JP4909520B2 - Modified polymer and rubber composition and tire using the same - Google Patents

Description

  The present invention relates to a modified polymer, and a rubber composition and a tire using the modified polymer. More specifically, the present invention relates to a carbon black and / or silica-based compounded rubber composition that enhances the interaction with carbon black and silica, and has a low exothermic property, excellent fracture characteristics, and excellent wear resistance, and The present invention relates to a rubber composition and a tire using the modified polymer.

In recent years, due to social demands for energy saving, demands for lower fuel consumption of automobiles are becoming more severe. 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 a tire, a technique by optimizing the tire structure has been studied, but the most common technique is to use a material with less heat generation as a rubber composition.
In order to obtain such a rubber composition with low heat generation, many technical developments have been made so far to improve the dispersibility of the filler used in the rubber composition. Among them, it is becoming most common to use a modified polymer obtained by modifying a diene polymer obtained by anionic polymerization using a lithium compound with a functional group that interacts with a filler.

  As a typical diene polymer obtained by the above-mentioned anionic polymerization, a method of modifying a polymerization active site with a tin compound used in a carbon black-containing rubber composition as a filler (Patent Document 1) or polymerization activity A method of introducing an amino group at the terminal (Patent Document 2), a method of introducing an amino group-containing alkoxysilyl group at the polymerization active terminal used in a carbon black and silica combined rubber composition, etc. (Patent Document 3), Obtained an intermediate modified product of a polymer to be reacted with the active site of a polymer having an organometallic active site, and then released the metal from the metallization site of the obtained intermediate modified product to obtain active protons. Modified polymers obtained by a method of regenerating (Patent Document 4) and the like are known.

  In addition, as a typical conjugated diene polymer having a high cis content obtained by coordination polymerization using a rare earth catalyst, an active terminus of a conjugated diene polymer having a high cis content is reacted with an alkoxysilane compound. To obtain a silane-modified conjugated diene polymer (Patent Document 5), obtained by polymerizing a diene monomer alone or with other monomers, and cis-1,4 in the conjugated diene portion of the main chain -A saccharide or modified saccharide having 4 or more carbon atoms after primary modification in which a hydrocarbyloxysilane compound is reacted with the active terminal of a conjugated diene polymer having an active terminal having a bond content of 75 mol% or more Selected from the group consisting of fatty acid esters of polyhydric alcohols containing at least one hydroxyl group and hydrocarbyloxysilane compounds Such as a second method for obtaining the primary modified by performing modified conjugated diene polymer (Patent Document 6) obtained by such modified polymer is reacted with one compound is known even without.

  However, as described above, due to the social demand for energy saving, the demand for lower fuel consumption of automobiles is becoming increasingly severe, and the interaction with carbon black and silica is further enhanced, and low heat generation, Modified polymers that further improve fracture properties and wear resistance are desired.

Japanese Patent Publication No. 5-87630 JP 62-207342 A JP 2001-131229 A JP 2004-182894 A Japanese translation of PCT publication No. 2003-514078 WO03 / 046020

  Under such circumstances, the present invention enhances the interaction with carbon black and silica when used in a rubber composition containing carbon black and / or silica, and is excellent in low heat buildup, breakability and wear resistance. An object of the present invention is to obtain a modified polymer and to provide a rubber composition and a tire using the modified polymer.

As a result of intensive studies to achieve the above object, the inventors of the present invention obtained a modified polymer obtained by reacting a specific compound as a modifier with a polymer having an active metal site, particularly a rubber composition, It discovered that the objective could be achieved by using for a tire. The present invention has been completed based on such findings.
That is, the gist of the present invention is as follows.
1. The following general formula (1)

[Wherein, A ¹ or A ² represents a nitrogen atom or C—R ¹³ 3, R ¹ , R ² or R ¹³ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and R ³ or R ⁴ Represents a hydrocarbon group having 1 to 18 carbon atoms, X ¹ is a hydrocarbon group having 1 to 11 carbon atoms, and in the group, an ether structure, a thioether structure, a hydroxyl group, a thiol group and an alkali metal compound thereof, An alkaline earth metal compound or an alkylsilyl compound may be contained. n is an integer of 1 to 3. ]
Or the following general formula (2)

[Wherein A ³ or A ⁴ represents a nitrogen atom or C—R ¹³ ; R ⁵ , R ⁶ , R ⁷ , R ⁸ or R ¹³ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms; R ⁹ or R ¹⁰ represents a hydrocarbon group having 1 to 18 carbon atoms, X ² is a hydrocarbon group having 1 to 11 carbon atoms, and includes an ether structure, a thioether structure, a hydroxyl group, a thiol group, and the like An alkali metal compound, an alkaline earth metal compound or an alkylsilyl compound may be contained. n is an integer of 1 to 3. ]
A modified polymer obtained by reacting a compound represented by formula (1) with a polymer having an active metal site, and a rubber composition, particularly a tire, using the modified polymer.
2. The following general formula (3)

[Wherein, A ¹ or A ² represents a nitrogen atom or C—R ¹³ , and R ¹ , R ^2, or R ¹³ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. ]
Or the following general formula (4)

[Wherein, A ³ or A ⁴ represents a nitrogen atom or C—R ¹³ , and R ⁵ , R ⁶ , R ⁷ , R ⁸ or R ¹³ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. ]
A compound represented by the following general formula (5)

[Wherein, A ⁵ represents an oxygen atom or a sulfur atom, R ¹¹ or R ¹² represents a hydrocarbon group having 1 to 18 carbon atoms, and X ³ represents a hydrocarbon group having 1 to 11 carbon atoms, It may contain an ether structure or a thioether structure. n is an integer of 1 to 3. ] A modified polymer obtained by reacting the compound (6) obtained by reacting with the compound represented by formula (1) with a polymer having an active metal site, and a rubber composition, particularly a tire, using the modified polymer.

3. After the primary modification in which a hydrocarbyloxysilane compound is reacted with an active metal site of the polymer, the following general formula (1)

[Wherein, A ¹ or A ² represents a nitrogen atom or C—R ¹³ , R ¹ , R ² or R ¹³ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and R ³ or R ⁴ represents A hydrocarbon group having 1 to 18 carbon atoms, wherein X ¹ is a hydrocarbon group having 1 to 11 carbon atoms, and includes an ether structure, a thioether structure, a hydroxyl group, a thiol group, or an alkali metal compound thereof, an alkali An earth metal compound or an alkylsilyl compound may be contained. n is an integer of 1 to 3. ]
Or the following general formula (2)

[Wherein A ³ or A ⁴ represents a nitrogen atom or C—R ¹³ ; R ⁵ , R ⁶ , R ⁷ , R ⁸ or R ¹³ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms; R ⁹ or R ¹⁰ represents a hydrocarbon group having 1 to 18 carbon atoms, X ² is a hydrocarbon group having 1 to 11 carbon atoms, and in the group, an ether structure, a thioether structure, a hydroxyl group, a thiol group or the like An alkali metal compound, an alkaline earth metal compound or an alkylsilyl compound may be contained. n is an integer of 1 to 3. ]
Or a compound represented by
The following general formula (3)

[Wherein, A ¹ or A ² represents a nitrogen atom or C—R ¹³ , and R ¹ , R ^2, or R ¹³ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. ]
Or the following general formula (4)

[Wherein, A ³ or A ⁴ represents a nitrogen atom or C—R ¹³ , and R ⁵ , R ⁶ , R ⁷ , R ⁸ or R ¹³ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. ]
A compound represented by the following general formula (5)

[Wherein, A ⁵ represents an oxygen atom or a sulfur atom, R ¹¹ or R ¹² represents a hydrocarbon group having 1 to 18 carbon atoms, and X ³ represents a hydrocarbon group having 1 to 11 carbon atoms, It may contain an ether structure or a thioether structure. n is an integer of 1 to 3. ] The modified polymer obtained by performing the secondary modification | denaturation which condenses the compound (6) obtained by making it react with the compound shown by this, and the rubber composition using this modified polymer, especially a tire.
4). The following general formula (3)

[Wherein, A ¹ or A ² represents a nitrogen atom or C—R ¹³ , and R ¹ , R ^2, or R ¹³ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. ]
Or the following general formula (4)

[Wherein, A ³ or A ⁴ represents a nitrogen atom or C—R ¹³ , and R ⁵ , R ⁶ , R ⁷ , R ⁸ or R ¹³ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. ]
A compound represented by the following general formula (5)

[Wherein, A ⁵ represents an oxygen atom or a sulfur atom, R ¹¹ or R ¹² represents a hydrocarbon group having 1 to 18 carbon atoms, and X ³ represents a hydrocarbon group having 1 to 11 carbon atoms, It may contain an ether structure or a thioether structure. n is an integer of 1 to 3. A compound obtained by reacting a compound (6) obtained by reacting with a compound represented by formula (I) and an organic alkali metal compound, organic alkaline earth metal compound or alkylsilyl halide compound, and a polymer having an active metal site; A modified polymer obtained by reaction, and a rubber composition using the modified polymer, particularly a tire.

5. 5. The polymer according to any one of 1 to 4 above, wherein the polymer is a diene (co) polymer using diene as a monomer.
6). 6. The polymer according to 5 above, wherein the polymer is a diene copolymer with an aromatic vinyl compound.
7). 6. The polymer as described in 5 above, wherein the diene is 1,3-butadiene or isoprene.
8). 7. The polymer as described in 6 above, wherein the aromatic vinyl compound is styrene.
9. 9. The polymer according to any one of 1 to 8 above, wherein the Mooney viscosity (100 ° C.) of the polymer is 10 to 150.
10. 10. The polymer according to any one of 1 to 9 above, wherein the polymer has a weight average molecular weight of 50,000 to 500,000.
11. A rubber composition comprising 10 parts by mass or more of the polymer according to any one of 1 to 10 above in 100 parts by mass of all rubber components.
12 The rubber composition as described in 11 above, comprising 10 to 100 parts by mass of a filler with respect to 100 parts by mass of all rubber components.
13. 13. The rubber composition as described in 12 above, wherein the filler contains carbon black and / or silica and is sulfur crosslinkable.
14 A tire comprising the rubber composition according to any one of 11 to 13 above.

  According to the present invention, a modified polymer that enhances the interaction with carbon black and silica and is excellent in low heat build-up, breakability, and wear resistance, and a carbon black and / or silica-containing rubber composition using the modified polymer and Tires can be provided.

  In the present invention, the above polymer is preferably a diene (co) polymer using diene as a monomer. Examples of the diene include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 2-phenyl-1,3-butadiene, 1,3-hexadiene, and the like. These may be used singly or in combination of two or more, and among them, 1,3-butadiene or isoprene is particularly preferable. Moreover, it is also preferable that the above-mentioned polymer is a diene copolymer with an aromatic vinyl compound. 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. These may be used alone or in combination of two or more, but among these, styrene is particularly preferred.

  The Mooney viscosity (100 ° C.) of the above polymer is preferably 10 to 150, and the weight average molecular weight is preferably 50,000 to 500,000. If the Mooney viscosity is less than 10 or the weight average molecular weight is less than 50,000, rubber properties such as fracture properties are deteriorated. On the other hand, if the Mooney viscosity exceeds 150 or the weight average molecular weight exceeds 500,000, workability is improved. It is because it becomes difficult to knead with a compounding agent badly.

The modifying agent used for modifying the polymer of the present invention is represented by the compound of the general formula (1), the compound of the general formula (2), or the general formula (3) or the general formula (4). The compound (6) obtained by reacting the compound with the compound represented by the general formula (5) is included. Among these, the compound of general formula (1) or the compound of general formula (2) is 0.1 to the compound of general formula (3) or the compound of general formula (4) heated to a temperature of 80 to 220 ° C. It can manufacture by making 10 mol times amount of the compound of General formula (5) react, dripping. The reaction time is about 5 minutes to 5 hours, although depending on the method of dropping and the amount of the compound to be reacted. This reaction usually does not use a reaction solvent when the compound of general formula (3) or the compound of general formula (4) is a liquid, but uses an organic solvent such as chloroform, dioxane, methanol, ethanol as a reaction solvent. May be. In addition, it is preferable to perform this reaction in the atmosphere of the gas which does not contain moisture, such as dry nitrogen and argon, so that a water | moisture content may not mix. When a reaction solvent is used, it is desirable to completely remove the reaction solvent before using it as a modifier.
By the above reaction, for example, when the compound of the general formula (5) has a hydroxyl group or a thiol group at the X ³ site, the reaction product is only the compound of the general formula (1) or the compound of the general formula (2). As a by-product, a dimer of the compound represented by the general formula (1) or the compound represented by the general formula (2), or a cyclic product formed by reacting a hydroxyl group or thiol group at the X ³ site with an alkoxy group bonded to silicon. These by-products may be separated by known fractionation and purification methods, or may be used for modifying the polymer as a mixture. That is, the compound (6) may be a mixture of a plurality of compounds.

Preferable examples of the compound of the general formula (1) used for the modification of the polymer of the present invention include 1- (3-trimethoxysilylpropoxy) -3-imidazol-1-yl-propan-2-ol, 1- (3-Triethoxysilylpropioxy) -3-imidazol-1-yl-propan-2-ol, 1- (3-trimethoxysilylpropoxy) -3- (2-methylimidazol-1-yl) -propane 2-ol, 1- (3-triethoxysilylpropioxy) -3- (2-methylimidazol-1-yl) -propan-2-ol, 1- (3-trimethoxysilylpropioxy) -3- (2-Ethylimidazol-1-yl) -propan-2-ol, 1- (3-triethoxysilylpropoxy) -3- (2-ethylimidazol-1-yl)- Lopan-2-ol, 1- (3-trimethoxysilylpropoxy) -3- (2-ethyl-4-methylimidazol-1-yl) -propan-2-ol, 1- (3-triethoxysilylpropiyl) And (oxy) -3- (2-ethyl-4-methylimidazol-1-yl) -propan-2-ol. In particular, 1- (3-trimethoxysilylpropioxy) -3-imidazol-1-yl-propan-2-ol or 1- (3-triethoxysilylpropoxy) -3-imidazol-1-yl-propane- 2-ol is preferred.
Moreover, as a suitable example of the compound of General formula (2) used for modification | denaturation of this invention polymer, 1- (3-trimethoxysilyl propoxy) -3-benzimidazol-1-yl-propan-2-ol is preferable. 1- (3-triethoxysilylpropioxy) -3-benzimidazol-1-yl-propan-2-ol, 1- (3-trimethoxysilylpropoxy) -3- (2-methylbenzimidazole-1 -Yl) -propan-2-ol, 1- (3-triethoxysilylpropioxy) -3- (2-methylbenzimidazol-1-yl) -propan-2-ol, 1- (3-trimethoxysilyl) Propioxy) -3- (2-ethylbenzimidazol-1-yl) -propan-2-ol, 1- (3-triethoxysilylpropioxy) -3- (2 Ethylbenzimidazol-1-yl) -propan-2-ol, 1- (3-trimethoxysilylpropoxy) -3- (2-ethyl-4-methylbenzimidazol-1-yl) -propan-2-ol 1- (3-triethoxysilylpropioxy) -3- (2-ethyl-4-methylbenzimidazol-1-yl) -propan-2-ol and the like. In particular, 1- (3-trimethoxysilylpropoxy) -3-benzimidazol-1-yl-propan-2-ol or 1- (3-triethoxysilylpropoxy) -3-benzimidazol-1-yl- Propan-2-ol is preferred.

Preferable examples of the compound of the general formula (3) used for the synthesis of the compound of the general formula (1) include pyrrole, pyrazole, imidazole, or a hydrogen atom of a carbon-hydrogen bond in these compounds having 1 to 18 carbon atoms. Examples thereof include a compound substituted with a monovalent hydrocarbon group. In particular, imidazole is preferable.
In addition, preferred examples of the compound of the general formula (4) used for the synthesis of the compound of the general formula (2) include indole, isoindole, 1H-indazole, benzindazole and the like. Benzindazole is particularly preferable.
And as a suitable example of the compound of General formula (5) used for the synthesis | combination of the compound of General formula (1) or the compound of General formula (2), (thio) epoxy group containing hydrocarbyl oxysilane compound can be mentioned. Specifically, 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, (2-glycidoxyethyl) methyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- Glycidoxypropyltriethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-Epoxycyclohexyl) ethyl (methyl) dimethoxysilane Beauty epoxy group in these compounds can be mentioned and those obtained by replacing the thioepoxy group. Of these, 3-glycidoxypropyltrimethoxysilane (GPMOS) or 2- (3,4-epoxycyclohexyltrimethoxysilane) is particularly preferable.

  In order to obtain the modified polymer of the present invention, a pre-prepared modifier used in the present invention is a polymer synthesized by anionic polymerization or a cis content obtained by using a rare earth catalyst or the like by coordination polymerization. It is necessary to react with the polymerization active site of a high conjugated diene polymer.

First, the case of anionic polymerization will be described.
When the modifier used in the present invention does not have a protic functional group such as a hydroxyl group, the active terminal, which is the polymerization active site of the polymer, reacts directly with the modifier, so that the modifier is directly introduced into the reaction system. What is necessary is just to introduce.

However, when the modifier used in the present invention has a protic functional group, active protons (active hydrogen) in the protic functional group are extracted by the active site of the polymer, so The functional group cannot be introduced as it is. Therefore, as a pretreatment, a protic functional group-containing modifier is reacted with an organic alkali metal or alkaline earth metal compound, and active protons in the protic functional group are alkylated or alkyl earthed (alkylated). Metal or alkyl earth metal).
In anionic polymerization, the active terminal of a normal polymer does not react with the proton functional group alkylated or alkyl earth metalized by the above pretreatment, and the alkoxy group in the modifier used in the present invention. To produce an intermediate modified product. This intermediate modified product is finally modified by removing lithium from the lithiated site and regenerating active protons. Such regeneration of active protons can be easily performed by treating with, for example, alcohol or water. At the same time, the active protons are regenerated in the intermediate modified polymer in the normal solvent removal and steam stripping steps in the drying process. be able to.

  Examples of the above-mentioned protic functional group include a hydroxyl group and a thiol group. Examples of the modifier having a protic functional group used in the present invention include 1- (3-trimethoxysilylpropoxy) -3-imidazol-1-yl-propan-2-ol. It is done. In addition, as the organic alkali metal compound or alkaline earth metal compound used for alkyl metallization or alkyl earth metallization, the same kind of polymerization initiator used for the polymerization of ordinary diene polymers is used. Organolithium compounds are preferred. As examples of the organic lithium compound, hydrocarbyl lithium and lithium amide compounds are preferably used. 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 lithium. , Phenyl lithium, 2-naphthyl lithium, 2-butyl-phenyl lithium, 4-phenyl-butyl lithium, cyclohexyl lithium, cyclopentyl lithium, reaction products of diisopropenylbenzene and butyl lithium, and the like. And n-butyllithium is preferred. On the other hand, as the lithium amide compound, for example, lithium hexamethylene imide, lithium pyrrolidide, lithium piperidide, lithium heptamethylene imide, lithium dodecamethylene imide, lithium dimethyl amide, lithium diethyl amide, lithium dibutyl amide, lithium dipropyl amide, lithium Diheptylamide, lithium dihexylamide, lithium dioctylamide, lithium di-2-ethylhexylamide, lithium didecylamide, lithium-N-methylpiperazide, lithium ethylpropylamide, lithium ethylbutyramide, lithium methylbutyramide, lithium ethylbenzylamide, Examples include lithium methyl phenethyl amide.

  There is no particular limitation on the method for producing the polymer having an organometallic type active site in the molecule, and any of solution polymerization method, gas phase polymerization method and bulk polymerization method can be used. A polymerization method is preferred. Moreover, any of a batch type and a continuous type may be sufficient as the superposition | polymerization form.

Next, the case of coordination polymerization using a rare earth catalyst or the like will be described.
In coordination polymerization using a rare earth catalyst or the like, after the primary modification in which a hydrocarbyloxysilane compound or the like is reacted with the active terminal of the polymer, the modifier used in the present invention is preferably present in the presence of a condensation accelerator. It is preferable to perform secondary modification to condense.

The hydrocarbyloxysilane compound used in the primary modification is preferably a (thio) epoxy group-containing or imine group-containing hydrocarbyloxysilane compound.
Examples of (thio) epoxy group-containing hydrocarbyloxysilane compounds include 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, (2-glycidoxyethyl) methyldimethoxysilane, and 3-glycidoxy. Propyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxy Preferred examples include (cyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane, and those obtained by replacing the epoxy group in these compounds with a thioepoxy group. Especially 3-glycid Shi trimethoxysilane (GPMOS) and 2- (3,4-epoxycyclohexyl trimethoxysilane is preferred.
Further, as the imine group-containing hydrocarbyloxysilane compound, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N- (1-methylethylidene) -3- (triethoxy Silyl) -1-propanamine, N-ethylidene-3- (triethoxysilyl) -1-propanamine, N- (1-methylpropylidene) -3- (triethoxysilyl) -1-propanamine, N- (4-N, N-dimethylaminobenzylidene) -3- (triethoxysilyl) -1-propanamine, N- (cyclohexylidene) -3- (triethoxysilyl) -1-propanamine and their triethoxy Trimethoxysilyl compounds corresponding to silyl compounds, methyldiethoxysilyl compounds, ethyldiethoxysilyl compounds, Preferred examples include tildimethoxysilyl compounds and ethyldimethoxysilyl compounds, among which N- (1-methylpropylidene) -3- (triethoxysilyl) -1-propanamine and N- ( 1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine is preferred.
Furthermore, the following can be mentioned as another hydrocarbyloxy compound. That is, as the imine (amidine) group-containing compound, 1- [3- (triethoxysilyl) propyl] -4,5-dihydroimidazole, 1- [3- (trimethoxysilyl) propyl] -4,5-dihydro Examples thereof include imidazole and 3- [10- (triethoxysilyl) decyl] -4-oxazoline. Among them, 3- (1-hexamethyleneimino) propyl (triethoxy) silane, (1-hexa Methyleneimino) methyl (trimethoxy) silane, 1- [3- (triethoxysilyl) propyl] -4,5-dihydroimidazole and 1- [3- (trimethoxysilyl) propyl] -4,5-dihydroimidazole are preferred Can be mentioned. N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole, N- (3-isopropoxysilylpropyl) -4,5-dihydroimidazole, N- (3-methyldiethoxysilylpropyl)- 4,5-dihydroimidazole and the like can be mentioned, among which N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole is preferable.
One of these hydrocarbyloxysilane compounds may be used alone, or two or more thereof may be used in combination. Moreover, the partial condensate of the said hydrocarbyl oxysilane compound can also be used.

Further, as the condensation accelerator used in the secondary modification, a combination of water and a metal compound generally known as a curing catalyst for alkoxy condensation curable room temperature crosslinking (RTV) silicone can be used. For example, a combination of tin carboxylate and / or titanium alkoxide and water can be preferably exemplified. There is no particular limitation on the method of charging the condensation accelerator into the reaction system. A solution of an organic solvent compatible with water such as alcohol may be used, or water may be directly injected, dispersed, or dissolved in the hydrocarbon solution using various chemical engineering techniques.
The condensation accelerator is preferably composed of at least one selected from the group consisting of metal compounds represented by the following (1) to (3) and water.
(1) Oxidation number 2 tin C 3-30 carboxylate
Sn (OCOR ¹⁴ ) ₂
[Wherein, R ¹⁴ is an organic group having 2 to 19 carbon atoms, and when there are a plurality of them, they may be the same or different. ]
(2) Tin compound having an oxidation number of 4 satisfying the following general formula
R ¹⁵ _r SnB ⁴ _t C ¹ _(4-tr)
[Wherein, r is an integer of 1 to 3, t is an integer of 1 or 2, and t + r is an integer of 3 or 4. R ¹⁵ is an aliphatic hydrocarbon group having 1 to 30 carbon atoms, and C ¹ is a hydroxyl group or a halogen. B ⁴ is (i) a carboxyl group having 2 to 30 carbon atoms, (ii) an α, γ-dionyl group having 5 to 30 carbon atoms, (iii) a hydrocarbyloxy group having 3 to 30 carbon atoms, and (iv) carbon. a group selected from the total trisubstituted (may be the same or different) has been siloxy group from hydrocarbyl groups and / or 1 carbon atoms of from C 1 20 hydrocarbyloxy group 20, if B ⁴ there are multiple It may be the same or different. ]
(3) Titanium compound with oxidation number 4 that satisfies the following general formula
B ⁵ xTiC ² _(4-x)
[Wherein x is an integer of 2 or 4. B ⁵ is (i) a siloxy group having a total of three substituents with an alkoxy group having 3 to 30 carbon atoms, (ii) an alkyl group having 1 to 30 carbon atoms and / or an alkoxy group having 1 to 20 carbon atoms, ^When there are a plurality of 5s, they may be the same or different. C ² is an α, γ-dionyl group having 5 to 30 carbon atoms. ]

Specific examples of the tin carboxylate include (1) a divalent tin dicarboxylate (particularly preferably a carboxylate having 8 to 20 carbon atoms) and (2) a tetravalent dihydrocarbyltin. Dicarboxylate [including bis (hydrocarbyl dicarboxylic acid) salt], bis (α, γ-diketonate), alkoxy halide, monocarboxylate hydroxide, alkoxy (trihydrocarbyl siloxide), alkoxy (dihydrocarbyl alkoxysiloxide) ), Bis (trihydrocarbylsiloxide), bis (dihydrocarbylalkoxysiloxide) and the like can be suitably used. The hydrocarbyl group directly bonded to tin preferably has 4 or more carbon atoms, particularly preferably 4 to 8 carbon atoms.
Examples of the titanium compound include tetraalkoxides of titanium having an oxidation number of 4, dialkoxybis (α, γ-diketonate), tetrakis (trihydrocarboxysiloxide), and tetraalkoxides are particularly preferably used. .
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 be used effectively.
These two agents forming the condensation accelerator may be added separately to the reaction system or mixed immediately before use as a mixture, but it is not preferable because the mixture will be decomposed if stored for a long period of time. .

  The amount of the condensation accelerator used is preferably 0.05 or more in terms of the molar ratio of the metal of the metal compound and the water effective for the reaction to the modifier used in the present invention present in the reaction system. The upper limit varies depending on the purpose and reaction conditions, but it is preferable that effective water having a molar ratio of about 0.5-3 to the total amount of hydrocarboxysilyl groups bonded to the polymer terminal in the stage before the condensation treatment is present. . Although the molar ratio of the metal of the metal compound and water effective for the reaction varies depending on the required reaction conditions, about 1 / 0.5-1 / 20 is preferable.

For the primary modification and the secondary modification in the present invention, both a solution reaction and a solid phase reaction can be used, but a solution reaction (a solution containing an unreacted monomer used during polymerization may be suitable). . Moreover, there is no restriction | limiting in particular about the form of this modification | denaturation reaction, You may carry out using a batch type reactor, You may carry out by a continuous type using apparatuses, such as a multistage continuous type reactor and an in-line mixer. In addition, it is important to carry out the modification reaction after completion of the polymerization reaction and before performing various operations necessary for solvent removal treatment, water treatment, heat treatment, polymer isolation, and the like.
As the temperature of the modification reaction, the polymerization temperature of the conjugated diene polymer can be used as it is. Specifically, a preferable range is 20 to 100 ° C. If the temperature is low, the viscosity of the polymer tends to increase, and if the temperature is high, the polymerization active terminal tends to be deactivated.

  In coordination polymerization using a rare earth catalyst or the like, as described above, after the primary modification in which a hydrocarbyloxysilane compound is reacted with the active terminal of the polymer, it is preferably used in the present invention in the presence of a condensation accelerator. It can be suitably modified by a method of performing secondary modification by condensing the modifying agent.

As a polymerization catalyst in coordination polymerization using a rare earth catalyst or the like, a known catalyst can be used, but it is formed by combining at least one compound selected from each of the following components (A), (B), and (C). Those are preferred. That is,
(A) Component A rare earth compound selected from the following (A1) to (A4), which may be used as it is as an inert organic solvent solution or supported on an inert solid (A1) rare earth with an oxidation number of 3 The compound is freely selected from a carboxyl group having 2 to 30 carbon atoms, an alkoxy group having 2 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, and an α, γ-diketonyl group having 5 to 30 carbon atoms. Or a Lewis base compound (especially free carboxylic acid, free alcohol, α, γ-diketone, cyclic ether, linear ether, trihydrocarbylphosphine, trihydrocarbyl phosphite, etc.) Complex compound). Specifically, there are neodymium tri-2-ethylhexanoate, a complex compound thereof with acetylacetone, neodymium trineodecanoate, a complex compound thereof with acetylacetone, neodymium tri-n-butoxide and the like.
(A2) A complex compound of a rare earth trihalide and a Lewis base. For example, there is a THF complex of neodymium trichloride.
(A3) An organic rare earth compound having an oxidation number of 3 in which at least one (substituted) allyl group is directly bonded to a rare earth atom. For example, there is a salt of tetraallyl neodymium and lithium.
(A4) An organic rare earth compound having an oxidation number of 2 or 3 in which at least one (substituted) cyclopentadienyl group is directly bonded to a rare earth atom, or this compound, a trialkylaluminum or a non-coordinating anion and a counter cation It is a reaction product with an ionic compound. An example is dimethylaluminum (μ-dimethyl) bis (pentamethylcyclopentadienyl) samarium.
As the rare earth element of the rare earth compound, lanthanum, neodymium, praseodymium, samarium and cadmium are preferable, and lanthanum, neodymium and samarium are more preferable.
Among the components (A), neodymium carboxylates and samarium substituted cyclopentadienyl compounds are preferred.

(B) Component At least one kind of organoaluminum compound selected from the following can be used at the same time.
(B1) Trihydrocarbylaluminum compound represented by the formula R ¹⁶ ₃ Al (wherein R ¹⁶ is a hydrocarbon group having 1 to 30 carbon atoms, which may be the same or different from each other)
(B2) Hydrocarbyl aluminum hydride represented by the formula R ¹⁷ ₂ AlH or R ¹⁷ AlH ₂ (wherein R ¹⁷ is a hydrocarbon group having 1 to 30 carbon atoms and may be the same or different from each other)
(B3) A hydrocarbylaluminoxane compound having a hydrocarbon group having 1 to 30 carbon atoms.
Examples of the component (B) include trialkylaluminum, dialkylaluminum hydride, alkylaluminum dihydride, and alkylaluminoxane. These compounds may be used as a mixture. In (B) component, combined use with an aluminoxane and another organoaluminum compound is preferable.

Component (C) A compound selected from the following, but is not necessarily required when (A) contains a halogen or a non-coordinating anion, and (B) contains an aluminoxane.
(C1) A group II, III, or IV inorganic or organic compound having a hydrolyzable halogen or a complex compound of these with a Lewis base. For example, alkyl aluminum dichloride, dialkyl aluminum chloride, silicon tetrachloride, tin tetrachloride, complexes of zinc chloride with Lewis bases such as alcohol, magnesium chloride and Lewis bases such as alcohol.
(C2) An organic halide having a structure selected from at least one tertiary alkyl halide, benzyl halide, and allyl halide. For example, benzyl chloride, t-butyl chloride, benzyl bromide, t-butyl bromide and the like.
(C3) A zinc halide or a complex compound of this with a Lewis base.
(C4) An ionic compound comprising a non-coordinating anion and a counter cation. For example, triphenylcarbonium tetrakis (pentafluorophenyl) borate is preferably used.

For the preparation of the catalyst, in addition to the components (A), (B), and (C), the same conjugated diene and / or non-conjugated diene monomer as the polymerization monomer may be used as necessary. Good.
In addition, part or all of the component (A) or the component (C) may be supported on an inert solid and used, and in this case, so-called gas phase polymerization can be performed.
The amount of the catalyst used can be set as appropriate. Usually, the component (A) is 0.001 to 0.5 mmol per 100 grams of monomer. Moreover, (B) component / (A) component is 5-1000 and (C) component / (A) component is 0.5-10 by molar ratio.

  Examples of the solvent used in the case of solution polymerization include organic solvents inert to the reaction, for example, hydrocarbon solvents such as aliphatic, alicyclic, and aromatic hydrocarbon compounds. Specifically, those having 3 to 8 carbon atoms are preferable, for example, 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.

In the present invention, the modified polymer obtained as described above, when blended with carbon black, can greatly increase its dispersibility and reinforcing properties due to hydrogen bonding with functional groups on the surface of carbon black. it can. Moreover, since it usually has a hydrocarbyloxysilane compound residue, it has a high affinity with silica at the same time.
Therefore, when the modified polymer in the present invention is applied to a carbon black and / or silica compounded rubber composition, the interaction with the carbon black and / or silica is enhanced, and low exothermic property, fracture characteristics and A modified polymer capable of improving wear resistance and exhibiting good workability, and a rubber composition and tire using the same can be obtained.

Next, the rubber composition of the present invention contains the above-mentioned modified polymer. Usually, a rubber component containing at least 10% by mass of the modified polymer and 100 parts by mass of silica and / or carbon black. A rubber composition containing 10 to 100 parts by mass is preferred. The rubber composition is preferably sulfur crosslinkable.
This modified polymer may be used alone or in combination of two or more. The rubber component used in combination with the modified polymer includes natural rubber and diene synthetic rubber. Examples of the diene synthetic rubber include styrene-butadiene copolymer (SBR), polybutadiene (BR), poly Examples include isoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, and mixtures thereof. Further, a part thereof may have a branched structure by using a polyfunctional modifier, for example, a modifier such as tin tetrachloride.

As said carbon black, arbitrary things can be selected and used from what is conventionally used as a reinforcing filler of rubber | gum. For example, FEF, SRF, HAF, ISAF, SAF and the like can be mentioned. The iodine adsorption amount (IA) is 40 mg / g or more, particularly 60 mg / g or more, the nitrogen adsorption specific surface area (N ₂ SA) is 40 m ² / g or more, particularly 60 m ² / g or more, and dibutyl phthalate Carbon black having an oil absorption (DBP: Method A) of 70 mL (milliliter) / 100 g or more, particularly 80 mL (milliliter) / 100 g or more is preferable. By using this carbon black, the effect of improving various physical properties is increased, but HAF, ISAF, and SAF, which are excellent in wear resistance, are particularly preferable.
There is no restriction | limiting in particular as said silica, It can select arbitrarily from what was conventionally used as a filler for reinforcement of rubber conventionally, and can be used.
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 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. Examples of the silane coupling agent include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, and bis (2-triethoxy). Silylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyl Trimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N, N-dimethylthioca Bamoylchitrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazole tetrasulfide, 3-triethoxysilylpropylbenzothiazolyl tetrasulfide, 3-triethoxy Silylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyltetra Sulfide, dimethoxymethylsilylpropyl benzothiazole tetrasulfide, etc. are mentioned, but from these points, such as reinforcing effect improvement effect, Scan (3-triethoxysilylpropyl) tetrasulfide and 3-trimethoxysilylpropyl benzothiazolyl tetrasulfide are preferable. These silane coupling agents may be used singly or in combination of two or more.

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.
In the rubber composition of the present invention, various chemicals usually used in the rubber industry, for example, a vulcanizing agent such as sulfur, a vulcanization accelerator, a process oil, an aging, are used as long as the object of the present invention is not impaired. An inhibitor, a scorch inhibitor, zinc white, stearic acid and the like can be contained.

The rubber composition of the present invention is obtained by kneading using a kneading machine such as a roll or an internal mixer, and is vulcanized after molding, starting with tire applications, anti-vibration rubber, belt, hose. It can also be used for other industrial products. In particular, it is suitably used as tire rubber, and can be applied to all tire members such as tread rubber (including cap rubber and base rubber), side rubber, ply rubber, and bead filler rubber.
In the present invention, a tire using a rubber composition has good fuel efficiency, particularly excellent fracture characteristics and wear resistance, and the processability of the rubber composition is good. Also excellent.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
The physical properties of the polymer and the vulcanized rubber composition were measured according to the following methods.

<Physical properties of polymer>
The Mooney viscosity of the (modified) polymer was measured at 100 ° C. using an RLM-01 type tester manufactured by Toyo Seiki Co., Ltd. The weight average molecular weight (Mw) of the (modified) polymer was measured by gel permeation chromatography [GPC: HLC-8020 manufactured by Tosoh Corporation, column: GMH-XL manufactured by Tosoh Corporation (two in series)]. The measurement was performed in terms of polystyrene using a monodisperse polystyrene as a standard using a differential refractive index (RI).

<Physical properties of vulcanized rubber composition>
(1) Low exothermic property Using a viscoelasticity measuring device (manufactured by Rheometrics), tan δ (50 ° C.) was measured at a temperature of 50 ° C., a strain of 10%, and a frequency of 15 Hz. The smaller tan δ (50 ° C.), the lower the heat generation.
(2) Fracture characteristics (tensile strength)
The strength (Tb) at the time of cutting was measured according to JIS K6301-1995.
(3) Abrasion resistance Using a Ramborn type abrasion tester, the amount of wear at a slip rate of 60% at room temperature was measured, and the abrasion resistance of Comparative Examples 1, 5, 7 and 9 was shown as an index. The larger the index, the better.

Production Example 1 Production of modifier (compound of general formula (1)) 3.4 g (0.05 mol) of imidazole was melted at 95 ° C. and stirred under an argon atmosphere while 3-glycidoxypropyltrimethoxysilane 11 0.8 g (0.05 mol) was added dropwise over 30 minutes. After completion of the dropwise addition, the reaction was further carried out at 95 ° C. for 1 hour. This reaction product A was obtained as a dark brown viscous liquid. When used for the modification reaction of anionic polymerization, 5 g of this reaction product A is dissolved in 18 mL of cyclohexane, and 10 mL of n-butyllithium (1.6 N hexane solution) is added and stirred sufficiently immediately before use for the modification reaction. Agent solution A was obtained.

Production Example 2 Production of Compound (Compound of General Formula (2)) 5.9 g (0.05 mol) of benzimidazole was dissolved in 15 mL of 1,4-dioxane and heated to reflux at 120 ° C. To this solution, 11.8 g (0.05 mol) of 3-glycidoxypropyltrimethoxysilane was added dropwise over 30 minutes while stirring under an argon atmosphere. After completion of the dropwise addition, the reaction was further continued at a temperature of 120 ° C. for 1 hour, and then the solvent was distilled off using a rotary evaporator. This reaction product B was obtained as a dark brown viscous liquid. When used for the modification reaction of anionic polymerization, 5 g of this reaction product B is dissolved in 14 mL of cyclohexane, and 8.8 mL of n-butyllithium (1.6 N hexane solution) is added and stirred thoroughly immediately before use for the modification reaction. Thus, a denaturant solution B was obtained.

Example 1
Into a dried and nitrogen-substituted 800 mL pressure-resistant glass container, a butadiene cyclohexane solution (16%) and a styrene cyclohexane solution (21%) are poured into a butadiene monomer 40 g and a styrene monomer 10 g, After injecting 0.24 mmol (mmol) of 2,2-ditetrahydrofurylpropane and adding 0.48 mmol of n-butyllithium (nBuLi), polymerization was performed in a hot water bath at 50 ° C. for 1.5 hours. . The polymerization conversion was almost 100%. After adding 0.96 mL of the modifier solution A to this polymerization system, a modification reaction was further performed at 50 ° C. for 30 minutes. To this polymerization system, 0.5 mL of a 5 mass% solution of 2,6-di-t-butyl-p-cresol (BHT) in isopropanol was added to stop the reaction. Then, the polymer A was obtained by drying according to a conventional method.

Example 2
In the production of the polymer A, a polymer B was obtained in the same manner except that 0.96 mL of the modifier solution B was added instead of the modifier solution A.

Comparative Example 1
In the production of polymer A, polymer C was obtained in the same manner except that 0.09 mmol of tin tetrachloride was added in place of the modifier solution A.

Comparative Example 2
In the production of the polymer A, a polymer D was obtained in the same manner except that 0.44 mmol of tetraethoxysilane was added instead of the modifier solution A.

Examples 3-6, Comparative Examples 3-6
The Mooney viscosity and weight average molecular weight of the modified SBRs (A) to (D) of Examples 1 and 2 and Comparative Examples 1 and 2 were measured by the above-described method, and the formulation shown in Table 1 was used for the examples. The carbon black compounded rubber compositions of Nos. 3 and 4 and Comparative Examples 3 and 4 were prepared, and low heat build-up, fracture characteristics, and abrasion resistance were measured by the above-described methods.
Furthermore, the silica compounded rubber compositions of Examples 5 and 6 and Comparative Examples 5 and 6 were prepared according to the formulation shown in Table 2. Similarly, the low exothermic property, fracture characteristics, and wear resistance were obtained by the above-described method. It was measured.
These results are shown in Table 3.

The scientific names or trade names of carbon black, silica, and organic chemicals used in Tables 1 and 2 are shown below.
Carbon black: Tokai Carbon Co., Ltd. Trademark: Seast KH (N339)
Silica: Nippon Silica Kogyo Co., Ltd. Trademark: Nipsil AQ
Coupling agent: Degussa silane coupling agent, trademark: Si69
Anti-aging agent 6C: N- (1,3-dimethyl-butyl) -N′-phenyl-p-phenylenediamine vulcanization accelerator DPG: Diphenylguanidine vulcanization accelerator DM: Mercaptobenzothiazyl disulfide vulcanization accelerator NS: Nt-butyl-2-benzothiazylsulfenamide

Production Example 3 Production of Catalyst Solution C In a dry, nitrogen-substituted 100 mL pressure-resistant glass container, 7.11 g of a butadiene cyclohexane solution (butadiene concentration: 15.2% by mass) and a cyclohexane solution of neodymium neodecanate (neodymium) were sequentially added. Concentration: 0.56 mol / L) 0.59 mL, Methylaluminoxane (MAO) (PMAO manufactured by Tosoh Finechem) in toluene solution (aluminum concentration: 3.23 mol / L) 10.32 mL, Diisobutylaluminum hexane solution (0. 90 mol / L) (Kanto Chemical Co., Inc.) 7.77 mL was added, and after aging at room temperature for 2 minutes, hexane solution of diethylaluminum chloride (0.95 mol / L) (Kanto Chemical Co., Ltd.) 1.45 mL was added. Aged for 15 minutes with occasional stirring. The neodymium concentration in the catalyst solution C thus obtained was 0.011 mol / L.

Example 7
To a 800 mL pressure-resistant glass container that has been dried and purged with nitrogen, a cyclohexane solution of 1,3-butadiene is added so that 1,3-butadiene becomes 50 g, and 2.28 mL (0.025 mmol in terms of neodymium) of catalyst solution C is added. Then, polymerization was carried out at 50 ° C. for 1.0 hour. The polymerization conversion at this time was almost 100%. Next, after adding 0.59 mmol of 3-glycidoxypropyltrimethoxysilane to the polymerization reaction system, a primary modification reaction was performed at 50 ° C. for 30 minutes. Thereafter, 179 mg of reaction product A, 1.76 mmol of bis (2-ethylhexanoate) tin and 1.76 mmol of water were further added, and then a second modification reaction was performed at 50 ° C. for 60 minutes. Thereafter, 0.5 mL of a 5% by mass solution of 2,6-di-t-butyl-p-cresol (BHT) in isopropanol is added to the polymerization reaction system to stop the polymerization reaction, and further, an isopropanol solution containing a trace amount of BHT. After reprecipitation in the medium, the polymer E was dried by a conventional method.

Example 8
In the production of polymer E, polymer F was obtained in the same manner except that 208 mg of reaction product B was added instead of reaction product A.

Comparative Example 7
In the production of polymer E, polymer G was obtained in the same manner except that reaction product A was not added.

Examples 9-12, Comparative Examples 8-9
The Mooney viscosity and weight average molecular weight of the modified BR (E) and (F) of Examples 7 and 8 and the modified BR (G) of Comparative Example 7 were measured by the above-mentioned methods, and the formulation shown in Table 4 Thus, carbon black compounded rubber compositions of Examples 9 and 10 and Comparative Example 8 were prepared, and low heat build-up, fracture characteristics, and wear resistance were measured by the above-described methods.
Furthermore, the silica compounded rubber compositions of Examples 11 and 12 and Comparative Example 9 were prepared according to the formulation shown in Table 5, and similarly, the low exothermic property, fracture characteristics, and wear resistance were measured by the above-described methods. . In addition, carbon black HAF in Table 4 was manufactured by Tokai Carbon Co., Ltd., trademark: Siest 3. The other compounding agents are the same as those in Tables 1 and 2.
These results are shown in Table 6.

  As is apparent from Tables 3 and 6, the modified (co) polymer of the present invention is an anionic polymerization or a coordination polymerization, and in the carbon black compounded rubber composition and the silica compounded rubber composition, Low heat generation, fracture characteristics and wear resistance are improved in a well-balanced manner. The tire for passenger cars using the rubber composition of Examples 3 to 6 using the modified SBR copolymer (A) or (B) of the present invention as a tread rubber has not only improved wear resistance but also low heat build-up. Therefore, rolling resistance was improved, and appearance characteristics were excellent due to good fracture characteristics. Further, radial tires for trucks and buses and tires for passenger cars using the rubber compositions of Examples 9 to 12 using the modified BR polymer (E) or (F) of the present invention as tread rubber have improved wear resistance. In addition, the rolling resistance was improved due to the low exothermic property, and the appearance performance was excellent due to the good fracture characteristics. Furthermore, passenger car tires using the rubber compositions of Examples 9 to 12 using the modified BR copolymer (E) or (F) of the present invention as side wall rubber have excellent fracture characteristics and good side appearance. Met.

  The rubber composition using the modified polymer of the present invention is not only suitably used for each member such as a tread, side wall, and bead rubber of a radial tire for passenger cars, a radial tire for trucks and buses, or other tires, but also a belt. It is also suitably used for various industrial rubber products such as conveyors.

Claims (13)

The following general formula (3)

[Wherein, A ¹ or A ² represents a nitrogen atom or C—R ¹³ , and R ¹ , R ^2, or R ¹³ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. ]
Or the following general formula (4)

[Wherein, A ³ or A ⁴ represents a nitrogen atom or C—R ¹³ , and R ⁵ , R ⁶ , R ⁷ , R ⁸ or R ¹³ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. ]
A compound represented by the following general formula (5)

[Wherein, A ⁵ represents an oxygen atom or a sulfur atom, R ¹¹ or R ¹² represents a hydrocarbon group having 1 to 18 carbon atoms, and X ³ represents a hydrocarbon group having 1 to 11 carbon atoms, It may contain an ether structure or a thioether structure. n is an integer of 1 to 3. ] The modified polymer obtained by making the compound (6) obtained by making it react with the compound shown by reacting with the polymer which has an active metal part. After the primary modification in which a hydrocarbyloxysilane compound is reacted with an active metal site of the polymer, the following general formula (1)

[Wherein, A ¹ or A ² represents a nitrogen atom or C—R ¹³ , R ¹ , R ² or R ¹³ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and R ³ or R ⁴ represents A hydrocarbon group having 1 to 18 carbon atoms, wherein X ¹ is a hydrocarbon group having 1 to 11 carbon atoms, and includes an ether structure, a thioether structure, a hydroxyl group, a thiol group, or an alkali metal compound thereof, an alkali An earth metal compound or an alkylsilyl compound may be contained. n is an integer of 1 to 3. ]
Or the following general formula (2)

[Wherein A ³ or A ⁴ represents a nitrogen atom or C—R ¹³ ; R ⁵ , R ⁶ , R ⁷ , R ⁸ or R ¹³ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms; R ⁹ or R ¹⁰ represents a hydrocarbon group having 1 to 18 carbon atoms, X ² is a hydrocarbon group having 1 to 11 carbon atoms, and in the group, an ether structure, a thioether structure, a hydroxyl group, a thiol group or the like An alkali metal compound, an alkaline earth metal compound or an alkylsilyl compound may be contained. n is an integer of 1 to 3. ]
Or a compound represented by
The following general formula (3)

[Wherein, A ¹ or A ² represents a nitrogen atom or C—R ¹³ , and R ¹ , R ^2, or R ¹³ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. ]
Or the following general formula (4)

[Wherein, A ³ or A ⁴ represents a nitrogen atom or C—R ¹³ , and R ⁵ , R ⁶ , R ⁷ , R ⁸ or R ¹³ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. ]
A compound represented by the following general formula (5)

[Wherein, A ⁵ represents an oxygen atom or a sulfur atom, R ¹¹ or R ¹² represents a hydrocarbon group having 1 to 18 carbon atoms, and X ³ represents a hydrocarbon group having 1 to 11 carbon atoms, It may contain an ether structure or a thioether structure. n is an integer of 1 to 3. ] The modified polymer obtained by performing the secondary modification | denaturation which condenses the compound (6) obtained by making it react with the compound shown by this. The following general formula (3)

[Wherein, A ¹ or A ² represents a nitrogen atom or C—R ¹³ , and R ¹ , R ^2, or R ¹³ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. ]
Or the following general formula (4)

[Wherein, A ³ or A ⁴ represents a nitrogen atom or C—R ¹³ , and R ⁵ , R ⁶ , R ⁷ , R ⁸ or R ¹³ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. ]
A compound represented by the following general formula (5)

[Wherein, A ⁵ represents an oxygen atom or a sulfur atom, R ¹¹ or R ¹² represents a hydrocarbon group having 1 to 18 carbon atoms, and X ³ represents a hydrocarbon group having 1 to 11 carbon atoms, It may contain an ether structure or a thioether structure. n is an integer of 1 to 3. A compound obtained by reacting a compound (6) obtained by reacting with a compound represented by formula (I) and an organic alkali metal compound, organic alkaline earth metal compound or alkylsilyl halide compound, and a polymer having an active metal site; A modified polymer obtained by reaction. The polymer according to any one of claims 1 to 3 , wherein the polymer is a diene (co) polymer using diene as a monomer. The polymer according to claim 4 , wherein the polymer is a diene copolymer with an aromatic vinyl compound. The polymer according to claim 4 , wherein the diene is 1,3-butadiene or isoprene. The polymer according to claim 5 , wherein the aromatic vinyl compound is styrene. Polymer according to any one of claims 1 to 7, wherein the Mooney viscosity of the polymer (100 ° C.) is characterized in that 10 to 150. The polymer according to any one of claims 1 to 8 , wherein the polymer has a weight average molecular weight of 50,000 to 500,000. A rubber composition comprising 10 parts by mass or more of the polymer according to any one of claims 1 to 9 in 100 parts by mass of all rubber components. The rubber composition according to claim 10 , comprising 10 to 100 parts by mass of a filler with respect to 100 parts by mass of all rubber components. The rubber composition according to claim 11 , wherein the filler contains carbon black and / or silica and is sulfur crosslinkable. A tire comprising the rubber composition according to any one of claims 10 to 12 .