JP2010121086A - Method of producing modified conjugated diene-based polymer, modified conjugated diene-based polymer and rubber composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of producing a modified conjugated diene-based polymer capable of producing rubber products excellent in low exothermic property, low temperature characteristics, abrasion resistance and the like without damaging processibility. <P>SOLUTION: The method of producing a modified conjugated diene-based polymer comprises a step of introducing a first alkoxysilyl group into an active terminal of a first conjugated diene-based polymer having <10% vinyl content, ≥75% cis 1,4-bond content and 250,000-800,000 weight-average molecular weight (Mw) and then condensing the material to obtain component (A), separately a step for introducing a second alkoxysilyl group into an active terminal of a second conjugated diene-based polymer having <10% vinyl content, ≥75% cis 1,4-bond content and 10,000-150,000 weight-average molecular weight (Mw) and then condensing the material to obtain component (B) and a step of mixing the (A) component and the (B) component. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing a modified conjugated diene polymer, a modified conjugated diene polymer, and a rubber composition. The present invention relates to a method for producing a modified conjugated diene polymer capable of producing an excellent rubber product, a modified conjugated diene polymer produced by this production method, and a rubber composition.

  In recent years, in connection with social demands for energy saving, demands for lower fuel consumption of automobiles are becoming more severe. In order to meet such demands, further reduction in rolling resistance is also demanded for tire performance. As a method for reducing the rolling resistance of the tire, there is a method of optimizing the tire structure, but the method using a material with less heat generation as the rubber composition is the most common.

  In order to obtain such a rubber composition with less exothermic property, silica is included as a filler. However, since the interaction between the rubber composition and silica is usually weak, there is a problem that a large amount of filler must be used in order to produce a material having desired properties.

  As a rubber composition that solves this problem, a functional group that interacts with a filler is used for the polymerization active terminal of a conjugated diene polymer obtained by anionic polymerization of a conjugated diene compound using an organolithium compound as a polymerization initiator. A rubber composition containing a modified conjugated diene polymer modified with an alkoxysilane derivative has been proposed.

  However, there are few examples of applying a rubber composition containing a modified conjugated diene polymer having a cis 1,4-polybutadiene structure, which is particularly important for tire sidewall rubber and tread rubber. Further, the modification effect in the rubber composition containing silica is not always sufficient. In particular, a rubber composition containing a modified conjugated diene polymer having a cis 1,4-polybutadiene structure has almost no modification effect due to the incorporation of silica.

  Therefore, in order to overcome the above disadvantages, by reacting the active terminal of the conjugated diene polymer having a high cis content obtained using the rare earth catalyst with an alkoxysilane derivative having a functional group that interacts with the filler, Attempts to obtain a terminally modified modified conjugated diene polymer and modification with an alkoxysilane derivative have been made (see Patent Documents 1 and 2, for example).

International Publication No. 03/046020 Pamphlet JP 2005-8870 A

  As a method for improving mechanical properties such as abrasion resistance of the rubber composition, there is a method for increasing the molecular weight of the conjugated diene polymer before modification. However, according to this method, an increase in Mooney viscosity cannot be suppressed, and there has been a problem that workability is deteriorated.

  The present invention has been made in view of such problems of the prior art, and the object of the present invention is excellent in low heat generation, low temperature characteristics, wear resistance, etc. without impairing workability. Another object of the present invention is to provide a method for producing a modified conjugated diene polymer capable of producing a rubber product.

  Another object of the present invention is to provide a modified conjugated diene polymer that can produce a rubber product that is excellent in low heat build-up, low temperature characteristics, wear resistance, etc. without impairing processability.

  Furthermore, the place made into the subject is providing the rubber composition which can manufacture the rubber product excellent in low exothermic property, low temperature characteristics, abrasion resistance, etc., without impairing workability.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have obtained a method of obtaining a high molecular weight component (A) having a predetermined property in a method for producing a modified conjugated diene polymer, It has been found that the above-mentioned problem can be achieved by adopting a production method comprising a step of obtaining a component (B) having a low molecular weight and a step of mixing the component (A) and the component (B), The present invention has been completed.

  Moreover, it discovered that the said subject could be achieved by obtaining a modified conjugated diene polymer by the manufacturing method of the modified conjugated diene polymer of this invention, and came to complete this invention.

  Furthermore, it has been found that the above problems can be achieved by including the modified conjugated diene polymer of the present invention in the rubber composition, and the present invention has been completed.

  That is, according to the present invention, the following modified conjugated diene polymer production method, modified conjugated diene polymer, and rubber composition are provided.

  [1] The vinyl content is less than 10%, the cis 1,4-bond content is 75% or more, and the polystyrene equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is 250,000 to 800,000. The first alkoxysilyl group is introduced into the active terminal of the first conjugated diene polymer having an active terminal using the first alkoxysilane compound, and the first alkoxysilyl group is condensed ( A) A step of obtaining the component, and separately, the vinyl content is less than 10%, the cis 1,4-bond content is 75% or more, and the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) is A second alkoxysilane compound is used for the active terminal of the second conjugated diene polymer having an active terminal, which is 10,000 to 150,000. A modified conjugated diene polymer comprising a step of introducing a coxysilyl group and condensing the second alkoxysilyl group to obtain the component (B), and a step of mixing the component (A) and the component (B). Manufacturing method.

  [2] At least one conjugate selected from the group consisting of 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene, at least one of the component (A) and the component (B). The method for producing a modified conjugated diene polymer according to the above [1], which has a structural unit derived from a diene compound.

[3] The above [1] or [2], wherein at least one of the following components (a) and (b) is added before condensing at least one of the first and second alkoxysilyl groups: A process for producing a modified conjugated diene polymer as described in 1.
(A) component; compound containing at least one element selected from the group consisting of titanium (Ti), zirconium (Zr), bismuth (Bi), aluminum (Al), and tin (Sn) (b) component; Carboxylic acid partial ester of polyhydric alcohol

[4] The above [1] to [1], wherein at least one of the first and second conjugated diene polymers is obtained by using a catalyst having the following components (c) to (e) as main components. [3] The method for producing a modified conjugated diene polymer according to any one of [3].
(C) component; a rare earth element-containing compound corresponding to atomic numbers 57 to 71 in the periodic table, or a reaction product of the rare earth element-containing compound and a Lewis base (d) component; alumoxane and general formula (1): AlR ¹ R ² Organoaluminum compound corresponding to at least one of the compounds represented by R ³ (In the general formula (1), R ¹ and R ² are each independently a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. R ³ represents a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ may be the same as or different from R ¹ or R ² .
(E) Component; Halogen-containing compound

[5] The above [1], wherein at least one of the first and second alkoxysilane compounds is an alkoxysilane compound having at least one functional group selected from the group consisting of the following (f) to (h): ] The manufacturing method of the modified conjugated diene polymer in any one of [4].
(F); epoxy group (g); isocyanate group (h); acyl group

  [6] A modified conjugated diene polymer obtained by the method for producing a modified conjugated diene polymer according to any one of [1] to [5].

  [7] A rubber composition comprising the modified conjugated diene polymer according to [6].

  [8] The rubber composition according to [7], comprising 100 parts by mass of a rubber component containing 20% by mass or more of the modified conjugated diene polymer and at least 20 to 120 parts by mass of silica and carbon black. object.

  [9] The rubber component is 20 to 100% by mass of the modified conjugated diene polymer, natural rubber, synthetic isoprene rubber, butadiene rubber, styrene / butadiene rubber, ethylene / α-olefin copolymer rubber, ethylene / α- 80 to 0% by mass of at least one rubber selected from the group consisting of olefin / diene copolymer rubber, acrylonitrile / butadiene copolymer rubber, chloroprene rubber, and halogenated butyl rubber (provided that modified conjugated diene polymer + rubber = 100% by mass), and the rubber composition according to [8].

  According to the method for producing a modified conjugated diene polymer of the present invention, a modified conjugated diene polymer capable of producing a rubber product excellent in low exothermic property, low temperature characteristics, wear resistance, etc. without impairing processability. There is an effect that can be manufactured.

  In addition, the modified conjugated diene polymer of the present invention has an effect that it is possible to produce a rubber product excellent in low heat build-up, low temperature characteristics, wear resistance and the like without impairing processability.

  Furthermore, the rubber composition of the present invention has an effect that it is possible to produce a rubber product excellent in low heat build-up, low temperature characteristics, wear resistance and the like without impairing processability.

  BEST MODE FOR CARRYING OUT THE INVENTION The best mode for carrying out the present invention will be described below, but the present invention is not limited to the following embodiment, and is based on the ordinary knowledge of those skilled in the art without departing from the gist of the present invention. It should be understood that modifications and improvements as appropriate to the following embodiments also fall within the scope of the present invention. In the present specification, when it is described as “conjugated diene polymer”, it indicates both the first and second conjugated diene polymers, and when it is described as “modifier”, When both the first and second alkoxysilyl compounds are shown and “alkoxysilyl group” is described, both the first and second alkoxysilyl groups are shown.

I. Method for Producing Modified Conjugated Diene Polymer The method for producing the modified conjugated diene polymer of the present invention comprises a step of obtaining component (A), a step of obtaining component (B) separately, a component (A), and ( B) mixing the components.

1 (A) component (A) component uses the 1st alkoxysilane compound for the active terminal of the 1st conjugated diene polymer, and uses the 1st alkoxy silyl group (henceforth "modification reaction"). After the introduction, the introduced first alkoxysilyl group can be condensed (hereinafter also referred to as “condensation reaction”). By mixing the component (A), it is possible to produce a modified conjugated diene polymer capable of producing a rubber product excellent in mechanical properties such as low heat buildup, low temperature characteristics, and abrasion resistance.

  The component (A) preferably has a structural unit derived from at least one conjugated diene compound selected from the group consisting of 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene.

(First conjugated diene polymer)
The first conjugated diene polymer has a vinyl content of less than 10%, a cis 1,4-bond content of 75% or more, and a weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) ( Hereinafter, it is a polymer of a conjugated diene compound having a molecular weight of 250,000 to 800,000, and has an active end.

  The vinyl content of the first conjugated diene polymer is less than 10%, preferably less than 5%, and more preferably less than 2%. If the vinyl content is 10% or more, mechanical properties such as wear resistance of the rubber product after vulcanization may be inferior. The vinyl content can be easily adjusted by controlling the temperature of the polymerization reaction.

  The cis 1,4-bond content of the first conjugated diene polymer is 75% or more, preferably 85% or more, and more preferably 90 to 99.9%. When the cis 1,4-bond content is less than 75%, mechanical properties such as wear resistance of the rubber product after vulcanization may be inferior. The cis 1,4-bond content can be easily adjusted by controlling the temperature of the polymerization reaction.

  The Mw of the first conjugated diene polymer is 250,000 to 800,000, preferably 270,000 to 700,000, and more preferably 300,000 to 600,000. If the Mw is less than 250,000, mechanical properties such as wear resistance of the rubber product after vulcanization may be inferior. On the other hand, if it exceeds 800,000, workability may be inferior. In addition, Mw can be adjusted by controlling the usage-amount of the catalyst used for a polymerization reaction.

2 Component (B) The component (B) is a second alkoxysilyl group (hereinafter also referred to as “modification reaction”) at the active terminal of the second conjugated diene polymer using a second alkoxysilane compound. After the introduction, the introduced second alkoxysilyl group can be condensed (hereinafter also referred to as “condensation reaction”). By mixing the component (B), it is possible to produce a modified conjugated diene polymer capable of producing a rubber product excellent in low heat build-up and low temperature characteristics without impairing processability.

  The component (B) preferably has a structural unit derived from at least one conjugated diene compound selected from the group consisting of 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene.

(Second conjugated diene polymer)
The second conjugated diene polymer is a polymer of a conjugated diene compound having a vinyl content of less than 10%, a cis 1,4-bond content of 75% or more, and an Mw of 10,000 to 150,000, and has an active terminal. have.

  The vinyl content of the second conjugated diene polymer is less than 10%, preferably less than 5%, and more preferably less than 2%. If the vinyl content is 10% or more, mechanical properties such as wear resistance of the rubber product after vulcanization may be inferior. The vinyl content can be easily adjusted by controlling the temperature of the polymerization reaction.

  The cis 1,4-bond content of the second conjugated diene polymer is 75% or more, preferably 85% or more, and more preferably 90 to 99.9%. When the cis 1,4-bond content is less than 75%, mechanical properties such as wear resistance of the rubber product after vulcanization may be inferior. The cis 1,4-bond content can be easily adjusted by controlling the temperature of the polymerization reaction.

  The Mw of the second conjugated diene polymer is 10,000 to 150,000, preferably 10,000 to 100,000, and more preferably 20,000 to 80,000. When Mw is less than 10,000, mechanical properties such as wear resistance of the rubber product after vulcanization may be inferior. On the other hand, if it exceeds 150,000, workability may be inferior. Mw can be easily adjusted by controlling the amount of catalyst used for the polymerization reaction.

3. Method for Preparing First and Second Conjugated Diene Polymers The first and second conjugated diene polymers can be prepared by polymerizing a conjugated diene compound (hereinafter also referred to as “polymerization reaction”). it can. The polymerization reaction is preferably performed using a catalyst in the presence of a solvent. When a solvent is used for the polymerization reaction, the solvent may be an inert organic solvent. For example, saturated aliphatic hydrocarbons having 4 to 10 carbon atoms such as butane, pentane, hexane and heptane; saturated alicyclic hydrocarbons having 6 to 20 carbon atoms such as cyclopentane and cyclohexane; 1-butene, 2-butene and the like Monoolefins; aromatic hydrocarbons such as benzene, toluene, xylene; halogenated carbonization such as methylene chloride, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, 1,2-dichloroethane, chlorobenzene, bromobenzene, chlorotoluene, etc. There are hydrogen and so on. In addition, the density | concentration of the conjugated diene compound in a solvent is 5-50 mass% normally, and it is preferable that it is 7-35 mass%.

  In the polymerization reaction, in order not to deactivate the active terminal of the conjugated diene polymer, it is necessary to take care to minimize the incorporation of a deactivating compound such as oxygen, water or carbon dioxide in the polymerization reaction system. is there.

  The temperature of the polymerization reaction is usually −30 to 200 ° C., preferably 0 to 150 ° C. Moreover, there is no restriction | limiting in particular about the form of polymerization reaction, You may carry out using a batch type reactor, and you may carry out by a continuous type using apparatuses, such as a multistage continuous type reactor.

  The conjugated diene compound is not particularly limited, and examples thereof include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, myrcene, and the like. There is. Among these, at least one conjugated diene compound selected from the group consisting of 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene is preferable. The conjugated diene compound used to prepare the first conjugated diene polymer and the conjugated diene compound used to prepare the second conjugated diene polymer may be the same, It may be different.

(Catalyst components)
The catalyst used for the polymerization reaction is preferably one having components (c) to (e) as main components. For the purpose of adjusting the molecular weight, the polymerization reaction may be carried out in the presence of hydrogen gas.
(C) component; a rare earth element-containing compound corresponding to atomic numbers 57 to 71 in the periodic table, or a reaction product of a rare earth element-containing compound and a Lewis base (d) component; alumoxane and general formula (1): AlR ¹ R ² R ^An organoaluminum compound corresponding to at least one of the compounds represented by ³ (in general formula (1), R ¹ and R ² each independently represent a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. And R ³ represents a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ may be the same as or different from R ¹ or R ² .
(E) Component; Halogen-containing compound

  The component (c) is a rare earth element-containing compound corresponding to atomic numbers 57 to 71 in the periodic table, or a reaction product of a rare earth element-containing compound and a Lewis base. Examples of rare earth elements corresponding to atomic numbers 57 to 71 in the periodic table include neodymium, praseodymium, cerium, lanthanum, and gadolinium. Among these, neodymium is preferable. The rare earth element-containing compound includes a rare earth element carboxylate, a rare earth element alkoxide, a rare earth element β-diketone complex, a rare earth element phosphate, or a rare earth element phosphate.

As a rare earth element carboxylate, for example, there is a compound represented by the general formula (2): (R ⁴ —CO ₂ ) ₃ M.
(In General Formula (2), M represents a rare earth element corresponding to atomic numbers 57 to 71 in the periodic table, and R ⁴ represents a hydrocarbon group having 1 to 20 carbon atoms.)

In the general formula (2), the hydrocarbon group having 1 to 20 carbon atoms represented as R ⁴ is preferably a linear, branched or cyclic, saturated or unsaturated alkyl group. Specific examples of the group represented by R ⁴ —CO ₂ include octanoic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, benzoic acid, naphthenic acid, versatic acid (trade names manufactured by Shell Chemical Co., Ltd.). And a carboxylic acid in which a carboxyl group is bonded to a tertiary carbon atom). Among these, 2-ethylhexanoic acid, naphthenic acid, and versatic acid are preferable. The carboxyl group is bonded to a primary, secondary or tertiary carbon atom.

As the rare earth element alkoxide, for example, there is a compound represented by the general formula (3) :( R ⁵ O) ₃ M.
(In General Formula (3), M represents a rare earth element corresponding to atomic numbers 57 to 71 in the periodic table, and R ⁵ represents a hydrocarbon group having 1 to 20 carbon atoms.)

In the general formula (3), the hydrocarbon group having 1 to 20 carbon atoms represented as R ⁵ is preferably a linear, branched or cyclic, and saturated or unsaturated alkyl group. Specific examples include 2-ethylhexyl group, oleyl group, stearyl group, phenyl group, and benzyl group. Among these, a 2-ethylhexyl group and a benzyl group are preferable.

  Specific examples of the β-diketone complex of a rare earth element β-diketone complex include an acetylacetone complex, a benzoylacetone complex, a propionylacetone complex, a valerylacetone complex, and an ethylacetylacetone complex. Among these, an acetylacetone complex and an ethylacetylacetone complex are preferable.

  Specific examples of phosphoric acid or phosphorous acid of rare earth element phosphates or rare earth element phosphites include bis (2-ethylhexyl) phosphate, bis (1-methylheptyl) phosphate, and bisphosphate. (P-nonylphenyl), phosphoric acid bis (polyethylene glycol-p-nonylphenyl), phosphoric acid (1-methylheptyl) (2-ethylhexyl), phosphoric acid (2-ethylhexyl) (p-nonylphenyl), 2- Mono-2-ethylhexyl ethylhexylphosphonate, mono-p-nonylphenyl 2-ethylhexylphosphonate, bis (2-ethylhexyl) phosphinic acid, bis (1-methylheptyl) phosphinic acid, bis (p-nonylphenyl) phosphinic acid, (1-methylheptyl) (2-ethylhexyl) phosphinic acid, (2-ethylhexyl) (p-no Butylphenyl) phosphinic acid and the like. Among these, bis (2-ethylhexyl) phosphate, bis (1-methylheptyl) phosphate, mono-2-ethylhexyl 2-ethylhexylphosphonate, and bis (2-ethylhexyl) phosphinic acid are preferable.

  Among those exemplified above, neodymium phosphate or neodymium carboxylate is particularly preferred, and carboxylates such as neodymium 2-ethylhexanoate and versatic acid salt are most preferred.

  A Lewis base is used to easily solubilize a rare earth element-containing compound in a solvent. For example, acetylacetone, tetrahydrofuran, pyridine, N, N-dimethylformamide, thiophene, diphenyl ether, triethylamine, an organic phosphorus compound, 1 There are divalent or divalent alcohols.

  The usage-amount of a Lewis base is 0-30 mol normally with respect to 1 mol of rare earth element compounds, and it is preferable that it is 1-10 mol. Moreover, the reaction product may be prepared and used in a polymerization reaction system, or may be separately prepared and used in advance.

  (C) When using the 1st and 2nd conjugated diene polymer, it is preferable that the usage-amount of a component is 0.00001-1.0 mmol with respect to 100 g of conjugated diene compounds, 0.0001- More preferably, it is 0.5 mmol. When the amount of component (c) used is less than 0.00001 mmol, the polymerization activity may be low. On the other hand, if it exceeds 1.0 mmol, the catalyst concentration becomes high, so that a decontacting step may be required. In addition, (c) component may be used individually by 1 type, and may be used in combination of 2 or more type.

The component (d) is an organoaluminum compound corresponding to at least one of the alumoxane and the compound represented by the general formula (1): AlR ¹ R ² R ³ .
(In General Formula (1), R ¹ and R ² each independently represent a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and R ³ represents a hydrocarbon group having 1 to 10 carbon atoms. (However, R ³ may be the same as or different from R ¹ or R ^2. )

  Examples of alumoxane include compounds having a structure represented by the general formula (4) or (5), fine chemicals, 23, (9), 5 (1994), J. Org. Am. Chem. Soc. 115, 4971 (1993); Am. Chem. Soc. 117, 6465 (1995).

（一般式（４）及び（５）中、Ｒ^６は、相互に独立に、炭素数１〜２０の炭化水素基を示し、ｎは２以上の整数を示す。）

(In General Formulas (4) and (5), R ⁶ independently represents a hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer of 2 or more.)

In general formulas (4) and (5), as the hydrocarbon group having 1 to 20 carbon atoms represented by R ⁶ , specifically, a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, t- A butyl group, a hexyl group, an isohexyl group, an octyl group, an isooctyl group, etc. can be mentioned. Among these, a methyl group, an ethyl group, an isobutyl group, and a t-butyl group are preferable, and a methyl group is particularly preferable. Moreover, n is an integer greater than or equal to 2, and it is preferable that it is an integer of 4-100.

  Specific examples of alumoxane include methylalumoxane, ethylalumoxane, n-propylalumoxane, n-butylalumoxane, isobutylalumoxane, t-butylalumoxane, hexylalumoxane, isohexylalumoxane, and the like. Can do.

  The alumoxane may be prepared using any known technique. For example, trialkylaluminum or dialkylaluminum monochloride is added to an organic solvent such as benzene, toluene, xylene, and water, water vapor, water vapor-containing nitrogen gas, or copper sulfate pentahydrate or aluminum sulfate 16 hydrate. It can be prepared by adding a salt having water of crystallization and reacting. In addition, alumoxane may be used individually by 1 type and may be used in combination of 2 or more type.

Specific examples of the compound represented by the general formula (1): AlR ¹ R ² R ³ include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, and triisobutyl. Aluminum, tri-t-butylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, diethylaluminum hydride, di-n-propylaluminum hydride, di-n-butylaluminum hydride, hydrogenated Diisobutylaluminum, hydrogenated dihexylaluminum, hydrogenated diisohexylaluminum, hydrogenated dioctylaluminum, hydrogenated diisooctylaluminum, ethylaluminum dihydride , It may be mentioned n- propyl aluminum dihydride, isobutyl aluminum dihydride and the like. Among these, triethylaluminum, triisobutylaluminum, diethylaluminum hydride, and diisobutylaluminum hydride are preferable. In addition, an organic aluminum compound may be used individually by 1 type, and may be used in combination of 2 or more type.

  The use ratio of the component (d) can be generally expressed as a molar ratio of Al to the component (c). Note that the Mw of the conjugated diene polymer can be controlled by appropriately setting the use ratio of the component (d). The molar ratio of component (c) to component (d) ((c) :( d)) is usually 1: 1 to 1: 500, preferably 1: 3 to 1: 250, More preferably, it is 5 to 1: 200. Outside these ranges, it is not preferable because it does not act as a highly active catalyst or requires a decontacting step.

  The component (e) is a halogen-containing compound. Examples of the halogen-containing compound include a reaction product of a metal halide and a Lewis base, diethylaluminum chloride, silicon tetrachloride, trimethylchlorosilane, methyldichlorosilane, dimethyldichlorosilane, methyltrichlorosilane, ethylaluminum dichloride, ethylaluminum sesquioxide. There are chloride, tin tetrachloride, tin trichloride, phosphorus trichloride, benzoyl chloride, t-butyl chloride and the like.

  Examples of the metal halide include beryllium chloride, beryllium bromide, beryllium iodide, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, calcium iodide, barium chloride, barium bromide and iodide. Barium, zinc chloride, zinc bromide, zinc iodide, cadmium chloride, cadmium bromide, cadmium iodide, mercury chloride, mercury bromide, mercury iodide, manganese chloride, manganese bromide, manganese iodide, rhenium chloride, odor Examples include rhenium iodide, rhenium iodide, copper chloride, copper iodide, silver chloride, silver bromide, silver iodide, gold chloride, gold bromide, and gold iodide. Among these, magnesium chloride, calcium chloride, barium chloride, manganese chloride, zinc chloride and copper chloride are preferable, and magnesium chloride, manganese chloride, zinc chloride and copper chloride are particularly preferable.

  Examples of the Lewis base include phosphorus compounds, carbonyl compounds, nitrogen compounds, ether compounds, alcohols, and the like. Specifically, phosphorus compounds such as tributyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, triethylphosphine, tributylphosphine, triphenylphosphine, diethylphosphinoethane, diphenylphosphinoethane; Acetylacetone, benzoylacetone, propionitrileacetone, valerylacetone, ethylacetylacetone, methyl acetoacetate, ethyl acetoacetate, phenylacetoacetate, dimethyl malonate, diethyl malonate, diphenyl malonate, acetic acid, octanoic acid, 2-ethylhexane Carbonyl such as acid, oleic acid, stearic acid, benzoic acid, naphthenic acid, versatic acid (trade name of Shell Chemical Co., which is a carboxylic acid having a carboxyl group bonded to a tertiary carbon atom) Compounds; nitrogen compounds such as triethylamine and N, N-dimethylacetamide; ether compounds such as tetrahydrofuran and diphenyl ether; alcohols such as 2-ethylhexyl alcohol, oleyl alcohol, stearyl alcohol, phenol, benzyl alcohol, 1-decanol and lauryl alcohol Can be mentioned. Among these, tri-2-ethylhexyl phosphate, tricresyl phosphate, acetylacetone, 2-ethylhexanoic acid, versatic acid, 2-ethylhexyl alcohol, 1-decanol, and lauryl alcohol are preferable.

  The usage-amount of a Lewis base is 0.01-30 mol normally per 1 mol of metal halides, and it is preferable that it is 0.5-10 mol. When the reaction product of the metal halide and the Lewis base is used, the amount of metal remaining in the conjugated diene polymer can be reduced.

  The use ratio of the component (e) can be represented by the molar ratio of the component (c) and the component (e). The molar ratio of the component (c) to the component (e) ((c) :( e)) is usually 1: 0.1 to 1:30, and should be 1: 0.2 to 1:15. preferable. Outside these ranges, it is not preferable because it does not act as a highly active catalyst or requires a decontacting step.

  As the catalyst component, in addition to the components (c) to (e), if necessary, at least one of a conjugated diene compound and a non-conjugated diene compound (also referred to as “other component” in the present specification), (c ) You may use in the ratio of 0-1000 mol per 1 mol of components. As the conjugated diene compound used as the other component, 1,3-butadiene, isoprene and the like can be used in the same manner as the conjugated diene compound used in the polymerization reaction. Examples of the non-conjugated diene compound include divinylbenzene, diisopropenylbenzene, triisopropenylbenzene, 1,4-vinylhexadiene, and ethylidene norbornene. Other components as the catalyst component are not essential, but when used together, there is an advantage that the catalytic activity is further improved.

(Method for preparing catalyst)
The catalyst can be prepared, for example, by reacting the components (c) to (e) dissolved in a solvent and, if necessary, other components. In that case, the addition order of each component may be arbitrary. Each component is preferably mixed, reacted, and aged in advance from the viewpoint of improving the polymerization activity and shortening the polymerization initiation time.

  The aging temperature is usually 0 to 100 ° C, and preferably 20 to 80 ° C. If the aging temperature is less than 0 ° C., aging may not be performed sufficiently. On the other hand, if it exceeds 100 ° C., the catalyst activity may decrease and the molecular weight distribution may spread, which is not preferable. The aging time is not particularly limited, and can be contacted in the line before being added to the polymerization reaction tank. Usually, 0.5 minutes or more is sufficient, and stable for several days.

4. Modification Reaction The modification reaction is a reaction in which an alkoxysilyl group is introduced into the active terminal of the prepared conjugated diene polymer using a modifier. 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, isolation of the conjugated diene polymer, and the like.

  The modification reaction is preferably carried out by a solution reaction (a solution containing an unreacted conjugated diene compound used in the polymerization reaction). Further, the type of the denaturation reaction is not particularly limited, and it may be performed using a batch reactor, or may be performed continuously using an apparatus such as a multistage continuous reactor or an inline mixer. The conjugated diene polymer is preferably one in which at least 10% of the polymer chains have living properties.

  As the temperature of the modification reaction, the temperature of the polymerization reaction can be applied. Specifically, 20-100 degreeC is preferable and 40-90 degreeC is still more preferable. When the temperature is lower than 20 ° C., the viscosity of the component (A) or the component (B) tends to increase, which is not preferable. On the other hand, if it exceeds 100 ° C., the active terminal of the conjugated diene polymer tends to be deactivated, which is not preferable. The reaction time for the denaturation reaction is usually 5 minutes to 5 hours, preferably 15 minutes to 1 hour.

The modifier is not particularly limited, but an alkoxysilane compound having at least one functional group selected from the group consisting of (f) to (h) is preferably used. The modifier may be a partial condensate or a mixture of a modifier and a partial condensate. The “partial condensate” herein refers to a product in which a part (not all) of the modifier SiOR is bonded to SiOSi by condensation. The first alkoxysilane compound and the second alkoxysilane compound may be the same or different.
(F); epoxy group (g); isocyanate group (h); acyl group

  Among the modifiers, as the epoxy group-containing alkoxysilane compound, specifically, 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, (2-glycidoxyethyl) methyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- ( Examples include 3,4-epoxycyclohexyl) ethyltriethoxysilane and 2- (3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane. Among these, 3-glycidoxypropyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane are preferable.

  Specific examples of the isocyanate group-containing alkoxysilane compound include 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-isocyanatepropylmethyldiethoxysilane, 3-isocyanatepropyltriisopropoxysilane, and the like. Can be mentioned. Among these, 3-isocyanatopropyltrimethoxysilane is preferable.

  Further, as the acyl group-containing alkoxysilane compound, specifically, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyl Roxypropyltriisopropoxysilane and the like can be mentioned. Among these, 3-methacryloyloxypropyltrimethoxysilane is preferable. In addition, a modifier | denaturant may be used individually by 1 type and may be used in combination of 2 or more type.

  The amount of the modifier used is preferably 0.000001 to 0.01, more preferably 0.00001 to 0.001, in terms of a molar ratio with respect to the conjugated diene polymer. If the amount used is less than 0.000001, the modification reaction may not proceed sufficiently and the dispersibility of the filler may not be sufficiently improved. On the other hand, if it exceeds 0.01, the modification reaction is sufficiently saturated, which is not economical.

  The addition method of the modifier is not particularly limited, and there are a method of adding all at once, a method of adding in divided portions, a method of adding continuously, and the like. Among these, the method of adding all at once is preferable.

5. Condensation reaction The condensation reaction is carried out in an aqueous solution. The temperature of the condensation reaction is usually 85 to 180 ° C, preferably 100 to 170 ° C, and more preferably 110 to 150 ° C. If the temperature is lower than 85 ° C., the condensation reaction proceeds slowly, and the reaction may not be completed, and the (A) component or the (B) component may change over time, resulting in quality problems. is there. On the other hand, if it exceeds 180 ° C., the aging reaction of the conjugated diene polymer proceeds and the physical properties may be lowered.

  The pH value of the aqueous solution is usually from 9 to 14, and preferably from 10 to 12. If the pH value is less than 9, the progress of the condensation reaction is slow, and the reaction may not be completed. Therefore, the (A) component or the (B) component changes with time, resulting in quality problems. There is a case. On the other hand, when it exceeds 14, a component derived from a large amount of alkali remains in the component (A) or the component (B) after isolation, and it may be difficult to remove the component.

  The reaction time is usually 5 minutes to 10 hours, preferably about 15 minutes to 5 hours. If the reaction time is less than 5 minutes, the condensation reaction may not proceed sufficiently. On the other hand, if it exceeds 10 hours, the condensation reaction is saturated, which is not economically preferable. In addition, the pressure of the reaction system at the time of condensation reaction is 0.01-20 Mpa normally, and it is preferable that it is 0.05-10 Mpa.

  The type of the condensation reaction is not particularly limited, and may be performed using a batch type reactor, or may be performed continuously using an apparatus such as a multistage continuous reactor. Further, the condensation reaction and the solvent removal may be performed simultaneously. After the condensation, a conventionally known post-treatment is performed to obtain the component (A) or the component (B).

In addition, it is preferable to add at least one of the components (a) and (b) (hereinafter also referred to as “condensation accelerator”) before the condensation reaction. This is used to promote the condensation reaction between the first alkoxysilyl groups or between the second alkoxysilyl groups.
(A) component; compound containing at least one element selected from the group consisting of titanium (Ti), zirconium (Zr), bismuth (Bi), aluminum (Al), and tin (Sn) (b) component; Carboxylic acid partial ester of polyhydric alcohol

  The condensation accelerator can be added before the modification reaction, but is preferably added after the modification reaction and before the start of the condensation reaction. When added before the modification reaction, the direct reaction with the active end of the conjugated diene polymer may occur, and the alkoxysilyl group may not be introduced into the active end. Moreover, when it adds after a condensation reaction start, a condensation promoter may not disperse | distribute uniformly but a catalyst performance may fall. The addition time of the condensation accelerator is usually 5 minutes to 5 hours after the start of the modification reaction, and preferably 15 minutes to 1 hour later.

  The component (a) is a compound containing at least one element selected from the group consisting of titanium (Ti), zirconium (Zr), bismuth (Bi), aluminum (Al), and tin (Sn).

  Specific examples of the compound containing titanium (Ti) include tetramethoxy titanium, tetraethoxy titanium, tetra n-propoxy titanium, tetra i-propoxy titanium, tetra n-butoxy titanium, tetra n-butoxy titanium oligomer, tetra sec. -Butoxytitanium, tetra-tert-butoxytitanium, tetra (2-ethylhexyl) titanium, bis (octanediolate) bis (2-ethylhexyl) titanium, tetra (octanediolate) titanium, titanium lactate, titanium dipropoxybis (triethanol Aminate), titanium dibutoxybis (triethanolaminate), titanium tributoxy systemate, titanium tripropoxy systemate, titanium Ripropoxyacetylacetonate, titanium dipropoxybis (acetylacetonate), titanium tripropoxyethylacetoacetate, titaniumpropoxyacetylacetonatebis (ethylacetoacetate), titanium tributoxyacetylacetonate, titanium dibutoxybis (acetylacetonate) ), Titanium tributoxyethyl acetoacetate, titanium butoxyacetylacetonate bis (ethylacetoacetate), titanium tetrakis (acetylacetonate), titanium diacetylacetonate bis (ethylacetoacetate), bis (2-ethylhexanoate) titanium Oxide, bis (laurate) titanium oxide, bis (naphthate) titanium oxide, bis Stearate) titanium oxide, bis (oleate) titanium oxide, bis (linoleate) titanium oxide, tetrakis (2-ethylhexanoate) titanium, tetrakis (laurate) titanium, tetrakis (naphthate) titanium, tetrakis (stearate) titanium, Examples thereof include tetrakis (oleate) titanium and tetrakis (linoleate) titanium.

  Specific examples of the compound containing zirconium (Zr) include tetraethoxy zirconium, tetra n-propoxy zirconium, tetra i-propoxy zirconium, tetra n-butoxy zirconium, tetra sec-butoxy zirconium, tetra tert-butoxy zirconium. , Tetra (2-ethylhexyl) zirconium, zirconium tributoxy systemate, zirconium tributoxyacetylacetonate, zirconium dibutoxybis (acetylacetonate), zirconium tributoxyethylacetoacetate, zirconiumbutoxyacetylacetonatebis (ethylacetoacetate) , Zirconium tetrakis (acetylacetonate), zirconium diacetylacetonate bis (ethylacetoacetate) ), Bis (2-ethylhexanoate) zirconium oxide, bis (laurate) zirconium oxide, bis (naphthate) zirconium oxide, bis (stearate) zirconium oxide, bis (oleate) zirconium oxide, bis (linoleate) zirconium Examples thereof include oxide, tetrakis (2-ethylhexanoate) zirconium, tetrakis (laurate) zirconium, tetrakis (naphthate) zirconium, tetrakis (stearate) zirconium, tetrakis (oleate) zirconium, tetrakis (linoleate) zirconium and the like.

  Further, as the compound containing bismuth (Bi), specifically, tris (2-ethylhexanoate) bismuth, tris (laurate) bismuth, tris (naphthate) bismuth, tris (stearate) bismuth, tris (oleate) ) Bismuth, tris (linoleate) bismuth and the like.

  Specific examples of the compound containing aluminum (Al) include triethoxyaluminum, tri-n-propoxyaluminum, tri-i-propoxyaluminum, tri-n-butoxyaluminum, trisec-butoxyaluminum, and tritert-butoxyaluminum. , Tri (2-ethylhexyl) aluminum, aluminum dibutoxy systemate, aluminum dibutoxyacetylacetonate, aluminum butoxybis (acetylacetonate), aluminum dibutoxyethylacetoacetate, aluminum tris (acetylacetonate), aluminum tris (ethyl) Acetoacetate), tris (2-ethylhexanoate) aluminum, tris (laurate) aluminum, tris (naphthate) aluminum Um, tris (stearate) aluminum, tris (oleate) aluminum, can be mentioned tris (linolate) aluminum and the like.

  Further, as the compound containing tin (Sn), specifically, bis (n-octanoate) tin, bis (2-ethylhexanoate) tin, bis (laurate) tin, bis (naphthoenate) tin, bis (Stearate) tin, bis (oleate) tin, dibutyltin diacetate, dibutyltin di-n-octanoate, dibutyltin di-2-ethylhexanoate, dibutyltin dilaurate, dibutyltin malate, dibutyltin bis (benzylmalate), dibutyltin bis (2 -Ethylhexyl malate), di-n-octyltin diacetate, di-n-octyltin di-n-octanoate, di-n-octyltin di-2-ethylhexanoate, di-n-octyltin dilaurate, di-n-octyltin malate, di-n -Octyl tin bis (ben Rumareto), di-n- octyl tin bis (2-ethylhexyl maleate) and the like.

  The component (b) is a carboxylic acid partial ester of a polyhydric alcohol. Specific examples include sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, and the like.

  As the use amount of the condensation accelerator, the molar ratio of the compound to the total amount of alkoxysilyl groups present in the reaction system is preferably 0.1 to 10, and particularly preferably 0.5 to 5. If the molar ratio is less than 0.1, the condensation reaction may not proceed sufficiently. On the other hand, if it exceeds 10, it is not economically preferable.

6 Mixing Step The mixing step is a step of mixing the prepared component (A) and component (B). The mixing method is not particularly limited, and may be a conventionally known method. For example, after isolating and drying each component, there is a method of kneading using a roll or the like.

II Modified Conjugated Diene Polymer The modified conjugated diene polymer of the present invention is obtained by “I Production Method of Modified Conjugated Diene Polymer”.

The Mooney viscosity (ML _{1 + 4} , 125 ° C.) of the modified conjugated diene polymer is preferably 20 to 80, and more preferably 30 to 50. If the Mooney viscosity is less than 20, the physical properties of rubber products such as fracture properties tend to decrease, which is not preferable. On the other hand, when it exceeds 80, workability is deteriorated and it may be difficult to knead with the compounding agent.

III Rubber Composition The rubber composition of the present invention contains a rubber component containing the modified conjugated diene polymer described in “II Modified Conjugated Diene Polymer”. Moreover, it is preferable that 20-120 mass parts of fillers are contained with respect to 100 mass parts of rubber components.

1 Rubber Component The rubber component is composed of a modified conjugated diene polymer and rubber (provided that the modified conjugated diene polymer + rubber = 100% by mass).

(1) Modified Conjugated Diene Polymer The modified conjugated diene polymer contained in the rubber component is a modified conjugated diene polymer described in “II Modified Conjugated Diene Polymer”. The content of the modified conjugated diene polymer is preferably 20% by mass or more, more preferably 30% by mass or more, and particularly preferably 40% by mass or more. If the content is less than 20% by mass, the low heat build-up and low temperature characteristics may be deteriorated.

(2) Rubber Rubbers included in rubber components are natural rubber, synthetic isoprene rubber, butadiene rubber, styrene / butadiene rubber, ethylene / α-olefin copolymer rubber, ethylene / α-olefin / diene copolymer rubber, acrylonitrile / butadiene. It is preferably at least one selected from the group consisting of copolymer rubber, chloroprene rubber, and halogenated butyl rubber. These may use what was prepared in accordance with the conventionally well-known method, and may use what is marketed.

  The rubber content is preferably 80% by mass or less, more preferably 70% by mass or less, and particularly preferably 60% by mass or less. If the content is more than 80% by mass, the low heat build-up and low temperature characteristics may be deteriorated.

2 Filler The filler is preferably at least one of silica and carbon black. The usage-amount of a filler is 20-120 mass parts normally with respect to 100 mass parts of rubber components, It is preferable that it is 30-100 mass parts, and it is still more preferable that it is 35-90 mass parts. If the amount used is less than 20 parts by mass, the effect of containing a filler may not be sufficiently exhibited. On the other hand, if it exceeds 120 parts by mass, the processability of the rubber composition may deteriorate.

(1) Silica Silica is not particularly limited, and examples thereof include wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, and aluminum silicate. Among these, wet silica is most preferred because it has the most remarkable effects of improving fracture resistance, wet grip properties and low rolling resistance, and low-temperature properties.

  When silica is used as the filler, a silane coupling agent can be blended for the purpose of further improving the reinforcement. Examples of the silane coupling agent include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, and bis (2-triethoxy). 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-dimethylthio Rubamoyl tetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzoyl tetrasulfide, 3-triethoxy Silylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyltetra Sulfide, dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide, and the like. Among these, bis (3-triethoxysilylpropyl) polysulfide and 3-trimethoxysilylpropylbenzothiazyl tetrasulfide are preferable from the viewpoint of improving the reinforcing property. In addition, these silane coupling agents may be used individually by 1 type, and may be used in combination of 2 or more type.

  In the rubber composition of the present invention, the rubber component contains a modified conjugated diene polymer in which an alkoxysilyl group having a high affinity with silica is introduced at the molecular terminal, so the blending amount of the silane coupling agent Can be reduced more than usual. Although the compounding quantity of a silane coupling agent changes with kinds etc. of a silane coupling agent, it is preferable that it is 1-20 mass% with respect to a silica, and it is still more preferable that it is 3-15 mass%. If the blending amount is less than 1% by mass, the effect is not sufficiently exhibited. On the other hand, if it exceeds 20% by mass, the rubber component may be gelled.

(2) Carbon black Carbon black is not particularly limited, and examples thereof include SRF, GPF, FEF, HAF, ISAF, and SAF. Among these, carbon black having an iodine adsorption amount (IA) of 60 mg / g or more and a dibutyl phthalate oil absorption (DBP) of 80 mL / 100 g or more is preferable, and HAF, ISAF, and SAF having excellent wear resistance are particularly preferable.

3 Other additives As long as the physical properties of the rubber composition of the present invention are not impaired, various chemicals usually used in the rubber industry, for example, vulcanizing agents, vulcanization accelerators, process oils, anti-aging agents Other additives such as an agent, a scorch inhibitor, zinc white, and stearic acid can be contained.

4. Method for Producing Rubber Composition The rubber composition of the present invention comprises a rubber component containing the modified conjugated diene polymer of the present invention, sealed together with a filler, if necessary, in an open kneader such as a roll, a Banbury mixer, etc. It can manufacture by kneading | mixing using kneading machines, such as a type kneader. It can be applied to various rubber products by performing vulcanization after molding. For example, it can be used for tire applications such as tire treads, under treads, carcass, sidewalls, bead parts, vibration proof rubber, fenders, belts, hoses, and other industrial products. It can be suitably used as a tread rubber.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. “Parts” in Examples and Comparative Examples are based on mass unless otherwise specified. Moreover, the measuring method of various physical-property values and the evaluation method of various characteristics are shown below.

[Mooney viscosity (ML _{1 + 4} , 100 ° C.)]: Measured according to JIS K6300 under conditions of preheating 1 minute, measurement time 4 minutes, temperature 100 ° C.

[Mooney viscosity (ML _{1 + 4} , 125 ° C.)]: Measured in accordance with JIS K6300 under conditions of preheating 1 minute, measurement time 4 minutes, temperature 125 ° C.

[Molecular Weight Distribution (Mw / Mn)]: Weight average molecular weight (Mw) and number average molecular weight (Mn) measured under the following conditions using a differential refractometer as a detector using HLC-8120GPC manufactured by Tosoh Corporation. It was calculated from the value of
Column: manufactured by Tosoh Corporation, column GMHHXL
Mobile phase; tetrahydrofuran Column temperature; 40 ° C

  [Cis 1,4-bond content (%) and vinyl content (%)]: Determined by infrared method (Morello method).

  [PH value of aqueous solution]: Measured with a pH meter.

[Tensile strength _T B (MPa)]: was measured in accordance with JIS K6301.

  [Low exothermicity (3% tan δ)] Using a dynamic spectrometer manufactured by Rheometrics, Inc., USA, measurement was performed under the conditions of tensile dynamic strain 3%, frequency 15 Hz, 50 ° C. Expressed by an index, the larger the value, the smaller the heat generation and the better.

  [Low-temperature characteristics (−20 ° C. G ′)]: Using a dynamic spectrometer manufactured by Rheometrics, Inc., USA, measurement was performed at a tensile dynamic strain of 0.1%, a frequency of 15 Hz, and −20 ° C. Expressed as an index, the larger the value, the better the low temperature characteristics (grip performance on snow and on ice).

  [Abrasion resistance]: Measured at room temperature with a slip ratio of 60% using a Lambourn type wear tester (manufactured by Shimada Giken Co., Ltd.). Expressed as an index, the larger the value, the better the wear resistance.

Example 1- (A) (Preparation of Component (A) of Modified Conjugated Diene Polymer A)
In a nitrogen atmosphere, a 5 L autoclave was charged with 2.4 kg of cyclohexane and 300 g of 1,3-butadiene under a nitrogen atmosphere. Separately, a cyclohexane solution of neodymium versatate (hereinafter also referred to as “NdVer”) (0.09 mmol), a toluene solution of methylalumoxane (hereinafter also referred to as “MAO”) (1.8 mmol), hydrogen, Diisobutylaluminum fluoride (hereinafter also referred to as “DIBAH”) (4.7 mmol) and diethylaluminum chloride (hereinafter also referred to as “DEAC”) (0.18 mmol) in toluene solution and 1,3-butadiene (4.5 mmol) A catalyst prepared by reaction aging at 50 ° C. for 30 minutes was charged, and a polymerization reaction was carried out at 80 ° C. for 60 minutes. The reaction conversion of 1,3-butadiene was almost 100%. 200 g of this polymer solution was extracted, a methanol solution containing 1.5 g of 2,4-di-tert-butyl-p-cresol was added, the polymerization reaction was stopped, and then the solvent was removed by steam stripping. The first conjugated diene polymer (1) was obtained by drying with a roll. The obtained first conjugated diene polymer (1) had an Mw of 35.7 million, a cis 1,4-bond content of 96.9%, and a vinyl content of 1.1%.

  Further, the remaining polymer solution was kept at a temperature of 60 ° C., a toluene solution of 3-glycidoxypropyltrimethoxysilane (hereinafter also referred to as “GPMOS”) (4.5 mmol) was added, and a denaturation reaction was performed for 30 minutes. It was. Thereafter, a methanol solution containing 1.5 g of 2,4-di-tert-butyl-p-cresol was added to obtain 2.5 kg of a modified polymer solution (1). Next, the modified polymer solution (1) is added to 20 L of an aqueous solution adjusted to pH 10 with sodium hydroxide, subjected to a condensation reaction with solvent removal at 110 ° C. for 2 hours, dried on a roll at 110 ° C., and modified conjugate The component (A) of the diene polymer A was obtained.

Example 1- (B) (Preparation of Component (B) of Modified Conjugated Diene Polymer A)
In a nitrogen atmosphere, a 5 L autoclave was charged with 2.4 kg of cyclohexane and 300 g of 1,3-butadiene under a nitrogen atmosphere. Separately, a cyclohexane solution of NdVer (0.09 mmol), a toluene solution of MAO (1.8 mmol), a toluene solution of DIBAH (14.8 mmol) and DEAC (0.18 mmol), and 1,3-butadiene A catalyst prepared by reaction aging (4.5 mmol) at 50 ° C. for 30 minutes was charged, and a polymerization reaction was performed at 80 ° C. for 60 minutes. The reaction conversion of 1,3-butadiene was almost 100%. 200 g of this polymer solution was extracted, a methanol solution containing 1.5 g of 2,4-di-tert-butyl-p-cresol was added, the polymerization reaction was stopped, and then the solvent was removed by steam stripping. The second conjugated diene polymer (1) was obtained by drying with a roll. Mw of the obtained second conjugated diene polymer (1) was 72,000, the cis 1,4-bond content was 94.6%, and the vinyl content was 1.1%.

  Furthermore, the remaining polymer solution was kept at a temperature of 60 ° C., a toluene solution of GPMOS (4.5 mmol) was added, and a denaturation reaction was performed for 30 minutes. Subsequently, a toluene solution of tetraisopropyl titanate (hereinafter also referred to as “IPOTi”) (13.5 mmol) was added and mixed for 30 minutes. Thereafter, a methanol solution containing 1.5 g of 2,4-di-tert-butyl-p-cresol was added to obtain 2.5 kg of a modified polymer solution (2). Next, the modified polymer solution (2) is added to 20 L of an aqueous solution adjusted to pH 10 with sodium hydroxide, subjected to a condensation reaction with solvent removal at 110 ° C. for 2 hours, dried with a roll at 110 ° C., and modified conjugate The component (B) of the diene polymer A was obtained.

Example 1- (C) (Production of Modified Conjugated Diene Polymer A)
70 g of component (A) of the resulting modified conjugated diene polymer A and 30 g of component (B) of the modified conjugated diene polymer A were kneaded with a roll at 110 ° C. for 3 minutes to obtain a modified conjugated diene polymer A. Manufactured. The Mooney viscosity (ML _{1 + 4} , 125 ° C.) of the modified conjugated diene polymer A was 42.

Example 2- (A) (Preparation of Component (A) of Modified Conjugated Diene Polymer B)
Example 1- (A), except that in Example 1- (A), the amount of DIBAH used was 4.3 mmol and a toluene solution of IPOTi (13.5 mmol) was added during the condensation reaction and mixed for 30 minutes. The component (A) of the modified conjugated diene polymer B was obtained by the same charging composition and polymerization method. The physical property values of the first conjugated diene polymer (2) after the polymerization reaction are shown in Table 1.

Example 2- (B) (Preparation of Component (B) of Modified Conjugated Diene Polymer B)
In Example 1- (B), except that the DIBAH usage was changed to 27.4 mmol, the modified conjugated diene polymer B (B ) Component was obtained. The physical property values of the second conjugated diene polymer (2) after the polymerization reaction are shown in Table 1.

Example 2- (C) (Production of Modified Conjugated Diene Polymer B)
80 g of component (A) of the resulting modified conjugated diene polymer B and 20 g of component (B) of the modified conjugated diene polymer B were kneaded for 3 minutes with a roll at 110 ° C., and modified conjugated diene polymer B Manufactured. The Mooney viscosity (ML _{1 + 4} , 125 ° C.) of the modified conjugated diene polymer B was 45.

Example 3- (A) (Preparation of Component (A) of Modified Conjugated Diene Polymer C)
In Example 1- (A), the amount of DIBAH used was 4.9 mmol, and a toluene solution of tris (2-ethylhexanoate) bismuth (hereinafter also referred to as “EHABi”) (13.5 mmol) was added during the condensation reaction. The component (A) of the modified conjugated diene polymer C was obtained by the same charging composition and polymerization method as in Example 1- (A) except that mixing was performed for 30 minutes. In addition, Table 1 shows the physical property values of the first conjugated diene polymer (3) after the polymerization reaction.

Example 3- (B) (Preparation of Component (B) of Modified Conjugated Diene Polymer C)
Example 1 Component (B) of modified conjugated diene polymer C was obtained by the same charging composition and polymerization method as in (B). The physical property values of the second conjugated diene polymer (3) after the polymerization reaction are shown in Table 1.

Example 3- (C) (Production of Modified Conjugated Diene Polymer C)
75 g of component (A) of the modified conjugated diene polymer C and 25 g of component (B) of the modified conjugated diene polymer C were kneaded with a roll at 110 ° C. for 3 minutes to obtain a modified conjugated diene polymer C. Manufactured. The Mooney viscosity (ML _{1 + 4} , 125 ° C.) of the modified conjugated diene polymer C was 41.

Example 4- (A) (Preparation of Component (A) of Modified Conjugated Diene Polymer D)
In Example 1- (A), the amount of DIBAH used was 4.8 mmol, and a toluene solution of bis (2-ethylhexanoate) zirconium oxide (hereinafter also referred to as “EHAZrO”) (13.5 mmol) was used during the condensation reaction. The component (A) of the modified conjugated diene polymer D was obtained by the same charging composition and polymerization method as in Example 1- (A) except that the components were added and mixed for 30 minutes. The physical property values of the first conjugated diene polymer (4) after the polymerization reaction are shown in Table 1.

Example 4- (B) (Preparation of Component (B) of Modified Conjugated Diene Polymer D)
In Example 1- (B), except that the amount of DIBAH used was changed to 8.8 mmol, the modified conjugated diene polymer D (B) was prepared by the same charging composition and polymerization method as Example 1- (B). ) Component was obtained. The physical property values of the second conjugated diene polymer (4) after the polymerization reaction are shown in Table 1.

Example 4- (C) (Production of Modified Conjugated Diene Polymer D)
The obtained modified conjugated diene polymer D (A) 85 g and the modified conjugated diene polymer D (B) component 15 g were kneaded with a roll at 110 ° C. for 3 minutes to give a modified conjugated diene polymer D. Manufactured. The Mooney viscosity (ML _{1 + 4} , 125 ° C.) of the modified conjugated diene polymer D was 42.

Example 5- (A) (Preparation of Component (A) of Modified Conjugated Diene Polymer E)
In Example 1- (A), the amount of DIBAH used was 4.6 mmol, and a toluene solution of tris (2-ethylhexanoate) aluminum (hereinafter also referred to as “EHAAl”) (13.5 mmol) was added during the condensation reaction. Then, the component (A) of the modified conjugated diene polymer E was obtained by the same charging composition and polymerization method as in Example 1- (A) except that the mixing was performed for 30 minutes. The physical property values of the first conjugated diene polymer (5) after the polymerization reaction are shown in Table 1.

Example 5- (B) (Preparation of Component (B) of Modified Conjugated Diene Polymer E)
Example 1 The component (B) of the modified conjugated diene polymer E was obtained by the same charging composition and polymerization method as in (B). The physical property values of the second conjugated diene polymer (5) after the polymerization reaction are shown in Table 1.

Example 5- (C) (Production of Modified Conjugated Diene Polymer E)
75 g of component (A) of the modified conjugated diene polymer E and 25 g of component (B) of the modified conjugated diene polymer E were kneaded with a roll at 110 ° C. for 3 minutes, and the modified conjugated diene polymer E Manufactured. The Mooney viscosity (ML _{1 + 4} , 125 ° C.) of the modified conjugated diene polymer E was 45.

Example 6- (A) (Preparation of Component (A) of Modified Conjugated Diene Polymer F)
In Example 1- (A), the amount of DIBAH used was 5.0 mmol, and a toluene solution of bis (2-ethylhexanoate) tin (hereinafter also referred to as “EHASn”) (13.5 mmol) was added during the condensation reaction. Then, the component (A) of the modified conjugated diene polymer F was obtained by the same charging composition and polymerization method as in Example 1- (A) except that the mixing was performed for 30 minutes. The physical property values of the first conjugated diene polymer (6) after the polymerization reaction are shown in Table 1.

Example 6- (B) (Preparation of Component (B) of Modified Conjugated Diene Polymer F)
Example 1 The component (B) of the modified conjugated diene polymer F was obtained by the same charging composition and polymerization method as in (B). The physical property values of the second conjugated diene polymer (6) after the polymerization reaction are shown in Table 1.

Example 6- (C) (Production of Modified Conjugated Diene Polymer F)
70 g of component (A) of the obtained modified conjugated diene polymer F and 30 g of component (B) of the modified conjugated diene polymer F were kneaded for 3 minutes with a roll at 110 ° C., and modified conjugated diene polymer F Manufactured. The Mooney viscosity (ML _{1 + 4} , 125 ° C.) of the modified conjugated diene polymer F was 41.

Example 7- (A) (Preparation of Component (A) of Modified Conjugated Diene Polymer G)
In Example 1- (A), the amount of DIBAH used was 3.6 mmol, GPMOS was changed to 3-isocyanatopropyltriethoxysilane (hereinafter also referred to as “IPEOS”), and sorbitan acid trioleate (hereinafter referred to as “STO”) during the condensation reaction. (A) of the modified conjugated diene polymer G with the same charging composition and polymerization method as in Example 1- (A), except that a toluene solution of (135 mmol) was added and mixed for 30 minutes. Ingredients were obtained. In addition, Table 1 shows the physical property values of the first conjugated diene polymer (7) after the polymerization reaction.

Example 7- (B) (Preparation of Component (B) of Modified Conjugated Diene Polymer G)
Modified conjugated diene polymer in the same charging composition and polymerization method as in Example 1- (B) except that GPMOS was replaced with IPEOS and IPOTi was replaced with STO (135 mmol) in Example 1- (B). A component (B) of G was obtained. The physical property values of the second conjugated diene polymer (7) after the polymerization reaction are shown in Table 1.

Example 7- (C) (Production of Modified Conjugated Diene Polymer G)
70 g of component (A) of the obtained modified conjugated diene polymer G and 30 g of component (B) of the modified conjugated diene polymer G were kneaded with a roll at 110 ° C. for 3 minutes, and the modified conjugated diene polymer G Manufactured. The Mooney viscosity (ML _{1 + 4} , 125 ° C.) of the modified conjugated diene polymer G was 44.

Example 8- (A) (Preparation of Component (A) of Modified Conjugated Diene Polymer H)
In Example 1- (A), DIBAH usage was 3.4 mmol, GPMOS was IPEOS, and a toluene solution of sorbitan acid monolaurate (hereinafter also referred to as “SML”) (135 mmol) was added during the condensation reaction. The component (A) of the modified conjugated diene polymer H was obtained by the same charging composition and polymerization method as in Example 1- (A) except that the mixing was performed for 30 minutes. In addition, Table 1 shows the physical property values of the first conjugated diene polymer (8) after the polymerization reaction.

Example 8- (B) (Preparation of Component (B) of Modified Conjugated Diene Polymer H)
Example 7- Component (B) of modified conjugated diene polymer H was obtained by the same charging composition and polymerization method as in (B). The physical property values of the second conjugated diene polymer (8) after the polymerization reaction are shown in Table 1.

Example 8- (C) (Production of Modified Conjugated Diene Polymer H)
70 g of component (A) of the resulting modified conjugated diene polymer H and 30 g of component (B) of the modified conjugated diene polymer H are kneaded with a roll at 110 ° C. for 3 minutes, and the modified conjugated diene polymer H Manufactured. The Mooney viscosity (ML _{1 + 4} , 125 ° C.) of the modified conjugated diene polymer H was 47.

Comparative Example 1 (Preparation of Modified Conjugated Diene Polymer I)
A modified conjugated diene polymer I was obtained by the same charging composition and polymerization method as in Example 1- (A) except that the amount of DIBAH used in Example 1- (A) was changed to 5.0 mmol. . The physical property values of the first conjugated diene polymer (9) are shown in Table 1.

Comparative Example 2 (Preparation of Modified Conjugated Diene Polymer J)
Example 1- (A) Except that the amount of DIBAH used in Example 1- (A) was 5.0 mmol and a toluene solution of IPOTi (13.5 mmol) was added during the condensation reaction and mixed for 30 minutes. A modified conjugated diene polymer J was obtained by the same charging composition and polymerization method as in Example 1. The physical property values of the first conjugated diene polymer (10) are shown in Table 1.

Comparative Example 3 (Preparation of Modified Conjugated Diene Polymer K)
In Example 1- (A), the amount of DIBAH used was 5.0 mmol, and a toluene solution of EHASn (13.5 mmol) was added during the condensation reaction and mixed for 30 minutes. Example 1- (A) A modified conjugated diene polymer K was obtained by the same charging composition and polymerization method as in Example 1. The physical property values of the first conjugated diene polymer (11) are shown in Table 1.

Comparative Example 4 (Polymer L)
It is a commercially available polybutadiene rubber (manufactured by JSR Corporation, trade name “polybutadiene rubber BR01”). The physical property values are shown in Table 1.

In Table 1, the abbreviated compound names are shown below.
GPMOS; 3-glycidoxypropyltrimethoxysilane IPOTi; tetraisopropyl titanate EHABi; tris (2-ethylhexanoate) bismuth EHAZrO; bis (2-ethylhexanoate) zirconium oxide EHAAl; tris (2-ethylhexano) Ate) aluminum EHASn; bis (2-ethylhexanoate) tin IPEOS; 3-isocyanatopropyltriethoxysilane STO; sorbitan acid trioleate SML; sorbitan acid monolaurate

Example 9
Using the modified conjugated diene polymer A produced in Example 1- (C), a rubber composition was produced according to the formulation shown in Table 2. The resulting rubber composition had a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 53. Further, the obtained rubber composition (1) was vulcanized at 150 ° C. for 12 minutes to prepare a vulcanized rubber. Tensile strength _{T B} of the vulcanized rubber is 20.3 MPa, the index of the low heat build-up (3% tanδ) is 132, the index of the low temperature properties (-20 ℃ G ') is 182, the abrasion resistance The index of was 125. The index value was calculated based on the vulcanized rubber of Comparative Example 8.

In Table 2, * 1 to * 7 are as follows.
* 1 Product name “Nipseal AQ” manufactured by Nippon Silica Kogyo Co., Ltd.
* 2 Product name “Fukkor Aromax # 3” manufactured by Fuji Kosan Co., Ltd.
* 3 Product name “Si69” (bis (3-triethoxysilylpropyl) tetrasulfide) manufactured by Degussa
* 4 Product name “NOCRACK 6C” (N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine), manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
* 5 Product name “Noxeller D” (1,3-diphenylguanidine), manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
* 6 Product name “Noxeller DM” (di-2-benzothiazolyl disulfide), manufactured by Ouchi Shinsei Chemical Co., Ltd.
* 7 Product name "Noxeller NS-F" (Nt-butyl-2-benzothiazolylsulfenamide), manufactured by Ouchi Shinsei Chemical Co., Ltd.

Examples 10-16 and Comparative Examples 5-8
Using the modified conjugated diene polymers B to K or the polymers L produced in Examples 2 to 8 and Comparative Examples 1 to 3, rubber compositions were produced by carrying out the compounding formulations shown in Table 2. The Mooney viscosity was measured for these rubber compositions. Further, the rubber composition was vulcanized at 150 ° C. for 12 minutes to prepare a vulcanized rubber, and the physical property values were evaluated. The results are shown in Table 3.

  From Table 3, the rubber composition containing the modified conjugated diene polymers A to H in which the high molecular weight component (A) and the low molecular weight component (B) are combined has a low Mooney viscosity at the time of blending and good processability. is there. It can also be seen that the vulcanized rubber is excellent in low heat build-up, low temperature characteristics and wear resistance.

  INDUSTRIAL APPLICABILITY The present invention is expected to be used in tire applications such as tire treads, under treads, carcass, sidewalls, and bead parts, as well as anti-vibration rubber, fenders, belts, hoses, and other industrial products. .

Claims (9)

Active terminal having a vinyl content of less than 10%, a cis 1,4-bond content of 75% or more, and a polystyrene equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 250,000 to 800,000 A first alkoxysilyl group is introduced into the active terminal of the first conjugated diene polymer having a first alkoxysilane compound, and the first alkoxysilyl group is condensed to form the component (A). And obtaining
Separately, the vinyl content is less than 10%, the cis 1,4-bond content is 75% or more, and the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) is 10,000 to 150,000. A second alkoxysilyl group is introduced into the active end of the second conjugated diene polymer having an active end using a second alkoxysilane compound, and the second alkoxysilyl group is condensed (B ) Obtaining an ingredient;
A step of mixing the component (A) and the component (B), and a method for producing a modified conjugated diene polymer.   At least one of the component (A) and the component (B) is at least one conjugated diene compound selected from the group consisting of 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene. The manufacturing method of the modified conjugated diene polymer of Claim 1 which has a structural unit derived from. The modified conjugated diene according to claim 1 or 2, wherein at least one of the following components (a) and (b) is added before condensing at least one of the first and second alkoxysilyl groups. A method for producing a polymer.
(A) component; compound containing at least one element selected from the group consisting of titanium (Ti), zirconium (Zr), bismuth (Bi), aluminum (Al), and tin (Sn) (b) component; Carboxylic acid partial ester of polyhydric alcohol 4. At least one of the first and second conjugated diene polymers is obtained using a catalyst having the following components (c) to (e) as main components. A method for producing a modified conjugated diene polymer according to Item.
(C) component; a rare earth element-containing compound corresponding to atomic numbers 57 to 71 in the periodic table, or a reaction product of the rare earth element-containing compound and a Lewis base (d) component; alumoxane and general formula (1): AlR ¹ R ² Organoaluminum compound corresponding to at least one of the compounds represented by R ³ (In the general formula (1), R ¹ and R ² are each independently a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. R ³ represents a hydrocarbon group having 1 to 10 carbon atoms, provided that R ³ may be the same as or different from R ¹ or R ² .
(E) Component; Halogen-containing compound The at least one of the first and second alkoxysilane compounds is an alkoxysilane compound having at least one functional group selected from the group consisting of the following (f) to (h). The manufacturing method of the modified | denatured conjugated diene type polymer as described in any one.
(F); epoxy group (g); isocyanate group (h); acyl group   The modified conjugated diene polymer obtained by the manufacturing method of the modified conjugated diene polymer as described in any one of Claims 1-5.   A rubber composition comprising the modified conjugated diene polymer according to claim 6. 100 parts by mass of a rubber component containing 20% by mass or more of the modified conjugated diene polymer,
The rubber composition according to claim 7, comprising 20 to 120 parts by mass of at least one of silica and carbon black. The rubber component is 20 to 100% by mass of the modified conjugated diene polymer,
From natural rubber, synthetic isoprene rubber, butadiene rubber, styrene / butadiene rubber, ethylene / α-olefin copolymer rubber, ethylene / α-olefin / diene copolymer rubber, acrylonitrile / butadiene copolymer rubber, chloroprene rubber, and halogenated butyl rubber The rubber composition according to claim 8, comprising at least one rubber selected from the group consisting of 80 to 0% by mass (provided that the modified conjugated diene polymer + rubber = 100% by mass).