JP2011088999A - Tire - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a tire having low rolling resistance and good abrasion resistance and to provide a winter tire having excellent on-ice performance and low rolling resistance. <P>SOLUTION: A rubber composition containing a rubber component and a filler is applied to the tire. The rubber component contains: a modified conjugate diene polymer obtained by a modification reaction in which a modifying agent comprising a silane compound and/or a partial condensate of the compound expressed by general formula (1) is made to react with the active terminal of a conjugate diene polymer having an organic metal active terminal having nucleophilic reactivity; and a modified conjugate diene polymer having a primary amino group and a silicon atom-containing functional group at a molecular chain terminal of the polymer. In formula (1), A<SP>1</SP>represents a hydrocarbyloxy group having 2 or more carbon atoms; A<SP>2</SP>represents a hydrolyzable functional group; R<SP>1</SP>represents a hydrocarbon group; R<SP>2</SP>represents a bivalent hydrocarbon group; X represents at least one kind of functional group selected from a saturated cyclic tertiary amine compound residue, unsaturated cyclic tertiary amine compound residue, nitrile group, and secondary amino group having an eliminable functional group; and A<SP>1</SP>and A<SP>2</SP>may be identical or different from each other. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a tire with low rolling resistance.

  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 wear resistance. However, in recent years, further reduction in fuel consumption of automobiles (reduction in rolling resistance of tires) has been desired from the viewpoint of energy saving and environmental problems.

By the way, the conventional winter tire lowers the glass transition point (Tg) in order to improve the performance on ice, and the temperature is low (here, the low temperature is a temperature during running on ice and is about −20 to 0 ° C.). ) Is often set to a low elastic modulus. However, since the elastic modulus at high temperature tends to decrease when the elastic modulus at low temperature is generally lowered, the conventional winter tire has high heat generation and rolling resistance (RR), and the market demand for reduction of rolling resistance. There was a problem that it was not able to cope with it enough.
Therefore, it is necessary to keep rolling resistance low even for winter tires that emphasize on-ice performance.

  On the other hand, in Patent Document 4, a rubber composition in which a foaming agent is blended with a rubber component, and the bubble rate after vulcanization and the dynamic elastic modulus at 0 ° C. and 60 ° C. are in a specific range. Winter tires (studless tires) that use modified conjugated diene polymers having a tertiary amino group-containing functional group as a rubber component of the rubber composition and used as a tread rubber of a tire have been proposed. In this proposal, using a modified conjugated diene polymer having a tertiary amino group-containing functional group, it was possible to achieve both a certain degree of performance on ice and a low rolling resistance.

  However, there is a strong demand for improving the performance of winter tires, and further improvements in on-ice performance and low rolling resistance are required.

JP 2001-158837 A JP 2005-232364 A JP-A-2005-290355 JP 2004-238619A

  Under such circumstances, an object of the present invention is to provide a tire with low rolling resistance and good wear resistance, and further to provide a winter tire with excellent performance on ice and low rolling resistance.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have determined that a modified conjugated diene heavy polymer modified by reacting a specific modifier as a rubber component of a rubber composition for a tire member, particularly a tread. It has been found that by using a modified conjugated diene polymer having a polymer and a primary amino group, not only rolling resistance can be reduced, but also on-ice performance and low rolling resistance can be highly compatible. The present invention has been completed based on such findings.

［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は飽和環状第３アミン化合物残基、不飽和環状第３アミン化合物残基、ニトリル基及び脱離可能な官能基を有する第２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。］
２． 前記ケイ素原子含有官能基が、ジアルコキシシラン化合物残基又はトリアルコキシシラン化合物残基である上記１に記載のタイヤ。
３． 前記変性共役ジエン重合体（ａ−２）が、下記一般式（２）又は下記一般式（３）で表わされる上記１又は２に記載のタイヤ。

［式中、Ｒ³及びＲ⁵は夫々独立に−ＯＲ、−ＯＨ又は炭素数１〜２０のアルキル基であり、Ｒ⁴は炭素数１〜２０のアルキレン基であり、Ｒは硫黄原子、酸素原子、窒素原子及び／又はハロゲン原子を有していても良い炭素数１〜２０のヒドロカルビル基である］

［式中、Ｒ⁶及びＲ⁸は夫々独立に−ＯＲ、−ＯＨ又は炭素数１〜２０のアルキル基であり、Ｒ⁷及びＲ⁹は夫々独立に炭素数１〜２０のアルキレン基であり、Ｒは硫黄原子、酸素原子、窒素原子及び／又はハロゲン原子を有していても良い炭素数１〜２０のヒドロカルビル基であり、ＭはＳｉ、Ｔｉ、Ｓｎ、Ｂｉ、Ｚｒ又はＡｌであり、Ｒ¹⁰は−ＯＨ、炭素数１〜３０のヒドロカルビル基、炭素数２〜３０のヒドロカルビルカルボキシル基、炭素数５〜２０の１，３−ジカルボニル含有基、炭素数１〜２０のヒドロカルビルオキシ基、並びに炭素数１〜２０のヒドロカルビル基及び／又は炭素数１〜２０のヒドロカルビルオキシ基で三置換されたシロキシ基からなる群から選ばれる基であり、複数のＲ¹⁰は同一でも異なっていても良く、ｋは｛（Ｍの価数）−２｝であり、ｎは０又は１である］ That is, the present invention is as follows.
1. Modification by reacting a modifying agent comprising a silane compound represented by the following general formula (1) and / or a partial condensate thereof with the active terminal of a conjugated diene polymer having an organometallic active terminal having nucleophilic reactivity A modified conjugated diene polymer (a-1) obtained by conducting a reaction, and a modified conjugated diene polymer (a-2) having a primary amino group and a silicon atom-containing functional group at the molecular chain terminal of the polymer; A tire characterized by applying a rubber composition containing a rubber component (R) and a filler (F).

[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 third group. It represents at least one functional group selected from an amine compound residue, an unsaturated cyclic tertiary amine compound residue, a nitrile group, and a second amino group having a detachable functional group. A ¹ and A ² may be the same or different. ]
2. 2. The tire according to 1 above, wherein the silicon atom-containing functional group is a dialkoxysilane compound residue or a trialkoxysilane compound residue.
3. The tire according to 1 or 2 above, wherein the modified conjugated diene polymer (a-2) is represented by the following general formula (2) or the following general formula (3).

[Wherein, R ³ and R ⁵ are each independently —OR, —OH or an alkyl group having 1 to 20 carbon atoms, R ⁴ is an alkylene group having 1 to 20 carbon atoms, and R is a sulfur atom, oxygen It is a C1-C20 hydrocarbyl group which may have an atom, nitrogen atom and / or halogen atom]

[Wherein R ⁶ and R ⁸ are each independently —OR, —OH or an alkyl group having 1 to 20 carbon atoms, and R ⁷ and R ⁹ are each independently an alkylene group having 1 to 20 carbon atoms, R is a hydrocarbyl group having 1 to 20 carbon atoms which may have a sulfur atom, an oxygen atom, a nitrogen atom and / or a halogen atom, M is Si, Ti, Sn, Bi, Zr or Al; ¹⁰ is —OH, a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyl carboxyl group having 2 to 30 carbon atoms, a 1,3-dicarbonyl-containing group having 5 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms, and A group selected from the group consisting of a hydrocarbyl group having 1 to 20 carbon atoms and / or a siloxy group trisubstituted by a hydrocarbyloxy group having 1 to 20 carbon atoms, and a plurality of R ¹⁰ may be the same or different; k is A (M of valency) -2}, n is 0 or 1]

  ADVANTAGE OF THE INVENTION According to this invention, a rolling tire with small rolling resistance and favorable abrasion resistance can be provided, and further, a winter tire having excellent performance on ice and low rolling resistance can be provided.

［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は飽和環状第３アミン化合物残基、不飽和環状第３アミン化合物残基、ニトリル基及び脱離可能な官能基を有する第２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。］ The tire of the present invention comprises a silane compound represented by the following general formula (1) and / or a partial condensate thereof at the active end of a conjugated diene polymer having an organometallic active end having nucleophilic reactivity. A modified conjugated diene polymer (a-1) obtained by performing a modification reaction in which a modifier is reacted, and a modified conjugated diene polymer having a primary amino group and a silicon atom-containing functional group at the molecular chain terminal of the polymer ( A rubber composition containing a rubber component (R) containing a-2) and a filler (F) is applied.

[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 third group. It represents at least one functional group selected from an amine compound residue, an unsaturated cyclic tertiary amine compound residue, a nitrile group, and a second amino group having a detachable functional group. A ¹ and A ² may be the same or different. ]

First, the modified conjugated diene polymer (a-1) according to the present invention will be described.
[Modified Conjugated Diene Polymer (a-1)]
The modified conjugated diene polymer (a-1) according to the present invention has the above general formula (1) as a modifier at the active terminal of the conjugated diene polymer having an organometallic active terminal having nucleophilic reactivity. It can be obtained by carrying out a modification reaction by reacting the silane compound and / or its partial condensate.

(Conjugated diene polymer having active terminal)
The conjugated diene polymer having an organometallic active terminal having nucleophilic reactivity used in the method of the present invention is obtained by copolymerizing a diene monomer alone or with another monomer, and its production The method is not particularly limited, and any of solution polymerization method, gas phase polymerization method and bulk polymerization method can be used, but 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 (CN bond) 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 a secondary amine and a lithium compound can be used for polymerization, but they 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.

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 target conjugated diene polymer is obtained by anionic polymerization in the presence of a randomizer, which is used as desired, using a lithium compound as a polymerization initiator.

  The hydrocarbon solvent is preferably one having 3 to 8 carbon atoms, such as propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, cyclohexane, propene, 1-butene, isobutene, trans-2. -Butene, cis-2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, benzene, toluene, xylene, ethylbenzene and the like. These may be used alone or in combination of two or more.

  The randomizer used as desired is a control of the microstructure of the conjugated diene polymer, such as an increase in 1,2 bonds in the butadiene portion in the styrene-butadiene copolymer, an increase in 3,4 bonds in the isoprene polymer, or the like. It is a compound having an effect 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 styrene-butadiene copolymer. The randomizer is not particularly limited, and any one of known compounds generally used as a conventional randomizer can be appropriately selected and used. Specifically, dimethoxybenzene, tetrahydrofuran, dimethoxyethane, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, 2,2-bis (2-tetrahydrofuryl) -propane, triethylamine, pyridine, N-methylmorpholine, N, N, N ′, Examples thereof include ethers such as N′-tetramethylethylenediamine and 1,2-dipiperidinoethane, and tertiary amines. Further, potassium salts such as potassium tert-amylate and potassium tert-butoxide, and sodium salts such as sodium tert-amylate can also be used.

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

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

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

(Modifier)
In the method for producing the modified conjugated diene polymer (a-1) according to the present invention, the active terminal of the conjugated diene polymer having an organometallic active terminal having nucleophilic reactivity obtained as described above. In addition, as a modifier, the general formula (1)

The silane compound represented by these and / or its partial condensate are made to react.
In the general formula (1), A ¹ represents a hydrocarbyloxy group having 2 or more carbon atoms, A ² represents a hydrolyzable functional group, R ¹ represents a hydrocarbon group, R ² represents a divalent hydrocarbon group, and X represents And at least one functional group selected from a saturated cyclic tertiary amine compound residue, an unsaturated cyclic tertiary amine compound residue, a nitrile group, and a second amino group having a detachable functional group. 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.
As described above, in 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 hydrocarbon having 1 to 18 carbon atoms. The group R ² is preferably a divalent hydrocarbon group having 1 to 20 carbon atoms.

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 is a saturated cyclic tertiary amine compound residue, an imidazole residue, a dihydroimidazole residue, an oxazole residue, a pyridyl group, a nitrile group, and a secondary amino group having 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 the group consisting of a saturated cyclic tertiary amine compound residue, an imidazole residue, a dihydroimidazole residue, and a dehydration group. It is preferably at least one selected from secondary amino groups having a separable 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 modifier used for the production of the modified conjugated diene polymer (a-1) according to the present invention is a silane compound represented by the general formula (1) and / or a partial condensate thereof as described above. Here, the partial condensate refers to a product in which a part (not all) of the SiOR groups of the silane compound represented by the general formula (1) are Si—O—Si bonded by condensation.
When the modifying agent for obtaining the modified conjugated diene polymer (a-1) according to the present invention is a bifunctional hydrocarbyloxysilane compound having two hydrocarbyloxy groups directly bonded to a silicon atom, a modification reaction Even if the hydrocarbyloxy group is consumed by the second amino group having a hydrolyzable functional group and a saturated cyclic tertiary amine compound residue, an unsaturated cyclic tertiary amine compound residue, a nitrile group and a detachable functional group Since at least one kind of functional group selected from among these is present, it preferably interacts with an inorganic filler such as silica.
On the other hand, in the case of a monofunctional hydrocarbyloxysilane compound having one hydrocarbyloxy group directly bonded to a silicon atom, the interaction with an inorganic filler such as silica is lowered.
On the other hand, in the case of a trifunctional hydrocarbyloxysilane compound having three hydrocarbyloxy groups that are 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 for obtaining the modified conjugated diene polymer (a-1) according to the present invention, it is preferable that the conjugated diene polymer having an active terminal to be used has at least 10% of the polymer chain having a living property. .

  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 an oxazole residue, as a specific example, 4- [3- [diethoxy (methyl) silyl] propyl] -oxazole, 4- [3- [diethoxy (ethyl) silyl] propyl] -oxazole, 4- [3- [dipropoxy (methyl) silyl] propyl] -oxazole, 4- [3- [dipropoxy (ethyl) silyl] propyl] -oxazole And oxazole compounds. Of these, 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.

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. .

The modified conjugated diene polymer (a-1) according to the present invention obtained as described above 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 (a-1) according to the present invention is preferably 10 to 150, more preferably _{15 to} 100. By setting the Mooney viscosity value within the above range, a rubber composition having excellent kneading workability and mechanical properties after vulcanization can be obtained.

(Condensation accelerator)
In the production of the modified conjugated diene polymer (a-1) according to the present invention, in order to accelerate the condensation reaction involving the bifunctional hydrocarbyloxysilane compound used as the aforementioned modifier, If necessary, the condensation reaction may be carried out in the presence of a condensation accelerator.
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. And acetylacetonate complex salts, more preferably titanium alkoxide, titanium carboxylate, tin carboxylate, bismuth carboxylate, zirconium alkoxide, zirconium carboxylate (especially hydrocarbyl carboxylate). Acid salt), zirconium alkoxide, aluminum alkoxide and aluminum carboxylate.

  Examples of the condensation accelerator made of a titanium compound include tetravalent titanium tetraalkoxide, dialkoxybis (β-diketonate), tetrakis (trihydrocarbyl oxide) and the like. Specifically, 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-pentanedio) G) 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, tetramethoxytitanium, tetraethoxy Titanium, tetra-n-propoxy titanium, tetraisopropoxy titanium, tetra-n-butoxy titanium, tetra-n-butoxy titanium oligomer, tetraisobutoxy titanium, tetra-sec-butoxy titanium, tetra-tert-butoxy titanium, bis ( Oreto ) Bis (2-ethylhexanoate) titanium, titanium dipropoxybis (triethanolamate), titanium dibutoxybis (triethanolamate), titanium tributoxy systemate, titanium tripropoxy systemate, titanium tripropoxyacetyl Acetonate, titanium dipropoxybis (acetylacetonate), titanium tripropoxy (ethyl acetoacetate), titanium propoxyacetylacetonate bis (ethylacetoacetate), titanium tributoxyacetylacetonate, titanium dibutoxybis (acetylacetonate) , Titanium tributoxyethyl acetoacetate, titanium butoxyacetylacetonate bis (ethylacetoacetate), titanium tetrakis (acetylacetonate), titanium diaceti Acetonate 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 (pentanedionate), 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.

  Condensation accelerators composed of tin compounds include tin carboxylates and alkoxides, and other compounds include divalent tin dicarboxylic acids {particularly bis (hydrocarbylcarboxylic acid) salts} and tetravalent dihydrocarbyltins. Dicarboxylate {including bis (hydrocarbylcarboxylic acid)} salt), bis (β-diketonate), alkoxy halide, monocarboxylate hydroxide, alkoxy (trihydrocarbylsiloxide), alkoxy (dihydrocarbylalkoxysiloxide) , Bis (trihydrocarbylsiloxide), bis (dihydrocarbylalkoxysiloxide) and the like can be suitably used. The hydrocarbyl group bonded to tin preferably has 4 or more carbon atoms, and particularly preferably has 4 to 8 carbon atoms. Of these, bis (2-ethylhexanoic acid) tin is particularly preferred.

  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. Water is preferably used in the form of a solution such as a simple substance or alcohol, or a dispersed micelle in a hydrocarbon solvent, and if necessary, in the reaction system such as adsorbed water on the solid surface or hydrated water of hydrate. Water that is potentially contained in a compound capable of releasing water can also be used effectively. Accordingly, it is also preferable to use a compound that can easily release water, such as a solid having adsorbed water or a hydrate, in combination with the condensation accelerator.

These metal compound and water forming the condensation accelerator may be added separately to the reaction system or mixed immediately before use as a mixture, but long-term storage of the mixture causes decomposition of the metal compound. It is not preferable.
In addition, water may be charged into the reaction system as a solution of an organic solvent compatible with water such as alcohol, or water is directly injected and dispersed in the hydrocarbon solution using various chemical engineering techniques. You may let them. Water may be added by steam stripping or the like after completion of the condensation reaction.
The number of moles of metal of the metal compound and water effective for the reaction is preferably 0.1 or more as a molar ratio to the total amount of hydrocarbyloxysilyl groups present in the reaction system. The upper limit varies depending on the purpose and reaction conditions, but 0.5 to 3 molar equivalents of effective water may be present with respect to the amount of hydrocarbyloxysilyl groups bonded to the polymer active site before the condensation treatment. preferable.

  The condensation reaction is preferably performed at a temperature of 20 ° C or higher, and more preferably in the range of 30 to 180 ° C. By setting the temperature during the condensation reaction within the above range, the condensation reaction can be efficiently advanced and completed, and the quality of the polymer can be improved by aging reaction of the resulting modified conjugated diene polymer (a-1) over time. Decrease etc. can be suppressed.

The condensation reaction time is about 0.5 minutes to 10 hours, preferably 0.5 minutes to 5 hours, more preferably 0.5 to 120 minutes, and still more preferably 3 minutes to 120 minutes. By setting the condensation reaction time within the above range, the condensation reaction can be completed smoothly. 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.

In the present invention, if desired, a known anti-aging agent or a short stop agent may be added for the purpose of stopping the polymerization reaction in the step after introducing the silane compound residue into the active site of the polymer. Further, after completion of the modification reaction or the condensation reaction, a condensation inhibitor such as a higher carboxylic acid ester of a polyhydric alcohol may be added to the reaction system.
After the modification treatment in this way, a conventionally known post-treatment such as desolvation such as steam stripping can be performed to obtain the desired modified polymer.

  When a difunctional hydrocarbyloxysilane compound having a protected secondary amino group is used as a modifier, it is converted to a free imino group by hydrolysis of the silyl protecting group in the protected amino group. can do. By removing the solvent from this, 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 step including the condensation treatment to the solvent removal to the dry polymer.

[Modified Conjugated Diene Polymer (a-2)]
The modified conjugated diene polymer (a-2) according to the present invention is characterized by having a primary amino group and a silicon atom-containing functional group at the molecular chain terminal (particularly the polymerization terminal terminal) of the polymer.
The silicon atom-containing functional group is preferably a dialkoxysilane compound residue or a trialkoxysilane compound residue. Here, the two alkoxy groups of the dialkoxysilane compound are each independently an alkoxy group having 1 to 20 carbon atoms which may have a substituent. Similarly, the three alkoxy groups of the trialkoxysilane compound are each independently an alkoxy group having 1 to 20 carbon atoms which may have a substituent.
A modified conjugated diene polymer (a-2) according to the present invention is obtained by carrying out a modification reaction in which a modifying agent comprising a compound having a primary amino group and the above silicon atom-containing functional group is reacted.

  As a suitable example of the modified conjugated diene polymer (a-2) according to the present invention, a modified conjugated diene polymer having a specific primary amino group-containing functional group, the following general formula (2) or the following general formula ( It is preferable that it is represented by 3).

ここで、Ｒ³及びＲ⁵は夫々独立に−ＯＲ、−ＯＨ又は炭素数１〜２０のアルキル基であり、Ｒ⁴は炭素数１〜２０のアルキレン基であり、Ｒは硫黄原子、酸素原子、窒素原子及び／又はハロゲン原子を有していても良い炭素数１〜２０のヒドロカルビル基である。

Here, R ³ and R ⁵ are each independently —OR, —OH or an alkyl group having 1 to 20 carbon atoms, R ⁴ is an alkylene group having 1 to 20 carbon atoms, and R is a sulfur atom or an oxygen atom. And a hydrocarbyl group having 1 to 20 carbon atoms which may have a nitrogen atom and / or a halogen atom.

ここで、Ｒ⁶及びＲ⁸は夫々独立に−ＯＲ、−ＯＨ又は炭素数１〜２０のアルキル基であり、Ｒ⁷及びＲ⁹は夫々独立に炭素数１〜２０のアルキレン基であり、Ｒは硫黄原子、酸素原子、窒素原子及び／又はハロゲン原子を有していても良い炭素数１〜２０のヒドロカルビル基であり、ＭはＳｉ、Ｔｉ、Ｓｎ、Ｂｉ、Ｚｒ又はＡｌであり、Ｒ¹⁰は−ＯＨ、炭素数１〜３０のヒドロカルビル基、炭素数２〜３０のヒドロカルビルカルボキシル基、炭素数５〜２０の１，３−ジカルボニル含有基、炭素数１〜２０のヒドロカルビルオキシ基、並びに炭素数１〜２０のヒドロカルビル基及び／又は炭素数１〜２０のヒドロカルビルオキシ基で三置換されたシロキシ基からなる群から選ばれる基であり、複数のＲ¹⁰は同一でも異なっていても良く、ｋは｛（Ｍの価数）−２｝であり、ｎは０又は１である］
なお、上記一般式（２）及び（３）の−(Polymer）は共役ジエン重合体のポリマー鎖である。
また、通常、Ｒ⁶とＲ⁸は同一であり、Ｒ⁷とＲ⁹は同一である。縮合される二つのポリマー鎖は、通常同一であるからである。

Here, R ⁶ and R ⁸ are each independently —OR, —OH or an alkyl group having 1 to 20 carbon atoms; R ⁷ and R ⁹ are each independently an alkylene group having 1 to 20 carbon atoms; Is a C1-C20 hydrocarbyl group which may have a sulfur atom, an oxygen atom, a nitrogen atom and / or a halogen atom, M is Si, Ti, Sn, Bi, Zr or Al, and R ¹⁰ Is —OH, a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyl carboxyl group having 2 to 30 carbon atoms, a 1,3-dicarbonyl-containing group having 5 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms, and carbon A group selected from the group consisting of a siloxy group trisubstituted by a hydrocarbyl group having 1 to 20 and / or a hydrocarbyloxy group having 1 to 20 carbon atoms, and a plurality of R ¹⁰ may be the same or different; Is And a (M of valency) -2}, n is 0 or 1]
In the above general formulas (2) and (3),-(Polymer) is a polymer chain of a conjugated diene polymer.
Usually, R ⁶ and R ⁸ are the same, and R ⁷ and R ⁹ are the same. This is because the two polymer chains to be condensed are usually the same.

In the above general formulas (2) and (3), R ³ , R ⁵ , R ⁶ and R ⁸ —OR include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec -Butoxy group, tert-butoxy group, pentyloxy group, allyloxy group, phenoxy group, benzyloxy group and the like, and these functional groups have a sulfur atom, an oxygen atom, a nitrogen atom and / or a halogen atom. May be. The sulfur atom may be contained in R as, for example, —SH, —S _X — (X is an integer of 1 to 5), or an epithio group. The oxygen atom may be contained in R as —OH, —O—, an epoxy group, an acyl group, or a carboxyl group. The nitrogen atom is an amino group (primary amino group, secondary amino group, or non-cyclic or cyclic tertiary amino group), imino group, imine residue, amidine group, isocyanate group, N-hydroxy group, N-oxide group. And may be contained in R as a cyano group.

Also, R ^3, the alkyl group of R ^5, carbon atoms of R ⁶ and R ⁸ 1 to 20, a methyl group, an ethyl group, a propyl group, an isopropyl group, n- butyl group, isobutyl group, sec- butyl group, Examples thereof include a tert-butyl group, a pentyl group, a hexyl group, and an octyl group.
The halogen atom which may be contained in R may be any of fluorine, chlorine, bromine and iodine, but chlorine or bromine is preferred.

Examples of the alkylene group having 1 to 20 carbon atoms of R ⁴ , R ⁷ and R ⁹ include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, a butane-1, 4-diyl group, butane-1,3-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, Nonane-1,9-diyl group, decane-1,10-diyl group and the like can be mentioned.

  Examples of the conjugated diene monomer used in the modified conjugated diene polymer (a-2) represented by the general formula (2) or the general formula (3) include 1.3-butadiene, isoprene, 1.3- Examples include pentadiene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, and 1,3-hexadiene. These may be used alone or in combination of two or more, and among these, 1,3-butadiene is particularly preferable. Examples of the modified conjugated diene polymer (a-2) include modified polybutadiene, modified polyisoprene, and modified butadiene-isoprene copolymer.

The modified conjugated diene polymer (a-2) represented by the general formula (2) is a hydrocarbyloxy having a primary amino group protected at the active end of a conjugated diene polymer obtained by anionic polymerization or coordination polymerization. It is obtained by carrying out a modification reaction in which a silane compound is reacted, and then removing the protecting group of the primary amino group protected by steam stripping or the like.
Further, the modified conjugated diene polymer (a-2) represented by the general formula (3) includes a first amino group and silicon protected at the active terminal of the conjugated diene polymer obtained by anionic polymerization or coordination polymerization. After a modification reaction in which a compound having an atom-containing functional group, particularly a hydrocarbyloxysilane compound having a protected primary amino group, is reacted, a condensation reaction is further performed using a specific condensation accelerator, followed by steam stripping or the like. It is obtained by removing the protecting group of the protected primary amino group.

Examples of the hydrocarbyloxysilane compound having a protected primary amino group include N, N-bis (trimethylsilyl) aminopropylmethyldimethoxysilane, 1-trimethylsilyl-2,2-dimethoxy-1-aza-2-silacyclo. Pentane, N, N-bis (trimethylsilyl) aminopropyltrimethoxysilane, N, N-bis (trimethylsilyl) aminopropyltriethoxysilane, N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane, N, N-bis (Trimethylsilyl) aminoethyltrimethoxysilane, N, N-bis (trimethylsilyl) aminoethyltriethoxysilane, N, N-bis (trimethylsilyl) aminoethylmethyldimethoxysilane or N, N-bis (trimethylsilyl) aminoethylmethyldie As specific examples of the hydrocarbyloxysilane compound having a ketimine residue, xysilane, 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 the corresponding diethyloxy to these diethoxy (methyl) silyl compounds (Ethyl) silyl compound, dipropoxy (methyl) silyl compound include a dipropoxy (ethyl) silyl compounds. Particularly preferably, N, N-bis (trimethylsilyl) aminopropylmethyldimethoxysilane, N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane or 1-trimethylsilyl-2,2-dimethoxy-1-aza-2-sila Cyclopentane, N- (1,3-dimethylbutylidene)-[diethoxy (methyl) silyl] -1-propanamine and N- (1,3-dimethylbutylidene)-[dipropoxy (methyl) silyl] -1- Mention may be made of propanamine.
The said hydrocarbyl oxysilane compound may be used individually by 1 type, and may be used in combination of 2 or more type.

In the condensation reaction for producing the modified conjugated diene polymer (a-2) represented by the general formula (3) according to the tire of the present invention, the hydrocarbyloxysilane introduced into the active site of the conjugated diene polymer It is preferable to perform condensation of compound residues or condensation with the unreacted hydrocarbyloxysilane compound in the presence of a condensation accelerator. As this condensation accelerator, the condensation accelerator used when producing the modified conjugated diene polymer (a-1) is used under the same conditions such as the amount used, temperature, pressure, reaction time and the like.
Moreover, the water used with a condensation accelerator and the water used when manufacturing a modified conjugated diene type polymer (a-1) are used by the same method.

  The deprotection treatment for removing the protected nitrogen atom protecting group after completion of the modification reaction or after the condensation reaction to produce a primary amino group is not limited to the above-mentioned solvent removal treatment using steam such as steam stripping. In any stage from the end of the modification reaction or the end of the condensation reaction to the removal of the solvent and the dry polymer, it was liberated by hydrolyzing the protecting group on the primary amino group in various ways as required. It can convert into a primary amino group and the deprotection process of the protected primary amino group derived from a hydrocarbyl oxysilane compound can be performed.

The modified conjugated diene polymer (a-2) according to the present invention is obtained, for example, as follows.
As the hydrocarbyloxysilane compound, N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane is used, and among the condensation accelerators, the divalent Sn bis (hydrocarbylcarboxylic acid) salt is used as the metal compound. When the protecting group of the nitrogen atom protected by steam stripping or the like is removed after the reaction is completed, a modified conjugated diene polymer (a-2) having a first amino group represented by the following formula (4) is obtained.

式中、ｎは０又は１である。

In the formula, n is 0 or 1.

  Next, the polymerization reaction system for obtaining the modified conjugated diene polymer (a-2) represented by the general formula (2) or the general formula (3) will be described. In order to introduce a compound containing a primary amino group into the active terminus of the conjugated diene polymer by a modifier, it is preferable that the polymer to be used has at least 10% polymer chain having a living property or pseudo-living property. Examples of such a polymerization reaction having a living property include anionic polymerization and coordination polymerization, and anionic polymerization is preferable.

Organic alkali metal compounds used as initiators for the above-mentioned anionic polymerization, particularly lithium compounds are preferred. As this lithium compound, hydrocarbyl lithium and lithium amide compound used in the production of the modified conjugated diene polymer (a-1) are used in the same amount as used in the production of the modified conjugated diene polymer (a-1). Preferably used.
Similarly to the production of the modified conjugated diene polymer (a-1), in the production of the modified conjugated diene polymer (a-2), when the former hydrocarbyl lithium is used, A conjugated diene polymer having a hydrocarbyl group and the other terminal being a polymerization active site is obtained. When the latter lithium amide compound is used, a conjugated diene polymer having a nitrogen-containing group (CN bond) at the polymerization initiation terminal and the other terminal being a polymerization active site is obtained.

There is no restriction | limiting in particular as a method of manufacturing a conjugated diene polymer by anionic polymerization, It is using the method and polymerization conditions (temperature, pressure, etc.) similar to the time of manufacture of a modified conjugated diene type polymer (a-1). it can.
Specifically, in an organic solvent inert to the reaction, for example, a hydrocarbon solvent such as an aliphatic, alicyclic or aromatic hydrocarbon compound, one or more conjugated diene monomers are A conjugated diene polymer having a target active terminal 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 the same as that used in the production of the modified conjugated diene polymer (a-1).
The monomer concentration in the solvent is preferably 5 to 50% by mass, more preferably 10 to 30% by mass.

  The randomizer used as desired is used to control the microstructure of the conjugated diene polymer, for example, to control the increase in 1,2 bonds in the butadiene polymer, 3,4 bonds in the isoprene polymer, and the like. As the randomizer, the same amount of use as in the production of the modified conjugated diene polymer (a-1) can be used.

  In the present invention, the above-described modifier is preferably added in a stoichiometric amount or in excess to the active end of the polymer to the polymer having an active end obtained as described above. , And reacting with the active terminal bonded to the polymer.

The modified conjugated diene polymer (a-2) according to the present invention preferably has a cis-1,4 bond content of 40% or more. It is because the low temperature characteristic of a rubber composition will deteriorate that it is less than 40%, and the performance on ice of a tire will deteriorate.
The cis-1,4 bond content and vinyl bond content are measured by the infrared method (Morello method).
The modified conjugated diene polymer (a-2) according to the present invention preferably has a weight average molecular weight (Mw) of 100,000 to 1,000,000, preferably 150,000 to 800,000. Is more preferable, and 150,000 to 600,000 is particularly preferable. Moreover, it is preferable that molecular weight distribution (Mw / Mn) is 1-3, and it is more preferable that it is 1.1-2.7. By making the weight average molecular weight of the modified conjugated diene polymer (a-2) within the above range, the decrease in the elastic modulus of the vulcanizate and the increase in the hysteresis loss can be suppressed, and the excellent low rolling resistance of the tire of the present invention can be achieved. In addition, excellent kneading workability of the rubber composition containing the modified conjugated diene polymer (a-2) can be obtained. Moreover, even if it mix | blends a modified conjugated diene polymer (a-2) with a rubber composition by making the molecular weight distribution of a modified conjugated diene polymer (a-2) into the said range, workability | operativity of a rubber composition is improved. It is not lowered, kneading is easy, and the physical properties of the rubber composition can be sufficiently improved.
Here, the weight average molecular weight (Mw) and the molecular weight distribution were measured by GPC [manufactured by Tosoh Corporation, HLC-8020] using a refractometer as a detector, and were shown in terms of polystyrene using monodisperse polystyrene as a standard. The column is GMHXL [manufactured by Tosoh] and the eluent is tetrahydrofuran.

[Rubber composition]
The rubber composition used for the tire of the present invention includes a rubber component (R) containing a modified conjugated diene polymer (a-1) and a modified conjugated diene polymer (a-2), and a filler (F). It is characterized by that.
(Rubber component)
The rubber component (R) of the rubber composition according to the tire of the present invention is 5 to 95% by mass of the modified conjugated diene polymer (a-1) and 95 to 5% by mass of the modified conjugated diene polymer (a-2). It is preferably composed of 0 to 50% by mass of another diene rubber used as desired, and 10 to 90% by mass of the modified conjugated diene polymer (a-1) and 90 to 90% of the modified conjugated diene polymer (a-2). It is more preferably composed of 10% by mass, particularly preferably composed of 20 to 80% by mass of the modified conjugated diene polymer (a-1) and 80 to 20% by mass of the modified conjugated diene polymer (a-2). .
Here, as other diene rubber, polybutadiene, polyisoprene, polybutadiene-polyisoprene copolymer other than the modified conjugated diene polymer (a-1) and the modified conjugated diene polymer (a-2) according to the present invention are used. Examples thereof include polymers, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-isoprene-butadiene terpolymers, ethylene-propylene-diene terpolymers, butyl rubber, and halogenated butyl rubber. Of these diene rubbers, natural rubber is preferred. If the modified conjugated diene polymer (a-1) 5 to 95% by mass and the modified conjugated diene polymer (a-2) 95 to 5% by mass are used in the rubber component (R), rolling resistance is preferably reduced. If the modified conjugated diene polymer (a-2) is 10% by mass or more, the performance on ice and the low rolling resistance are more preferably compatible, and the modified conjugated diene polymer (a-1) is also preferable for the same reason. It is particularly preferable to use 10 to 90% by mass and 90 to 10% by mass of the modified conjugated diene polymer (a-2).

When the tire of the present invention is a tire other than a winter tire (for example, a summer tire or an all-season tire), the modified conjugated diene polymer (a-1) 40 to 95% by mass in the rubber component (R) and The modified conjugated diene polymer (a-2) is preferably 60 to 5% by mass, the modified conjugated diene polymer (a-1) 50 to 80% by mass, and the modified conjugated diene polymer (a-2) 60 to 60% by mass. More preferably, it is 20 mass%.
On the other hand, when the tire of the present invention is for winter, the modified conjugated diene polymer (a-1) 5 to 40% by mass and the modified conjugated diene polymer (a-2) 95 to 60 in the rubber component (R). The content is preferably 10% by mass, and more preferably 10 to 40% by mass of the modified conjugated diene polymer (a-1) and 90 to 60% by mass of the modified conjugated diene polymer (a-2).

  In the rubber composition used in the tire of the present invention, the modified conjugated diene polymer (a-1) is preferably a modified styrene-butadiene copolymer (hereinafter abbreviated as “modified SBR”), and is modified. The conjugated diene polymer (a-2) is preferably a modified butadiene polymer (hereinafter abbreviated as “modified BR”).

(Filler)
The rubber composition according to the tire of the present invention is preferably 5 to 200 parts by mass of the filler (F), more preferably 20 to 120 parts by mass, and still more preferably 30 to 100 parts by mass of the rubber component (R). 100 parts by mass are included. When the filler (F) is less than 5 parts by mass, the modified conjugated diene polymer (a-2) represented by the general formula (2) or the general formula (3) and the filler (F) will be described later. This is because the interaction cannot be enjoyed, and when the filler (F) exceeds 200 parts by mass, the rolling resistance of the tire is remarkably increased.
In the present invention, the filler (F) is preferably carbon black and / or an inorganic filler, and the inorganic filler is preferably silica.
Since the modified conjugated diene polymer (a-1) and the modified conjugated diene polymer (a-2) react with both carbon black and silica, the dispersibility of both carbon black and silica is improved. In addition, since the dynamic loss tangent tan δ at 60 ° C. of the tread rubber composition is remarkably reduced, the rolling resistance of the tire of the present invention is further reduced.
From the above viewpoint, the combination of carbon black and silica as filler (F) (carbon black 10-90 mass% and silica 90-10 mass%, more preferably carbon black 20-80 mass% and silica 80-20 mass) %) Is more preferable.

The carbon black suitably used as the filler (F) preferably has a nitrogen adsorption specific surface area (measured in accordance with N ₂ SA, JIS K 6217-2: 2001) of 70 to 200 m ² / g. Examples of the carbon black in this range include SAF-HS, SAF, ISAF-HS, ISAF, ISAF-LS, IISAF, N285, N339, HAF-HS, HAF, and HAF-LS. The carbon black nitrogen adsorption specific surface area is particularly preferably from 85 to 180 m ² / g.

As the silica suitably used as the inorganic filler, any commercially available silica can be used, and wet silica, dry silica, and colloidal silica are particularly preferable. The BET specific surface area (measured according to ISO 5794/1) of silica is preferably 100 m ² / g or more, more preferably 150 m ² / g or more, particularly preferably 170 m ² / g or more. Examples of such silicas are those manufactured by Tosoh Silica Co., Ltd., trade names “Nipsil AQ” (BET specific surface area = 190 m ² / g), “Nipsil KQ”, and Degussa's trade name “Ultra Gil VN3” (BET specific surface area = 175 m ^2. / G) and other commercial products can be used.

As inorganic fillers other than silica, alumina (Al ₂ O ₃ ), alumina-hydrate (Al ₂ O ₃ .H ₂ O), aluminum hydroxide [Al (OH) ₃ ], aluminum carbonate [Al ₂ ( CO _{3) 2],} magnesium hydroxide [Mg (OH) _2], magnesium oxide (MgO), magnesium carbonate (MgCO _3), talc _{(3MgO · 4SiO 2 · H 2} O), attapulgite (5MgO · 8SiO ₂ · 9H ₂ O), titanium white (TiO ₂ ), titanium black (TiO _2n-1 ), calcium oxide (CaO), calcium hydroxide [Ca (OH) ₂ ], aluminum magnesium oxide (MgO · Al ₂ O ₃ ), clay (Al ₂ O ₃ .2SiO ₂ ), kaolin (Al ₂ O ₃ .2SiO ₂ .2H ₂ O), pyrophyllite (Al ₂ O ₃ .4SiO ₂ .H ₂ O), bentonite (A l ₂ O ₃ .4SiO ₂ .2H ₂ O), aluminum silicate (Al ₂ SiO ₅ , Al ₄ .3SiO ₄ .5H ₂ O, etc.), magnesium silicate (Mg ₂ SiO ₄ , MgSiO ₃ etc.), silicic acid Calcium (Ca ₂ · SiO ₄ etc.), aluminum calcium silicate (Al ₂ O ₃ · CaO · 2SiO ₂ etc.), magnesium calcium silicate (CaMgSiO ₄ ), calcium carbonate (CaCO ₃ ), zirconium oxide (ZrO ₂ ), Examples thereof include zirconium hydroxide [ZrO (OH) ₂ · nH ₂ O], zirconium carbonate [Zr (CO ₃ ) ₂ ], crystalline aluminosilicate, and the like.

(Silane coupling agent)
When silica is blended in the rubber composition according to the tire of the present invention, it is preferable that 1 to 20% by mass of a silane coupling agent is blended with respect to silica. 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 sulfur-containing alkoxysilane compounds such as carbamoyl tetrasulfide and dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide. From the viewpoint of improving the strength, etc., bis (3-triethoxysilylpropyl) polysulfide and 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide are preferable.
One of these silane coupling agents may be used alone, or two or more thereof may be used in combination.

  Since the rubber composition used in the tire of the present invention uses a modified polymer in which a functional group having high affinity with silica is introduced into the molecular active site as a rubber component, the amount of the silane coupling agent is , It can be reduced more than usual. Although the compounding quantity of a preferable silane coupling agent changes with kinds etc. of a silane coupling agent, Preferably it selects in the range of 1-20 mass% with respect to a 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.

When the tire of the present invention is a winter tire, the tread of the tire of the present invention preferably has 5 to 50% by volume of air bubbles in the rubber matrix. The bubble rate (Vs) can be calculated by the following equation.
Vs = (ρ ₀ / ρ ₁ −1) × 100 (%)
(Wherein, [rho ₁ represents the density of the rubber composition after vulcanization ^{(g / cm 3), ρ} 0 represents the density of the solid phase portion in the rubber composition after vulcanization (g / cm ^3). )
The density of the rubber composition after vulcanization and the density of the solid phase part in the rubber composition after vulcanization are calculated from the mass in ethanol and the mass in air. Further, the bubble ratio (Vs) can be appropriately changed depending on the type and amount of the foaming agent and foaming aid described later.
The reason why the bubble rate is preferably 5% by volume or more is that the effect of improving the performance on ice is higher, and that the bubble rate is preferably 50% by volume or less is preferable for fracture resistance and wear resistance. It is because it improves more. From these viewpoints, the bubble ratio is more preferably 10 to 35% by volume, and further preferably 15 to 30% by volume.

  Examples of the foaming agent used in the rubber composition according to the winter tire of the present invention include azodicarbonamide (ADCA), dinitrosopentamethylenetetramine (DPT), dinitrosopentastyrenetetramine, benzenesulfonylhydrazide derivatives, p, p'- Oxybisbenzenesulfonyl hydrazide (OBSH), ammonium bicarbonate generating carbon dioxide, sodium bicarbonate, ammonium carbonate, nitrososulfonylazo compound generating nitrogen, N, N'-dimethyl-N, N'-dinitrosophthalamide , Toluenesulfonyl hydrazide, p-toluenesulfonyl semicarbazide, p, p′-oxybisbenzenesulfonyl semicarbazide and the like. Among these foaming agents, azodicarbonamide (ADCA) and dinitrosopentamethylenetetramine (DPT) are preferable from the viewpoint of production processability. Moreover, these foaming agents may be used individually by 1 type, and may use 2 or more types together.

  There is no restriction | limiting in particular as a form of the said foaming agent, According to the objective, it can select suitably from particulate form, liquid form, etc. The form of the foaming agent can be observed using, for example, a microscope. Moreover, the average particle diameter of a particulate foaming agent can be measured using a Coulter counter etc., for example.

  The foaming agent is preferably used in combination with urea, zinc stearate, zinc benzenesulfinate, zinc white or the like as a foaming aid. These may be used individually by 1 type and may use 2 or more types together. By using a foaming aid in combination, the foaming reaction can be promoted to increase the degree of completion of the reaction, and unnecessary deterioration can be suppressed over time.

The rubber composition according to the winter tire of the present invention is a short fiber made of a thermoplastic resin, and the rubber composition is heated until the temperature of the rubber composition reaches the maximum vulcanization temperature when vulcanized. You may contain the short fiber characterized by melting or softening in the matrix of a thing. Here, the compounding quantity of this short fiber is 0.2-10 mass parts normally with respect to 100 mass parts of said rubber components (R), Preferably it is 0.5-5 mass parts. The maximum vulcanization temperature means the maximum temperature reached by the rubber composition during vulcanization. For example, in the case of mold vulcanization, it means the maximum temperature that the rubber composition reaches from the time when the rubber composition enters the mold until the rubber composition exits the mold and cools. The maximum vulcanization temperature can be measured, for example, by embedding a thermocouple in the rubber composition.
When the rubber composition according to the winter tire of the present invention contains the short fiber, after vulcanization, there are long bubbles in the tread, and the long bubbles are exposed on the surface due to wear of the tread, and holes are formed. A part is formed and functions as a drainage channel for efficient drainage. Here, the hole portion may be any one of a hole shape, a hollow shape, and a groove shape. Moreover, since the surface of the hole part of the tread is covered with a solidified protective layer of melted or softened short fibers, it is excellent in water channel shape retention, water channel edge wear, water channel retention during load input, and the like. As thickness of a protective layer, 0.5-50 micrometers is preferable.

  The material of the short fiber is not particularly limited as long as it is a thermoplastic resin having the thermal characteristics, and can be appropriately selected according to the purpose. Preferred examples of the short fibers having the thermal characteristics include short fibers made of a crystalline polymer having a melting point lower than the maximum vulcanization temperature. The short fiber made of the crystalline polymer will be described as an example. The larger the difference between the melting point of the short fiber and the maximum vulcanization temperature of the rubber composition, the faster the vulcanization of the rubber composition. The short fibers melt. On the other hand, when the melting point of the short fiber is too close to the maximum vulcanization temperature of the rubber composition, the short fiber does not melt quickly at the initial stage of vulcanization, and the short fiber melts at the end of vulcanization. At the end of vulcanization, the air present in the short fibers diffuses and is dispersed or taken into the vulcanized rubber composition, and a sufficient amount of air is retained in the melted short fibers. Not. On the other hand, if the melting point of the short fiber is too low, the short fiber is melted by heat at the time of kneading the rubber composition, poor dispersion due to fusion of the short fibers at the kneading stage, and short fiber at the kneading stage. Is disadvantageous in that it is divided into a plurality of lengths, and short fibers are dissolved in the rubber composition and dispersed microscopically.

  The upper limit of the melting point (or softening point) of the short fiber is not particularly limited, but is preferably selected in consideration of the above points. Generally, it is higher than the maximum vulcanization temperature of the rubber composition. It is preferably lower by 10 ° C. or higher, and more preferably lower by 20 ° C. or higher. The industrial vulcanization temperature of the rubber composition is generally about 190 ° C. at the maximum. For example, when the maximum vulcanization temperature is set to 190 ° C., the melting point of the short fiber is Is usually selected within a range of 190 ° C. or lower, preferably 180 ° C. or lower, and more preferably 170 ° C. or lower. On the other hand, considering the kneading of the rubber composition, the melting point (or softening point) of the short fibers is preferably 5 ° C. or more, more preferably 10 ° C. or more, and more preferably 20 ° C. with respect to the maximum temperature during kneading. The above is particularly preferable. Assuming that the maximum temperature in kneading the rubber composition is, for example, 95 ° C., the melting point of the short fibers is preferably 100 ° C. or higher, more preferably 105 ° C. or higher, and particularly preferably 115 ° C. or higher. The melting point of the short fibers can be measured using a known melting point measuring device or the like. For example, the melting peak temperature measured using a DSC measuring device can be used as the melting point.

  The short fiber may be formed from the above-described crystalline polymer, may be formed from an amorphous polymer, or may be formed from a crystalline polymer and an amorphous polymer. However, in the present invention, it is preferably formed from an organic material containing a crystalline polymer from the viewpoint that the viscosity change occurs suddenly at a certain temperature due to the phase transition and viscosity control is easy. More preferably, it is formed only from a functional polymer.

  Examples of the crystalline polymer include polyethylene (PE), polypropylene (PP), polybutylene, polybutylene succinate, polyethylene succinate, syndiotactic-1,2-polybutadiene (SPB), polyvinyl alcohol (PVA), Single-composition polymers such as polyvinyl chloride (PVC), those having a melting point controlled to an appropriate range by copolymerization, blending, or the like can be used, and those obtained by adding additives to these can also be used. These may be used individually by 1 type and may use 2 or more types together. Among these crystalline polymers, polyolefins and polyolefin copolymers are preferable, polyethylene (PE) and polypropylene (PP) are more preferable in terms of general availability and easy access, polyethylene (PE) in terms of low melting point and easy handling. ) Is particularly preferred.

  Examples of the non-crystalline polymer include polymethyl methacrylate (PMMA), acrylonitrile / butadiene / styrene copolymer (ABS), polystyrene (PS), polyacrylonitrile, copolymers thereof, and blends thereof. Etc. These may be used individually by 1 type and may use 2 or more types together. The crystalline polymer and the amorphous polymer may be used in combination.

  There is no restriction | limiting in particular as the fineness of the said short fiber, Although it can select suitably according to the objective, 1-1100 dTex is preferable and 2-900 dTex is more preferable from a viewpoint of improving the said performance on ice and snow. The average diameter (D) of the short fibers is not particularly limited and may be appropriately selected depending on the intended purpose. In the vulcanized rubber obtained by vulcanizing a rubber composition containing the short fibers In addition, in order to efficiently form a long bubble that can function as a micro drainage groove to be described later, 0.03 to 0.3 mm is preferable, and 0.06 to 0.25 mm is more preferable. If the average diameter (D) is less than 0.03 mm, it is difficult to form a long cylindrical foaming groove, and it is not preferable in that many yarn breaks occur during the production of the short fibers, and 0.3 mm is preferable. When it exceeds, the average diameter (diameter) of the said short fiber will become large, and the number of cylindrical foaming grooves will decrease in the same compounding quantity, and there exists a tendency for drainage efficiency to worsen.

The rubber composition used for the tread of the winter tire of the present invention has an average major axis (average maximum diameter) of 5 to 1000 μm, preferably 5 to 500 μm of fine particles 3 to 30 with respect to 100 parts by mass of the rubber component (R). It is preferable that a mass part is included.
This fine particle (1) scratches the road surface on ice on the tread surface, and (2) the fine particle is detached from the tread, and a hole is formed in the surface layer part of the tread (tread surface and its vicinity). It forms and drains the melted water from the ice on the ice.
Here, if the average major axis of the fine particles is 5 μm or more, the effect of improving μ on ice is enhanced, and if the average major axis of the fine particles is 1,000 μm or less, the fracture resistance and wear resistance are improved.
Further, it is preferable to contain 3 parts by mass or more of fine particles because the effect of improving μ on ice is enhanced, and it is preferable to contain 30 parts by mass or less of fine particles because the fracture resistance and wear resistance are improved. It is.
The average major axis is obtained by randomly selecting 100 fine particles with an SEM or TEM electron microscope, measuring each major axis, and arithmetically averaging the measured 100 major axes.

  Further, the fine particles preferably have an aspect ratio of 1.1 or more, and preferably have corners. More preferably, the aspect ratio is 1.2 or more, and further preferably 1.3 or more. here. The presence of corners means that the entire surface is not a spherical surface or a smooth curved surface. Fine particles having corners can be used from the beginning for the fine particles of the present invention, but even if the fine particles are spherical, they can be used with the corners existing on the surface of the fine particles, and more Corners can be present.

  The fine particles blended in the rubber composition used for the tread of the winter tire of the present invention are not limited to those described above, and may be present after vulcanization as fine particles without being softened by vulcanization of the tire. good. As the fine particles, fine particles having a Mohs hardness of 2 or more are preferable. For example, gypsum fine particles, calcite fine particles, fluorite fine particles, feldspar fine particles, quartz fine particles, olivine fine particles, iron fine particles, eggshell powder, zirconium oxide fine particles, calcium carbonate Fine particles, silica fine particles, wollastonite fine particles, alkali feldspar fine particles, inorganic fine particles such as porous natural glass (for example, Mohs hardness 5) fine particles, vegetative fine particles such as walnut shells and other seed shells and fruit nuclei, (meta) Organic cured fine particles such as acrylic cured resin fine particles, epoxy cured resin fine particles, zinc oxide whiskers, glass fibers, aluminum whiskers, polyester fibers, nylon fibers, polyvinyl formal fibers, aromatic polyamide fibers, etc. Examples include short fibers that do not melt, but more preferred , Mohs hardness of 5 or more silica glass (Mohs hardness 6.5), quartz (Mohs hardness 7.0), and the like can be given fused alumina (Moh hardness 9.0). Among these, alumina (aluminum oxide) such as single crystal alumina and polycrystalline alumina, silica glass, and the like are particularly preferable because they are inexpensive and can be used easily.

  As described above, it is preferable that the fine particles are detached from the tread to form a hole in the tread surface layer portion (tread surface and its vicinity). For this purpose, the fine particles are bonded to the tread rubber composition by vulcanization. It is desirable that the vulcanized adhesive strength is low.

  When the fine particles are blended in the rubber composition used in the tread of the winter tire of the present invention, or when the fine particles are not blended, the fine particle-containing organic fibers may be blended. Here, the fine particle-containing organic fiber is preferably blended in an amount of 0.1 to 30 parts by weight, more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the rubber component (R). It is more preferable to blend ~ 15 parts by mass. Moreover, it is preferable that the average fiber diameter of fine particle containing organic fiber is 10-1000 micrometers. This fine particle-containing organic fiber melts or softens in the matrix of the rubber composition until the temperature of the rubber composition reaches the maximum vulcanization temperature when the tire is vulcanized. It consists of the same material as the short fibers that sometimes melt or soften. The method for measuring the average fiber diameter of the fine particle-containing organic fibers is the same as the method for measuring the average long diameter of the fine particles.

  The rubber composition according to the tire of the present invention is preferably sulfur crosslinkable, and sulfur is suitably used as a vulcanizing agent. As the usage-amount, it is preferable to mix | blend 0.1-10 mass parts of sulfur content (total amount of sulfur of sulfur and a sulfur donor) with respect to 100 mass parts of rubber components (R). This is because within this range, the necessary elastic modulus and strength of the vulcanized rubber composition can be ensured and fuel efficiency can be obtained. In this respect, it is more preferable to blend 0.5 to 7 parts by mass of the sulfur content.

  In the rubber composition according to the tire of the present invention, various chemicals usually used in the rubber industry, for example, vulcanizing agents other than sulfur, vulcanization accelerators, and processes, are used as long as the object of the present invention is not impaired. Oils, anti-aging agents, anti-scorch agents, zinc white, stearic acid, thermosetting resins, thermoplastic resins, and the like can be included.

  The vulcanization accelerator that can be used in the present invention is not particularly limited, and examples thereof include M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), and CZ (N-cyclohexyl-2-benzothiazyl). Sulfenamide) and guanidine vulcanization accelerators such as DPG (diphenylguanidine) can be used, and the amount used is 0.1 with respect to 100 parts by mass of the rubber component (R). -5.0 mass parts is preferable, More preferably, it is 0.2-3.0 mass parts.

Examples of the plasticizer that can be used in the rubber composition according to the tire of the present invention include phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, di- (2-ethylhexyl) phthalate, and di-n-octyl phthalate. Etc. are used. 0-50 mass parts is preferable with respect to 100 mass parts of rubber components (R), and 0-30 mass parts is more preferable. If it is 50 mass parts or less, it can suppress that the tensile strength of a vulcanized rubber and low heat generating property (low fuel consumption property) deteriorate.
Furthermore, examples of the anti-aging agent that can be used in the rubber composition according to the tire of the present invention include 3C (N-isopropyl-N′-phenyl-p-phenylenediamine, 6C [N- (1,3-dimethylbutyl)- N'-phenyl-p-phenylenediamine], AW (6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline), a high-temperature condensate of diphenylamine and acetone, and the like. Is preferably 0.1 to 6.0 parts by mass, and more preferably 0.3 to 5.0 parts by mass with respect to 100 parts by mass of the rubber component (R).

  The rubber composition according to the tire of the present invention is obtained by kneading using a kneading machine such as a Banbury mixer, a roll, an internal mixer, or the like, and processed by extrusion molding, etc. It becomes.

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 mentioned, and the rubber composition according to the present invention can be used for any of these, but it is used for a tread. In the case of a tread having a cap / base two-layer structure, the cap tread is particularly preferably used.
A tire using the rubber composition according to the present invention for a tread has low rolling resistance and 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.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
The bound vinyl content, bound styrene content, rolling resistance performance, abrasion resistance and on-ice performance were measured according to the following methods.
(1) Bonded vinyl content of butadiene portion of modified SBR and modified BR (mass% based on the total diene portion)
It calculated | required by the infrared method (Morello method).
(2) Bonded styrene content of modified SBR (mass% in copolymer)
Obtained by 270 MHz ¹ H-NMR.
(3) Rolling resistance performance In accordance with SAE J2452, the rolling resistance of the pneumatic radial tire was measured, and the rolling resistance of the tire of Comparative Example 1 was defined as 100, and the index was expressed by the following formula. It shows that rolling resistance is so small that index value is large.
Rolling resistance performance (index) = (Rolling resistance of tire of Comparative Example 1 / Rolling resistance of test tire) × 100
(4) Abrasion resistance Using a sample cut from a tread of a pneumatic radial tire, the amount of wear with a slip rate of 60% at room temperature (23 ° C.) using a Lambone-type wear tester in accordance with JIS K 6264-2: 2005 Was measured and expressed as an index according to the following formula, assuming that the wear resistance of the control was 100. The larger the index, the better.
Abrasion resistance (index) = (Abrasion amount of tire of Comparative Example 1 / Abrasion amount of test tire) × 100
(5) On-ice performance At the test course on the ice surface, test tires were mounted on all four wheels of the passenger car and the braking distance on the ice surface was measured at an initial speed of 20 km. . The larger the value, the better the performance on ice.
Performance on ice (index) = (braking distance of tire of comparative example 1 / braking distance of test tire) × 100

Synthesis Example 1 Synthesis of modifier A A 1-cyano-3-triethoxysilylpropane 1 mol / liter cyclohexane solution was prepared in a 300 ml pressure-resistant glass container that had been dried and purged with nitrogen so that it was equimolar with this. A 1 mol / liter diethyl ether solution of methyllithium was added dropwise to the solution and stirred well to give a modifier solution (A) of 1-cyano-3- [diethoxy (methyl) silyl] -propane as the modifier A. Prepared.

Synthesis Example 2 Synthesis of Modifier B Same as Synthesis Example 1 except that 1- (3-triethoxysilylpropyl) -imidazole was used instead of 1-cyano-3-triethoxysilylpropane in Synthesis Example 1. Then, a modifier solution (B) of 1- [3- [diethoxy (methyl) silyl] propyl] -imidazole as the modifier B was prepared.

Synthesis Example 3 Synthesis of Modifier C The same as Synthesis Example 1 except that 2- (2-triethoxysilylethyl) -pyridine was used instead of 1-cyano-3-triethoxysilylpropane in Synthesis Example 1. Then, 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 The same as Synthesis Example 1 except that 4- (3-triethoxysilylpropyl) -oxazole was used instead of 1-cyano-3-triethoxysilylpropane in Synthesis Example 1. Then, a modifier solution (D) of 4- [3- [diethoxy (methyl) silyl] propyl] -oxazole as the modifier D was prepared.

Synthesis Example 5 Synthesis of Modifier E Synthesis Example 1 except that N-methyl-N- (trimethylsilyl) aminopropyltriethoxysilane was used instead of 1-cyano-3-triethoxysilylpropane in Synthesis Example 1. In the same manner as above, a modifier solution (E) of N-methyl-N- (trimethylsilyl) aminopropylmethyldiethoxysilane as the modifier E was prepared.

Synthesis Example 6 Synthesis of modifier G In a nitrogen atmosphere, 36 g of 3-aminopropylmethyldiethoxysilane (manufactured by Gelest) was added as an aminosilane moiety to 400 ml of dichloromethane solvent in a glass flask equipped with a stirrer, followed by further protection. 48 ml of trimethylsilane chloride (manufactured by Aldrich) and 53 ml of triethylamine were added to the solution as the site, and the mixture was stirred for 17 hours at room temperature. Thereafter, the solvent was removed by applying the reaction solution to an evaporator to obtain a reaction mixture. The reaction mixture was distilled under reduced pressure under 5 mm / Hg conditions to obtain 40 g of N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane as the modifier G as a fraction at 130 to 135 ° C.

The above five modifiers A to E were used as modifiers in Production Examples 1 to 5 of modified SBR (a-1) described later.
Moreover, the modifier G was used as a modifier in Production Example 7 of Modified BR (a-2) described later.
In addition, tin tetrachloride is used as the modifier F, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine is used as the modifier H, and tetraethoxysilane is used as the modifier I. It was.

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 2-6
In Production Example 1, modified SBR-B to F were obtained in the same manner as Production Example 1 except that the modifiers B to F were used in place of the modifier A. Table 1 shows the bound styrene content of the modified SBR-BF obtained and the bound vinyl content of the butadiene moiety.

Production Example 7
Into a pressure-resistant glass container having an internal volume of about 900 ml that has been dried and purged with nitrogen, 283 g of cyclohexane, 100 g of 1,3-butadiene monomer, and 0.015 mmol of 2,2-ditetrahydrofurylpropane are injected as a cyclohexane solution. After adding 50 mmol of n-butyllithium (BuLi), polymerization was carried out in a 50 ° C. warm water bath equipped with a stirrer for 4.5 hours. The polymerization conversion rate was almost 100%. To this polymerization system, 0.50 mmol of N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane as a modifier G was added as a cyclohexane solution and stirred at 50 ° C. for 30 minutes. Thereafter, the reaction was further stopped by adding 0.5 ml of a 5 mass% solution of 2,6-di-tert-butyl-p-cresol (BHT) in 5% by weight of isopropanol. G was obtained. The bound vinyl content of the obtained modified BR-G is shown in Table 2.

Production Example 8
In Production Example 7, 0.50 mmol of N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane was used as a modifier H, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1- A modified conjugated diene polymer H was obtained in the same manner as in Production Example 7, except that the amount was changed to 0.50 mmol of propanamine. The bound vinyl content of the obtained modified BR-H is shown in Table 2.

Production Example 9
In Production Example 7, a modified conjugate was obtained in the same manner as in Production Example 7 except that 0.50 mmol of N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane was changed to 0.50 mmol of tetraethoxysilane as modifier I. Diene polymer I was obtained. Table 2 shows the bound vinyl content of the obtained modified BR-I.

Production Example 10
Into a pressure-resistant glass container having an internal volume of about 900 ml that has been dried and purged with nitrogen, 283 g of cyclohexane, 100 g of 1,3-butadiene monomer, and 0.015 mmol of 2,2-ditetrahydrofurylpropane are injected as a cyclohexane solution. After adding 50 mmol of n-butyllithium (BuLi), polymerization was carried out in a 50 ° C. warm water bath equipped with a stirrer for 4.5 hours. The polymerization conversion rate was almost 100%. Thereafter, 0.5 ml of an isopropanol 5% by mass solution of 2,6-di-tert-butyl-p-cresol (BHT) was added to stop the reaction, followed by drying in accordance with a conventional method, whereby unmodified BR Got. The resulting unmodified BR had a vinyl bond content of 20% and a weight average molecular weight (Mw) of 300,000.

Examples 1-6 and Comparative Examples 1-3
Formulations shown in Table 3 using modified SBR-A, B, C, D, E, F obtained in Production Examples 1 to 6 and modified BR-G, H and I obtained in Production Examples 7 to 9 According to I, each rubber composition was prepared, and nine types of rubber compositions were respectively arranged on the treads of radial tires (tire size 195 / 60R15), and nine types of radial tires were produced according to a conventional method. Each type of tire was evaluated for rolling resistance performance and wear resistance according to the above-described methods. The results are shown in Table 4.

[note]
* 1 Modified SBR: Modified SBR-A, B, C, D, E, F obtained in Production Examples 1 to 6 [Modified SBR-A, B, C, D, E are modified conjugated dienes according to the present invention. It is a system polymer (a-1). ]
* 2 Modified BR: Modified BR-G, H and I obtained in Production Examples 7 to 9 [Modified BR-G and H are modified conjugated diene polymers (a-2) according to the present invention. ]
* 3 Carbon black: ISAF {N ₂ SA (m ² / g) = 115 (m ² / g)}, manufactured by Asahi Carbon Co., Ltd., trade name “Asahi # 80”
* 4 Silica: Tosoh Silica, trade name “Nipsil AQ” (BET specific surface area = 190 m ² / g)
* 5 Silane coupling agent: bis (3-triethoxysilylpropyl) tetrasulfide, manufactured by Degussa, trade name “Si69”
* 6 Softener: Product name “AO Mix Oil” manufactured by Sankyo Oil Chemical Co., Ltd.
* 7 Anti-aging agent 6C: N- (1,3 dimethylbutyl) -N′-phenyl-p-phenylenediamine, manufactured by Seiko Chemical Co., Ltd., trade name “Ozonon 6C”
* 8 Fine particles: Alumina powder, average major axis 60 μm, Showa Denko K.K., trade name “Standard Alumina A-12”
* 9 Vulcanization accelerator DPG: Diphenylguanidine, manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., trade name “Noxeller D”
* 10 Vulcanization accelerator DM: Dibenzothiazyl disulfide, manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., trade name “Noxeller DM”
* 11 Vulcanization accelerator NS: N-tert-butyl-2-benzothiazolylsulfenamide, manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., trade name “Noxeller NS”
* 12 Vulcanization accelerator CZ: N-cyclohexyl-2-benzothiazolylsulfenamide, manufactured by Ouchi Shinsei Chemical Co., Ltd., trade name “Noxeller CZ”
* 13 Foaming agent: {dinitrosopentamethylenetetramine (DPT)} / urea} = 1/1 mixed product

Examples 7-12 and Comparative Examples 4-6
Formulations shown in Table 3 using modified SBR-A, B, C, D, E, F obtained in Production Examples 1 to 6 and modified BR-G, H and I obtained in Production Examples 7 to 9 According to II, each rubber composition was prepared, and nine kinds of rubber compositions were respectively arranged on the treads of radial tires (tire size 195 / 60R15), and nine kinds of radial tires were produced according to a conventional method. Each type of tire was evaluated for rolling resistance performance and wear resistance according to the above-described methods. The results are shown in Table 5.

Examples 13 to 18 and Comparative Examples 7 to 9
Formulations shown in Table 3 using modified SBR-A, B, C, D, E, F obtained in Production Examples 1 to 6 and modified BR-G, H and I obtained in Production Examples 7 to 9 According to III, each rubber composition was prepared, and nine kinds of rubber compositions were respectively arranged on the treads of radial tires (tire size 195 / 60R15), and nine kinds of radial tires were produced according to a conventional method. Each type of tire was evaluated for rolling resistance performance and wear resistance according to the above-described methods. The results are shown in Table 6.

Examples 19-24 and Comparative Examples 10-12
Formulations shown in Table 3 using modified SBR-A, B, C, D, E, F obtained in Production Examples 1 to 6 and modified BR-G, H and I obtained in Production Examples 7 to 9 According to IV (winter tire compounding system), each rubber composition was prepared, and nine types of rubber compositions were arranged on the tread of a studless tire (tire size 195 / 60R15), which is a winter tire, respectively. The studless tires were manufactured according to a conventional method, and the performance on ice and the rolling resistance performance of each of these nine tires were evaluated according to the above methods. The results are shown in Table 7.

  The tire of the present invention is suitably used for tires for passenger cars, light vehicles, light trucks and trucks and buses, and particularly suitable for use as summer radial tires, all-season radial tires, and winter studless radial tires. It is done.

Claims (23)

Modification by reacting a modifying agent comprising a silane compound represented by the following general formula (1) and / or a partial condensate thereof with the active terminal of a conjugated diene polymer having an organometallic active terminal having nucleophilic reactivity A modified conjugated diene polymer (a-1) obtained by conducting a reaction, and a modified conjugated diene polymer (a-2) having a primary amino group and a silicon atom-containing functional group at the molecular chain terminal of the polymer; A tire characterized by applying a rubber composition containing a rubber component (R) and a filler (F).

[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 third group. It represents at least one functional group selected from an amine compound residue, an unsaturated cyclic tertiary amine compound residue, a nitrile group, and a second amino group having a detachable functional group. A ¹ and A ² may be the same or different. ] In 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, R ¹ is a hydrocarbon group having 1 to 18 carbon atoms, R The tire according to claim 1, wherein ² is a divalent hydrocarbon group having 1 to 20 carbon atoms. In the general formula (1), tire according to claim 1 or 2 A ² is a hydrocarbyloxy group having 1 to 18 carbon atoms. The tire according to claim 2 or 3, wherein R ² in the general formula (1) is an alkanediyl group having 2 to 10 carbon atoms. The tire according to any one of claims 2 to 4, wherein A ¹ in the general formula (1) is an ethoxy group. The tire according to any one of claims 2 to 5, wherein R ¹ in the general formula (1) is a methyl group.   The tire according to any one of claims 1 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.   X in the general formula (1) is a saturated cyclic tertiary amine compound residue, an imidazole residue, a dihydroimidazole residue, an oxazole residue, a pyridyl group, a nitrile group, and a secondary amino group having a detachable functional group. The tire according to any one of claims 1 to 6, which is a monovalent group having at least one nitrogen-containing functional group selected from the inside.   9. The nitrogen-containing functional group is at least one selected from a saturated cyclic tertiary amine compound residue, an imidazole residue, a dihydroimidazole residue and a second amino group having a detachable functional group. The tire according to any one of the above.   The conjugated diene polymer (a-1) having an organometallic active terminal having nucleophilic reactivity is obtained by using a hydrocarbyl lithium or lithium amide compound as a polymerization initiator, and a conjugated diene compound alone or a conjugated diene compound and an aromatic vinyl compound. The tire according to any one of claims 1 to 9, wherein the tire is obtained by anionic polymerization.   The tire according to claim 10, wherein the conjugated diene compound is at least one selected from 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene.   The tire according to claim 10 or 11, wherein the aromatic vinyl compound is styrene.   The tire according to claim 1, wherein the silicon atom-containing functional group is a dialkoxysilane compound residue or a trialkoxysilane compound residue. The tire according to any one of claims 1 to 13, wherein the modified conjugated diene polymer (a-2) is represented by the following general formula (2) or the following general formula (3).

[Wherein, R ³ and R ⁵ are each independently —OR, —OH or an alkyl group having 1 to 20 carbon atoms, R ⁴ is an alkylene group having 1 to 20 carbon atoms, and R is a sulfur atom, oxygen It is a C1-C20 hydrocarbyl group which may have an atom, nitrogen atom and / or halogen atom]

[Wherein R ⁶ and R ⁸ are each independently —OR, —OH or an alkyl group having 1 to 20 carbon atoms, and R ⁷ and R ⁹ are each independently an alkylene group having 1 to 20 carbon atoms, R is a hydrocarbyl group having 1 to 20 carbon atoms which may have a sulfur atom, an oxygen atom, a nitrogen atom and / or a halogen atom, M is Si, Ti, Sn, Bi, Zr or Al; ¹⁰ is —OH, a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyl carboxyl group having 2 to 30 carbon atoms, a 1,3-dicarbonyl-containing group having 5 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms, and A group selected from the group consisting of a hydrocarbyl group having 1 to 20 carbon atoms and / or a siloxy group trisubstituted by a hydrocarbyloxy group having 1 to 20 carbon atoms, and a plurality of R ¹⁰ may be the same or different; k is A (M of valency) -2}, n is 0 or 1]   The tire according to any one of claims 1 to 14, wherein the modified conjugated diene polymer (a-2) has a nitrogen-containing group at a polymerization initiation terminal of the polymer.   100 parts by mass of rubber component (R) in which the rubber composition is composed of 5 to 95% by mass of the modified conjugated diene polymer (a-1) and 95 to 5% by mass of the modified conjugated diene polymer (a-2). The tire in any one of Claims 1-15 containing 5-200 mass parts of said fillers (F) with respect to a part.   The tire according to any one of claims 1 to 16, wherein the filler (F) is carbon black and / or an inorganic filler.   The tire according to claim 17, wherein the inorganic filler is silica.   The tire according to any one of claims 1 to 18, wherein the rubber composition is applied to a tread.   The tire according to claim 19, wherein the tread has 5 to 50% by volume of air bubbles in a rubber matrix.   The tire according to any one of claims 1 to 20, wherein the rubber composition further comprises 3 to 30 parts by mass of fine particles having an average major axis of 5 to 1000 µm with respect to 100 parts by mass of the rubber component (R).   The tire according to claim 21, wherein the tread has a hole portion formed by detaching the fine particles in a surface layer portion.   The tire according to any one of claims 20 to 22, wherein the tire is a winter tire.