JP5451167B2 - Modified low molecular weight conjugated diene polymer - Google Patents

Description

  The present invention relates to a modified low molecular weight conjugated diene polymer, a rubber composition using the same, and a tire. More specifically, the present invention relates to a modified low molecular weight conjugated diene polymer and a rubber containing the same, which provide a tire having an appropriate storage elastic modulus and improved low heat buildup without reducing wear resistance. The present invention relates to a composition and a tire having the above-described properties using the rubber composition.

  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 (improving the low heat buildup) and improving the fracture characteristics and the wear resistance.

On the other hand, with respect to 100 parts by mass of the rubber component containing 10% by mass or more of the modified conjugated diene polymer, 20 parts by mass or more of the reinforcing filler and a low molecular weight having specific properties instead of a softener such as aroma oil. A rubber composition containing 5 to 60 parts by mass of an aromatic vinyl compound-conjugated diene compound copolymer or a modified copolymer thereof is disclosed (for example, see Patent Documents 4 and 5). These rubber compositions also have the effect of improving fracture characteristics, wear resistance, low heat build-up, and the like.
However, in recent years, from the viewpoints of energy saving and environmental problems, further reduction in fuel consumption of automobiles (reduction in rolling resistance of tires) and improvement in wear resistance are desired.

  By the way, as a rubber composition applied to the tread portion of the tire, a rubber composition having a moderately high storage elastic modulus (G ′) is preferable from the viewpoint of dry grip performance. Therefore, a rubber composition having a low loss tangent (tan δ) (low exothermic property) and an appropriate storage elastic modulus (G ′) is demanded. On the other hand, as means for improving the storage elastic modulus (G ′) of the rubber composition, a method of increasing the blending amount of carbon black blended in the rubber composition or N, N as described in Patent Document 6 is used. A technique for blending a bismaleimide having a specific structure such as'-(4,4'-diphenylmethane) -bismaleimide, or a reactive group and a filler for a rubber component such as polyethylene glycol dimaleate as described in Patent Document 7. A technique for blending a compound having an adsorbing group is known.

However, when the blending amount of carbon black in the rubber composition is increased, the storage elastic modulus (G ′) of the rubber composition can be improved, but at the same time, the loss tangent (tan δ) of the rubber composition increases. Further, there is a problem that the low heat build-up of the rubber composition is lowered, and further, the Mooney viscosity of the rubber composition is increased and the processability is lowered.
In addition, when the rubber composition contains a compound having a reactive group for the bismaleimide or rubber component and an adsorbing group for the filler, the storage elastic modulus (G ′) of the rubber composition can be improved. The loss tangent (tan δ) of the rubber composition is substantially the same, and the low heat build-up of the rubber composition cannot be sufficiently improved.

Further, as a rubber composition having a high storage elastic modulus (G ′) and a low loss tangent (tan δ), a rubber component (A) 100 containing 10% by mass or more of a modified conjugated diene polymer having at least one functional group. 20 parts by mass or more of the reinforcing filler (B), 5-80% by mass of the aromatic vinyl compound, and 10-80% by mass of the vinyl bond of the conjugated diene compound part, A rubber composition obtained by blending 5 to 60 parts by mass of a low molecular weight aromatic vinyl compound-conjugated diene compound copolymer (C) having a polystyrene-reduced weight average molecular weight of 5,000 to 300,000 measured by chromatography. It is disclosed (for example, see Patent Document 8).
This technology aims to achieve both low heat generation and dry grip performance. However, considering the burden on the global environment, further reduction in heat generation will be necessary in the future.

JP 2001-158837 A JP 2005-232364 A JP-A-2005-290355 WO2006 / 093051 pamphlet WO2007 / 032209 Pamphlet JP 2002-121326 A JP 2003-176378 A JP 2006-241358 A

  The present invention has been made under such circumstances, and has a rubber composition that provides a tire having an appropriate storage elastic modulus and an improved low heat build-up without reducing wear resistance, and An object of the present invention is to provide a tire using the rubber composition.

    As a result of intensive studies to achieve the above object, the present inventors have modified a specific amine functional group obtained by using a low molecular weight conjugated diene polymer having a molecular weight in a specific range. It was found that the conjugated diene polymer obtained can provide a rubber composition suitable for the purpose. The present invention has been completed based on such findings.

That is, the present invention
[1] A primary amino group and / or a secondary amino group-containing group protected with a detachable group and 2 or 3 hydrocarbyls as a modifier at the active end of a conjugated diene polymer having an active end After reacting and modifying a silane compound formed by bonding an oxy group and / or a halogen atom to the same silicon atom, in the presence of a condensation accelerator comprising any compound of titanium, zirconium, and tin , Amine-based functional group-modified conjugate having an amino group protected with a protic amino group and / or a detachable group in the molecule and a functional group containing a silicon atom, obtained by a condensation reaction involving a silane compound A modified low molecular weight conjugated diene polymer, characterized in that it is a diene polymer and has a weight average molecular weight of 10,000 to 200,000 before modification,
[2] The modified low molecular weight conjugated diene polymer according to the above [1], wherein the functional group containing a silicon atom is a silane group formed by bonding a hydrocarbyloxy group and / or a hydroxy group to a silicon atom,
[3] The above [2], wherein the polymerization terminal has an amino group protected with a protic amino group and / or a detachable group and a silicon atom formed by bonding a hydrocarbyloxy group and / or a hydroxy group. Modified low molecular weight conjugated diene polymer,
[4] In the above [3], an amino group protected with a protic amino group and / or a detachable group and a silicon atom bonded to a hydrocarbyloxy group and / or a hydroxy group at the same polymerization active terminal Modified low molecular weight conjugated diene polymer as described,
[5] The modified low molecular weight conjugate according to any one of [1] to [4], wherein the protic amino group is at least one selected from a primary amino group, a secondary amino group, and salts thereof. Diene polymer,
[6] The above [1] to [4], wherein the amino group protected with a detachable group is an N, N-bis (trimethylsilyl) amino group and / or an N- (trimethylsilyl) imino group. Modified low molecular weight conjugated diene polymer,
[7] The modified low molecular weight conjugated diene polymer according to any one of the above [2] to [6], wherein one or two hydrocarbyloxy groups and / or hydroxy groups are bonded to a silicon atom,
[8] The modifier is represented by the general formula (1)

[Wherein A ¹ is a halogen atom or a hydrocarbyloxy group having 1 to 20 carbon atoms, R ² is a hydrocarbon group R ³ is a hydrocarbon group, L ¹ is a detachable functional group, and L ² is detachable. When it is a possible group or a hydrocarbon group and L ² is a detachable functional group, it may have the same structure as L ¹ or a different structure, and L ¹ and L ² may be bonded. n represents 0 or 1, and m represents 1 or 2. ]
General formula (2)

(Wherein R ⁴ is a hydrocarbon group having 1 to 20 carbon atoms, R ⁵ is a hydrocarbon group having 1 to 12 carbon atoms, A ² and A ³ are each independently a halogen atom or hydrocarbyloxy having 1 to 20 carbon atoms. Group L ³ is a detachable functional group or hydrocarbon group, L ⁴ is a detachable functional group, k is 0 or 1, and f is an integer of 1 to 10.)
And general formula (3)

(In the formula, A ⁴ represents a halogen atom or a hydrocarbyloxy group having 1 to 20 carbon atoms, R ⁶ represents a hydrocarbon group having 1 to 20 carbon atoms, R ⁷ represents a hydrocarbon group having 1 to 12 carbon atoms, and L ⁵ represents desorption. A separable functional group or hydrocarbon group, q represents ˜0 or 1)
The modified low molecular weight conjugated diene polymer according to any one of [1] to [7], selected from silane compounds represented by :
[ 9 ] The modified low molecular weight conjugate of [ 8] above, wherein the modifier is N, N-bis (trimethylsilyl) aminopropyl (methyl) dimethoxysilane or N, N-bis (trimethylsilyl) aminopropyl (methyl) diethoxysilane. Diene polymer,
[ 10 ] The modifier is 1-trimethylsilyl-2-ethoxy-2-methyl-1-aza-2-silacyclopentane, 1-trimethylsilyl-2-methoxy-2-methyl-1-aza-2-silacyclopentane. The modification according to [ 8 ] above, which is 1-trimethylsilyl-2,2-diethoxy-1-aza-2-silacyclopentane or 1-trimethylsilyl-2,2-dimethoxy-1-aza-2-silacyclopentane. Low molecular weight conjugated diene polymer ,
[11 ] The modified low molecular weight conjugated diene polymer according to any one of the above [1] to [10], wherein the condensation accelerator is an alkoxide, carboxylate or acetylacetonate complex of titanium, zirconium, bismuth or aluminum,
[ 12 ] Any one of [1] to [11] above, wherein the conjugated diene polymer having an active terminal is obtained by anionic polymerization using an alkali metal compound as a polymerization initiator or by coordination polymerization using a rare earth metal compound. Modified low molecular weight conjugated diene polymer as described in 1.
[ 13 ] The modified low molecular weight conjugated diene polymer according to any one of the above [1] to [ 12 ], which is a copolymer of a conjugated diene compound and an aromatic vinyl compound,
[ 14 ] The modified low molecular weight conjugated diene polymer according to [ 13], wherein the conjugated diene compound is 1,3-butadiene and the aromatic vinyl compound is styrene,
[ 15 ] (A) The rubber component having a weight average molecular weight exceeding 150,000 and 100 parts by mass thereof, (B) the modified low molecular weight conjugated diene polymer 10 to 55 of any one of [1] to [ 14 ] above. A rubber composition comprising mass parts,
[ 16 ] The rubber composition according to [ 15 ] above, further comprising (C) a reinforcing filler in a proportion of 20 to 120 parts by mass with respect to 100 parts by mass of the component (A).
[ 17 ] (C) The rubber composition according to the above [ 16 ], wherein the reinforcing filler is carbon black and / or silica.
[ 18 ] Furthermore, (D) the rubber composition of [ 17 ] above containing 1 to 20% by mass of a silane coupling agent with respect to silica, and [ 19 ] any of [ 15 ] to [ 18 ] above A tire characterized by using a rubber composition for a tire member,
Is to provide.

  According to the present invention, a modified low molecular weight conjugated diene polymer and a rubber composition containing the same that give a tire having an appropriate storage elastic modulus and an improved low heat build-up without reducing wear resistance And a tire having the above-described properties using the rubber composition.

First, the modified low molecular weight conjugated diene polymer of the present invention will be described.
[Modified low molecular weight conjugated diene polymer]
The modified low molecular weight conjugated diene polymer of the present invention is an amine functional group-modified conjugated diene polymer having an amino group protected with a protic amino group and / or a detachable group in the molecule, The previous weight average molecular weight is 10,000 to 200,000.

(Functional group for modification)
The modified low molecular weight conjugated diene polymer of the present invention is modified as a functional group for modification in the molecule by modifying a low molecular weight conjugated diene polymer having a weight average molecular weight in the range of 10,000 to 200,000. A protic amino group which is an amine functional group and / or an amino group protected with a detachable group is introduced, and a functional group containing a silicon atom is preferably further introduced.
Examples of the functional group containing a silicon atom include a silane group formed by bonding a hydrocarbyloxy group and / or a hydroxy group to a silicon atom.
Such a functional group for modification may be present at any of the polymerization initiation terminal, side chain and polymerization active terminal of the conjugated diene polymer. In the present invention, it is preferably a polymerization terminal, more preferably the same polymerization. A silicon atom having an amino group protected with a protic amino group and / or a detachable group and a hydrocarbyloxy group and / or a hydroxy group, particularly preferably one or two hydrocarbyloxy groups, And / or a silicon atom having a hydroxy group bonded thereto.

Examples of the protic amino group include at least one selected from a primary amino group, a secondary amino group, and salts thereof.
On the other hand, examples of the amino group protected with a detachable group include N, N-bis (trihydrocarbylsilyl) amino group and N- (trihydrocarbylsilyl) imino group. Preferably, the hydrocarbyl group is carbon. The trialkylsilyl group which is a C1-C10 alkyl group can be mentioned, Especially preferably, a trimethylsilyl group can be mentioned.
Examples of primary amino groups protected with a detachable group include N, N-bis (trimethylsilyl) amino group, and examples of secondary amino groups protected with a detachable group include N A-(trimethylsilyl) imino group can be mentioned. The N- (trimethylsilyl) imino group-containing group may be an acyclic imine residue or a cyclic imine residue.

The amine functional group-modified conjugated diene polymer in the present invention is a primary amino group protected with a detachable group as a modifier at the active end of a conjugated diene polymer having an active end and / or 2 A silane compound in which a secondary amino group-containing group, 2 or 3 hydrocarbyloxy groups and / or halogen atoms are bonded to the same silicon atom is preferably reacted and modified.
(Conjugated diene polymer having active terminal)
In order to effectively perform the modification reaction, as the conjugated diene polymer having an active end, an organic alkali metal compound is used as a polymerization initiator, and a conjugated diene compound, or a conjugated diene compound and an aromatic vinyl compound are anions. It is preferable to be obtained by polymerization.
Examples of the conjugated diene compound include 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene. In the present invention, 1,3-butadiene is preferable.
Examples of the aromatic vinyl compound include styrene, α-methylstyrene, 1-vinylnaphthalene, 3-vinyltoluene, ethylvinylbenzene, divinylbenzene, 4-cyclohexylstyrene, 2,4,6-trimethylstyrene, and the like. However, styrene is preferred in the present invention.
In the present invention, as a conjugated diene polymer having an active terminal, polybutadiene obtained by anionic polymerization of 1,3-butadiene using an organic alkali metal compound as a polymerization initiator, or styrene and 1,3-butadiene SBR obtained by copolymerizing anion by anionic polymerization is preferable.
As the anionic polymerization method, a solution polymerization method is particularly preferable, and the polymerization mode may be either a batch type or a continuous type. As the organic alkali metal compound, a lithium compound is particularly preferable.
The monomer concentration in the solvent in the solution polymerization method is preferably 5 to 50% by mass, more preferably 10 to 30% by mass.

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

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

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

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

There is no restriction | limiting in particular as a method of manufacturing a conjugated diene polymer by anionic polymerization using the said lithium compound as a polymerization initiator, A conventionally well-known method can be used.
Specifically, in an organic solvent inert to the reaction, for example, a hydrocarbon solvent such as an aliphatic, alicyclic or aromatic hydrocarbon compound, 1,3-butadiene alone or styrene and 1,3-butadiene Can be anionically polymerized in the presence of the randomizer used, if desired, using the lithium compound as a polymerization initiator to obtain polybutadiene or SBR having the desired active terminal.

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

Further, the randomizer used as desired can control the microstructure of the conjugated diene compound, for example, to control the 1,2-bond content of the butadiene unit of the polymer using butadiene as the monomer, It has effects such as randomizing butadiene units and styrene units of a copolymer using styrene and butadiene as monomers. 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 ′, Mention may be made of ethers such as N′-tetramethylethylenediamine and 1,2-dipiperidinoethane, and tertiary amines. Further, potassium salts such as potassium-t-amylate and potassium-t-butoxide, and sodium salts such as sodium-t-amylate can also be used.
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, all raw materials involved in the polymerization, such as polymerization initiators, randomizers, solvents, and monomers, should be used after removal of reaction inhibitors such as water, oxygen, carbon dioxide, and protic compounds. Is desirable.

<Properties of conjugated diene polymer before modification>
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.
In the present invention, the weight average molecular weight of the conjugated diene polymer before modification needs to be 10,000 to 200,000, preferably 20,000 to 150,000, more preferably 30,000 to 150,000. When the weight average molecular weight is less than 10,000, the effect of improving the storage elastic modulus is small, whereas when it exceeds 200,000, the workability of the rubber composition is lowered.
In addition, the said weight average molecular weight is the value of polystyrene conversion measured by the gel permeation chromatography method (GPC method).

(Modifier)
In the present invention, a primary amino group protected with a detachable group and / or 2 is used as a modifying agent to react with the active end of the conjugated diene polymer having an active end obtained as described above. A silane compound in which a secondary amino group-containing group and a hydrocarbyloxy group are bonded to the same silicon atom is preferably used.
Preferred examples of such a modifier include silane compounds selected from the following general formula (1), general formula (2), and general formula (3).

In the general formula (1), A ¹ is a halogen atom or a hydrocarbyloxy group having 1 to 20 carbon atoms, R ² is a hydrocarbon group R ³ is a hydrocarbon group, L ¹ is a detachable functional group, and L ² is When it is a detachable group or hydrocarbon group and L ² is a detachable functional group, it may be the same structure as L ¹ or a different structure, and L ¹ and L ² may be bonded. Absent. n represents 0 or 1, and m represents 1 or 2.
The hydrocarbon group represented by R ² is preferably a gate having 1 to 20 carbon atoms, and the hydrocarbon group represented by R ³ is preferably one having 1 to 12 carbon atoms.
In the general formula (2), R ⁴ is a hydrocarbon group having 1 to 20 carbon atoms, R ⁵ is a hydrocarbon group having 1 to 12 carbon atoms, A ² and A ³ are each independently a halogen atom or 1 to 1 carbon atom. 20 hydrocarbyloxy groups, L ³ is a detachable functional group or hydrocarbon group, and L ⁴ is a detachable functional group. K represents 0 or 1, and f represents an integer of 1 to 10.
In the general formula (3), A ⁴ is a halogen atom or a hydrocarbyloxy group having 1 to 20 carbon atoms, R ⁶ is a hydrocarbon group having 1 to 20 carbon atoms, and R ⁷ is a hydrocarbon having 1 to 12 carbon atoms. Group, L ⁵ represents a detachable functional group or hydrocarbon group, and q represents ˜0 or 1.
Thus, N in the general formulas (1) to (3) has a form in which the primary amino group or the secondary amino group is caged with a functional group that can be eliminated.

In the general formulas (1) to (3), among A ^{1 to} A ⁴ , the halogen atom is preferably Cl, Br or I, and the hydrocarbyloxy group having 1 to 20 carbon atoms is carbon. It is preferable that it is a hydrocarbyloxy group of number 1-10. Examples of the hydrocarbyloxy group having 1 to 10 carbon atoms include an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, and an aralkyloxy group having 7 to 10 carbon atoms. Among these, an alkoxy group having 1 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 an alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, various pentoxy groups, various hexoxy groups, Examples include various heptoxy groups, various octoxy groups, various decyloxy groups, cyclopetyloxy groups, cyclohexyloxy groups, and the like. Among these, alkoxy groups having 1 to 6 carbon atoms are preferable, and methoxy groups are particularly preferable. And ethoxy groups are preferred.

In the general formulas (1) to (3), examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ² , R ⁴ , and R ⁶ include an alkyl group having 1 to 18 carbon atoms and 2 to 2 carbon atoms. 18 alkenyl groups, aryl groups having 6 to 18 carbon atoms, aralkyl groups having 7 to 18 carbon atoms, and the like. Among these, from the viewpoint of the reactivity and performance of the modifier, those having 1 to 18 carbon atoms. An alkyl group is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable. 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.

In the general formula (1) to (3), the R ^3, R ^5, and hydrocarbon group having 1 to 12 carbon atoms represented by R ^7, in view of the performance of modifier, from 1 to 12 carbon atoms Alkanediyl groups are more preferred, alkanediyl groups having 2 to 10 carbon atoms are more preferred, and alkanediyl groups having 2 to 6 carbon atoms are particularly preferred.
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.

In the general formula (1), L ¹ is a detachable functional group, and L ² is a detachable functional group or a hydrocarbon group. When L ² is a detachable functional group, it may be the same structure as L ¹ or a different structure, and L ¹ and L ² may be bonded.
In the general formula (2), L ³ is a detachable functional group or hydrocarbon group, and L ⁴ is a detachable functional group. In the general formula (3), L ⁵ is a detachable functional group or a hydrocarbon group.
Examples of the detachable functional group in L ^{1 to} L ⁴ include a trihydrocarbylsilyl group, preferably a trialkylsilyl group in which the hydrocarbyl group is an alkyl group having 1 to 10 carbon atoms. Particularly preferred is a trimethylsilyl group.
Examples of primary amino groups protected with a detachable group include N, N-bis (trimethylsilyl) amino group, and examples of secondary amino groups protected with a detachable group include N A-(trimethylsilyl) imino group can be mentioned.
The hydrocarbon group in L ^2, L ³ and L ^5, preferably a hydrocarbon group having 1 to 20 carbon atoms. For the hydrocarbon group of 1 to 20 carbon atoms is as indicated in the description of the aforementioned R ^2, R ⁴ and R ^6.

  In the present invention, as the silane compound represented by the general formula (1), a bifunctional hydrocarbyloxysilane compound in which m is 2 is preferable. By using such a bifunctional silane compound as a modifier, the resulting modified conjugated diene copolymer can introduce a highly efficient modified end and has an interaction with an inorganic filler such as silica. growing.

As a silane compound represented by the general formula (1), for example, when m has a primary amino group protected by 2 functional groups that can be eliminated, N, N-bis ( Trimethylsilyl) aminopropyl (methyl) dimethoxysilane, N, N-bis (trimethylsilyl) aminopropyl (methyl) diethoxysilane, N, N-bis (trimethylsilyl) aminopropyl (methyl) dipropoxysilane, N, N-bis ( Trimethylsilyl) aminopropyl (ethyl) dimethoxysilane, N, N-bis (trimethylsilyl) aminopropyl (ethyl) diethoxysilane, N, N-bis (trimethylsilyl) aminopropyl (ethyl) dipropoxysilane, N, N-bis ( Trimethylsilyl) aminoethyl (methyl) dimethoxysilane, N, N-bis Trimethylsilyl) aminoethyl (methyl) diethoxysilane, N, N-bis (trimethylsilyl) aminoethyl (methyl) dipropoxysilane, N, N-bis (trimethylsilyl) aminoethyl (ethyl) dimethoxysilane, N, N-bis ( Bifunctional alkoxysilane compounds such as trimethylsilyl) aminoethyl (ethyl) diethoxysilane, N, N-bis (trimethylsilyl) aminoethyl (ethyl) dipropoxysilane; N, N-bis (trimethylsilyl) aminopropyl (methyl) methoxychlorosilane N, N-bis (trimethylsilyl) aminopropyl (methyl) ethoxychlorosilane, N, N-bis (trimethylsilyl) aminoethyl (methyl) methoxychlorosilane, N, N-bis (trimethylsilyl) aminoethyl (meth) B) Bifunctional alkoxychlorosilane compounds such as ethoxychlorosilane; N, N-bis (trimethylsilyl) aminopropyl (methyl) dichlorosilane, N, N-bis (trimethylsilyl) aminopropyl (methyl) dichlorosilane, N, N-bis ( Bifunctional chlorosilane compounds such as trimethylsilyl) aminoethyl (methyl) dichlorosilane and N, N-bis (trimethylsilyl) aminoethyl (methyl) dichlorosilane can be exemplified.
Among these, N, N-bis (trimethylsilyl) aminopropyl (methyl) dimethoxysilane, N, N-bis (trimethylsilyl) aminopropyl (methyl) diethoxysilane and N, N-bis (trimethylsilyl) aminopropyl (methyl) ) Dipropoxysilane is preferred.

Further, the compound represented by the general formula (1) includes, for example, a case where m is 1 and L ² is a hydrocarbon group and has a secondary amino group protected by a detachable functional group. N-methyl-N-trimethylsilylaminopropyl (methyl) dimethoxysilane, N-methyl-N-trimethylsilylaminopropyl (methyl) diethoxysilane, N-ethyl-N-trimethylsilylaminopropyl (methyl) diethoxysilane, etc. Bifunctional alkoxysilane compounds and the like can be mentioned.

In the general formula (2), a bifunctional compound in which k is 1 is preferable for the same reason as in the general formula (1).
In the general formula (2), when f is 1, the silane compound represented by the general formula (2) is a detachable functional group 2 in the compound represented by the general formula (1). In the case of having a primary amino group protected by an individual and in the case of having a secondary amino group protected by one detachable functional group, the same compounds as the exemplified compounds can be exemplified.

In the general formula (3), a bifunctional silane compound in which q is 1 is preferable for the same reason as in the general formula (1).
Examples of the silane compound represented by the general formula (3) include 1-trimethylsilyl-2-ethoxy-2-methyl-1-aza-2-silacyclopentane, 1-trimethylsilyl-2-methoxy-2-methyl- 1-aza-2-silacyclopentane, 1-trimethylsilyl-2,2-diethoxy-1-aza-2-silacyclopentane, 1-trimethylsilyl-2,2-dimethoxy-1-aza-2-silacyclopentane, etc. Is mentioned.

The modifier in the present invention may be a compound having a primary amino group or secondary amino group-containing group protected with a detachable functional group and a silicon-containing hydrolyzable functional group, and the general formula ( It is not limited to the silane compounds represented by 1) to (3).
For example, (2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentan-1-yl) propyl (methyl) dimethoxysilane, (2,2,5,5-tetramethyl- 1-aza-2,5-disilacyclopentan-1-yl) propyl (methyl) diethoxysilane, N-trimethylsilyl (hexamethyleneimin-2-yl) propyl (methyl) dimethoxysilane, N-trimethylsilyl (Hexamethyleneimin-2-yl) propyl (methyl) diethoxysilane, N-trimethylsilyl (pyrrolidin-2-yl) propyl (methyl) dimethoxysilane, N-trimethylsilyl (pyrrolidin-2-yl) propyl (methyl) diethoxy Silane, N-trimethylsilyl (piperidin-2-yl) propyl (methyl) dimethoxy Lan, N-trimethylsilyl (piperidin-2-yl) propyl (methyl) diethoxysilane, N-trimethylsilyl (imidazol-2-yl) propyl (methyl) dimethoxysilane, N-trimethylsilyl (imidazol-2-yl) propyl (methyl) ) Diethoxysilane, N-trimethylsilyl (4,5-dihydroimidazol-5-yl) propyl (methyl) dimethoxysilane, N-trimethylsilyl (4,5-dihydroimidazol-5-yl) propyl (methyl) diethoxysilane, etc. Can also be used.

In the present invention, among the modifiers, in particular, N, N-bis (trimethylsilyl) aminopropyl (methyl) dimethoxysilane, N, N-bis (trimethylsilyl) aminopropyl (methyl) diethoxysilane, 1-trimethylsilyl 2-Ethoxy-2-methyl-1-aza-2-silacyclopentane is preferred.
These modifiers may be used alone or in combination of two or more.

(Denaturation reaction)
In the modification reaction in the present invention, modification is performed by reacting the active terminal of the conjugated diene polymer having an organic alkali metal active terminal with at least one selected from the aforementioned modifiers.
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.
In this modification reaction, it is preferable that the conjugated diene polymer to be used has at least 10% of polymer chains having a living property.

In the modification reaction with the above modifier, the amount of the modifier used is preferably 0.5 to 200 mmol / kg · conjugated diene polymer. The content is more preferably 1 to 100 mmol / kg · conjugated diene polymer, and particularly preferably 2 to 50 mmol / kg · conjugated diene polymer. Here, the conjugated diene polymer means the mass of only a polymer not containing an additive such as an anti-aging agent added at the time of production or after production. By making the usage-amount of a modifier into the said range, the amine functional group modified conjugated diene type polymer which has a desired property is obtained.
The method for adding the modifier is not particularly limited, and examples thereof include a batch addition method, a division addition method, and a continuous addition method. preferable.

(Condensation reaction)
In the present invention, in order to accelerate the condensation reaction involving the hydrocarbyloxysilane compound used as the aforementioned modifier, after the modification reaction, the condensation reaction may be performed in the presence of a condensation accelerator as necessary. Good.
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 (long period type) is used.
As the condensation accelerator, at least one selected from a titanium compound, a tin compound, a zirconium compound, a bismuth compound, and an aluminum compound is preferably used, and more preferably, the alkoxide or carboxyl of each of the above elements. Acid salt and acetylacetonate complex salt, more preferably titanium alkoxide, titanium carboxylate, tin carboxylate, bismuth carboxylate, zirconium alkoxide, zirconium carboxylate, aluminum alkoxide and It is an aluminum carboxylate.

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

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

  Examples of the condensation accelerator made 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 ( Examples include 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 above 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 carried out in the presence of water. As the water, a form such as a simple substance, a solution of alcohol or the like, a dispersed micelle in a hydrocarbon solvent, etc. are suitably used. Water that is potentially contained in a compound capable of releasing water in the reaction system, such as water adsorbed in water and hydrated water of hydrates, 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 metal compound.
The two of the condensation accelerator and water may be added separately to the reaction system or mixed immediately before use as a mixture, but long-term storage of the mixture is preferable because it causes decomposition of the condensation accelerator. Absent.
The molar ratio between the condensation accelerator and water effective for the reaction varies depending on the required reaction conditions, but is preferably about 1 / 0.5 to 1/20.

Moreover, it is preferable to perform reaction using this condensation accelerator at the temperature of 20 degreeC or more, Furthermore, the range of 30-120 degreeC is preferable. The reaction time is preferably about 0.5 to 120 minutes, more preferably 3 to 60 minutes.
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 addition, when a hydrocarbyloxysilane compound having a protected primary amino group and / or secondary amino group was used as a modifying agent, it was liberated by hydrolysis of a removable group in the protected amino group. Can be converted to an amino group. By removing this solvent, a dried polymer having a primary amino group or a secondary amino group can be obtained. In addition, the deprotection treatment of the protective primary amino group and / or secondary amino group derived from the modifier is performed as necessary at any stage from the stage including the condensation treatment to the solvent removal to the dry polymer. Can do.

The amine functional group-modified low molecular weight conjugated diene polymer thus obtained is formed by bonding a silicon atom having a nitrogen-containing functional group to the polymer terminal, and the nitrogen-containing functional group is primary. Examples thereof include an amino group, a secondary amino group and a salt thereof, and a structure having at least one selected from a primary amino group and a secondary amino group protected with a detachable group.
Moreover, the thing of the structure where a hydrocarbyloxy group and / or a hydroxy group couple | bond with the silicon atom which has the said nitrogen-containing functional group can also be mentioned.
In the amine functional group-modified low molecular weight conjugated diene polymer having such a structure, the nitrogen-containing functional group has a good interaction with carbon black or silica, whereas the hydrocarbyloxysilane group And silanol groups have particularly excellent interaction with silica. Therefore, the rubber composition containing the modified low molecular weight conjugated diene polymer described later in place of a softening agent such as aroma oil has a moderate storage elastic modulus and low exothermicity without reducing wear resistance. The tire which improved can be given.
The modified low molecular weight conjugated diene rubber preferably has a glass transition point (Tg) of 0 ° C. or lower. If this glass transition point exceeds 0 ° C., tire performance at low temperatures may be significantly deteriorated.

Next, the rubber composition of the present invention will be described.
[Rubber composition]
The rubber composition of the present invention comprises (A) a rubber component having a weight average molecular weight of more than 150,000 and 100 parts by mass of (B) 10 to 55 mass of the modified low molecular weight conjugated diene polymer of the present invention described above. It is characterized by including a part.
((A) rubber component)
In the rubber composition of the present invention, the rubber component used as the component (A) is not particularly limited as long as the weight average molecular weight exceeds 150,000, and may be an unmodified rubber, which is conventionally known. It may be a modified rubber which is modified by the above method. Examples of such unmodified or modified rubber include natural rubber, synthetic isoprene rubber, butadiene rubber, styrene-butadiene rubber, ethylene-α-olefin copolymer rubber, ethylene-α-olefin-diene copolymer rubber, chloroprene rubber, Examples thereof include at least one selected from non-modified rubbers and modified rubbers such as halogenated butyl rubber and a copolymer of styrene and isobutylene having a halogenated methyl group.
The weight average molecular weight of the rubber component (A) needs to exceed 150,000 from the viewpoint of performance as a matrix rubber, preferably 150,000 to 2,000,000, and more preferably 150,000 to 1,000,000. .

((B) Modified low molecular weight conjugated diene polymer)
As the component (B) in the rubber composition of the present invention, the modified low molecular weight conjugated diene polymer of the present invention described above is used.
Examples of the modified low molecular weight conjugated diene polymer include a modified low molecular weight styrene-butadiene copolymer (hereinafter sometimes abbreviated as modified LM-SBR) and a modified low molecular weight polybutadiene (hereinafter referred to as modified LM-BR). May be abbreviated as)).
In the rubber composition of the present invention, the modified low molecular weight conjugated diene polymer as the component (B) is usually used in place of a softening agent such as aroma oil, and the blending amount thereof is (A) It is 10-55 mass parts with respect to 100 mass parts of rubber components. If the blending amount of the component (B) is within the above range, the effect of the present invention is exhibited well. A preferable compounding amount is 15 to 50 parts by mass.

Carbon black and / or silica can be used as the reinforcing filler (C) in the rubber composition of the present invention.
Carbon black is not particularly limited, and for example, SRF, GPF, FEF, HAF, 1SAF, SAF, etc. are used, iodine adsorption amount (IA) is 60 mg / g or more, and dibutyl phthalate oil absorption amount (DBP) is 80 ml / 100 g. The above carbon black is preferable. By using carbon black, the effect of improving grip performance and fracture resistance is increased, but HAF, ISAF, and SAF, which are excellent in wear resistance, are particularly preferable.
On the other hand, the silica is not particularly limited, and can be arbitrarily selected from those conventionally used as reinforcing fillers for rubber.
Examples of the silica include wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, and the like. Wet silica that is noticeable is preferred.

  In the present invention, as the (C) reinforcing filler, only carbon black may be used, silica alone may be used, or carbon black and silica may be used in combination. The reinforcing filler is preferably 20 to 120 parts by weight, more preferably 25 to 100 parts by weight, with respect to 100 parts by weight of the rubber component (A), from the viewpoint of reinforcing properties and the effect of improving various properties thereby. More preferably, it mix | blends in the ratio of 30-90 mass parts. By setting the amount of carbon black and / or silica within the above range, factory workability such as kneading workability is excellent, and desired fracture characteristics can be obtained as a rubber composition.

((D) Silane coupling agent)
In the rubber composition of the present invention, when silica is used as the reinforcing filler, a silane coupling agent can be blended for the purpose of further improving the reinforcing property and low exothermic property.
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-dimethylthiocarbamo Yl tetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzothiazolyl tetrasulfide, 3-triethoxy Ethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyl Tetrasulfide, dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide, and the like are mentioned. Among these, bis (3-toe Liethoxysilylpropyl) polysulfide and 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide are preferred.
One of these silane coupling agents may be used alone, or two or more thereof may be used in combination.

  In the rubber composition of the present invention, the compounding amount of the silane coupling agent varies depending on the type of the silane coupling agent and the like, but is preferably selected in the range of 1 to 20% by mass with respect to silica. If this amount is less than 1% by mass, the effect as a coupling agent is hardly exhibited, and if it exceeds 20% by mass, the rubber component may be gelled. From the viewpoints of the effect as a coupling agent and the prevention of gelation, a more preferable blending amount of this silane coupling agent is in the range of 5 to 15% by mass.

(Preparation and use of rubber composition)
In the rubber composition of the present invention, various chemicals usually used in the rubber industry, for example, a vulcanizing agent, a vulcanization accelerator, an anti-aging agent, an anti-scorch agent, as desired, as long as the object of the present invention is not impaired. , Zinc white, stearic acid and the like.
As said vulcanizing agent, sulfur etc. are mentioned, The usage-amount is 0.1-10.0 mass parts as a sulfur content with respect to 100 mass parts of rubber components, More preferably, it is 1.0-5. 0 parts by mass. If the amount is less than 0.1 parts by mass, the rupture strength, wear resistance, and low heat build-up of the vulcanized rubber may be reduced. If the amount exceeds 10.0 parts by mass, rubber elasticity is lost.

  The vulcanization accelerator that can be used in the present invention is not particularly limited, and examples thereof include M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), and CZ (N-cyclohexyl-2-benzothiazyl). Sulfenamide) and other guanidine vulcanization accelerators such as DPG (diphenylguanidine) can be used, and the amount used is 0.1-5. 0 mass part is preferable, More preferably, it is 0.2-3.0 mass part.

  Further, the rubber composition of the present invention is obtained by kneading using a kneader such as an open kneader such as a roll, a closed kneader such as a Banbury mixer, and vulcanized after molding. Applicable to various rubber products. For example, it can be used for tire applications such as tire treads, under treads, carcass, sidewalls, bead parts, anti-vibration rubber, fenders, belts, hoses and other industrial products. It is suitably used as a tread rubber for fuel-efficient tires, large tires, and high-performance tires, which have an excellent balance of heat generation, wear resistance, dry grip performance, and breaking strength.

Next, the tire of the present invention will be described.
[tire]
The tire of the present invention is characterized by using the above-described rubber composition of the present invention for a tire member.
Preferred examples of the tire member include a tread, a base tread, and a sidewall, and the rubber composition of the present invention can be used for any of these, and it is particularly preferable to use the tread.
A tire using the rubber composition of the present invention for a tread has low rolling resistance and excellent fuel economy, maintains dry grip performance, and has excellent fracture characteristics and wear resistance. In addition, as gas with which the tire of the present invention is filled, normal or air with a changed oxygen partial pressure, or an inert gas such as nitrogen is exemplified. When the rubber composition of the present invention is used for a tread, for example, it is extruded on a tread member, and is pasted and molded by a usual method on a tire molding machine to form a raw tire. The green tire is heated and pressed in a vulcanizer to obtain a tire.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
Various characteristics were determined according to the following methods.
<Rubber composition after vulcanization>
(1) Loss tangent (tan δ) and storage modulus (G ′)
Using a viscoelasticity measuring device manufactured by Rheometrics, tan δ and storage elastic modulus (G ′) were measured at a temperature of 50 ° C., a frequency of 52 Hz, and a strain of 1.0%. displayed. tan δ indicates that the lower the index value, the better the low heat build-up. G ′ indicates that the larger the index value, the better the dry grip performance.
(2) Abrasion resistance Using a Ramborn-type abrasion tester, the amount of abrasion with a slip rate of 25% at room temperature was measured, and the reciprocal of the amount of abrasion of the control was represented as an index. It shows that it is excellent in abrasion resistance, so that an index | exponent is large.
<Non-modified / modified low molecular weight SBR, modified low molecular weight BR, matrix SBR>
(3) Microstructure and bound styrene content The microstructure of the polymer was determined by the infrared method (Morero method), and the bound styrene content of the polymer was determined from the integral ratio of the ¹ H-NMR spectrum.
(4) Weight average molecular weight (Mw)
Gel permeation chromatography [GPC: Tosoh HLC-8020, column: Tosoh GMH-XL (two in series), detector: differential refractometer (RI)], modified with low molecular weight based on monodisperse polystyrene The weight average molecular weight (Mw) before modification of SBR and modified low molecular weight BR, Mw of unmodified low molecular weight SBR and matrix SBR (unmodified) were determined.

Production Example 1 Production of Unmodified LM-SBR To an 800 mL pressure-resistant glass container dried and purged with nitrogen, 300 g of cyclohexane, 40 g of 1,3-butadiene, 13 g of styrene, 0.90 mmol of ditetrahydrofurylpropane were added, and n After adding 0.90 mmol of -butyllithium, a polymerization reaction was carried out at 50 ° C. for 2 hours. The polymerization conversion rate at this time was almost 100%. Thereafter, 0.5 mL of an isopropanol solution (concentration: 5% by mass) of 2,6-di-t-butyl-p-cresol is added to the polymerization reaction system to stop the polymerization reaction, and further dried according to a conventional method. Unmodified low molecular weight SBR (unmodified LM-SBR) was obtained.
This unmodified LM-SBR had a bound styrene content of 25% by weight, a bound vinyl content of the butadiene portion of 65 mol%, and Mw of 80,000.

Production Example 2 Production of Modified LM-SBR A <Production of LM-SBR with Active End>
In the same manner as in Production Example 1, a polymerization reaction was performed to obtain LM-SBR having an active end.
<Modification reaction process>
Next, 0.43 mmol of modifier-A was added to the polymerization reaction system, and a modification reaction was further performed at 50 ° C. for 30 minutes.
<Post-polymerization treatment>
Next, 2,6-di-tert-butyl-p-cresol in an isopropanol solution (concentration: 5% by mass) 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 LM-SBR A.
The modifier-A is 3-N, N-bis (trimethylsilyl) aminopropyl (methyl) diethoxysilane.

Production Example 3 Production of Modified LM-SBR B In the modification reaction step in Production Example 2, 0.85 mmol of modifier-A was added, and after 15 minutes of modification reaction at 50 ° C., tetrakis was used as the condensation accelerator (a). Modified LM-SBR B was obtained in the same manner as in Production Example 2 except that 0.80 mmol of (2-ethylhexyloxy) titanium was added and the reaction was further performed at 50 ° C. for 15 minutes.

Production Example 4 Production of Modified LM-SBR C In the modification reaction step in Production Example 2, 0.85 mmol of modifier-A was added and the modification reaction was carried out at 50 ° C. for 15 minutes, and then bis was used as the condensation accelerator (b). Modified LM-SBR C was obtained in the same manner as in Production Example 2, except that 0.80 mmol of (2-ethylhexanoate) tin was added and the reaction was further performed at 50 ° C. for 15 minutes.

Production Example 5 Production of Modified LM-SBR D In the modification reaction step in Production Example 2, 0.85 mmol of modifier-A was added, and after 15 minutes of modification reaction at 50 ° C., bis was used as a condensation accelerator (c). Modified 2-LM-SBR D was obtained in the same manner as in Production Example 2, except that 0.80 mmol of (2-ethylhexanoate) zirconium oxide was added and the reaction was further carried out at 50 ° C. for 15 minutes.

Production Example 6 Production of Modified LM-SBR E Modified LM-SBR E was prepared in the same manner as in Production Example 2 except that Modification Agent-B was used instead of Modification Agent-A in the modification reaction step in Production Example 2. Obtained.
The modifier-B is 3-N, N-bis (trimethylsilyl) aminopropyltriethoxysilane.

Production Example 7 Production of Modified LM-SBR F Modified LM-SBR F was produced in the same manner as in Production Example 2 except that Modification Agent-C was used instead of Modification Agent-A in the modification reaction step in Production Example 2. Obtained.
The modifier-C is 3-N, N-bis (trimethylsilyl) aminopropyl (dimethyl) ethoxysilane.

Production Example 8 Production of Modified LM-SBR G Similar to Production Example 2 except that 0.225 mmol of modifier-D (tin tetrachloride) was used instead of modifier-A in the modification reaction step in Production Example 2. In this way, modified LM-SBR G was obtained.

Production Example 9 Production of Modified LM-SBR H Modified LM-SBR in the same manner as in Production Example 2 except that, in the modification reaction step in Production Example 2, modifier-E0.85 mmol was used instead of modifier-A. H was obtained.
The modifier-E is N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine.

Production Example 10 Production of Modified LM-SBR I Similar to Production Example 2 except that 0.225 mmol of modifier-F (tetraethoxysilane) was used instead of modifier-A in the modification reaction step in Production Example 2. In this way, modified LM-SBR I was obtained.

Production Example 11 Production of Modified LM-SBR J <Production of LM-SBR with Active End>
After adding 300 g of cyclohexane, 21 g of 1,3-butadiene, 32 g of styrene, 0.90 mmol of ditetrahydrofurylpropane, and further adding 0.90 mmol of n-butyllithium to an 800 mL pressure-resistant glass container that has been dried and purged with nitrogen, A polymerization reaction was carried out at 0 ° C. for 2 hours to obtain LM-SBR having an active end. The polymerization conversion rate at this time was almost 100%.
<Modification reaction>
Next, 0.85 mmol of modifier-A was added to the polymerization reaction system, and after 30 minutes of modification reaction at 50 ° C., 0.80 mmol of tetrakis (2-ethylhexyloxy) titanium was added as a condensation accelerator (a). The reaction was further carried out at 50 ° C. for 15 minutes.
<Post-polymerization treatment>
Next, 2,6-di-tert-butyl-p-cresol in an isopropanol solution (concentration: 5% by mass) 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 LM-SBR J.
The unmodified LM-SBR had a bound styrene content of 60% by mass, a bound vinyl content of the butadiene portion of 65 mol%, and an Mw of 80,000.

Production Example 12 Production of Modified Liq-SBR <Production of Liq-SBR with Active End>
After adding 300 g of cyclohexane, 40 g of 1,3-butadiene, 13 g of styrene, 23 mmol of ditetrahydrofurylpropane, and further adding 23 mmol of n-butyllithium to an 800 mL pressure-resistant glass container that has been dried and purged with nitrogen, 2 hours at 50 ° C. A polymerization reaction was performed to obtain liquid SBR (Liq-SBR) having an active end. The polymerization conversion rate at this time was almost 100%.
<Modification reaction>
Next, 20 mmol of modifier-A was added to the polymerization reaction system, and after a modification reaction at 50 ° C. for 30 minutes, 18 mmol of tetrakis (2-ethylhexyloxy) titanium was added as a condensation accelerator (a), and further 50 ° C. The reaction was carried out for 15 minutes.
<Post-polymerization treatment>
Next, post-polymerization treatment was performed in the same manner as in Production Example 11 to obtain modified Liq-SBR.
The unmodified Liq-SBR had a bound styrene content of 25% by mass, a bound vinyl content of the butadiene portion of 65 mol%, and Mw of 3000.

Production Example 13 Production of Modified HM-SBR <Production of HM-SBR with Active End>
After adding 300 g of cyclohexane, 40 g of 1,3-butadiene, 13 g of styrene, 0.40 mmol of ditetrahydrofurylpropane, and further adding 0.40 mmol of n-butyllithium to an 800 mL pressure-resistant glass container that has been dried and purged with nitrogen, Polymerization reaction was carried out at 2 ° C. for 2 hours to obtain high molecular weight SBR (HM-SBR) having an active end. The polymerization conversion rate at this time was almost 100%.
<Modification reaction>
Next, 0.35 mmol of modifier-A was added to the polymerization reaction system, and after 30 minutes of modification reaction at 50 ° C., 0.30 mmol of tetrakis (2-ethylhexyloxy) titanium was added as a condensation accelerator (a). The reaction was further carried out at 50 ° C. for 15 minutes.
<Post-polymerization treatment>
Next, post-polymerization treatment was performed in the same manner as in Production Example 11 to obtain modified HM-SBR.
The unmodified HM-SBR had a bound styrene content of 25% by mass, a bound vinyl content of the butadiene portion of 65 mol%, and Mw of 220,000.

Production Example 14 Production of Modified LM-BR To an 800 mL pressure-resistant glass container that has been dried and purged with nitrogen, 300 g of cyclohexane, 55 g of 1,3-butadiene, 0.90 mmol of ditetrahydrofurylpropane, and 0.90 mmol of n-butyllithium are further added. Then, a polymerization reaction was carried out at 50 ° C. for 2 hours to obtain a low molecular weight polybutadiene (LM-BR) having an active end. The polymerization conversion rate at this time was almost 100%.
<Modification reaction>
Next, 0.85 mmol of modifier-A was added to the polymerization reaction system, and after 30 minutes of modification reaction at 50 ° C., 0.80 mmol of tetrakis (2-ethylhexyloxy) titanium was added as a condensation accelerator (a). The reaction was further carried out at 50 ° C. for 15 minutes.
<Post-polymerization treatment>
Next, post-polymerization treatment was performed in the same manner as in Production Example 11 to obtain modified LM-BR.
The unmodified LM-BR had a bound vinyl content of 65 mol%, a cis-1,4 bond content of 16 mol%, and an Mw of 80,000.

Production Example 15 Production of Matrix SBR (Unmodified) To an 800 mL pressure-resistant glass container dried and purged with nitrogen, 300 g of cyclohexane, 40 g of 1,3-butadiene, 13 g of styrene, 0.20 mmol of ditetrahydrofurylpropane were added, and n- After adding 0.20 mmol of butyllithium, a polymerization reaction was performed at 50 ° C. for 1.5 hours. The polymerization conversion rate at this time was almost 100%. Thereafter, 0.5 mL of an isopropanol solution of 2,6-di-p-cresol (concentration: 5% by mass) is added to the polymerization reaction system to stop the polymerization reaction, followed by drying according to a conventional method, and the matrix SBR ( Unmodified) was obtained.
This unmodified matrix SBR had a bound styrene content of 25% by weight, a bound vinyl content of the butadiene portion of 65 mol%, and Mw of 400,000.
The conditions and results of Production Examples 1 to 10 are shown in Table 1, and the conditions and results of Production Examples 11 to 15 are shown in Table 1.

［注］
変性剤−Ａ：３−Ｎ，Ｎ−ビス（トリメチルシリル）アミノプロピル（メチル）ジエトキシシラン
縮合促進剤（ａ）：テトラキス（２−エチルヘキシルオキシ）チタン
縮合促進剤（ｂ）：ビス（２−エチルヘキサノエート）スズ
縮合促進剤（ｃ）：ビス（２−エチルヘキサエート）酸化ジルコニウム
変性剤−Ｂ：３−Ｎ，Ｎ−ビス（トリメチルシリル）アミノプロピルトリエトキシシラン
変性剤−Ｃ：３−Ｎ，Ｎ−ビス（トリメチルシリル）アミノプロピル（ジメチル）エトキシシラン
変性剤−Ｄ：四塩化スズ
変性剤−Ｅ：Ｎ−（１，３−ジメチルブチリデン）−３−（トリエトキシシリル）−１−プロパンアミン
変性剤−Ｆ：テトラエトキシシラン

[note]
Modifier-A: 3-N, N-bis (trimethylsilyl) aminopropyl (methyl) diethoxysilane Condensation accelerator (a): Tetrakis (2-ethylhexyloxy) titanium Condensation accelerator (b): Bis (2-ethyl Hexanoate) tin condensation accelerator (c): bis (2-ethylhexaate) zirconium oxide modifier-B: 3-N, N-bis (trimethylsilyl) aminopropyltriethoxysilane modifier-C: 3-N , N-bis (trimethylsilyl) aminopropyl (dimethyl) ethoxysilane Modifier-D: Tin tetrachloride Modifier-E: N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propane Amine modifier-F: Tetraethoxysilane

Examples 1-6 and Comparative Examples 1-4
Natural rubber and matrix SBR (unmodified) obtained in Production Example 15 were used as the matrix rubber, and those shown in Table 3 were used as softeners. Each rubber was in accordance with the compounding formulas I and II shown in Table 2. A composition was prepared.
Each rubber composition was vulcanized at 160 ° C. for 15 minutes to obtain a vulcanized rubber, and the abrasion resistance, loss tangent (tan δ) and storage elastic modulus (G ′) of the vulcanized rubber were determined. It was set as a control, and the index was displayed as 100.
The higher the index value, the better the wear resistance, the lower the index value, the lower the heat generation, and the higher the index value, the better the dry grip performance of G ′.
The results are shown in Table 3.

［注］
１）製造例１５で製造したマトリックスＳＢＲ（無変性）、
２）ＩＳＡＦ、窒素吸着比表面積（Ｎ₂ＳＡ）＝１１１ｍ²／ｇ
３）東ソーシリカ社製「ニプシルＡＱ」
４）アロマオイル及び／又は製造例１〜１４で得られた無変性、変性共役ジエン系重合体
５）Ｎ−（１，３−ジメチルブチル）−Ｎ’−フェニル−ｐ−フェニレンジアミン
６）デグサ社製「Ｓｉ６９」、ビス（３−トリエトキシシリルプロピル）テトラスルフィド
７）メルカプトベンゾチアジルジスルフィド
８）ジフェニルグアニジン
９）Ｎ−ｔ−ブチル−２−ベンゾチアゾリルスルフェンアミド

[note]
1) Matrix SBR (unmodified) produced in Production Example 15
2) ISAF, nitrogen adsorption specific surface area (N ₂ SA) = 111 m ² / g
3) “Nipsil AQ” manufactured by Tosoh Silica Corporation
4) Aroma oil and / or unmodified, modified conjugated diene polymer obtained in Production Examples 1-14 5) N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine 6) Degussa "Si69", bis (3-triethoxysilylpropyl) tetrasulfide 7) mercaptobenzothiazyl disulfide 8) diphenylguanidine 9) Nt-butyl-2-benzothiazolylsulfenamide

Examples 7-9 and Comparative Examples 5-10
As the matrix rubber, natural rubber and the matrix SBR (unmodified) obtained in Production Example 15 were used, and the softeners shown in Table 4 were used. A rubber composition was prepared.
Each rubber composition was vulcanized at 160 ° C. for 15 minutes to obtain a vulcanized rubber, and the abrasion resistance, loss tangent (tan δ) and storage elastic modulus (G ′) of the vulcanized rubber were determined. It was set as a control, and the index was displayed as 100.
The higher the index value, the better the wear resistance, the lower the index value, the lower the heat generation, and the higher the index value, the better the dry grip performance of G ′.
The results are shown in Table 4.

[note]
The following can be seen from Tables 3 and 4.
It turns out that Examples 1-9 of this invention are excellent in abrasion resistance, low heat_generation | fever property, and dry grip property in both carbon black compounding or silica compounding compared with Comparative Examples 1-10.

  The rubber composition containing the modified low molecular weight conjugated diene polymer of the present invention can have a moderate storage elastic modulus and can provide a tire with improved low heat buildup without reducing wear resistance.

Claims (19)

A primary amino group and / or a secondary amino group-containing group protected with a releasable group and 2 or 3 hydrocarbyloxy groups as a modifying agent at the active end of the conjugated diene polymer having an active end After reacting and modifying a silane compound formed by bonding a halogen atom to the same silicon atom, the silane compound is formed in the presence of a condensation accelerator composed of any one of titanium, zirconium, and tin. Amine-based functional group-modified conjugated diene-based polymer having an amino group protected with a protic amino group and / or a detachable group in the molecule and a functional group containing a silicon atom, which is obtained by performing a condensation reaction involved. A modified low molecular weight conjugated diene polymer having a weight average molecular weight of 10,000 to 200,000 before modification.   The modified low molecular weight conjugated diene polymer according to claim 1, wherein the functional group containing a silicon atom is a silane group formed by bonding a hydrocarbyloxy group and / or a hydroxy group to a silicon atom.   The modified low molecular weight according to claim 2, having an amino group protected with a protic amino group and / or a detachable group at a polymerization terminal and a silicon atom formed by bonding a hydrocarbyloxy group and / or a hydroxy group. Conjugated diene polymer.   The modified low molecular weight of claim 3 having an amino group protected with a protic amino group and / or a detachable group and a silicon atom bonded to a hydrocarbyloxy group and / or a hydroxy group at the same polymerization active terminal. Molecular weight conjugated diene polymer.   The modified low molecular weight conjugated diene polymer according to any one of claims 1 to 4, wherein the protic amino group is at least one selected from a primary amino group, a secondary amino group, and salts thereof.   The modified low molecular weight conjugated diene according to any one of claims 1 to 4, wherein the amino group protected with a detachable group is an N, N-bis (trimethylsilyl) amino group and / or an N- (trimethylsilyl) imino group. Polymer.   The modified low molecular weight conjugated diene polymer according to any one of claims 2 to 6, wherein one or two hydrocarbyloxy groups and / or hydroxy groups are bonded to a silicon atom. The modifier is represented by the general formula (1)

[Wherein A ¹ is a halogen atom or a hydrocarbyloxy group having 1 to 20 carbon atoms, R ² is a hydrocarbon group R ³ is a hydrocarbon group, L ¹ is a detachable functional group, and L ² is detachable. In the case of a functional group or a hydrocarbon group and L ² is a detachable functional group, it may be the same structure as L ¹ or a different structure, and L ¹ and L ² may be bonded. n represents 0 or 1, and m represents 1 or 2. ]
General formula (2)

(Wherein R ⁴ is a hydrocarbon group having 1 to 20 carbon atoms, R ⁵ is a hydrocarbon group having 1 to 12 carbon atoms, A ² and A ³ are each independently a halogen atom or hydrocarbyloxy having 1 to 20 carbon atoms. Group L ³ is a detachable functional group or hydrocarbon group, L ⁴ is a detachable functional group, k is 0 or 1, and f is an integer of 1 to 10.)
And general formula (3)

(In the formula, A ⁴ represents a halogen atom or a hydrocarbyloxy group having 1 to 20 carbon atoms, R ⁶ represents a hydrocarbon group having 1 to 20 carbon atoms, R ⁷ represents a hydrocarbon group having 1 to 12 carbon atoms, and L ⁵ represents desorption. A separable functional group or hydrocarbon group, q represents ˜0 or 1)
The modified low molecular weight conjugated diene polymer according to any one of claims 1 to 7, which is selected from silane compounds represented by:   The modified low molecular weight conjugated diene system according to claim 8, wherein the modifying agent is N, N-bis (trimethylsilyl) aminopropyl (methyl) dimethoxysilane or N, N-bis (trimethylsilyl) aminopropyl (methyl) diethoxysilane. Polymer.   The modifier is 1-trimethylsilyl-2-ethoxy-2-methyl-1-aza-2-silacyclopentane, 1-trimethylsilyl-2-methoxy-2-methyl-1-aza-2-silacyclopentane, The modified low molecular weight conjugated diene according to claim 8, which is trimethylsilyl-2,2-diethoxy-1-aza-2-silacyclopentane or 1-trimethylsilyl-2,2-dimethoxy-1-aza-2-silacyclopentane. Polymer.   The modified low molecular weight conjugated diene polymer according to any one of claims 1 to 10, wherein the condensation accelerator is an alkoxide, carboxylate or acetylacetonate complex of titanium, zirconium, bismuth or aluminum.   The modified low molecular weight according to any one of claims 1 to 11, wherein the conjugated diene polymer having an active end is obtained by anionic polymerization using an alkali metal compound as a polymerization initiator or by coordination polymerization using a rare earth metal compound. Conjugated diene polymer.   The modified low molecular weight conjugated diene polymer according to any one of claims 1 to 12, which is a copolymer of a conjugated diene compound and an aromatic vinyl compound.   The modified low molecular weight conjugated diene polymer according to claim 13, wherein the conjugated diene compound is 1,3-butadiene and the aromatic vinyl compound is styrene.   (A) The rubber component having a weight average molecular weight exceeding 150,000, and 100 parts by mass thereof, (B) 10 to 55 parts by mass of the modified low molecular weight conjugated diene polymer according to any one of claims 1 to 14 A rubber composition comprising the rubber composition.   Furthermore, the rubber composition of Claim 15 which contains 20-120 mass parts of (C) reinforcement filler with respect to 100 mass parts of (A) component.   The rubber composition according to claim 16, wherein the reinforcing filler (C) is carbon black and / or silica.   Furthermore, the rubber composition of Claim 17 which contains 1-20 mass% of (D) silane coupling agents with respect to a silica.   A tire comprising the rubber composition according to any one of claims 15 to 18 as a tire member.