R ³⁰ may be the same or different, each linear or branched alkyl group having 1 to 6 carbon atoms; And a monovalent hydrocarbon group selected from the group consisting of phenyl groups, and t is an integer or fraction in the range of 3-5. ] In the modifier represented by the general formula (1), A ¹ is a hydrocarbyloxy group having 2 to 18 carbon atoms, A ² is a hydrocarbyloxy group having 1 to 18 carbon atoms or a halogen atom, and R ¹ is 1 to 18 carbon atoms. The tire using the rubber composition according to claim 1, wherein R ² is a divalent hydrocarbon group having 1 to 20 carbon atoms. In denaturing agent represented by the general formula (1), tire A ² is produced using the rubber composition according to claim 1 or 2 hydrocarbyloxy group having 1 to 18 carbon atoms. The tire using the rubber composition according to claim 2 or 3, wherein R ² in the general formula (1) is an alkanediyl group having 2 to 10 carbon atoms. A tire using the rubber composition according to any one of claims 2 to 4, wherein A ¹ in the general formula (1) is an ethoxy group. A tire using the rubber composition according to any one of claims 2 to 5, wherein R ¹ in the general formula (1) is a methyl group.   The rubber composition according to any one of claims 2 to 6, wherein, in general formula (1), the unsaturated cyclic tertiary amine compound residue in X is an imidazole residue, a dihydroimidazole residue, an oxazole residue or a pyridyl group. Tire using things.   Secondary in which X in general formula (1) has a ketimine residue, a saturated cyclic tertiary amine compound residue, an imidazole residue, a dihydroimidazole residue, a pyridyl group, a nitrile group, an isocyanate group and a detachable functional group The tire using the rubber composition according to claim 7, which is a monovalent group having at least one nitrogen-containing functional group selected from amino groups.   The nitrogen-containing functional group is at least one selected from a saturated cyclic tertiary amine compound residue, a ketimine residue, an imidazole residue, a dihydroimidazole residue, and a secondary amino group having a detachable functional group. A tire using the rubber composition according to claim 8.   A conjugated diene polymer having an organometallic active terminal having nucleophilic reactivity is a conjugated diene compound alone or a conjugated diene compound and an aromatic vinyl, using an organic alkali metal compound containing C-Li or N-Li as a polymerization initiator. A tire using the rubber composition according to any one of claims 1 to 9, wherein the tire is obtained by anionic polymerization of a compound.   The tire using the rubber composition according to claim 10, wherein the conjugated diene compound is at least one selected from 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene.   The tire using the rubber composition according to claim 10 or 11, wherein the aromatic vinyl compound is styrene.   The tire using the rubber composition according to claim 1, wherein the functional group capable of binding to silica of the component (C) is an alkoxysilane group. The component (C) represented by the general formula (3) is represented by the chemical formula (7),

Chemical formula (8), and

Chemical formula (9)

[In the formula, each L is independently an alkanediyl or alkenediyl group having 1 to 9 carbon atoms. A tire using the rubber composition according to claim 1, wherein the tire is a silane coupling agent represented by the formula:   The tire using the rubber composition according to claim 1, wherein r in the general formula (4) is 1. The rubber composition according to claim 1, wherein g, d, and h in (a), (b), and (c) in R ¹⁷ of the general formula (4) are 2 or more and 3 or less as an average value. tire. The R ¹⁷ in the general formula (4) is (c): R ²¹ —S _d —R ²² —S _h —R ²³ , and R ²¹ , R ²² and R ²³ are hexylene groups. A tire using the described rubber composition.   The tire using the rubber composition according to claim 1, wherein the component (C) in the general formula (5) contains the oligomerized or polymerized organosilane of the general formula (5).   The component (C) in the general formula (5) is dimethylethoxysilylpropyl mercaptan, methyldiethoxysilylpropyl mercaptan, diethylethoxysilylpropyl mercaptan, ethyldiethoxysilylpropyl mercaptan, dimethylmethoxysilylpropyl mercaptan, methyldimethoxysilylpropyl mercaptan. 2. A tire using the rubber composition according to claim 1, which is diethylmethoxysilylpropyl mercaptan or ethyldimethoxysilylpropyl mercaptan. R ¹ in the general formula (6) is selected from the group consisting of methyl, ethyl, n-propyl and isopropyl groups, and R ² and R ³ are methyl, ethyl, n-propyl, isopropyl, n-butyl, n-hexyl. And a tire using the rubber composition according to claim 1, which is selected from the group consisting of phenyl groups. The component (C) in the general formula (6) is represented by the following general formula (10),

[Wherein t represents a range of 3 to 5. A tire using the rubber composition according to claim 20, which is bis-monoethoxydimethylsilylpropyl tetrasulfide (MESPT) represented by the formula:   The tire using the rubber composition according to any one of claims 1 to 21, wherein the amount of silica relative to the total amount of filler is 20% by mass or more in terms of mass ratio.   23. The carbon black as a reinforcing filler is contained in an amount of 10 parts by mass or more based on 100 parts by mass of the rubber component, and the total amount of carbon black and silica is in the range of 40 to 160 parts by mass. A tire using the rubber composition described in 1.   A tire using the rubber composition according to any one of claims 1 to 23 as a tread member.