JP2011057946A - Rubber composition and tire using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a rubber composition which is particularly excellent in the interaction of a rubber component and carbon black and/or silica, improves the dispersibility of these filling materials, and provides a tire superior in low heat generation property, wear resistance or the like. <P>SOLUTION: The rubber composition contains: (A) 100 pts.mass of a rubber component containing ≥10 mass% of a modified conjugated diene-based polymer, obtained by reacting, as a modifying agent, a silane compound having a specific structure and/or a partial condensate thereof to an active terminal of a conjugated diene-based polymer having an organometallic active terminal with nucleophilic reactivity; (B) 20-120 pts.mass in total of silica and/or carbon black; and (C) a compound expressed by general formula (2): Q-A-B (wherein, Q represents a bipolar nitrogen atom-containing part, B represents oxazoline part, thiazoline part, alkoxy silane part or allyltin part, and A represents a linking atom or group for forming a bridge between Q and B). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a rubber composition and a tire using the rubber composition. More specifically, the present invention relates to a rubber composition capable of giving a tire excellent in low heat build-up, wear resistance, etc., and a tire having the above-mentioned performance using this rubber composition as a tire member. is there.

  In recent years, demands for reducing the fuel consumption of automobiles are becoming more severe in connection with the movement of global carbon dioxide emission regulations due to the social demand for energy saving and the increasing interest in environmental problems. In order to meet such demands, a reduction in rolling resistance has also been demanded for tire performance. As a technique for reducing the rolling resistance of the tire, although a technique by optimizing the tire structure has been studied, the most common technique is to use a material having lower heat generation as the rubber composition.

  In order to obtain such a rubber composition having a low exothermic property, many technical developments have been made on modified rubbers for rubber compositions using silica or carbon black as a filler. Among them, a method in which the polymerization active terminal of a conjugated diene polymer obtained by anionic polymerization using organolithium is modified with an alkoxysilane derivative containing a functional group that interacts with a filler has been proposed as effective. (For example, see Patent Documents 1, 2, and 3).

  Each of these alkoxysilane derivatives is a silicon compound having an alkoxy group directly bonded to a silicon atom in the molecule and a nitrogen-containing functional group that interacts with the filler. The modified conjugated diene polymer obtained by modification has the effect of reducing the rolling resistance of the tire and improving the fracture characteristics and wear resistance. However, in recent years, from the viewpoints of energy saving and environmental problems, further reduction in fuel consumption of automobiles (reduction in rolling resistance of tires) and improvement in wear resistance are desired.

  On the other hand, a first part Q that can be bonded to the polymer by adding to a plurality of unsaturated carbon-carbon bonds in the molecular structure of the polymer, and a second part that can be bonded to one or more surface groups of one or more fillers By using a polymer-filler coupling compound of the QA-B type having B and a linking atom or group A that forms a bridge between Q and B, one or more of them in the polymer composition It is disclosed that dispersion of the filler can be improved (for example, see Patent Document 4).

JP 2001-158837 A JP 2005-232364 A JP-A-2005-290355 Special table 2008-517071 gazette

  Under such circumstances, the present invention is particularly excellent in the interaction between the rubber component and carbon black and / or silica, and can further improve the dispersibility of these fillers, such as low heat buildup and wear resistance. It is an object of the present invention to provide a rubber composition capable of providing a tire excellent in the above and a tire having the above-described performance using the rubber composition.

  As a result of intensive studies to achieve the above object, the inventors of the present invention contain a rubber component containing a modified conjugated diene polymer obtained by using a specific modifier and silica and / or carbon black. In addition, the present inventors have found that the object can be achieved by a rubber composition containing the above-mentioned QAB type compound having a coupling function between a rubber component and silica or carbon black. The present invention has been completed based on such findings.

That is, the present invention
[1] A conjugated diene polymer having an organometallic active terminal having nucleophilic reactivity has a general formula (1) as a modifier at the active terminal.

［式中、Ａ¹は炭素数２以上のヒドロカルビルオキシ基、Ａ²は加水分解性官能基、Ｒ¹は炭化水素基、Ｒ²は二価の炭化水素基を示し、Ｘは飽和環状３級アミン化合物残基、不飽和環状３級アミン化合物残基、ケチミン残基、ニトリル基、（チオ）イソシアナート基、（チオ）エポキシ基及び脱離可能な官能基を有する２級アミノ基の中から選ばれる少なくとも一種の官能基を示す。Ａ¹及びＡ²は同一でも異なっていてもよい。］

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. ]

And (B) silica and / or carbon with respect to 100 parts by mass of a rubber component containing 10% by mass or more of a modified conjugated diene polymer obtained by reacting the silane compound represented by While containing 20 to 120 parts by mass of black in total, (C) General formula (2)
Q-A-B (2)
Wherein Q represents a dipolar nitrogen atom-containing moiety, B represents an oxazoline moiety, a thiazoline moiety, an alkoxysilane moiety or an allyltin moiety, and A represents a linking atom or group that forms a bridge between Q and B. Show.)
A rubber composition comprising a compound represented by:
[2] The rubber composition according to [1] above, wherein the modified conjugated diene polymer is subjected to a condensation reaction treatment in the presence of a condensation accelerator after reacting the modifier.
[3] The rubber composition according to the above [1] or [2], which comprises (B) 0.02 to 20% by mass of the compound (C) with respect to the total amount of (B) silica and / or carbon black,
[4] 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. 1 to 18 hydrocarbon groups, R ² is a divalent hydrocarbon group having 1 to 20 carbon atoms, the rubber composition according to any one of the above [1] to [3],
[5] The rubber composition according to the above [4], wherein in the modifying agent represented by the general formula (1), A ² is a hydrocarbyloxy group having 1 to 18 carbon atoms,
[6] The rubber composition according to the above [4] or [5], wherein R ² in the general formula (1) is an alkanediyl group having 2 to 10 carbon atoms.
[7] Any of the above [4] 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 Any rubber composition,

[8] X in the general formula (1) is 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. The rubber composition according to any one of the above [4] to [6], which is a monovalent group having at least one nitrogen-containing functional group
[9] A conjugated diene polymer having an organometallic active terminal having nucleophilic reactivity is a conjugated diene compound alone or a conjugated diene compound using an organic alkali metal compound containing C-Li or N-Li as a polymerization initiator. The rubber composition according to any one of the above [1] to [8], which is obtained by anionic polymerization of an aromatic vinyl compound;
[10] The rubber composition according to the above [9], wherein the conjugated diene compound is at least one selected from 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene.
[11] The rubber composition according to the above [9] or [10], wherein the aromatic vinyl compound is styrene,
[12] (A) The rubber component is 10 to 100% by mass of the modified conjugated diene polymer, natural rubber, synthetic isoprene rubber, butadiene rubber, styrene-butadiene rubber, ethylene-α-olefin copolymer rubber, ethylene-α. -The above [1] to [1] consisting of 90 to 0% by mass of at least one selected from olefin-diene copolymer rubber, chloroprene rubber, halogenated butyl rubber and a copolymer of styrene and isobutylene having a halogenated methyl group 11] any rubber composition,
[13] Dipolar nitrogen in which Q in the compound represented by the general formula (2) can add a 1,3-dipole to an unsaturated carbon-carbon bond in the molecular structure of the rubber component (A) The rubber composition according to any one of the above [1] to [12], which is a containing part,
[14] The rubber composition according to [13], wherein Q is nitrone, nitrile oxide, or nitrileimine,
[15] In B in the compound represented by the general formula (2), the alkoxysilane moiety is represented by the general formula (3).
-Si (OR ³ ) ₃ (3)
(In the formula, R ³ represents a hydrocarbon group having 1 to 6 carbon atoms, and three OR ³ may be the same or different from each other.)
The rubber composition according to any one of the above [1] to [14], which comprises a group represented by:
[16] In B in the compound represented by the general formula (2), the allyl tin moiety is represented by the general formula (4).
^{_{-CH = CHCH 2 Sn (R 4}} ) 3 ··· (4)
(In the formula, R ⁴ represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. ⁴ may be the same or different.
The rubber composition according to any one of the above [1] to [14], which comprises a group represented by:
[17] The rubber composition according to any one of the above [1] to [16], wherein the rubber component (A) contains 50% by mass or more of the modified conjugated diene polymer.
[18] The rubber composition according to any one of the above [1] to [17], wherein the modified conjugated diene polymer is a modified aromatic vinyl-conjugated diene copolymer,
[19] A tire using the rubber composition according to any one of [1] to [18] as a tire member, and [20] a tire member comprising a tread, a base tread, a sidewall, and a side reinforcement. The tire according to [19], which is any one of rubber and bead filler,
Is to provide.

  According to the present invention, a tire that is particularly excellent in the interaction between the rubber component and carbon black and / or silica, can further improve the dispersibility of these fillers, and has excellent low heat buildup and wear resistance. It is possible to provide a rubber composition that can be provided, and a tire having the performance described above using the rubber composition.

The rubber composition of the present invention comprises (A) a silane represented by the following general formula (1) as a modifier at the active end of a conjugated diene polymer having an organometallic active end having nucleophilic reactivity. 20 to 120 parts by mass of (B) silica and / or carbon black with respect to 100 parts by mass of a rubber component containing 10% by mass or more of a modified conjugated diene polymer obtained by reacting a compound and / or a partial condensate thereof. And (C) a QA-B type compound described later having a coupling function between the rubber component and silica or carbon black.
In the present invention, the modified conjugated diene polymer refers to both a modified conjugated diene homopolymer and a copolymer.

[(A) Rubber component]
In the rubber composition of the present invention, the rubber component used as the component (A) is a general formula described later as a modifier at the active terminal of the conjugated diene polymer having an organometallic active terminal having nucleophilic reactivity. It is necessary to contain 10% by mass or more of a modified conjugated diene polymer obtained by reacting the silane compound represented by (1) and / or a partial condensate thereof.

(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.
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 piperidide, lithium heptamethylene imide, and lithium dodecamethylene imide are preferable, In particular, lithium hexamethylene imide and lithium pyrrolidide are suitable.

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

A method for producing a conjugated diene polymer by anionic polymerization using the lithium compound as a polymerization initiator is not particularly limited, and a conventionally known method can be used.
Specifically, in an organic solvent inert to the reaction, for example, a hydrocarbon solvent such as an aliphatic, alicyclic or aromatic hydrocarbon compound, 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 a randomizer to be 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 and trans-2. -Butene, cis-2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, benzene, toluene, xylene, ethylbenzene and the like. These may be used alone or in combination of two or more.

  The 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 present invention, the active terminus of the conjugated diene polymer having an organometallic active terminus having nucleophilic reactivity obtained as described above is represented by 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 compounds, dipropoxy (methyl) silyl compounds, dipropoxy (ethyl) silyl compounds, etc. corresponding to silyl compounds 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-isocyanato-3- [diethoxy (methyl ) Silyl] -propane, 1-isocyanato-3- [diethoxy (ethyl) silyl] -propane, 1-isocyanato-3- [dipropoxy (methyl) silyl] -propane, 1-isocyanato-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] -oxa Lumpur, 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-isocyanato-3- [diethoxy (methyl) silyl] -propane, 1-isocyanato-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 made 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, zirconium butoxyacetylacetonatebis (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 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 thus obtained 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 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.

((A) Composition of rubber component)
The rubber component (A) in the rubber composition of the present invention contains the modified conjugated diene polymer obtained as described above in a proportion of 10% by mass or more. In the present invention, as the modified conjugated diene polymer, a modified aromatic vinyl-conjugated diene copolymer is preferable, and a modified styrene-butadiene copolymer is more preferable. The preferable content of the modified conjugated diene polymer in the rubber component is 50% by mass or more, and more preferably 70% by mass or more. By setting the modified conjugated diene polymer in the rubber component to 10% 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. Examples of 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, and ethylene-α-olefin. -At least 1 sort (s) chosen from the copolymer of styrene and isobutylene which have a diene copolymer rubber, chlorobrene rubber, halogenated butyl rubber, and a halogenated methyl group can be mentioned. The content of the rubber component that can be used together in the rubber component (A) is 90% by mass or less, preferably 50% by mass or less, more preferably 30% by mass or less.

[(B) Silica and / or carbon black]
In the rubber composition of the present invention, silica and / or carbon black is used as the filler of the component (B).
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), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, and the like. Wet silica that is noticeable is preferred.

Carbon black is not particularly limited. For example, SRF, GPF, FEF, HAF, 1SAF, SAF and the like are used, iodine adsorption amount (IA) is 60 mg / g or more, and dibutyl phthalate oil absorption amount (DBP) is 80 ml / 100 g. The above carbon black is preferable. By using carbon black, the effect of improving grip performance and fracture resistance is increased, but HAF, ISAF, and SAF, which are excellent in wear resistance, are particularly preferable.
One type of silica and / or carbon black may be used, or two or more types may be used in combination.

  The total amount of silica and / or carbon black is 20 to 120 parts by mass with respect to 100 parts by mass of the rubber component, and 25 to 100 parts by mass is preferable from the viewpoint of the reinforcing effect and the effect of improving various physical properties thereby. By setting the amount of carbon black and / or silica within the above range, factory workability such as kneading workability is excellent, and desired fracture characteristics can be obtained as a rubber composition.

(Silane coupling agent)
In the rubber composition of the present invention, when silica is used as the reinforcing filler, a silane coupling agent can be blended for the purpose of further improving the reinforcement and low heat build-up.
Examples of the silane coupling agent include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, and bis (2-sodium trisulfide). Ethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercapto Ethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N, N-dimethylthioca Vamoyl tetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzothiazolyl tetrasulfide, 3- Triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethylthio Examples include carbamoyl tetrasulfide and dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide. (3-Triethoxysilylpropyl) polysulfide and 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide are preferred.
One of these silane coupling agents may be used alone, or two or more thereof may be used in combination.

  In the rubber composition of the present invention, since a modified polymer having a functional group having high affinity for silica introduced in the molecular active site is used as the rubber component, the amount of the silane coupling agent is usually This can be reduced more than in the case of. The blending amount of the preferred silane coupling agent varies depending on the type of the silane coupling agent, but is preferably selected in the range of 1 to 20% 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 20% by mass, the rubber component may be gelled. From the viewpoint 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 5 to 15% by mass.

[(C) QAB type compound]
In the rubber composition of the present invention, a QAB type compound having a bipolar nitrogen-containing portion is used as the component (C). This QA-B type compound has the general formula (2)
Q-A-B (2)
Wherein Q represents a dipolar nitrogen atom-containing moiety, B represents an oxazoline moiety, a thiazoline moiety, an alkoxysilane moiety or an allyltin moiety, and A represents a linking atom or group that forms a bridge between Q and B. Show.)
It is a compound which has a structure represented by these.
Q in the compound represented by the general formula (2) is a dipolar capable of adding a 1,3-dipole to the unsaturated carbon-carbon bond in the molecular structure of the rubber component (A) described above. A nitrogen-containing portion is preferred. Examples of such Q include nitrone, nitrile oxide, and nitrile imine.

B in the compound represented by the general formula (2) is an oxazoline part, a thiazoline part, an alkoxysilane part or an allyltin part. Here, as the alkoxysilane moiety, for example, the general formula (3)
-Si (OR ³ ) ₃ (3)
(In the formula, R ³ represents a hydrocarbon group having 1 to 6 carbon atoms, preferably a linear or branched alkyl group, and the three OR ³ may be the same or different. .)
The thing containing group represented by these can be mentioned.
Moreover, as an allyltin part in said B, for example, General formula (4)
^{_{-CH = CHCH 2 Sn (R 4}} ) 3 ··· (4)
(In the formula, R ⁴ represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. ⁴ may be the same or different.
The thing containing group represented by these can be mentioned.

On the other hand, examples of the connecting atom or group represented by A in the general formula (2) include, for example, an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, and carbon. The aralkylene group of several 7-20 can be mentioned.
Further, the A is represented by the general formula (5)
−A ^a − (Z−A ^b ) _k − (5)
Wherein A ^a and A ^b are each independently an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms or an aralkylene group having 7 to 20 carbon atoms. Z represents an ether bond, a thioether bond or a carbonyl bond, and k is an integer of 1 to 4.)
The bivalent group represented by these can be included.

In the present invention, examples of the QAB type compound represented by the general formula (2) include 4- (2-oxazolyl) -phenyl-N-methyl-nitrone, 4- (2-thiazolyl)- Phenyl-N-methyl-nitrone, 4- (2-oxazolyl) -phenyl-N-phenyl-nitrone, 4- (2-thiazolyl) -phenyl-N-phenyl-nitrone, phenyl-N-4- (2-oxazolyl) ) -Phenyl-nitrone, phenyl-N-4- (2-thiazolyl) -phenyl-nitrone, 4-tolyl-N-4- (2-oxazolyl) -phenyl-nitrone, 4-tolyl-N-4- (2 -Thiazolyl) -phenyl-nitrone, 4-methoxyphenyl-N-4- (2-oxazolyl) -phenyl-nitrone, 4-methoxyphenyl-N-4- (2-thiazolyl) Phenyl-nitrone, 4- (2-oxazolyl) -phenyl-nitrile oxide, 4- (2-thiazolyl) -phenyl-nitrile oxide, 4- (2-oxazolyl) -phenyl-N-methyl-nitrileimine, 4- ( 2-thiazolyl) -phenyl-N-methyl-nitrileimine, 4- (2-oxazolyl) -phenyl-N-phenyl-nitrileimine, 4- (2-thiazolyl) -phenyl-N-phenyl-nitrileimine, phenyl- N-4- (2-oxazolyl) -phenyl-nitrileimine, phenyl-N-4- (2-thiazolyl) -phenyl-nitrileimine and the like can be mentioned. These may be used individually by 1 type and may be used in combination of 2 or more type. Among these compounds, 4- (2-oxazolyl) -phenyl-N-methyl-nitrone (4OPMN), 4- (2-oxazolyl) -phenyl-N-phenyl-nitrone (4OPPN) and phenyl-N-4 -(2-Oxazolyl) -phenyl-nitrone (P4OPN) is preferred.
In addition, the manufacturing method of the QAB type compound represented by General formula (2) is described in detail in Japanese translations of PCT publication No. 2008-517071.

(Action of Q-A-B type compound)
In the rubber composition of the present invention, the QAB type compound used as the component (C) has the following action.
The Q-A-B type compound has, as Q, a dipolar nitrogen-containing moiety such as nitrone, nitrile oxide, nitrileimine, etc., and this dipolar nitrogen-containing moiety is present in (A) the molecular structure of the rubber component. 1,3-dipole addition to the unsaturated carbon-carbon bond. On the other hand, B has an oxazoline part, a thiazoline part, an alkoxysilane part, an allyltin part, etc., and these react with the surface group of silica and / or carbon black of the component (B) which is a reinforcing filler. .
Therefore, the QA-B type compound has an action of coupling the rubber component and the reinforcing filler, and improves the dispersion of the reinforcing filler such as silica and carbon black in the rubber component, As a result, the rubber composition of the present invention can provide a tire excellent in low heat buildup and wear resistance.

In the rubber composition of the present invention, the Q-A-B type compound of the component (C) is composed of silica and / or carbon of the component (B) from the viewpoint of the balance between the dispersion effect of the reinforcing filler and the economic efficiency. It is preferable to make it contain in the ratio of 0.05-20 mass% with respect to the total amount of black,
It is more preferable to make it contain in the ratio of 0.1-10 mass%, and it is still more preferable to make it contain in the ratio of 0.3-5 mass%.

The rubber composition of the present invention was obtained using a bifunctional hydrocarbyloxysilane derivative having two hydrocarbyloxy groups directly bonded to silicon atoms and having a specific functional group in the same molecule as a modifier. By containing the modified conjugated diene polymer, this polymer exhibits excellent interaction with silica and carbon black, and exhibits excellent performance such as low heat buildup and wear resistance.
Furthermore, by containing the Q-A-B type compound described above, this has the effect of coupling the rubber component and silica, carbon black, etc., and the silica, carbon black, etc. into the rubber component Dispersion is further improved, and performance such as low heat generation and wear resistance is further improved.

[Preparation and use of rubber composition]
In the rubber composition of the present invention, various chemicals usually used in the rubber industry, for example, a vulcanizing agent, a vulcanization accelerator, a process oil, and an anti-aging agent, as long as the object of the present invention is not impaired. Further, a scorch inhibitor, zinc white, stearic acid, and the like can be contained.
Further, the rubber composition 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 vulcanized after molding. Applicable to various rubber products. For example, tire tires such as tire treads, under treads, carcass, sidewalls, side reinforcing rubbers, bead parts (especially bead fillers), as well as anti-vibration rubber, fenders, belts, hoses and other industrial products. Although it can be used, it is particularly suitably used as a rubber for a tread of a fuel-efficient tire, a large tire, or a high-performance tire having an excellent balance between low heat generation and wear resistance.

[tire]
The tire of the present invention is characterized by using the above-described rubber composition of the present invention 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 of the present invention can be used for any of these, but particularly for a tread. Is preferred.
A tire using the rubber composition of the present invention for a tread has low rolling resistance, excellent fuel efficiency, and excellent 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.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
The microstructure of the modified styrene-butadiene rubber (modified SBR) (bound vinyl content and bound styrene content), loss tangent (tan δ) and abrasion resistance of the vulcanized rubber composition were evaluated by the following methods.
(1) Bonded vinyl content of the conjugated diene moiety of the modified SBR (mol% based on the total diene moiety)
Obtained by 270 MHz ¹ H-NMR.
(2) Bonded styrene content of modified SBR (mass% in polymer)
Obtained by 270 MHz ¹ H-NMR.
(3) Loss tangent (tan δ) of rubber composition after vulcanization
Using a dynamic spectrometer manufactured by Rheometrics, Inc. in USA, the measurement was carried out under the conditions of tensile dynamic strain 1%, frequency 10 Hz, 50 ° C., and the index was expressed by taking the reciprocal of tan δ of Comparative Example 1 as 100. It shows that it is excellent in low exothermic property, so that the value of an index | exponent is large.
(4) Abrasion resistance of rubber composition after vulcanization Using a Rambourn type abrasion tester, the amount of wear with a slip rate of 25% at room temperature was measured, and the reciprocal of the amount of wear in Comparative Example 1 was taken as an index. . It shows that it is excellent in abrasion resistance, so that an index | exponent is large.

Synthesis Example 1 Synthesis of Modifier A Prepare a 1 mol / liter cyclohexane solution of N-methyl-N- (trimethylsilyl) aminopropyltriethoxysilane in a dry, nitrogen-substituted 300 ml pressure-resistant glass container. A modifier solution of N-methyl-N- (trimethylsilyl) aminopropylmethyldiethoxysilane as modifier A is added dropwise by stirring dropwise with a 1 mol / liter diethyl ether solution of methyllithium so as to have a molarity. (A) was prepared.

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

Synthesis Example 3 Synthesis of Modifier C Synthesis Example 1 except that 2- (2-triethoxysilylethyl) -pyridine was used instead of N-methyl-N- (trimethylsilyl) aminopropyltriethoxysilane in Synthesis Example 1. In the same manner as in Example 1, a modifier solution (C) of 2- [2- [diethoxy (methyl) silyl] ethyl] -pyridine as the modifier C was prepared.

Synthesis Example 4 Synthesis of Modifier D In Synthesis Example 1, instead of N-methyl-N- (trimethylsilyl) aminopropyltriethoxysilane, N- (1,3-dimethylbutylidene) -3- (tripropoxysilyl) N- (1,3-dimethylbutylidene) -3- [dipropoxy (methyl) silyl] -1-propanamine as the modifier D in the same manner as in Synthesis Example 1 except that 1-propanamine was used. A denaturant solution (D) was prepared.

4 types of modifiers A to D obtained in Synthesis Examples 1 to 4 above, and 5 types of modifiers E to I below, a total of 9 types of modifiers, are N of SBR A to D and SBR E to I described below. Used as a modifier for production examples.
Modification agent A: N-methyl-N- (trimethylsilyl) aminopropylmethyldiethoxysilane (Synthesis Example 1)
Modification agent B: 1- [3- [diethoxy (methyl) silyl] propyl] -imidazole (Synthesis Example 2)
Modification agent C: 2- [2- [diethoxy (methyl) silyl] ethyl] -pyridine (Synthesis Example 3)
Modification agent D: N- (1,3-dimethylbutylidene) -3- [dipropoxy (methyl) silyl] -1-propanamine (Synthesis Example 4)
・ Modifier E: SnCl ₄ (tin tetrachloride)
・ Modifier F: N-methyl-N- (trimethylsilyl) aminopropyltriethoxysilane ・ Modifier G: 1- (3-triethoxysilylpropyl) -imidazole ・ Modifier H: 2- (2-triethoxysilyl) Ethyl) -pyridine-modifying agent I: N- (1,3-dimethylbutylidene) -3- [tripropoxysilyl] -1-propanamine

Synthesis Example 5 Synthesis of QA-B type compound-1 To a stirred mixture containing 15.0 g of 4-formyl-benzoyl chloride (1 equivalent) in 300 ml of chloroform was added 2-amino acid at -10 ° C. 10.9 g of a solution prepared by dissolving ethanol (2 equivalents) in 200 ml of chloroform was added dropwise. After the addition, the resulting mixture was stirred at 25 ° C. for 2 hours and the resulting white precipitate was removed by filtration. The filtrate was then dried on a rotavapor to give 17.4 g of a yellow liquid, 4-formyl-N- (2-hydroxyethyl) -benzamide.
50 ml of concentrated sulfuric acid was added dropwise to 4-formyl-N- (2-hydroxyethyl) -benzamide (17.4 g) with stirring, and the mixture was heated at 100 ° C. for 1 hour. The solution was added dropwise with stirring to a mixture of 500 ml of 20% by weight aqueous sodium hydroxide and 500 ml of chloroform, and the temperature was maintained by cooling to less than 15 ° C. Next, the organic phase was separated and dried to obtain 6.3 g of 4- (2-oxazolyl) -benzaldehyde.
A mixture of 6.3 g (1 equivalent) of 4- (2-oxazolyl) -benzaldehyde and 3.9 g (1 equivalent) of N-phenyl-hydroxyamine was refluxed in 100 ml of ethanol for 30 minutes and concentrated to a volume of 50 ml. . 50 ml of water was added and the mixture was cooled in a refrigerator at 5 ° C. overnight. Isolation by filtration and drying gave white crystals, yielding 6.7 g of 4- (2-oxazolyl) -phenyl-N-phenyl-nitrone (QAB type compound-1).

Synthesis Example 6 Synthesis of Q-A-B type compound-2 A solution prepared by dissolving 185.6 g (1.00 mol) of p-nitro-benzoyl chloride in 450 mL of warm benzene was dissolved in 63.5 g of ethanolamine in 1350 mL of water. (1.04 mol) was added to the mixture. Next, 830 mL of 5 mass% sodium hydroxide solution was gradually added. A white precipitate containing p-nitro-N- (2-hydroxyethyl) benzamide formed, which was filtered and dried. The mass of the dried p-nitro-N- (2-hydroxyethyl) benzamide powder was 196 g (0.93 mol) (yield 93%).
While stirring 132 mL (1.8 mol) of thionyl chloride, 196 g of p-nitro-N- (2-hydroxyethyl) benzamide powder was added dropwise. After vigorous reaction, the resulting mixture was poured into 1 L of ether. An insoluble material containing p-nitro-N- (2-chloroethyl) benzamide was formed in ether and the insoluble material was filtered and dried to give 192 g (0.84 mol) of p-nitro-N- (2-Chloroethyl) benzamide was obtained (90% yield).
192 g of p-nitro-N- (2-chloroethyl) benzamide was added to 1 L of methanol and the solution was refluxed. 900 mL of 5% by weight sodium hydroxide was added to the refluxing solution with stirring. The resulting solution was poured into 2 kg ice and water. Insoluble material, including p-nitro-phenyl-2-oxazoline, formed in ice and water, which was filtered and dried to give 150 g (0.78 mol) of white powder p-nitro-phenyl-2- Oxazoline was obtained (yield 93%).
150 g p-nitro-phenyl-2-oxazoline and 46 g (0.86 mol) ammonium chloride were added to 1 L methanol and 1 L water. The solution was heated to 60 ° C. To the heated solution was slowly added 102 g (1.56 mol) zinc powder. The resulting mixture was filtered, cooled and dried. A pale yellow crystalline precipitate was formed, which contained 105 g (0.51 mol) of pN- (hydroxy-amino) -phenyl-2-oxazoline (65% yield).
A mixture containing 105 g pN- (hydroxy-amino) -phenyl-2-oxazoline and 53 g (0.51 mol) benzaldehyde in 1 L ethanol was refluxed for 30 minutes and concentrated to a volume of 500 mL. 150 mL of water was added to the mixture and the mixture was cooled. A pale yellow precipitate was formed, which was filtered and dried. The precipitate contained 83 g (0.31 mol) of phenyl-N- [4- (2-oxazolyl) phenyl] nitrone (QAB type compound-2) (yield 60%, overall) Reaction yield of 31%).

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. Table 1 shows the bound styrene content of the modified SBR A and the bound vinyl content of the butadiene moiety.

Production Examples 2-9
In Production Example 1, modified SBR B to I were obtained in the same manner as Production Example 1 except that the modifiers B to I were used in place of the modifier A. Table 1 shows the bound styrene content of the modified SBR B to I and the bound vinyl content of the butadiene moiety.

Examples 1-4 and Comparative Examples 1-14
Using the modified SBR A to I obtained in the production example, according to the formulation 1 to 4 shown in Table 2, after kneading each component of the first stage, by adding each component of the second stage to this, Each rubber composition was prepared.
This unvulcanized rubber composition was vulcanized at 165 ° C. for 15 minutes, and then measured for dynamic loss tangent (tan δ) to evaluate low heat buildup and wear resistance. The low heat build-up and wear resistance are shown as indices with Comparative Examples 1 and 9 as 100. Low exothermic properties and wear resistance are more excellent physical properties as the index value is higher. These results are shown in Table 3.

[note]
1) Modified SBR: used in Production Examples 1 to 9 2) Polyisoprene rubber: “IR2200” manufactured by JSR Corporation
3) Aroma oil: “Aromax # 3” manufactured by Fuji Kosan Co., Ltd.
4) Carbon Black (ISAF-HS): “Diamond Black N234” manufactured by Mitsubishi Chemical Corporation
5) Carbon Black (FEF): “Diamond Black E” manufactured by Mitsubishi Chemical Corporation
6) Silica: “AQ” manufactured by Tosoh Silica Corporation
7) Silane coupling agent: “Si69” manufactured by Degussa
8) QAB type compound-1: 4- (2-oxazolyl) -phenyl-N-phenyl-nitrone obtained in Synthesis Example 5 is used 9) QAB type compound-2: Synthesis Example 6 10) Anti-aging agent 6C: “Ocrack 6C” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
11) Vulcanization accelerator DPG: “Noxeller D” manufactured by Ouchi Shinsei Chemical Co., Ltd.
12) Vulcanization accelerator DM: “Oxeller DM” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
13) Vulcanization accelerator NS: “Noxeller NS-F” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.

  The rubber composition of the present invention is particularly excellent in the interaction between the rubber component and carbon black and / or silica, can further improve the dispersibility of these fillers, and is excellent in low heat buildup and wear resistance. Tires can be given.

Claims (20)

At the active end of the conjugated diene polymer having an organometallic active end having nucleophilic reactivity, a 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. ]
And (B) silica and / or carbon with respect to 100 parts by mass of a rubber component containing 10% by mass or more of a modified conjugated diene polymer obtained by reacting the silane compound represented by While containing 20 to 120 parts by mass of black in total, (C) General formula (2)
Q-A-B (2)
Wherein Q represents a dipolar nitrogen atom-containing moiety, B represents an oxazoline moiety, a thiazoline moiety, an alkoxysilane moiety or an allyltin moiety, and A represents a linking atom or group that forms a bridge between Q and B. Show.)
The rubber composition characterized by including the compound represented by these.   The rubber composition according to claim 1, wherein the modified conjugated diene polymer is subjected to a condensation reaction treatment in the presence of a condensation accelerator after reacting with the modifier.   The rubber composition according to claim 1 or 2, comprising (B) 0.05 to 20% by mass of the compound (C) with respect to the total amount of (B) silica and / or carbon black. 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 rubber composition according to claim 1, wherein R ² is a divalent hydrocarbon group having 1 to 20 carbon atoms. The rubber composition according to claim 4, wherein A ² is a hydrocarbyloxy group having 1 to 18 carbon atoms in the modifier represented by the general formula (1). The rubber composition according to claim 4 or 5, wherein R ² in the general formula (1) is an alkanediyl group having 2 to 10 carbon atoms.   The rubber composition according to any one of claims 4 to 6, wherein in 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. object.   X in the general formula (1) 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. The rubber composition according to any one of claims 4 to 7, which is a monovalent group having a nitrogen-containing group.   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. The rubber composition according to any one of claims 1 to 8, which is obtained by anionic polymerization of a compound.   The rubber composition according to claim 9, wherein the conjugated diene compound is at least one selected from 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene.   The rubber composition according to claim 9 or 10, wherein the aromatic vinyl compound is styrene.   (A) The rubber component is 10 to 100% by mass of a modified conjugated diene polymer, natural rubber, synthetic isoprene rubber, butadiene rubber, styrene-butadiene rubber, ethylene-α-olefin copolymer rubber, ethylene-α-olefin- It consists of at least one kind selected from diene copolymer rubber, chloroprene rubber, halogenated butyl rubber, and a copolymer of styrene and isobutylene having a halogenated methyl group. The rubber composition as described.   Q in the compound represented by the general formula (2) is a dipolar nitrogen-containing moiety capable of adding a 1,3-dipole to an unsaturated carbon-carbon bond in the molecular structure of the rubber component (A). The rubber composition according to any one of claims 1 to 12.   The rubber composition according to claim 13, wherein Q is nitrone, nitrile oxide or nitrileimine. In B in the compound represented by the general formula (2), the alkoxysilane moiety is represented by the general formula (3).
-Si (OR ³ ) ₃ (3)
(In the formula, R ³ represents a hydrocarbon group having 1 to 6 carbon atoms, and three OR ³ may be the same or different from each other.)
The rubber composition in any one of Claims 1-14 containing group represented by these. In B in the compound represented by the general formula (2), the allyltin moiety is represented by the general formula (4).
^{_{-CH = CHCH 2 Sn (R 4}} ) 3 ··· (4)
(In the formula, R ⁴ represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. ⁴ may be the same or different.
The rubber composition in any one of Claims 1-14 containing group represented by these.   The rubber composition according to any one of claims 1 to 16, wherein the rubber component (A) contains 50% by mass or more of the modified conjugated diene polymer.   The rubber composition according to any one of claims 1 to 17, wherein the modified conjugated diene polymer is a modified aromatic vinyl-conjugated diene copolymer.   A tire comprising the rubber composition according to claim 1 as a tire member.   The tire according to claim 19, wherein the tire member is one of a tread, a base tread, a sidewall, a side reinforcing rubber, and a bead filler.