WO2013094693A1

WO2013094693A1 - Rubber composition for tires, and tire using same

Info

Publication number: WO2013094693A1
Application number: PCT/JP2012/083103
Authority: WO
Inventors: 成晃松尾; 礼子矢木; 亮多玉手
Original assignee: 株式会社ブリヂストン
Priority date: 2011-12-20
Filing date: 2012-12-20
Publication date: 2013-06-27

Abstract

In order to provide a rubber composition for tires, which has remarkably improved low loss tangent by improving dispersibility of a white filler such as silica, and a tire using the rubber composition for tires, this rubber composition for tires is configured to contain a white filler and at least one of the compounds represented by formulae (I) and (II) in at least one rubber component (A) that is selected from among natural rubbers and/or diene-based synthetic rubbers, with the rubber component (A) containing a conjugated diene polymer that has at least one atom selected from among an Si atom, an Su atom, a sulfur atom, an oxygen atom and a Ti atom at a polymerization-active terminal or a polymerization initiating terminal or in a polymer chain. (In formula (I), R₁ represents a linear, branched or cyclic alkyl or alkenyl group having 1-24 carbon atoms or a group represented by formula (III); and each of R₂ and R₃ represents a hydrogen atom, a hydroxyl group, a hydroxyalkyl group or a hydroxyalkyl group having an oxyalkylene unit, and R₂ and R₃ may be the same as or different from each other.) (In formula (II), R₄ is the same as the above-described R₁; R₅ represents a hydroxyl group, a hydroxyalkyl group or a hydroxyalkyl group having an oxyalkylene unit.) (In formula (III), A represents a single bond or an alkyl or alkenyl group having 1-24 carbon atoms; B represents a carbonyl group, an ester group, an amino group, an amide group, an ether group, a hydroxyl group, a hydroxyalkyl group or a hydroxyalkylene group; and R₆ is the same as the above-described R₁.)

Description

Rubber composition for tire and tire using the same

The present invention relates to a tire rubber composition and a tire using the same, and more specifically, the tire rubber is improved in dispersibility of a white filler such as silica in the tire rubber composition and excellent in low loss performance. The present invention relates to a composition and a tire using the composition.

With the recent social demands for energy conservation, silica has been used as a filler to achieve both low loss performance (low fuel consumption) and grip on wet roads for the purpose of saving fuel consumption in automobiles. Formulation is frequently used.
The silica used tends to aggregate particles due to hydrogen bonding of silanol groups, which are surface functional groups, and it is necessary to lengthen the kneading time in order to improve the dispersion of the silica in the rubber. Further, since the dispersion of silica in the rubber is insufficient, the Mooney viscosity of the rubber composition is increased, and the processability such as extrusion is inferior. Furthermore, since the surface of the silica particles is acidic, the basic substance used as a vulcanization accelerator is adsorbed, the rubber composition is not sufficiently vulcanized, and the storage elastic modulus does not increase. Was. For this reason, there has been a demand for improvement in processability and the like in a silica-containing rubber composition.

Conventionally, as a technique for improving processability and the like in a silica-containing rubber composition, for example,
1) As processing aid for improving dispersion of reinforcing silica filler in rubber composition, polar terminal showing weak chemical reactivity with silica and non-polar showing weak chemical reactivity with elastic polymer A technique of adding an amide compound having a terminal (fatty acid amide) to a silica-containing rubber (for example, see Patent Document 1);
2) A technique for improving fuel economy and wear resistance by using silica surface-treated with a dialkanolamide and a silane coupling agent (see, for example, Patent Document 2) is known.

However, Patent Document 1 describes that processability is improved by adding an amide compound (fatty acid amide) having a structure different from that of the present invention to silica-containing rubber, but the silica dispersion effect is still sufficient. However, although the said patent document 2 uses the silica surface-treated with dialkanol amide and a silane coupling agent, the subject that this is also not enough as an improvement of the dispersibility of silica, and a low-loss performance. There is something.

On the other hand, in a silica-containing diene rubber composition, a rubber composition characterized in that 1 to 10 parts by weight of a specific tall oil fatty acid imidazoline is added to 100 parts by weight of the diene rubber component, and the rubber A pneumatic tire using the composition for a tire tread (for example, see Patent Document 3) is known.
However, the rubber composition of Patent Document 3 improves the processability by adding a specific tall oil fatty acid imidazoline to the silica-containing diene rubber composition, and at the same time has low heat buildup and wear resistance after vulcanization. However, this rubber composition still has a problem that the dispersibility of silica and the low loss performance are not sufficient.

JP 2003-533574 A (claims, examples, etc.) JP 2010-59272 A (Claims, Examples, etc.) JP 2008-13619 A (Claims, Examples, etc.)

The present invention intends to solve the above-mentioned problems of the prior art, and improves the dispersibility of white fillers such as silica in the rubber composition to further improve the dispersibility of white fillers. Thus, an object of the present invention is to provide a tire rubber composition and a tire using the same, in which the low loss performance is remarkably improved.

As a result of intensive investigations in view of the above-mentioned problems of the prior art, the present inventors have found that a white filler and a specific compound are used for at least one rubber component selected from natural rubber and / or diene-based synthetic rubber. The rubber composition for tires described above and a tire using the tire composition can be obtained by containing a specific conjugated diene polymer as the rubber component, and the present invention is completed. It came to do.

That is, the present invention resides in the following (1) to (11).
(1) For at least one rubber component (A) selected from natural rubber and / or diene-based synthetic rubber, at least one of compounds represented by the following general formulas (I) and (II): And the rubber component (A) contains at least one selected from a silicon atom, a tin atom, a sulfur atom, an oxygen atom and a titanium atom, in a polymerization active terminal, a polymerization start terminal and a polymerization chain. A rubber composition for tires comprising a conjugated diene polymer contained in any of the above.

[In the above formula (I), R ₁ represents an alkyl or alkenyl group having 1 to 24 carbon atoms, a group represented by the following formula (III), wherein the alkyl group and alkenyl group are linear or branched. Either a chain or a ring may be used, and R ₂ and R ₃ may be a hydrogen atom, a hydroxyl group, a hydroxyalkyl group, or a hydroxyalkyl group having an oxyalkylene unit, and these may be the same or different. ]

[In the above formula (II), R ₄ represents an alkyl group or alkenyl group having 1 to 24 carbon atoms, and the alkyl group and alkenyl group may be linear, branched or cyclic, and , R ₅ is a hydroxyl group, a hydroxyalkyl group, or a hydroxyalkyl group having an oxyalkylene unit. ]

[In the above formula (III), A is a single bond or an alkyl or alkenyl group having 1 to 24 carbon atoms, and B is a carbonyl group, an ester group, an amino group, an amide group, an ether group, a hydroxyl group, R ₆ represents a C 1-24 alkyl group or alkenyl group, and the alkyl group and alkenyl group may be linear, branched, or cyclic. ]
(2) The rubber composition for tires according to (1), wherein the conjugated diene polymer is a (co) polymer of a conjugated diene compound.
(3) The tire rubber composition according to (1), wherein the conjugated diene polymer is a copolymer of an aromatic vinyl compound and a conjugated diene compound.
(4) The above (1), wherein the conjugated diene polymer contains an aromatic vinyl compound unit of 0% by mass to 60% by mass and the vinyl bond content in the conjugated diene moiety is 5% by mass to 80% by mass. Or the rubber composition for tires according to (3).
(5) The conjugated diene polymer is obtained by subjecting a polymerization active end to a compound containing at least one selected from a silicon atom, a tin atom, a sulfur atom, an oxygen atom and a titanium atom after the polymerization reaction. The tire rubber composition according to any one of the above (1) to (4), which is a modified conjugated diene polymer.
(6) The modified conjugated diene polymer has the following general formula (IV) at the active site of the conjugated diene polymer having an organometallic active site in the molecule.
RaMXb ......... (IV)
[In the formula (IV), each R independently 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. M is tin or silicon and X is independently chlorine, bromine or iodine. A is an integer of 0 to 3, b is an integer of 1 to 4, and a + b = 4], and an organic metal compound represented by the general formula (V)
R ¹ aM (OR ² ) b (V)
[In the formula (V), each of R ¹ and R ² independently 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, and 7 to 7 carbon atoms. Selected from the 20 aralkyl groups, M is tin or silicon. A is an integer of 0 to 3, b is an integer of 1 to 4, and a + b = 4]}, and a condensate thereof. The tire rubber composition according to the above (5), which is a modified conjugated diene polymer obtained by reacting with a rubber.
(7) The modified conjugated diene polymer has the following general formula (VI): at the active site of the conjugated diene polymer having an organometallic active site in the molecule.

[In the formula (VI), a + b + c = 4 (where b is an integer of 1 to 3, a is an integer of 0 to 2, and c is an integer of 1 to 3), and D is a saturated cyclic tertiary amine compound] Residue, unsaturated cyclic tertiary amine compound residue, imine residue, nitrile group, (thio) isocyanate group, (thio) epoxy group, isocyanuric acid trihydrocarbyl ester residue, carbonic acid dihydrocarbyl ester residue, nitrile group Pyridine group, (thio) ketone group, (thio) aldehyde group, amide group, (thio) carboxylic acid hydrocarbyl ester residue, metal salt residue of (thio) carboxylic acid ester residue, carboxylic acid anhydride residue, A carboxylic acid halogen compound residue and at least one functional group selected from a hydrolyzable group-containing secondary amino group or mercapto group, and the same when a plurality of Ds are present It may be different also I.
R ¹ is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms or a halogen atom, and is the same when R ¹ is plural. May be different. R ² is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when R ² is plural, they are the same or different. May be. R ³ is a divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when R ³ is plural, they may be the same or different. Good. ] The rubber composition for tires as described in said (5) which is the modified conjugated diene type polymer obtained by making the modifier represented by this and the condensate react.
(8) Modified conjugate obtained by reacting the modified conjugated diene polymer with a condensate of an alkoxysilane compound represented by the following general formula (V) and a modifying agent represented by the following general formula (VI) The rubber composition for tires according to (5) above, which is a diene polymer.
R ¹ aM (OR ² ) b (V)
{[In the formula (V), R ¹ and R ² are each independently 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, and 7 carbon atoms. Selected from ˜20 aralkyl groups and M is tin or silicon. A is an integer of 0 to 3, b is an integer of 1 to 4, and a + b = 4]

[In the formula (VI), a + b + c = 4 (where b is an integer of 1 to 3, a is an integer of 0 to 2, and c is an integer of 1 to 3), and D is a saturated cyclic tertiary amine compound] Residue, unsaturated cyclic tertiary amine compound residue, imine residue, nitrile group, (thio) isocyanate group, (thio) epoxy group, isocyanuric acid trihydrocarbyl ester residue, carbonic acid dihydrocarbyl ester residue, nitrile group Pyridine group, (thio) ketone group, (thio) aldehyde group, amide group, (thio) carboxylic acid hydrocarbyl ester residue, metal salt residue of (thio) carboxylic acid ester residue, carboxylic acid anhydride residue, A carboxylic acid halogen compound residue and at least one functional group selected from a hydrolyzable group-containing secondary amino group or mercapto group, and the same when a plurality of Ds are present It may be different also I.
R ¹ is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms or a halogen atom, and is the same when R ¹ is plural. May be different. R ² is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when R ² is plural, they are the same or different. May be. R ³ is a divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when R ³ is plural, they may be the same or different. . ]}
(9) The tire rubber composition according to any one of (5) to (8), wherein the modified conjugated diene polymer further contains a nitrogen atom.
(10) The rubber component contains 5 to 200 parts by weight of a white filler and 0.5 to 15 parts by weight of the compound represented by the formula (I) with respect to 100 parts by weight of the rubber component. The tire rubber composition according to any one of the above (1) to (9).
(11) A tire comprising the tire rubber composition according to any one of (1) to (10) above.

According to the present invention, there is provided a tire rubber composition in which low loss performance is remarkably improved by further improving dispersibility of a white filler such as silica in the tire rubber composition, and a tire using the same. Is done.

Hereinafter, embodiments of the present invention will be described in detail.
<Rubber composition for tire>
The rubber composition for tires of the present invention comprises a white filler and the following general formulas (I) and (II) with respect to at least one rubber component (A) selected from natural rubber and / or diene-based synthetic rubber. And at least one selected from the group consisting of a silicon atom, a tin atom, a sulfur atom, an oxygen atom and a titanium atom in the rubber component (A). It contains a conjugated diene polymer contained in either the initiation terminal or the polymer chain.

[In the above formula (III), A is a single bond or an alkyl or alkenyl group having 1 to 24 carbon atoms, and B is a carbonyl group, an ester group, an amino group, an amide group, an ether group, a hydroxyl group, R ₆ represents a C 1-24 alkyl group or alkenyl group, and the alkyl group and alkenyl group may be linear, branched, or cyclic. ]

<Rubber component (A)>
In the tire rubber composition of the present invention, as the rubber component (A), at least one rubber component selected from natural rubber and / or diene-based synthetic rubber is used.
Rubber components that can be used include natural rubber (NR), diene synthetic rubber, unmodified styrene-butadiene copolymer (SBR), polybutadiene rubber (BR), polyisoprene rubber (IR), butyl rubber. (IIR), an ethylene-propylene copolymer, and the like can be used. These rubber components may be used singly or as a blend of two or more.
The rubber component (A) of the present invention contains at least one selected from a silicon atom, a tin atom, a sulfur atom, an oxygen atom and a titanium atom in any of the polymerization active terminal, the polymerization starting terminal and the polymerization chain. It is necessary to contain a conjugated diene polymer.
This is because the dispersibility of the white filler such as silica is further improved by incorporating the conjugated diene polymer having the above characteristics into the rubber component (A). That is, when a white filler such as silica is contained in the rubber component (A) containing the conjugated diene polymer having the above characteristics, the surface area of the white filler increases, and the surface area of the white filler increases. As a result, the reaction point of the silica dispersant (hydrophobizing agent) composed of the compound represented by the general formula (I), formula (II) or the like increases. Thereby, by weakening the interaction (aggregation) between white fillers such as silica with a silica dispersant (hydrophobizing agent) comprising a compound represented by general formula (I), formula (II) or the like, silica or the like The dispersibility of the white filler is further improved.

The conjugated diene polymer used in the present invention can be produced as a polymer having an organometallic active site in the molecule, and the production method is not particularly limited, and is a solution polymerization method, a gas phase polymerization method, Any of the bulk polymerization methods 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 is preferably one selected from alkali metals and alkaline earth metals, and lithium metal is particularly preferable.
In the solution polymerization method, for example, a target polymer can be produced by anionic polymerization of a conjugated diene compound alone or a conjugated diene compound and an aromatic vinyl compound using a lithium compound as a polymerization initiator. As the conjugated diene polymer in the present embodiment, a conjugated diene polymer obtained by copolymerizing a (co) polymer of a conjugated diene compound or a conjugated diene compound and an aromatic vinyl compound from the viewpoint that the glass transition temperature can be controlled. Polymers are preferred. In the present invention, the (co) polymer means a polymer or a copolymer.

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.
The active site may be present in the polymer molecule, and may be present in any of the polymerization active terminal, the polymerization initiation terminal, and the polymerization chain. When the polymer is obtained by anionic polymerization using an alkali metal compound and / or an alkaline earth metal compound as a polymerization initiator, generally, the active site is located at the end of the polymer.
For example, when the compound containing at least one selected from a silicon atom, a tin atom, a sulfur atom, an oxygen atom and a titanium atom is reacted with the active terminal, the conjugated diene polymer in the present invention can be obtained. .

Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 2-phenyl-1,3-butadiene, 1,3-hexadiene, and the like. These may be used alone or in combination of two or more, and among these, 1,3-butadiene and isoprene 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, 4-cyclohexyl. Examples thereof include styrene and 2,4,6-trimethylstyrene. These may be used singly or in combination of two or more, but among these, styrene is particularly preferable.
Further, when copolymerization is performed using a conjugated diene compound and an aromatic vinyl compound as monomers, the use of 1,3-butadiene and styrene, respectively, in terms of practicality such as the availability of monomers, And anionic polymerization characteristics are particularly preferred in view of the living property.
When the solution polymerization method is used, the monomer concentration in the solvent is preferably in the range of 5 to 50% by mass, more preferably in the range of 10 to 30% by mass. When copolymerization is performed 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 1 to 60% by mass, more preferably 5 to 45%. A range of mass% is preferred.

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, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-octyllithium, n- Examples include decyl lithium, phenyl lithium, 2-naphthyl lithium, 2-butyl-phenyl lithium, 4-phenyl-butyl lithium, cyclohexyl lithium, cyclopentyl lithium, reaction products of diisopropenylbenzene and butyl lithium. Of these, n-butyllithium is preferred.

On the other hand, as the lithium amide compound, for example, lithium hexamethylene imide, lithium pyrrolidide, lithium piperidide, lithium heptamethylene imide, lithium dodecamethylene imide, lithium dimethylamide, lithium diethylamide, lithium dibutylamide, lithium dipropylamide, Lithium diheptylamide, lithium dihexylamide, lithium dioctylamide, lithium di-2-ethylhexylamide, lithium didecylamide, lithium-N-methylpiperazide, lithium ethylpropylamide, lithium ethylbutyramide, lithium methylbutyramide, lithium ethylbenzylamide And lithium methylphenethylamide.

Among these, in terms of the interaction effect on white fillers such as silica and the ability to initiate polymerization, cyclic such as lithium hexamethylene imide, lithium pyrrolidide, lithium piperidide, lithium heptamethylene imide, lithium dodecamethylene imide, etc. Lithium amide is preferred, and lithium hexamethylene imide and lithium pyrrolidide are particularly preferred.
These lithium amide compounds are generally prepared in advance from a secondary amine and a lithium compound in the polymerization, but can also be prepared in-polymerization 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.

There is no restriction | limiting in particular as a method of manufacturing a conjugated diene polymer by anionic polymerization using the said lithium compound as a polymerization initiator, A conventionally well-known method can be used.
Specifically, in an organic solvent inert to the reaction, for example, in a hydrocarbon solvent such as an aliphatic, alicyclic or aromatic hydrocarbon compound, a conjugated diene compound or a conjugated diene compound and an aromatic vinyl compound are used. The desired conjugated diene polymer can be obtained by subjecting the lithium compound as a polymerization initiator to anionic polymerization in the presence of a randomizer to be used, if desired.

The hydrocarbon solvent preferably has 3 to 8 carbon atoms. For example, propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, cyclohexane, propene, 1-butene, isobutene, trans- Examples include 2-butene, cis-2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, benzene, toluene, xylene, and ethylbenzene. These may be used alone or in combination of two or more.

The randomizer used as desired is control of the microstructure of the conjugated diene polymer, such as an increase in 1,2 bonds in the butadiene moiety in the butadiene-styrene copolymer, an increase in 3,4 bonds in the isoprene polymer, etc. Alternatively, 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 or styrene units in a butadiene-styrene copolymer. The randomizer is not particularly limited, and any one of known compounds generally used as a conventional randomizer can be appropriately selected and used. Specifically, dimethoxybenzene, tetrahydrofuran, dimethoxyethane, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, bistetrahydrofurylpropane, triethylamine, pyridine, N-methylmorpholine, N, N, N ′, N′-tetramethylethylenediamine, 1, And ethers such as 2-dipiperidinoethane and tertiary amines. Further, potassium salts such as potassium-t-amylate and potassium-t-butoxide, and sodium salts such as sodium-t-amylate can also be used.
One of these randomizers may be used alone, or two or more thereof may be used in combination. The amount used is preferably selected in the range of 0.01 to 1000 molar equivalents per mole of lithium compound.

The temperature in this polymerization reaction is preferably selected in the range of 0 to 150 ° C., more preferably in the range of 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.
When a polymer is obtained as an elastomer, the glass transition point (Tg) obtained by differential thermal analysis of the obtained polymer or copolymer is preferably in the range of −110 ° C. to −15 ° C. It is difficult to obtain a polymer having a glass transition point of less than −110 ° C., and when it exceeds −15 ° C., the viscosity becomes too high in the room temperature region, which may make handling difficult.

On the other hand, when the modified conjugated diene polymer is produced by coordination polymerization using a rare earth metal compound as a polymerization initiator, the following (A) component, (B) component, and (C) component may be used in combination: preferable.
The component (a) used for the coordination polymerization is selected from a rare earth metal compound, a complex compound of a rare earth metal compound and a Lewis base, and the like. Here, examples of rare earth metal compounds include rare earth element carboxylates, alkoxides, β-diketone complexes, phosphates and phosphites, and Lewis bases include acetylacetone, tetrahydrofuran, pyridine, N, N -Dimethylformamide, thiophene, diphenyl ether, triethylamine, organophosphorus compounds, monovalent or divalent alcohols, etc. As the rare earth element of the rare earth metal compound, lanthanum, neodymium, praseodymium, samarium and gadolinium are preferable, and among these, neodymium is particularly preferable. Specific examples of component (a) include neodymium tri-2-ethylhexanoate, complex compounds thereof with acetylacetone, neodymium trineodecanoate, complex compounds thereof with acetylacetone, neodymium tri-n-butoxide, and the like. It is done. These components (a) may be used alone or in combination of two or more.

The component (b) used in the coordination polymerization is selected from organoaluminum compounds. Specifically, as the organoaluminum compound, a trihydrocarbyl aluminum compound represented by the formula: R ¹² ₃ Al, a hydrocarbyl aluminum hydride represented by the formula: R ¹² ₂ AlH or R ¹² AlH ₂ (in the formula, R ¹² are each independently a hydrocarbon group having 1 to 30 carbon atoms), hydrocarbylaluminoxane compounds having a hydrocarbon group having 1 to 30 carbon atoms, and the like. Specific examples of the organoaluminum compound include trialkylaluminum, dialkylaluminum hydride, alkylaluminum dihydride, and alkylaluminoxane. These compounds may be used alone or in combination of two or more. In addition, as (b) component, it is preferable to use aluminoxane and another organoaluminum compound in combination.

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

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

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

In the conjugated diene polymer of the present invention, the content of the aromatic vinyl compound unit is 0% by mass or more and 60% by mass as an unmodified and / or modified low molecular weight diene copolymer in the form of an unmodified product or before modification. %, More preferably 1% by mass to 60% by mass, and the vinyl bond content of the conjugated diene moiety is preferably 5% by mass to 80% by mass. If the content of the aromatic vinyl compound unit and the vinyl bond content of the conjugated diene compound portion are not within the above ranges, sufficient compatibility between ensuring the workability of the rubber composition and reducing the loss tangent (tan δ) of the rubber composition is achieved. It may not be possible.
The content of the aromatic vinyl compound unit is more preferably 10% by mass to 50% by mass, and the vinyl bond content of the conjugated diene moiety is preferably 10% by mass to 70% by mass.

The conjugated diene polymer in the present invention is a modified conjugate obtained by subjecting a polymerization active terminal to a compound containing at least one selected from a silicon atom, a tin atom, a sulfur atom, an oxygen atom and a titanium atom after the polymerization reaction. A diene polymer is preferred.

Here, the conjugated diene polymer having a polymerizable active terminal is conjugated with an aromatic vinyl compound using an organic alkali metal compound, preferably a lithium compound, as described in the production of the conjugated diene polymer. The diene compound can be obtained by anionic polymerization in the same manner as described above. In this case, the reaction conditions are appropriately selected so that the resulting low molecular weight diene copolymer having an active terminal has the above-described properties.
Nitrogen-containing compounds, silicon-containing compounds, tin-containing compounds, and the like can be used as modifiers that are reacted with the active ends of the low molecular weight diene copolymer thus obtained.
Examples of nitrogen-containing compounds that can be used as the modifying agent include bis (diethylamino) benzophenone, dimethylimidazolidinone, N-methylpyrrolidone, 4-dimethylaminobenzylideneaniline, and the like. By using these nitrogen-containing compounds as modifiers, functional groups containing nitrogen such as substituted and unsubstituted amino groups, amide groups, imino groups, imidazole residues, nitrile groups, and pyridyl groups can be introduced.
In the modification reaction in the present invention, the low molecular weight diene copolymer having an active terminal to be used is preferably such that at least 10% of the polymer chain has a living property.

In the present invention, the first modified conjugated diene polymer to be a conjugated diene copolymer is the following with respect to the conjugated diene polymer having an organometallic active site in the molecule thus obtained. Formula (VI):

[In the formula (VI), a + b + c = 4 (where b is an integer of 1 to 3, a is an integer of 0 to 2, and c is an integer of 1 to 3), and D is a saturated cyclic tertiary amine compound] Residue, unsaturated cyclic tertiary amine compound residue, imine residue, nitrile group, (thio) isocyanate group, (thio) epoxy group, isocyanuric acid trihydrocarbyl ester residue, carbonic acid dihydrocarbyl ester residue, nitrile group , Pyridine group, (thio) ketone group, (thio) aldehyde group, amide group, (thio) carboxylic acid ester residue, metal salt of (thio) carboxylic acid ester residue, carboxylic acid anhydride residue, carboxylic acid halogen It is a compound residue and at least one functional group selected from a secondary amino group or a mercapto group having a hydrolyzable group, and when D is plural, they may be the same or different. It may be.
R ¹ is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms or a halogen atom, and is the same when R ¹ is plural. May be different. R ² is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when R ² is plural, they are the same or different. May be. R ³ is a divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when R ³ is plural, they may be the same or different. Good. It can be obtained by reacting a modifier represented by

In the general formula (VI), R ¹ and R ² are each an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aryl group having 7 to 18 carbon atoms. Aralkyl group and the like can be mentioned. Here, the alkyl group and alkenyl group may be linear, branched or cyclic, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group. , Sec-butyl, tert-butyl, pentyl, hexyl, octyl, decyl, dodecyl, cyclopentyl, cyclohexyl, vinyl, propenyl, allyl, hexenyl, octenyl, cyclo A pentenyl group, a cyclohexenyl group, etc. are mentioned. The aryl group may have a substituent such as a lower alkyl group on the aromatic ring, and examples thereof include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. Furthermore, the aralkyl group may have a substituent such as a lower alkyl group on the aromatic ring, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.

The divalent inert hydrocarbon group having 1 to 20 carbon atoms in R ³ is preferably an alkylene group having 1 to 20 carbon atoms. The alkylene group may be linear, branched or cyclic, but a linear one is particularly preferable. Examples of the linear alkylene group include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, a decamethylene group, and a dodecamethylene group.

Examples of the saturated cyclic tertiary amine compound residue in D include a hexamethyleneimino group, a pyrrolidinyl group, a piperidinyl group, a heptamethyleneimino group, and a dodecamethyleneimino group. Examples of amine compound residues include imidazole residues, dihydroimidazole residues, oxazole residues, and pyridyl groups.
The D includes a ketimine residue, a saturated cyclic tertiary amine compound residue, an imidazole residue, a dihydroimidazole residue, a pyridine 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.

In the general formula (VI), among the functional groups in D, the imine residue includes ketimine, aldimine and amidine residues, and the (thio) carboxylic acid hydrocarbyl ester is unsaturated such as acrylate or methacrylate. Includes residues of carboxylic acid esters. Examples of the metal of the metal salt residue of (thio) carboxylic acid include alkali metals, alkaline earth metals, aluminum, tin, and zinc.

Among the functional groups in the monovalent group represented by D, examples of the secondary amino group having a hydrolyzable group 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 glycidoxy group, 3,4-epoxycyclohexyl group, and those obtained by replacing the epoxy ring in these groups with a thioepoxy ring.

In the present invention, the modifier used in the conjugated diene polymer 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.
Moreover, when the modifier used 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 interacts with an inorganic filler such as silica. Since the modifying group to be introduced 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 this modification reaction, the conjugated diene polymer having an active terminal to be used is preferably one in which at least 10% of the polymer chains have living properties.

Examples of the hydrocarbyloxysilane compound represented by the general formula (VI) include, for example, (thio) epoxy group-containing hydrocarbyloxysilane compounds such as 2-glycidoxyethyltrimethoxysilane and 2-glycidoxyethyltriethoxysilane. (2-glycidoxyethyl) methyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, 2- (3 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane and the epoxy group in these compounds to thioepoxy Base There may be mentioned those obtained by replacing, among these, 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyl triethoxysilane are particularly preferred.

Further, as imine residue-containing hydrocarbyloxysilane compounds, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N- (1-methylethylidene) -3- (tri Ethoxysilyl) -1-propanamine, N-ethylidene-3- (triethoxysilyl) -1-propanamine, N- (1-methylpropylidene) -3- (triethoxysilyl) -1-propanamine, N -(4-N, N-dimethylaminobenzylidene) -3- (triethoxysilyl) -1-propanamine, N- (cyclohexylidene) -3- (triethoxysilyl) -1-propanamine and their tris Trimethoxysilyl compounds corresponding to ethoxysilyl compounds, methyldiethoxysilyl compounds, ethyldiethoxysilyl compounds , Methyldimethoxysilyl compounds, ethyldimethoxysilyl compounds, etc., among which N- (1-methylpropylidene) -3- (triethoxysilyl) -1-propanamine and N- (1, 3-Dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine is particularly preferred.

Examples of the imine (amidine) residue-containing compound include 1- [3- (triethoxysilyl) propyl] -4,5-dihydroimidazole, 1- [3- (trimethoxysilyl) propyl] -4,5- Dihydroimidazole, N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole, N- (3-isopropoxysilylpropyl) -4,5-dihydroimidazole, N- (3-methyldiethoxysilylpropyl) Examples include -4,5-dihydroimidazole, and among these, N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole is preferable.

As the bifunctional hydrocarbyloxysilane compound represented by the general formula (VI), for example, when D 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-dihydroimi Sol, 1- [3- [dipropoxy (ethyl) silyl] propyl] -4,5-dihydroimidazole, etc., 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 (VI), for example, when D 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) ) Silyl] propyl] -pyridine, 4- [3- [diethoxy (ethyl) silyl] propyl] -pyridine, 4- [3- [dipropoxy (methyl) silyl] propyl] -pyridine, 4- [3- [dipropoxy ( Pyridine compounds such as ethyl) 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 (VI), for example, when D 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] -oki Tetrazole, 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.

Furthermore, other hydrocarbyloxysilane compounds include the following. That is, as the carboxylic acid hydrocarbyl ester residue-containing compound, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyl Examples thereof include triisopropoxysilane, among which 3-methacryloyloxypropyltrimethoxysilane is preferable.

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

Further, as the carboxylic acid anhydride residue, 3-triethoxysilylpropyl succinic anhydride residue, 3-trimethoxysilylpropyl succinic anhydride residue, 3-methyldiethoxysilylpropyl succinic anhydride residue Among them, among them, 3-triethoxysilylpropyl succinic anhydride residue is preferable.

In the present invention, the hydrocarbyloxysilane compound having the above characteristic structure is preferably added in a stoichiometric amount or in excess of the active site, more preferably 0.3 molar equivalent or more of the apparent active site. (Normally, one mole of the modifying hydrocarbyloxysilane compound corresponds to several mole equivalents of the active site), the hydrocarbyloxysilane compound is reacted with the active site, and the active site is substantially hydrocarbyloxysilane compound. After introducing the residue, a method of adding a condensation accelerator is used.

Examples of such a condensation accelerator include a compound containing a tertiary amino group, or among group 3, 4, 5, 12, 13, 14, and 15 of the periodic table (long period type). An organic compound containing one or more elements belonging to any of the above can be used. Further, as a condensation accelerator, an alkoxide, a carboxyl containing at least one metal selected from the group consisting of titanium (Ti), zirconium (Zr), bismuth (Bi), aluminum (Al), and tin (Sn). It is preferably an acid salt or an acetylacetonate complex salt.
The condensation accelerator used here can be added before the modification reaction, but is preferably added to the modification reaction system during and / or after the modification reaction. When added before the denaturation reaction, a direct reaction with the active end occurs, and for example, a hydrocarboxy group having a protected primary amino group at the active end may not be introduced.
It is preferable to add the condensation accelerator to the reaction system immediately after the modification in which the hydrocarbylsilane compound residue is introduced. However, the polymer modified by the reaction is dried and then blended, preferably blended. In the first stage, a condensation accelerator may be added.
In this modification reaction, the conjugated diene polymer used preferably has at least 20% of polymer chains having the active site.

The second modified conjugated diene polymer in the present invention has the following general formula (IV) at the active site of the conjugated diene polymer having an organometallic active site in the molecule.
R _a MX _b ……… (IV)
[In the formula (IV), each R independently 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 having 7 to 20 carbon atoms. Selected from the group, M is tin or silicon, and X is independently chlorine, bromine or iodine. A is an integer of 0 to 3, b is an integer of 1 to 4, and a + b = 4), and the general formula (V)
R ¹ _a M (OR ² ) _b (V)
[In the above formula (V), R ¹ and R ² are each independently 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, and 7 carbon atoms. Selected from ˜20 aralkyl groups and M is tin or silicon. A is an integer of 0 to 3, b is an integer of 1 to 4, and a + b = 4], and at least one modifier selected from alkoxysilane compounds represented by Obtained by reaction.

The method for producing the polymer having an organometallic active site in the molecule is the same as in the case of the first modified conjugated diene polymer.
The modified conjugated diene polymer modified with at least one of the coupling agents represented by the general formulas (IV) and (V) has at least one tin-carbon bond or silicon-carbon bond. In the general formulas (IV) and (V), R or R ¹ and R ² each independently represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl having 6 to 20 carbon atoms. Group or an aralkyl group having 7 to 20 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, an n-butyl group, a neophyll group, a cyclohexyl group, an n-octyl group, and a 2-ethylhexyl group. . M is tin or silicon, and X is independently chlorine, bromine or iodine. In the general formulas (IV) and (V), a is an integer of 0 to 3, and b is an integer of 1 to 4, provided that a + b = 4.
As the coupling agent represented by the general formula (IV), tin tetrachloride, RSnCl ₃ , R ₂ SnCl ₂ , R ₃ SnCl and the like are preferable, and tin tetrachloride is particularly preferable. Moreover, as a coupling agent represented by general formula (V), tetraalkoxysilane, trialkoxysilane, and dialkoxysilane are preferable, and tetraethoxysilane is particularly preferable.

The third modified diene polymer in the present invention is a modification obtained by reacting a condensate of an alkoxysilane compound represented by the general formula (VI) with a modifier represented by the general formula (VI). It is a conjugated diene polymer.
The alkoxysilane compound represented by the general formula (V) and the modifier represented by the general formula (VI) are as described above.

The method for producing the polymer having an organometallic active site in the molecule is the same as in the case of the first modified conjugated diene polymer.
Further, the kind of the condensation accelerator and the condensation reaction conditions are also as described in the production of the first modified conjugated diene polymer.

It is preferable that the modified conjugated diene polymer in the present invention modified with the modifier described above contains a nitrogen atom. In general, in a rubber composition in which a white filler such as silica is blended with a rubber component containing a modified conjugated diene polymer having a nitrogen-containing functional group, the dispersibility of the white filler such as silica in the rubber component is improved. Moreover, since the hysteresis loss of the rubber component is reduced, the low loss performance can be remarkably improved. Therefore, in the present invention, by using a modified conjugated diene polymer having a nitrogen-containing functional group together with a white filler such as silica, the dispersibility of the white filler such as silica is greatly improved. The low loss performance in the rubber composition can be remarkably improved while sufficiently exerting the reinforcing effect of the white filler.

In the present invention, the modification reaction for obtaining the first modified conjugated diene polymer and the second modified conjugated diene polymer can be carried out using either a solution reaction or a solid phase reaction. It may contain unreacted monomers used during the polymerization.). Moreover, there is no restriction | limiting in particular about the form of this modification | denaturation reaction, You may carry out using a batch type reactor, You may carry out by a continuous type using apparatuses, such as a multistage continuous type reactor and an in-line mixer. In addition, it is important that the modification reaction is carried out after reaching the conversion rate at which the completion of the polymerization reaction is desired, and before performing a solvent removal treatment, a water treatment, a heat treatment or the like.

The temperature of the modification reaction is preferably 20 ° C. or higher, but the polymerization temperature of the conjugated diene polymer can be used as it is, and a more preferable range is 30 to 120 ° C. When the reaction temperature is lowered, the viscosity of the polymer is excessively increased and the dispersibility of the reaction product tends to be deteriorated. On the other hand, when the reaction temperature increases, the polymerization active site tends to be deactivated easily.
The amount of the modifier used is preferably in the range of 0.25 to 3.0 mol, more preferably in the range of 0.5 to 1.5 mol, relative to 1 mol of the polymerization initiator used for the production of the conjugated diene polymer. .

In the present invention, the modification with the modifier is performed on the active site in the conjugated diene polymer, but the active site may be in the polymer molecule, and the position thereof is not particularly limited.
However, the rubber component contains a modified conjugated diene polymer obtained by modifying at least one molecular terminal with a modifier composed of a compound containing a functional group that interacts with a white filler such as silica. From the viewpoint of low loss performance of the obtained rubber composition for tires, it is particularly preferable, and from this viewpoint, the active site in the polymer is preferably present at the end of the conjugated diene polymer.

The rubber composition for tires of the present invention contains the above-mentioned modified conjugated diene polymer (first polymer, second polymer) as a rubber component. Here, the content of the modified conjugated diene polymer in the rubber component (A) is preferably in the range of 5 to 80 parts by mass with respect to 100 parts by mass of the rubber component (A).
When the content of the modified conjugated diene polymer in the rubber component is 5 parts by mass or more, the effect of improving the dispersibility of the white filler such as silica can be exhibited, while 80 parts by mass or less. By doing so, the effect of the present invention can be exhibited without deteriorating workability. The content is more preferably in the range of 15 parts by mass or more and 60 parts by mass or less.

<White filler>
Next, examples of the white filler used in the tire rubber composition of the present invention include silica, aluminum hydroxide, alumina, clay, calcium carbonate and the like. Among these, silica and hydroxide are used from the viewpoint of reinforcement. Aluminum is preferred and silica is particularly preferred.
Silica that can be used is not particularly limited, and those used in commercially available rubber compositions can be used, among which wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), colloidal silica, etc. are used. In particular, the use of wet silica is preferred.

The content of these white fillers is preferably in the range of 5 to 200 parts by weight, more preferably in the range of 10 to 150 parts by weight, even more preferably, with respect to 100 parts by weight of the rubber component. , Preferably in the range of 20 to 120 parts by mass. In particular, in the case of the present invention, the effect of the present invention can be exhibited even if the silica content is as high as 60 parts by mass or more based on 100 parts by mass of the rubber component.
The content of the white filler is preferably 5 parts by mass or more from the viewpoint of improving the fracture characteristics with respect to 100 parts by mass of the rubber component, and is preferably 200 parts by mass or less from the viewpoint of workability.

When silica is used as the white filler to be used, it is preferable to use a silane coupling agent from the viewpoint of reinforcing properties.
The silane coupling agent that can be used is not particularly limited, and examples thereof include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, and bis (3-triethoxysilylpropyl) disulfide. Bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltri Ethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-nitropropyltrimethoxysilane, 3-nitropropyltriethoxysilane, 3-chloropropylmethoxysilane, 3- Lolopropyltriethoxysilane, 2-chloroethyltrimethoxysilane, 2-chloroethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N, N- Dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazole tetrasulfide, 3-triethoxysilylpropylbenzothiazole tetrasulfide, 3-triethoxysilyl Propyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mer At least one of ptopropyldimethoxymethylsilane, 3-nitropropyldimethoxymethylsilane, 3-chloropropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, dimethoxymethylsilylpropylbenzothiazole tetrasulfide, etc. Is mentioned.

The content of these silane coupling agents varies depending on the content of silica, but is preferably 1 to 20 parts by weight, more preferably 6 parts from the viewpoint of heat generation, with respect to 100 parts by weight of silica. A range of ˜12 parts by weight is desirable.
The content of the silane coupling agent is preferably 1 part by mass or more from the viewpoint of the effect of adding the coupling agent to 100 parts by mass of silica, and from the viewpoint of maintaining reinforcement and exothermicity, the content is 20 parts by mass or less. preferable.

<Other fillers>
In the present invention, carbon black or the like can be used as a reinforcing filler in addition to the white filler.
Carbon black that can be used is not particularly limited, and grades such as FEF, SRF, HAF, ISAF, and SAF can be used.
The content of these carbon blacks is also not particularly limited, but is preferably 0 to 250 parts by weight, more preferably 10 to 250 parts by weight with respect to 100 parts by weight of the rubber component. . In addition, from a viewpoint of maintaining exothermic property, 200 parts by mass or less is preferable.

<Compounds Represented by General Formula (I) and Formula (II)>
The compounds represented by the following general formula (I) and general formula (II) used in the present invention further improve the dispersibility of white fillers such as silica in the rubber component (A) containing the conjugated diene polymer. Therefore, it is contained for improving the low loss performance and exhibiting the effects of the present invention.

In the formula (I), R ₁ represents an alkyl group or alkenyl group having 1 to 24 carbon atoms, or a group represented by the above formula (III). The alkyl group and alkenyl group having 1 to 24 carbon atoms may be linear, branched, or cyclic. For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t- Butyl, pentyl, isopentyl, hexyl, isoheptyl, 2-ethylhexyl, octyl, isononyl, decyl, dodecyl, isotridecyl, tetradecyl, hexadecyl, isocetyl, octadecyl, isostearyl Alkyl groups such as docosyl group and tetracosyl group, allyl group, 3-butenyl group, methallyl group, 2-methyl-3-butenyl group, 3-methyl-3-butenyl group, 1,1, -dimethyl-2-propenyl And alkenyl groups such as 4-pentenyl group, oleyl group and tetracosilylene group. Is an alkyl group or alkenyl group having 6 to 18 carbon atoms, more preferably 11 to 18 carbon atoms, and the alkyl group and alkenyl group may be linear, branched or cyclic, a heptyl group, 2-ethylhexyl group, undecyl group, tridecyl group, pentadecyl group, heptadecyl group, heptadecenyl group. Preferred examples of the fatty acid used as a raw material include octanoic acid, lauric acid, tetradecanoic acid, myristic acid, stearic acid, and oleic acid.
In the above formula (I), when R ₁ is a group represented by the above formula (III), A is a single bond or an alkyl or alkenyl group having 1 to 24 carbon atoms, and B is a carbonyl group. , Ester group, amino group, amide group, ether group, hydroxyl group, hydroxyalkyl group, hydroxyalkylene group, and R ₆ is an alkyl group or alkenyl group having 1 to 24 carbon atoms as in R ₁ above. The alkyl group and alkenyl group may be linear, branched or cyclic.

Among the compounds represented by the general formulas (I) and (II), preferable compounds include the following compounds (1) to (5).
(1) In the above formula (I), R ₁ is the above-mentioned alkyl group or alkenyl group having 1 to 24 carbon atoms (including linear, branched and cyclic), and R ₂ is a hydroxyalkyl group And a hydroxyalkyl group having an oxyalkylene unit [— (R ₇ O) mH: R ₇ is an alkylene group having 1 to 6 carbon atoms], and R ₃ is a hydroxyalkyl group, a hydroxy having an oxyalkylene unit. Examples thereof include an amine compound having an alkyl group [— (R ₈ O) n—H: R ₈ is an alkylene group having 1 to 6 carbon atoms, and m + n is a number of 1 to 20].
Specific examples of amine compounds that can be used in this compound include N-tridecylethanolamine, N-octylethanolamine, N-laurylethanolamine, N-decylethanolamine, N-dodecylethanolamine, N-alkylethanolamines such as N-tetradecylethanolamine, N-hexadecylethanolamine, N-octadecylethanolamine, N-octadecenylethanolamine, N-alkenylethanolamine, POE (2) octylamine, POE (4) Decylamine, POE (2) dodecylamine, POE (5) dodecylamine, POE (15) dodecylamine, POE (2) tetradecylamine, POE (2) hexadecylamine, POE (2) octadecylamine, OE (20) octadecylamine, POE (2) octadecenylamine, POE (2) laurylamine, POP (2) octylamine, POP (4) decylamine, POP (2) dodecylamine, POP (5) dodecylamine, POP (15) dodecylamine, POP (2) tetradecylamine, POP (2) hexadecylamine, POP (2) octadecylamine, POP (20) octadecylamine, POP (2) octadecenylamine, POE (n) indicates that an average of n mol of polyoxyethylene is added, and POP (n) indicates that an average of n mol of polyoxypropylene is added. ] Etc. are mentioned. In addition, the synthesis | combining method of the said compound is known, can be obtained by various manufacturing methods, and may use a commercially available thing.

(2) In the formula (I), at least one of R ₁ and R ₂ represents a group represented by the following formula (VII), and at least one of R ₂ and R ₃ represents the following formula ( VIII).

In the above formula (VII), R ₉ represents an alkyl group or alkenyl group having 1 to 24 carbon atoms, and the alkyl group and alkenyl group may be any of linear, branched, and cyclic, and X Is an alkylene group having 1 to 6 carbon atoms. In the above formula (VIII), R ₁₀ is an alkylene group having 1 to 6 carbon atoms, y means an average number of added moles and is a number from 0 to 5, and z is from 1 to 3. Examples include amine derivatives that become integers.
Specific examples of amine derivatives contained in this compound include N-lauroylaminopropyl-N, N-dimethylamine, N-lauroylaminoethyl-N, N-diethylamine, N-lauroylaminopropyl-N, N-diethylamine, N-palmitoylaminopropyl-N, N-dimethylamine, N-palmitoylaminoethyl-N, N-diethylamine, N-stearoylaminopropyl-N, N-dimethylamine, N-stearoylaminoethyl-N, Examples thereof include at least one of N-diethylamine, di (N-lauroylaminoethyl) -N-methylamine, and tri (N-lauroylaminoethyl) amine. Among them, N-lauroylaminopropyl-N, N-dimethyl Amine, N-lauroylaminoethyl- , N-diethylamine, N-palmitoylaminopropyl-N, N-dimethylamine, N-palmitoylaminoethyl-N, N-diethylamine, N-stearoylaminopropyl-N, N-dimethylamine, and N-stearoylaminoethyl- N, N-diethylamine and the like can be mentioned. In addition, the synthesis | combining method of the said compound is known, can be obtained by various manufacturing methods, and may use a commercially available thing.

(3) In the formula (I), R ₁ is a group represented by the formula (III). In the formula (III), A is a single bond, B is a carbonyl group (—CO—), R _6. Is an alkyl group or alkenyl group having 1 to 24 carbon atoms (including linear, branched and cyclic), and R ₂ is a hydroxyalkyl group or a hydroxyalkyl group having an oxyalkylene unit [— ( R ₇ O) n—H: R ₇ is an alkylene group having 1 to 6 carbon atoms, n is a number of 1 to 5], and monoalkanolamide in which R ₃ is a hydrogen atom.
Specific examples of monoalkanolamides that can be used in this compound include octanoic acid monoethanolamide, octanoic acid monoisopropanepropanolamide, POE (2) octanoic acid monoethanolamide, lauric acid monoethanolamide, lauric acid Mention may be made of at least one of monoisopropanolamide, stearic acid monoethanolamide, oleic acid monoethanolamide, POE (2) lauric acid monoethanolamide, among which lauric acid monoisopropanolamide, lauric acid monoethanolamide, stearic acid It is desirable to use monoethanolamide, oleic acid monoethanolamide, POE (2) lauric acid monoethanolamide. In addition, the synthesis method of the said monoalkanolamide is known, can be obtained by various manufacturing methods, and may use a commercially available thing.

(4) In the formula (I), R ₁ is a group represented by the formula (III). In the formula (III), A is a single bond, B is a carbonyl group (—CO—), R _6. Is an alkyl group or alkenyl group having 1 to 24 carbon atoms (including linear, branched and cyclic), and R ₂ and R ₃ are each independently a hydroxyalkyl group or an oxyalkylene unit. Hydroxyalkyl groups having [— (R ₇ O) m—H, — (R ₈ O) m—H: R ₇ and R ₈ are alkylene groups having 1 to 6 carbon atoms, and m and n are 2 to The number of 8] dialkanolamide.
Specific examples of dialkanolamides contained in this compound include octanoic acid diethanolamide, octanoic acid diisopropanolamide, lauric acid diethanolamide, POE (5) lauric acid diethanolamide, stearic acid diethanolamide, There may be mentioned at least one of oleic acid diethanolamide and POE (5) oleic acid diethanolamide. Among them, lauric acid diethanolamide, stearic acid diethanolamide, and oleic acid diethanolamide are preferable. In addition, the synthesis method of the said dialkanolamide is known, can be obtained by various manufacturing methods, and may use a commercially available thing.

(5) In the above formula (II), R ₄ is an alkyl group or alkenyl group having 1 to 24 carbon atoms (including linear, branched and cyclic) as in R ₁ above. R ₅ may be an imidazoline compound which is a hydroxyl group, a hydroxyalkyl group, or a hydroxyalkyl group having an oxyalkylene unit.
Specific examples of imidazoline compounds contained in this compound include 1-hydroxyethyl-2-undecylimidazoline, 1-hydroxyethyl-2-methylimidazoline, 1-hydroxyethyl-2-propylimidazoline, Hydroxyethyl-2-heptyluimidazoline, 1-hydroxyethyl-2-nonylimidazoline, 1-hydroxyethyl-2-undecylimidazoline, 1-hydroxypropyl-2-methylimidazoline, 1-hydroxypropyl-2-propylimidazoline, 1 -Hydroxypropyl-2-heptylimidazoline, 1-hydroxypropyl-2-nonylimidazoline, 1-hydroxypropyl-2-undecylimidazoline, 1-hydroxybutyl-2-undecylimidazoline, etc. It is. In addition, the synthesis | combining method of the said imidazoline compound is known, can be obtained by various manufacturing methods, and may use a commercially available thing.

The (total) content of the compounds represented by the above formula (I), formula (II) and the like is preferably 0.5 to 15 parts by mass, more preferably 100 parts by mass with respect to the rubber component. From the viewpoint of exerting further effects of the present invention, 1 to 15 parts by mass is preferable, and 1 to 10 parts by mass is more preferable. Further, the content of these compounds is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, and even more preferably 2 to 12 parts by mass with respect to 100 parts by mass of the white filler.

<Preparation of tire rubber composition>
In the rubber composition for tires of the present invention, in addition to the rubber component, the white filler, the compound represented by the above formula (I), the formula (II) and the like, a compounding agent usually used in the rubber industry, For example, an antioxidant, a softener, stearic acid, zinc white, a vulcanization accelerator, a vulcanization accelerator, a vulcanizer, and the like may be appropriately selected and contained within a range that does not impair the object of the present invention. it can. As these compounding agents, commercially available products can be suitably used.

The rubber composition for tires of the present invention includes a rubber component, a white filler, a compound represented by the above formula (I), formula (II) and the like, and various compounding agents appropriately selected as necessary. Is obtained by kneading using a kneader such as a roll or an internal mixer, preferably by kneading by two-stage kneading (first stage, second stage), heating, extruding, etc. It can be used for tire tire applications such as tire treads, undertreads, carcass, sidewalls, and bead portions.

The reason why the rubber composition for tires thus configured improves the dispersibility of white dispersants such as silica in the rubber composition for tires and significantly improves the low loss performance is as follows. Is inferred.
That is, in the rubber composition for a tire of the present invention, the rubber component containing the conjugated diene polymer having the above characteristics improves the dispersibility of a white filler such as silica. That is, when a white filler such as silica is added to the rubber component containing the conjugated diene polymer having the above characteristics, the surface area of the white filler increases, and the surface area of the white filler such as silica increases. Thus, the reaction point of the silica dispersant (hydrophobizing agent) composed of the compound represented by the above formula (I), formula (II) or the like increases. Thereby, by weakening the interaction (aggregation) between white fillers such as silica with a silica dispersant (hydrophobizing agent) comprising a compound represented by formula (I), formula (II), etc. The dispersibility of the white filler is further improved. By these synergistic effects, a rubber composition for tires with significantly improved low loss performance can be obtained.

<Tire>
Next, the tire of this invention is manufactured by a normal method using the rubber composition for tires of this invention. That is, if necessary, the tire rubber composition of the present invention containing various compounding agents as described above is extruded into a tread member, for example, as a tire member at an unvulcanized stage, and a tire molding machine The above is pasted and molded by a usual method to form a green tire. The green tire is heated and pressed in a vulcanizer to obtain a tire. Since the tire of the present invention thus obtained is excellent in low heat build-up, the low loss performance is very good, and the processability of the rubber composition is good, so that the productivity is also excellent. It will be a thing. 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.

Next, the present invention will be described in more detail with reference to production examples, examples and comparative examples, but the present invention is not limited to the following examples.

<Production of Modified Conjugated Diene Polymer>
[Production Example 1: Modified conjugated diene polymer (1), modified SSBR1]
Add 1,3-butadiene in cyclohexane and styrene in cyclohexane to a dry, nitrogen-substituted 800 ml pressure-resistant glass container so that 60 g of 1,3-butadiene and 15 g of styrene are added, and 2,2-ditetrahydrofuryl is added. 0.70 mmol of propane was added, and lithium hexamethyleneimide [HMI-Li; hexamethyleneimine (HMI) / lithium (Li) molar ratio = 0.9] prepared in the polymerization system was used as a polymerization initiator at a lithium equivalent of 0. The polymerization reaction was carried out in a warm water bath at 50 ° C. for 1.5 hours using .70 mmol. The polymerization addition rate at this time was almost 100%.

[Production Example 2: Modified conjugated diene polymer (2), modified SSBR2]
Add 1,3-butadiene in cyclohexane and styrene in cyclohexane to a dry, nitrogen-substituted 800 ml pressure-resistant glass container so that 60 g of 1,3-butadiene and 15 g of styrene are added, and 2,2-ditetrahydrofuryl is added. After adding 0.70 mmol of propane and further adding 0.70 mmol of n-butyllithium, a polymerization reaction was carried out in a hot water bath at 50 ° C. for 1.5 hours. The polymerization addition rate at this time was almost 100%.
Next, 0.20 mmol of tetraethoxysilane was added to the polymerization reaction system, and a modification reaction was further performed at 50 ° C. for 30 minutes.

[Production Example 3: Modified conjugated diene polymer (3), modified SSBR3]
In the production of the modified conjugated diene polymer (2), 0.20 mmol of tetraethoxysilane was changed to 0.63 mmol of N- (1,3-dimethyl1-butylidene) -3- (triethoxysilyl) -1-propanamine. A modified conjugated diene polymer (3) was obtained in the same manner as in the production of the modified conjugated diene polymer (2) except that.

[Production Example 4: Production of dispersant 2, 1-hydroxyethyl-2-undecylimidazoline]
A 4-necked flask was charged with 200 g (1 mol) of lauric acid and 109.2 g of aminoethylethanolamine (hereinafter abbreviated as “AEEA”), and then stirred while passing 80 ° C. warm water through a reflux condenser. Heated to 140 ° C. Thereafter, the reaction pressure was set to 400 mmHg over 1 hour, and amidation was performed by reacting for 2 hours. Thereafter, the pressure was returned to normal pressure with N ₂ , and NaH ₂ PO ₄ : 3.0 g (0.025 mol) was added. Next, the reaction temperature was lowered to 200 ° C. and the pressure was lowered to 200 mmHg over 1.5 hours, and aging was performed for 1 hour under these conditions. Further, the pressure was lowered to 10 mmHg over about 1.5 hours, and the reaction was carried out for 1 hour under these conditions to remove excess AEEA, thereby obtaining 253 g of 1-hydroxyethyl-2-undecylimidazoline.

[Examples 1 to 27 and Comparative Examples 1 to 17]
The rubber composition was prepared by mixing the components of the first stage type and amount with the compounding formulations shown in Tables 1 to 3 below, and then kneading the components of the second stage type and amount. It was done by doing.
About each obtained rubber composition for tires, it evaluated by the following measuring method by the low fuel consumption property which is low loss performance.
These results are shown in Tables 1 to 3 below.

[Measurement method of fuel efficiency]
Using a viscoelasticity measuring device (manufactured by Rheometrics), tan δ was measured at a temperature of 50 ° C., a strain of 5%, and a frequency of 15 Hz. The larger this value, the better the fuel efficiency.

In Table 1 to Table 3, * 1 to * 12 are as follows.
* 1: Solution polymerization SBR manufactured by Asahi Kasei Co., Ltd., trade name “Toughden 2000”
* 2: Product name “# 80” manufactured by Asahi Carbon Co., Ltd.
* 3: manufactured by Tosoh Silica Co., Ltd., nip seal AQ, BET surface area 220 m ² / g
* 4: Bis (3-triethoxysilylpropyl) disulfide (average sulfur chain length 2.35), silane coupling agent manufactured by Evonik, trade name “Si75” (registered trademark)
* 5: N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine, manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., trade name “NOCRACK 6C”
* 6: Amiate 102, manufactured by Kao Corporation, POE (2) laurylamine * 7: Production Example 4, 1-hydroxyethyl-2-undecylimidazoline * 8: Alkanolamine, manufactured by Kao Corporation, lauric acid monoethanolamide * 9: 1,3-diphenylguanidine, manufactured by Sanshin Chemical Industry Co., Ltd., trade name “Sunseller D”
* 10: Di-2-benzothiazolyl disulfide, manufactured by Sanshin Chemical Industry Co., Ltd., trade name “Sunceller DM”
* 11: N-tert-butyl-2-benzothiazolylsulfenamide, manufactured by Sanshin Chemical Industry Co., Ltd., trade name “Suncellor NS”
* 12: RSS # 1

As is clear from Tables 1 to 3, the rubber compositions for tires of Examples 1 to 27, which are within the scope of the present invention, have lower fuel consumption than Comparative Examples 1 to 17, which are outside the scope of the present invention. It turned out to be excellent.

The rubber composition for tires of the present invention can be suitably used for tire members of pneumatic tires such as tire treads, under treads, carcass, sidewalls, and bead portions.

Claims

For at least one rubber component (A) selected from natural rubber and / or diene-based synthetic rubber, a white filler and at least one compound represented by the following general formulas (I) and (II): And the rubber component (A) contains at least one selected from a silicon atom, a tin atom, a sulfur atom, an oxygen atom and a titanium atom in any one of a polymerization active terminal, a polymerization start terminal and a polymerization chain. A rubber composition for tires comprising a conjugated diene polymer.

[In the above formula (I), R 1 represents an alkyl or alkenyl group having 1 to 24 carbon atoms, a group represented by the following formula (III), wherein the alkyl group and alkenyl group are linear or branched. Either a chain or a ring may be used, and R 2 and R 3 may be a hydrogen atom, a hydroxyl group, a hydroxyalkyl group, or a hydroxyalkyl group having an oxyalkylene unit, and these may be the same or different. ]

[In the above formula (II), R 4 represents an alkyl group or alkenyl group having 1 to 24 carbon atoms, and the alkyl group and alkenyl group may be linear, branched or cyclic, and , R 5 is a hydroxyl group, a hydroxyalkyl group, or a hydroxyalkyl group having an oxyalkylene unit. ]

[In the above formula (III), A is a single bond or an alkyl or alkenyl group having 1 to 24 carbon atoms, and B is a carbonyl group, an ester group, an amino group, an amide group, an ether group, a hydroxyl group, Represents any one of a hydroxyalkyl group and a hydroxyalkylene group, and R 6 represents an alkyl group or an alkenyl group having 1 to 24 carbon atoms, and the alkyl group and the alkenyl group are any of linear, branched and cyclic But it ’s okay. ]
The tire rubber composition according to claim 1, wherein the conjugated diene polymer is a (co) polymer of a conjugated diene compound.
The tire rubber composition according to claim 1, wherein the conjugated diene polymer is a copolymer of an aromatic vinyl compound and a conjugated diene compound.
The conjugated diene polymer contains 0% by mass or more and 60% by mass or less of an aromatic vinyl compound unit, and the vinyl bond content in the conjugated diene part is 5% by mass or more and 80% by mass or less. The rubber composition for tires as described.
The conjugated diene polymer is a modified conjugated diene obtained by subjecting a polymerization active terminal to a compound containing at least one selected from a silicon atom, a tin atom, a sulfur atom, an oxygen atom and a titanium atom after the polymerization reaction. The tire rubber composition according to any one of claims 1 to 4, which is a polymer.
The modified conjugated diene polymer has the following general formula (IV) at the active site of the conjugated diene polymer having an organometallic active site in the molecule.
RaMXb ......... (IV)
{In the formula (IV), R each independently 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, and an aralkyl group having 7 to 20 carbon atoms. M is tin or silicon and X is independently chlorine, bromine or iodine. A is an integer of 0 to 3, b is an integer of 1 to 4, and a + b = 4), and the general formula (V)
R 1 aM (OR 2 ) b (V)
[In the formula (V), each of R 1 and R 2 independently 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, and 7 to 7 carbon atoms. Selected from 20 aralkyl groups, M is tin or silicon, and X is each independently chlorine, bromine or iodine. A is an integer of 0 to 3, b is an integer of 1 to 4, and a + b = 4]}, and a condensate thereof. The tire rubber composition according to claim 5, which is a modified conjugated diene-based polymer obtained by reacting with a rubber.
The modified conjugated diene polymer has the following general formula (VI) at the active site of the conjugated diene polymer having an organometallic active site in the molecule:

[In the formula (VI), a + b + c = 4 (where b is an integer of 1 to 3, a is an integer of 0 to 2, and c is an integer of 1 to 3), and D is a saturated cyclic tertiary amine compound] Residue, unsaturated cyclic tertiary amine compound residue, imine residue, nitrile group, (thio) isocyanate group, (thio) epoxy group, isocyanuric acid trihydrocarbyl ester residue, carbonic acid dihydrocarbyl ester residue, nitrile group Pyridine group, (thio) ketone group, (thio) aldehyde group, amide group, (thio) carboxylic acid hydrocarbyl ester residue, metal salt residue of (thio) carboxylic acid ester residue, carboxylic acid anhydride residue, A carboxylic acid halogen compound residue and at least one functional group selected from a hydrolyzable group-containing secondary amino group or mercapto group, and the same when a plurality of Ds are present It may be different also I.
R 1 is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms or a halogen atom, and is the same when R 1 is plural. May be different. R 2 is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when R 2 is plural, they are the same or different. May be. R 3 is a divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when R 3 is plural, they may be the same or different. Good. The rubber composition for tires according to claim 5, which is a modified conjugated diene polymer obtained by reacting a modifier represented by the formula:
The modified conjugated diene polymer is obtained by reacting a condensate of an alkoxysilane compound represented by the following general formula (V) with a modifier represented by the following general formula (VI). The tire rubber composition according to claim 5, which is a coalescence.
R 1 aM (OR 2 ) b (V)
{[In the formula (V), R 1 and R 2 are each independently 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, and 7 carbon atoms. Selected from ˜20 aralkyl groups and M is tin or silicon. A is an integer of 0 to 3, b is an integer of 1 to 4, and a + b = 4]

[In the formula (VI), a + b + c = 4 (where b is an integer of 1 to 3, a is an integer of 0 to 2, and c is an integer of 1 to 3), and D is a saturated cyclic tertiary amine compound] Residue, unsaturated cyclic tertiary amine compound residue, imine residue, nitrile group, (thio) isocyanate group, (thio) epoxy group, isocyanuric acid trihydrocarbyl ester residue, carbonic acid dihydrocarbyl ester residue, nitrile group Pyridine group, (thio) ketone group, (thio) aldehyde group, amide group, (thio) carboxylic acid hydrocarbyl ester residue, metal salt residue of (thio) carboxylic acid ester residue, carboxylic acid anhydride residue, A carboxylic acid halogen compound residue and at least one functional group selected from a hydrolyzable group-containing secondary amino group or mercapto group, and the same when a plurality of Ds are present It may be different also I.
R 1 is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms or a halogen atom, and is the same when R 1 is plural. May be different. R 2 is a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when R 2 is plural, they are the same or different. May be. R 3 is a divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and when R 3 is plural, they may be the same or different. . ]
The tire rubber composition according to any one of claims 5 to 8, wherein the modified conjugated diene polymer further contains a nitrogen atom.
The white rubber is contained in an amount of 5 to 200 parts by mass and the compound represented by the formula (I) is contained in an amount of 0.5 to 15 parts by mass with respect to 100 parts by mass of the rubber component. 10. The tire rubber composition according to any one of 1 to 9.
A tire comprising the tire rubber composition according to any one of claims 1 to 10.