JP5282531B2 - Method for producing hydrogenated conjugated diene polymer rubber, hydrogenated conjugated diene polymer rubber, composition thereof, and rubber molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing hydrogenated conjugated diene-based polymerization rubber, by which the hydrogenated conjugated diene-based polymerization rubber having high Mooney viscosity, excellent shape stability and excellent processability can be obtained successfully. <P>SOLUTION: The method for manufacturing the hydrogenated conjugated diene-based polymerization rubber includes the steps of: hydrogenating such a conjugated diene-based polymer that an alkoxysilyl group and a (protected) primary amino group are bonded to a polymer comprising a conjugated diene unit at the least and the vinyl bond content of the conjugated diene portion is 20-70% so that the hydrogenated rate of the conjugated diene portion is &ge;50% to obtain a hydrogenated diene-based polymer; and reacting at least one compound of metal halides and organic acidic compounds with the obtained hydrogenated diene-based polymer to obtain the hydrogenated conjugated diene-based polymerization rubber. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a method for producing a hydrogenated conjugated diene polymer rubber, a hydrogenated conjugated diene polymer rubber, a composition thereof, and a rubber molded product. More specifically, a method for producing a hydrogenated conjugated diene polymer rubber having a high Mooney viscosity and excellent shape stability, and a water produced by such a method. The present invention relates to a conjugated diene polymer rubber, a rubber composition thereof, and a rubber molded product.

  In an engine room of an automobile or the like, an anti-vibration rubber for engine mounting is disposed. Diene rubbers such as natural rubber (NR) are widely used as a material for the vibration-proof rubber. In addition, ethylene / α-olefin copolymer rubber is known as a material for vibration-insulating rubbers such as wire covering materials, electrical insulation materials, general industrial rubber products, and civil engineering and building materials. The characteristics were not always sufficient.

  Therefore, recently, a rubber composition in which a cross-linked product obtained by cross-linking a functional group-containing polymer with a metal component is blended with an ethylene / α-olefin copolymer rubber (for example, see Patent Document 1), ethylene / α -A rubber composition in which a functional group-containing polymer and a silica-based filler are blended with an olefin copolymer rubber (for example, see Patent Document 2) is disclosed.

JP 2004-67831 A JP 2004-83622 A

  However, the rubber compositions described in Patent Documents 1 and 2 have a low Mooney viscosity and poor shape stability (for example, poor cold flow), so that the shape changes during storage of the polymer rubber and is difficult to handle. There was a problem.

  The present invention has been made in view of such problems of the prior art, and can produce a hydrogenated conjugated diene polymer rubber having a high Mooney viscosity, excellent shape stability, and good workability. The present invention provides a method for producing a hydrogenated conjugated diene polymer rubber, a hydrogenated conjugated diene polymer rubber obtained by such a method, a composition thereof, and a rubber molded product.

  According to the present invention, the following method for producing a hydrogenated conjugated diene polymer rubber, a hydrogenated conjugated diene polymer rubber, a composition thereof, and a rubber molded article are provided.

[1] A conjugated diene system in which an alkoxysilyl group and an optionally protected primary amino group are bonded to a polymer containing at least a conjugated diene unit, and the vinyl bond content of the conjugated diene moiety is 20 to 70% The polymer is hydrogenated so that the hydrogenation rate of the conjugated diene moiety is 50% or more to obtain a hydrogenated diene polymer, and the obtained hydrogenated diene polymer is added to a metal halide compound. A method for producing a hydrogenated conjugated diene polymer rubber comprising a step of obtaining a hydrogenated conjugated diene polymer rubber by reacting at least one compound with an organic compound having an acidic group .

[2] The hydrogenated conjugated diene polymer rubber according to [1], wherein a conjugated diene compound homopolymer or a copolymer of a conjugated diene compound and an aromatic vinyl compound is used as the polymer containing the conjugated diene unit. Manufacturing method.

[3] The process for producing a hydrogenated conjugated diene polymer rubber according to [1] or [2], wherein a metal halide that generates hydrogen halide by hydrolysis is used.

[4] As the metal halogen compound, at least one metal selected from the group consisting of silicon (Si), tin (Sn), aluminum (Al), zinc (Zn), titanium (Ti), and zirconium (Zr). The method for producing a hydrogenated conjugated diene polymer rubber according to any one of [1] to [3], wherein an atom-containing one is used.

[5] Examples of the metal halogen compound include trimethylsilyl chloride, dimethyldichlorosilane, methyltrichlorosilane, silicon tetrachloride, methyldichlorosilane, tin tetrachloride, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, zinc chloride, tetrachloride. The method for producing a hydrogenated conjugated diene polymer rubber according to any one of the above [1] to [4], wherein at least one compound selected from the group consisting of titanium, titanocene dichloride, zirconium tetrachloride, and zirconocene dichloride is used.

[6] Any of the above [1] to [5], wherein at least one compound selected from the group consisting of an acidic phosphate compound, a carboxylic acid compound, and a sulfonic acid compound is used as the organic compound having an acidic group . A process for producing a hydrogenated conjugated diene polymer rubber as described in 1.

[7] As the organic acidic compound, butyl phosphate, dibutyl phosphate, 2-ethylhexyl phosphate, bis (2-ethylhexyl) phosphate, tridecyl polyoxyethylene glycolate phosphate, bis (tridecyl polyoxy phosphate) [1] to [6], wherein at least one compound selected from the group consisting of ethylene glycolate), nonylphenyl polyoxyethylene glycolate phosphate, and bis (nonylphenyl polyoxyethylene glycolate) phosphate is used. A method for producing a hydrogenated conjugated diene polymer rubber according to any one of the above.

[8] The method for producing a hydrogenated conjugated diene polymer rubber according to any one of [1] to [7], wherein a polymer obtained by the following reaction (I) is used as the conjugated diene polymer.

  Reaction (I): An initiator containing at least one of an organic alkali metal and an organic alkaline earth metal is added to a hydrocarbon solvent containing a conjugated diene compound or a conjugated diene compound and an aromatic vinyl compound. A polymer is obtained by anionic polymerization, and at least one of a compound represented by the following general formula (1) and a compound represented by the following general formula (2) is reacted at the polymerization active terminal of the obtained polymer. Let

(However, in the general formula (1), ^{R 1} is an alkylene group having 1 to 12 carbon atoms, an alkyl group or an aryl group of ^{R 2} and ^{R 3} carbon atoms each independently 1 to ^{20, R} 4, R ⁵ and R ⁶ are each independently an alkyl group or aryl group having 1 to 20 carbon atoms, or two of them may be bonded to each other to form a ring containing a silicon atom to which they are bonded. Well, g is an integer from 1 to 2, and f is an integer from 1 to 10.)

(However, in General Formula (2), the definitions of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are the same as those in General Formula (1), and e is an integer of 1 to 2). is there.)

[9] In the step of reacting at least one of the metal halide compound and the organic compound having an acidic group, an addition that is added to the hydrogenated diene polymer during the polymerization of the conjugated diene polymer The total number of moles of organic groups contained in the organic alkali metal and organic alkaline earth metal as the agent and the organic alkali metal and organic alkaline earth metal as the hydrogen catalyst activator added during the hydrogenation. [1] The hydrogenated conjugated diene polymer rubber is obtained by reacting an amount of a compound in which the total number of moles of the halogen atom in the halogen compound and the acidic group in the organic compound having an acidic group is 0.5 to 10 times. ] The manufacturing method of the hydrogenated conjugated diene type polymer rubber in any one of [8].

[10] A hydrogenated conjugated diene polymer rubber obtained by the method for producing a hydrogenated conjugated diene polymer rubber according to any one of [1] to [9].

[11] A rubber component and a filler are contained, and at least the hydrogenated conjugated diene-based polymer rubber according to [10] is included as the rubber component, and 5 parts of the filler with respect to 100 parts by mass of the rubber component. A hydrogenated conjugated diene polymer rubber composition containing -200 parts by mass.

[12] The rubber component includes a rubber component other than the hydrogenated conjugated diene polymer rubber, and a ratio of the mass of the hydrogenated conjugated diene polymer rubber to the total mass of the rubber component is 20% by mass or more. The hydrogenated conjugated diene polymer rubber composition according to the above [11].

[13] The hydrogenated conjugated diene polymer rubber composition according to [11] or [12], wherein the filler is at least one of silica and carbon black.

[14] A rubber molded article comprising a crosslinked rubber composition obtained by crosslinking the hydrogenated conjugated diene polymer rubber composition according to any one of [11] to [13].

  According to the present invention, a method for producing a hydrogenated conjugated diene polymer rubber, which can produce a hydrogenated conjugated diene polymer rubber having a high Mooney viscosity, excellent shape stability, and good processability, A hydrogenated conjugated diene polymer rubber obtained by the production method, a composition thereof, and a rubber molded product can be provided.

  Hereinafter, although the best mode for carrying out the present invention will be described, the present invention is not limited to the following embodiment. That is, it is understood that modifications and improvements as appropriate to the following embodiments also belong to the scope of the present invention based on ordinary knowledge of those skilled in the art without departing from the spirit of the present invention. Should.

[1] Method for producing hydrogenated conjugated diene polymer rubber:
In the method for producing a hydrogenated conjugated diene polymer rubber according to this embodiment, a conjugated diene moiety in which an alkoxysilyl group and an optionally protected primary amino group are bonded to a polymer containing at least a conjugated diene unit. A hydrogenated diene polymer was obtained by hydrogenating a conjugated diene polymer having a vinyl bond content of 20 to 70% so that the hydrogenation rate of the conjugated diene portion was 50% or more. By reacting a hydrogenated diene polymer with at least one of a metal halogen compound and an organic compound having an acidic group (hereinafter sometimes referred to as “organic acidic compound”) , a hydrogenated conjugated diene is obtained. This is a method for producing a hydrogenated conjugated diene polymer rubber comprising a step of obtaining a polymer polymer rubber.

  By the production method including the steps described above, a hydrogenated conjugated diene polymer rubber having high Mooney viscosity and excellent shape stability, that is, low cold flow can be easily produced. Furthermore, the hydrogenated conjugated diene polymer rubber obtained in this manner is easy to vulcanize when obtaining a rubber composition, and is obtained by crosslinking an excellent rubber composition and the rubber composition. A rubber molded product comprising the crosslinked rubber composition can be obtained satisfactorily.

[1-1] Conjugated diene polymer:
In the method for producing a hydrogenated conjugated diene polymer rubber according to the present embodiment, the conjugated diene polymer used as the base polymer may be protected with an alkoxysilyl group in a polymer containing at least a conjugated diene unit. It is a conjugated diene polymer having a vinyl bond content of 20 to 70% in the conjugated diene moiety to which a secondary amino group is bonded.

  That is, this conjugated diene polymer is a polymer containing at least a conjugated diene unit (hereinafter sometimes referred to as “diene polymer”), and a specific modifier (for example, a primary amino group and an alkoxysilyl group). And a polymer (conjugated diene polymer) containing an alkoxysilyl group and a primary amino group which may be protected.

  The polymer containing at least a conjugated diene unit (diene polymer) is preferably a homopolymer of a conjugated diene compound or a copolymer of a conjugated diene compound and an aromatic vinyl compound. Such a conjugated diene polymer is excellent in hysteresis loss characteristics, wear resistance, and fracture characteristics.

  The content of an optionally protected primary amino group bonded to the conjugated diene polymer (hereinafter sometimes simply referred to as “primary amino group”) is preferably 0.5 to 200 mmol / kg. -It is a polymer. The content is more preferably 1 to 100 mmol / kg · polymer, and particularly preferably 2 to 50 mmol / kg · polymer.

  Here, “mmol / kg · polymer” means the number of moles (mmol) of primary amino groups relative to the total mass (kg) of the polymer component. The total mass of the above-described polymer component means the mass of only the polymer component that does not contain an additive such as an anti-aging agent added during or after production.

  The primary amino group may be bonded to any of the polymerization initiation terminal, the polymerization termination terminal, the polymer main chain, and the side chain, but can suppress the loss of energy from the polymer terminal and improve the hysteresis loss characteristics. From this point, it is preferably introduced at the polymerization initiation terminal or the polymerization termination terminal.

  Moreover, when the number of primary amino groups bonded to the polymer exceeds 200 mmol / kg · polymer, the interaction with a filler (reinforcing agent) such as carbon black or silica is high in the rubber composition. It may become too much and a compounding viscosity may improve and workability may deteriorate. On the other hand, when the number of primary amino groups is less than 0.5 mmol / kg · polymer, it becomes difficult to obtain interaction with the filler.

  The content of the alkoxysilyl group bonded to the polymer is preferably 0.5 to 200 mmol / kg · polymer. The content is more preferably 1 to 100 mmol / kg · polymer, and particularly preferably 2 to 50 mmol / kg · polymer.

  The alkoxysilyl group may be bonded to any of the polymerization initiation terminal, the polymerization termination terminal, the polymer main chain, and the side chain, but it can improve hysteresis loss characteristics by suppressing energy loss from the polymer terminal. It is preferably introduced at the end of polymerization.

  In addition, when the number of alkoxysilyl groups bonded to the polymer exceeds 200 mmol / kg / polymer, the interaction with the filler (reinforcing agent) such as carbon black or silica becomes too high in the rubber composition. As a result, the compounding viscosity may be improved and the processability may be deteriorated. On the other hand, when the number of alkoxysilyl groups is less than 0.5 mmol / kg · polymer, it becomes difficult to obtain an interaction with the filler.

  Further, as described above, the conjugated diene polymer used in the production method of the present embodiment needs to have a vinyl bond content of the conjugated diene portion of 20 to 70%. When the vinyl bond content of the conjugated diene moiety is less than 20%, the low temperature resistance is remarkably deteriorated. On the other hand, if the vinyl bond content of the conjugated diene moiety exceeds 70%, the vibration-proof property is lowered. Here, the “vinyl bond content” in the present specification is the total content of 1,2-vinyl bond and 3,4-vinyl bond calculated by the Hampton method using an infrared analysis method.

  In addition, although it does not specifically limit, It is preferable that the vinyl bond content of the conjugated diene part of this conjugated diene polymer is 30 to 60%, and it is still more preferable that it is 35 to 45%.

  Moreover, although it does not specifically limit, It is preferable that the weight average molecular weights of the conjugated diene polymer used for the manufacturing method of this embodiment are 200,000 to 1.7 million, and 200,000 to 600,000. Is more preferable, and 200,000 to 400,000 is particularly preferable.

  If the weight average molecular weight is less than 200,000, it may be difficult to achieve high vibration isolation performance. On the other hand, if it exceeds 1.7 million, the viscosity is too high, the workability is lowered, the kneading tendency tends to be poor, and it may be difficult to sufficiently exhibit the vibration proofing property. Here, in this specification, “weight average molecular weight (Mw)” is a value in terms of polystyrene using gel permeation chromatography (GPC).

  The polymer containing at least a conjugated diene unit used in the conjugated diene polymer is preferably a homopolymer of a conjugated diene compound or a copolymer of a conjugated diene compound and an aromatic vinyl compound. Specifically, a styrene-butadiene copolymer (SBR) can be cited as a preferred example.

  Such a conjugated diene polymer includes, for example, a conjugated diene compound or a hydrocarbon solvent containing a conjugated diene compound and an aromatic vinyl compound containing at least one of an organic alkali metal and an organic alkaline earth metal. An anionic polymerization is carried out by adding an agent to obtain a polymer, and the resulting polymer is obtained by adding a compound having a protected primary amino group and an alkoxysilyl group and reacting with the end of the living polymer. be able to. As a more specific method, the following reaction (I) can be mentioned, for example.

  Reaction (I): Anionic polymerization by adding an initiator containing at least one of an organic alkali metal and an organic alkaline earth metal to a conjugated diene compound or a hydrocarbon solvent containing a conjugated diene compound and an aromatic vinyl compound. A polymer is obtained, and at least one of a compound represented by the following general formula (1) and a compound represented by the following general formula (2) is reacted with the polymerization active terminal of the obtained polymer.

However, in the general formula (1), ^{R 1} is an alkylene group having 1 to 12 carbon atoms, an alkyl group or an aryl group of ^{R 2} and ^{R 3} carbon atoms each independently 1 to ^{20, R} 4, R ⁵ and R ⁶ are each independently an alkyl group or aryl group having 1 to 20 carbon atoms, or two of them may be bonded to each other to form a ring containing a silicon atom to which they are bonded. , G is an integer of 1 to 2, and f is an integer of 1 to 10.

However, in the general formula (2), the definitions of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are the same as those in the general formula (1), and e is an integer of 1 to 2. .

  According to the reaction (I), the primary amino group and the alkoxysilyl group can be easily introduced simultaneously in a one-step reaction, and a high introduction rate can be obtained.

The general formula (1) and general formula (2), the alkylene group having 1 to 12 carbon atoms of R ^1, for example, a methylene group, an ethylene group and propylene group.

^The alkyl groups ^{R 2, R 3, R 4} , R 5 and carbon atoms as ^{R 6} 1 to 20, for example, a methyl group, an ethyl group, and propyl group.

  Moreover, as an aryl group, a phenyl group, a toluyl group, and a naphthyl group can be mentioned, for example.

In addition, when two of R ⁴ , R ⁵ , and R ⁶ are bonded to form a ring containing a silicon atom to which they are bonded, a 4- to 7-membered ring is preferable.

  An example of the protective group for protecting the amino group is an alkylsilyl group. Examples of the alkylsilyl group include a trimethylsilyl group, a triethylsilyl group, a triphenylsilyl group, a methyldiphenylsilyl group, and an ethylmethylphenylsilyl group.

  Examples of the compound having a protected primary amino group and alkoxysilyl group include N, N-bis (trimethylsilyl) aminopropylmethyldimethoxysilane, 1-trimethylsilyl-2,2-dimethoxy-1-aza-2- Silacyclopentane, N, N-bis (trimethylsilyl) aminopropyltrimethoxysilane, N, N-bis (trimethylsilyl) aminopropyltriethoxysilane, N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane, N, N -Bis (trimethylsilyl) aminoethyltrimethoxysilane, N, N-bis (trimethylsilyl) aminoethyltriethoxysilane, N, N-bis (trimethylsilyl) aminoethylmethyldimethoxysilane, and N, N-bis (trimethylsilyl) aminoethyl It can be exemplified methyl diethoxy silane. Preferably, N, N-bis (trimethylsilyl) aminopropylmethyldimethoxysilane, N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane, or 1-trimethylsilyl-2,2-dimethoxy-1-aza-2 -Silacyclopentane.

The reaction of the living polymer terminal (for example, P ^- Li ⁺ ) and N, N-bis (trimethylsilyl) aminopropylmethyldimethoxysilane can be represented by the following reaction formula (3).

  In the above reaction formula (3), P represents a polymer containing a conjugated diene unit (specifically, a polymer of a conjugated diene compound or a copolymer of a conjugated diene compound and an aromatic vinyl compound). ing.

Similarly, the reaction between the terminal of the living polymer (for example, P ^- Li ⁺ ) and 1-trimethylsilyl-2,2-dimethoxy-1-aza-2-silacyclopentane is represented by the following reaction formula (4). Can do.

  In addition, the 1-trimethylsilyl-2,2-dimethoxy-1-aza-2-silacyclopentane described above can react with two molecules of the living polymer terminal, and at that time, it can be represented by the following reaction formula (5). Can do.

  Moreover, the conjugated diene polymer used in the method for producing the hydrogenated conjugated diene polymer rubber of the present embodiment is, for example, a conjugated diene compound or a hydrocarbon solvent containing a conjugated diene compound and an aromatic vinyl compound. A lithium amide initiator represented by the following general formula (6) or general formula (7) is added and anionic polymerized to obtain a polymer, and the resulting polymer is represented by the following general formula (8) It can be obtained by adding an alkoxysilane compound and reacting with the terminal of the living polymer.

However, in the general formula (6), the definitions of R ¹ , R ⁴ , R ⁵ and R ⁶ are the same as those in the general formula (1).

However, in the general formula (7), the definition of R ¹ is the same as that in the general formula (1), and R ⁷ and R ⁸ are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group. , D is an integer of 1-7.

However, in the general formula (8), the definition of ^{R 2} and ^{R 3} are the same as the general formula (1), X is a halogen atom, c is an integer of 0 to 2, b is 1 to 4 [However, c + b is an integer of 2 to 4.]

  The conjugated diene polymer thus obtained is a polymer obtained by polymerizing a conjugated diene compound, or a conjugated diene compound, an aromatic vinyl compound, and optionally a third monomer that can be copolymerized.

  Examples of the conjugated diene constituting the conjugated diene polymer include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, and 1,3-pentadiene. , And mixtures thereof.

  As content of a conjugated diene unit, it is preferable that it is 60-100 mass% in all the monomers, It is still more preferable that it is 80-100 mass%, It is especially preferable that it is 90-100 mass%. For example, if it is less than 60% by mass, the hysteresis loss may increase.

  Examples of the aromatic vinyl compound include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, and 4-tert-butyl. Styrene, divinylbenzene, tert-butoxystyrene, vinylbenzyldimethylamine, (4-vinylbenzyl) dimethylaminoethyl ether, N, N-dimethylaminoethylstyrene, 2-t-butylstyrene, 3-t-butylstyrene, 4 -T-butyl styrene, vinyl pyridine, a mixture thereof, etc. can be mentioned.

  Of these, styrene is particularly preferred. The content of the structural unit derived from such an aromatic vinyl compound is preferably 40% by mass or less, more preferably 30% by mass or less, and more preferably 25% by mass or less in all monomers. It is particularly preferred. If it exceeds 40% by mass, the vibration-proof property may be deteriorated.

  Examples of the third monomer include acrylonitrile, methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, hydroxyethyl methacrylate, and hydroxyethyl acrylate. The content of the structural unit derived from the third monomer is preferably 40% by mass or less in all monomers, more preferably 30% by mass or less, and particularly preferably 25% by mass or less. . If it exceeds 40% by mass, the vibration-proof property may be deteriorated.

[1-1A] Preparation method of conjugated diene polymer:
Next, a method (first method) for preparing a conjugated diene polymer used in the method for producing a hydrogenated conjugated diene polymer rubber according to this embodiment will be described.

  The polymerization reaction for obtaining the conjugated diene polymer, and the reaction between the primary amino group (protected primary amino group) and the compound having an alkoxysilyl group are usually performed at a temperature of 0 to 120 ° C. It is performed in a range, and may be a constant temperature condition or an elevated temperature condition.

  The hydrolysis for deprotecting the protected primary amino group is preferably performed in a temperature range of 80 to 150 ° C, and more preferably in a temperature range of 90 to 120 ° C. Moreover, it is preferable to carry out by reacting for 10 minutes or more by adding two or more moles of water or acidic water of the compound having a protected primary amino group and alkoxysilyl group. The reaction time is more preferably 30 minutes or longer. The polymerization method may be either a batch polymerization method or a continuous polymerization method.

  Examples of organic alkali metal and organic alkaline earth metal initiators used in the polymerization include n-butyllithium, sec-butyllithium, alkyllithium such as t-butyllithium, alkylene diene such as 1,4-dilithiobutane. Lithium, phenyllithium, stilbene lithium, lithium naphthalene, sodium naphthalene, potassium naphthalene, n-butylmagnesium, n-hexylmagnesium, ethoxycalcium, calcium stearate, t-butoxystrontium, ethoxybarium, isopropoxybarium, ethyl mercaptobarium t- Examples include butoxybarium, phenoxybarium, diethylaminobarium, and barium stearate.

  The organic alkali metal as the initiator can be used for the copolymerization of a conjugated diene and an aromatic vinyl compound as a reaction product with a secondary amine compound or a tertiary amine compound. As the organic alkali metal to be reacted with the secondary amine compound or the tertiary amine compound, an organic lithium compound is preferable. More preferable examples include n-butyl lithium, sec-butyl lithium, and t-butyl lithium.

  The usage-amount of an initiator is 0.002-0.1 millimoles in conversion of an alkali metal atom or alkaline-earth metal atom with respect to 1g of total amounts of a conjugated diene compound, an aromatic vinyl compound, and another compound. It is preferably 0.005 to 0.03 mmol.

  Examples of secondary amine compounds to be reacted with an organic alkali metal include dimethylamine, diethylamine, dipropylamine, di-n-butylamine, di-sec-butylamine, dipentylamine, dihexylamine, di-n-octylamine, Di- (2-ethylhexyl) amine, dicyclohexylamine, N-methylbenzylamine, diallylamine, morpholine, piperazine, 2,6-dimethylmorpholine, 2,6-dimethylpiperazine, 1-ethylpiperazine, 2-methylpiperazine, 1- Benzylpiperazine, piperidine, 3,3-dimethylpiperidine, 2,6-dimethylpiperidine, 1-methyl-4- (methylamino) piperidine, 2,2,6,6-tetramethylpiperidine, pyrrolidine, 2,5-dimethyl Pyrrolidine, azetidine , Hexamethyleneimine, heptamethyleneimine, 5-benzyloxyindole, 3-azaspiro [5,5] undecane, 3-azabicyclo [3.2.2] nonane may be mentioned carbazole.

  Examples of the tertiary amine compound to be reacted with the organic alkali metal include N, N-dimethyl-o-toluidine, N, N-dimethyl-p-toluidine, N, N-dimethyl-m-toluidine, α- Picoline, β-picoline, γ-picoline, benzyldimethylamine, benzyldiethylamine, benzyldipropylamine, benzyldibutylamine, (o-methylbenzyl) dimethylamine, (m-methylbenzyl) dimethylamine, (p-methylbenzyl) Dimethylamine, N, N-tetramethylene-o-toluidine, N, N-heptamethylene-o-toluidine, N, N-hexamethylene-o-toluidine, N, N-trimethylenebenzylamine, N, N-tetra Methylenebenzylamine, N, N-hexamethylenebenzylamine, N, N-tetra Tylene (o-methylbenzyl) amine, N, N-tetramethylene (p-methylbenzyl) amine, N, N-hexamethylene (o-methylbenzyl) amine, N, N-hexamethylene (p-methylbenzyl) amine Etc.

  For the polymerization, diethyl ether, di-n-butyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, tetrahydrofuran, 2 , 2- (bistetrahydrofurfuryl) propane, bistetrahydrofurfuryl formal, methyl ether of tetrahydrofurfuryl alcohol, ethyl ether of tetrahydrofurfuryl alcohol, butyl ether of tetrahydrofurfuryl alcohol, α-methoxytetrahydrofuran, dimethoxybenzene, dimethoxyethane Ether compounds and / or triethylamine, etc. Lysine, N, N, N ′, N′-tetramethylethylenediamine, dipiperidinoethane, methyl ether of N, N-diethylethanolamine, ethyl ether of N, N-diethylethanolamine, N, N-diethylethanol A tertiary amine compound such as butyl ether of amine can be added to the polymerization system to adjust the microstructure (vinyl bond content) of the conjugated diene portion of the conjugated diene polymer.

  Examples of the hydrocarbon solvent include pentane, hexane, heptane, octane, methylcyclopentane, cyclohexane, benzene, toluene, xylene and the like. Of these, cyclohexane and heptane are preferred.

  The amount of the hydrocarbon solvent used is preferably such that the total concentration of the conjugated diene compound, aromatic vinyl compound, and other compounds is 5 to 30% by mass, and more preferably 7 to 20% by mass.

  In the production of a conjugated diene polymer, when the reactivity of the initiator used is to be improved, the aromatic vinyl compound introduced into the polymer is randomly arranged, or the aromatic vinyl compound When it is intended to impart a single chain, a potassium compound may be added together with the polymerization initiator.

  Examples of the potassium compound added together with the polymerization initiator include potassium isopropoxide, potassium t-butoxide, potassium t-amyloxide, potassium n-heptaoxide, potassium benzyloxide, and potassium alkoxide represented by potassium phenoxide. Potassium phenoxide; potassium salts such as isovaleric acid, caprylic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linolenic acid, benzoic acid, phthalic acid, 2-ethylhexanoic acid; dodecylbenzenesulfonic acid, tetradecylbenzene Potassium salts of organic sulfonic acids such as sulfonic acid, hexadecylbenzenesulfonic acid, octadecylbenzenesulfonic acid; diethyl phosphite, diisopropyl phosphite, diphenyl phosphite, dibutyl phosphite, phosphorous acid Lauryl such as potassium salt of organic phosphite moiety ester.

  These potassium compounds are preferably added in an amount of 0.005 to 0.5 mol per gram atomic equivalent of alkali metal as an initiator. If it is less than 0.005 mol, the effect of adding a potassium compound (initiator reactivity improvement, aromatic vinyl compound randomization or single-chain addition) may not appear, while if it exceeds 0.5 mol, polymerization activity As a result, the productivity is greatly reduced, and the modification efficiency in the reaction of modifying the polymer terminal with a functional group is lowered.

  When producing a conjugated diene polymer, it is also possible to add a coupling agent in combination with an alkoxysilane compound having an amino group (hereinafter sometimes referred to as “amino group-containing alkoxysilane compound”). . Specific examples of the coupling agent are as follows. This coupling agent is added at the stage of producing a conjugated diene polymer with the above-described amino group-containing alkoxysilane compound (specifically, before the amino group-containing alkoxysilane compound).

  That is, as a coupling agent used in combination with an amino group-containing alkoxysilane compound and reacting with a polymerization active terminal, (a) at least one compound of an isocyanate compound and an isothiocyanate compound, (b) an amide compound and an imide At least one of the compounds, (c) at least one of a pyridyl-substituted ketone compound and a pyridyl-substituted vinyl compound, (d) a silicon compound, (e) an ester compound, (f) a ketone compound, and (g) tin There may be mentioned at least one compound selected from the group consisting of compounds.

  Among these compounds, as the isocyanate compound or thioisocyanate compound as component (a), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, polymeric type diphenylmethane Preferred examples include diisocyanate (C-MDI), isophorone diisocyanate, hexamethylene diisocyanate, 1,3,5-benzenetriisocyanate, phenyl-1,4-diisothiocyanate, and the like. .

  As the amide compound or imide compound as component (b), succinic acid amide, phthalic acid amide, N, N, N ′, N′-tetramethylphthalic acid amide, oxamide, N, N, N ′, N′— Preferable examples include amide compounds such as tetramethyl oxamide, succinimides, N-methyl succinimides, maleimides, N-methyl maleimides, phthalimides, N-methyl phthalimides, and the like.

  Preferred examples of the pyridyl-substituted ketone compound or pyridyl-substituted vinyl compound as component (c) include dibenzoylpyridine, diacetylpyridine, divinylpyridine and the like.

  As the silicon compound as component (d), dibutyldichlorosilicon, methyltrichlorosilicon, methyldichlorosilicon, tetrachlorosilicon, triethoxymethylsilane, triphenoxymethylsilane, trimethoxysilane, methyltriethoxysilane, 4,5- Preferred examples include epoxyheptylmethyldimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, and the like.

  (E) As an ester compound which is a component, diethyl adipate, diethyl malonate, diethyl phthalate, diethyl glutarate, diethyl maleate, etc. can be mentioned as a suitable example.

  Specific examples of the ketone compound as component (f) include N, N, N ′, N′-tetramethyl-4,4′-diaminobenzophenone, N, N, N ′, N′-tetraethyl (4,4 '-Diamino) -benzophenone, N, N-dimethyl-1-aminobenzoquinone, N, N, N', N'-tetramethyl-1,3-diaminobenzoquinone, N, N-dimethyl-1-aminoanthraquinone, N , N, N ′, N′-tetramethyl-1,4-diaminoanthraquinone and the like can be mentioned as preferred examples.

  (G) As a tin compound which is a component, tetrachlorotin, tetrabromotin, trichlorobutyltin, trichloromethyltin, trichlorooctyltin, dibromodimethyltin, dichlorodimethyltin, dichlorodibutyltin, dichlorodioctyltin, 1,2- Bis (trichlorostannyl) ethane, 1,2-bis (methyldichlorostannylethane), 1,4-bis (trichlorostannyl) butane, 1,4-bis (methyldichlorostannyl) butane, ethyltin tristearate Preferred examples include rate, butyltin trisoctanoate, butyltin trisstearate, butyltin trislaurate, dibutyltin bisoctanoate, dibutyltin bisstearate, dibutyltin bislaurate, and the like.

  These compounds to be reacted with the polymerization active terminal in combination with the amino group-containing alkoxysilane compound can be used singly or in combination of two or more.

  The amount of the coupling agent used is preferably 1 mol or less as the amount of the substituent capable of coupling in the coupling agent per gram atomic equivalent of the alkali metal of the initiator, More preferably, it is less than or equal to mol. For example, when the amount exceeds 1 mol, the reaction rate when reacting at least one of the compound represented by the general formula (1) and the compound represented by the general formula (2) is expected to decrease. Performance may not be obtained.

  Next, another method (second method) for producing a conjugated diene polymer used in the method for producing a hydrogenated conjugated diene polymer rubber of this embodiment will be described. As another method for producing a conjugated diene polymer, a conjugated diene or a conjugated diene and an aromatic vinyl compound are represented by the general formula (6) or the general formula (7) in a hydrocarbon solvent. An anion polymerization is performed using a lithium amide initiator to obtain a polymer, and the resulting polymer is reacted with the end of the living polymer by adding an alkoxysilane compound represented by the general formula (8).

  The polymerization reaction with the lithium amide initiator in which the primary amino group is protected and the reaction with the alkoxysilane compound are performed, for example, in a temperature range of 0 to 120 ° C., and may be performed under constant temperature conditions or elevated temperature conditions. . The hydrolysis for deprotecting the protected primary amino group is, for example, 2 of lithium amide initiator in which the primary amino group is protected in the temperature range of 80 to 150 ° C., preferably 90 to 120. It can be carried out by adding double moles or more of water or acidic water and reacting for 10 minutes or more, preferably 30 minutes or more. The polymerization method may be either a batch polymerization method or a continuous polymerization method.

  In addition, it should be understood that matters other than those described below are applied as they are or with modifications obvious to those skilled in the art described in the above method (first method).

  Examples of the lithium amide initiator represented by the general formula (6) include 3- [N, N-bis (trimethylsilyl)]-1-propyllithium, 3- [N, N-bis (trimethylsilyl)]- 2-methyl-1-propyllithium, 3- [N, N-bis (trimethylsilyl)]-2,2-dimethyl-1-propyllithium, 4- [N, N-bis (trimethylsilyl)]-1-butyllithium , 5- [N, N-bis (trimethylsilyl)]-1-pentyllithium and 8- [N, N-bis (trimethylsilyl)]-1-octyllithium.

  Examples of the lithium amide initiator represented by the general formula (7) include 3- (2,2,5,5, -tetramethyl-2,5-disila-1-azacyclopentane) -1 -Propyl lithium, 2-methyl-3- (2,2,5,5, -tetramethyl-2,5-disila-1-azacyclopentane) -1-propyl lithium, 2,2-dimethyl-3- ( 2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentane) -1-propyllithium, 4- (2,2,5,5, -tetramethyl-2,5-disila -1-Azacyclopentane) -1-butyllithium, 6- (2,2,5,5, -tetramethyl-2,5-disila-1-azacyclopentane) -1-hexyllithium and the like. it can.

  The lithium amide initiator may be a synthetic product obtained by reacting a corresponding halide and an organic lithium compound in a hydrocarbon solvent. The reaction between halide and organolithium may be performed in advance in a reaction vessel separate from the polymerization reactor.

  Furthermore, examples of the alkoxysilane compound represented by the above formula (8) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetratoluoxysilane, methyltrimethoxysilane, and methyl. Triethoxysilane, methyltripropoxysilane, methyltributoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, ethyltriphenoxysilane, dimethyldimethoxysilane, dimethyldi Ethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, die Distearate propoxysilane, diethyl dibutoxy silane, diethyl diphenoxy silane,

  Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltributoxysilane, vinyltriphenoxysilane, allyltriphenoxysilane, octenyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane And phenyltributoxysilane, phenyltriphenoxysilane, trimethoxychlorosilane, triethoxychlorosilane, tripropoxychlorosilane, tributoxychlorosilane, triphenoxychlorosilane, dimethoxydichlorosilane, dipropoxydichlorosilane, and diphenoxydichlorosilane.

  As the conjugated diene polymer described so far, for example, a conjugated diolefin (co) polymer rubber described in International Publication No. WO 03/029299 A1 relating to an international application by the present applicant is preferably used. be able to.

[1-2] Hydrogenation (Preparation of hydrogenated diene polymer):
In the method for producing a hydrogenated diene polymer rubber of this embodiment, the conjugated diene polymer described above is hydrogenated to obtain a hydrogenated diene polymer having a hydrogenation rate of 50% or more. Thus, hydrogenation has the advantage that heat resistance improves. Moreover, when the hydrogenation rate is low, the elongation of the rubber composition may be deteriorated.

  There are no particular restrictions on the method for hydrogenating the conjugated diene polymer in which the alkoxysilyl group and the primary amino group which may be protected are bonded, and the reaction conditions are not particularly limited. Can do. For example, under hydrogen pressure of 20 to 150 ° C. and 0.1 to 10 MPa, the hydrogenation catalyst can be present. The hydrogenation rate can be appropriately determined by changing the amount of the hydrogenation catalyst, the hydrogen pressure during the hydrogenation reaction, the reaction time, and the like.

  Examples of the hydrogenation catalyst include titanium (Ti), vanadium (V), cobalt (Co), nickel (Ni), zirconium (Zr), ruthenium (Ru), rhodium (Rh), palladium (Pd), hafnium ( And compounds containing atoms such as Hf), rhenium (Re), and platinum (Pt).

  More specific hydrogenation catalysts include metallocene compounds containing atoms such as Ti, Zr, Hf, Co, Ni, Pd, Pt, Ru, Rh, Re, etc .; Pd, Ni, Pt, Rh, Ru, etc. Supported heterogeneous catalyst in which a metal atom is supported on a support such as carbon, silica, alumina, diatomaceous earth; a combination of an organic salt of metal atom such as Ni or Co or an acetylacetone salt and a reducing agent such as organoaluminum Homogeneous Ziegler-type catalysts; organometallic compounds or complexes containing Ru, Rh, etc .; fullerenes or carbon nanotubes that occlude hydrogen.

  Among these, a metallocene compound containing any atom of Ti, Zr, Hf, Co, and Ni is preferable from the viewpoint that a hydrogenation reaction can be performed in a homogeneous system in an inert organic solvent. Furthermore, a metallocene compound containing any of Ti, Zr, and Hf is preferable. In particular, a hydrogenation catalyst obtained by reacting a titanocene compound with an alkyl lithium is preferable because it is an inexpensive and industrially useful catalyst.

The hydrogenation rate of the hydrogenated diene polymer is 50% or more, preferably more than 70%, and more preferably 72% or more. When the hydrogenation rate is less than 50%, the heat resistance is lowered. The upper limit of the hydrogenation rate is not particularly limited, but is substantially 93% or less. Here, in the present specification, the “hydrogenation rate” is a value calculated from a 270 MHz, ¹ H-NMR spectrum using a carbon tetrachloride solution as a solvent.

  The hydrogenated diene polymer preferably has a molecular weight distribution (Mw / Mn) of 1.0 to 4.0, more preferably 1.0 to 3.5, and more preferably 1.0 to 4.0. Particularly preferred is 3.0. If the molecular weight distribution is more than 3.0, it may be difficult to achieve high vibration isolation performance. The molecular weight distribution is represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn). The “number average molecular weight (Mn)” referred to in this specification is a gel permeation chromatography (GPC). ) In terms of styrene equivalent molecular weight.

  In the method for producing a hydrogenated conjugated diene polymer rubber of this embodiment, a hydrogenation catalyst activator of an organic alkali metal and an organic alkaline earth metal is used as an activator for activating the hydrogenation catalyst. it can. Examples of such a hydrogenation catalyst activator include n-butyllithium.

[1-3] Preparation of hydrogenated conjugated diene polymer rubber:
Next, in the method for producing a hydrogenated conjugated diene polymer rubber according to the present embodiment, at least one of a metal halide compound and an organic acidic compound is added to the hydrogenated diene polymer obtained as described above. A hydrogenated conjugated diene polymer rubber is obtained by reacting the compound.

  By comprising in this way, the hydrogenated conjugated diene type | system | group polymer rubber with high Mooney viscosity and excellent shape stability can be manufactured. The hydrogenated conjugated diene polymer rubber obtained by the production method of the present embodiment is considered to have a strong interaction between molecules through alkoxysilyl groups bonded to the polymer.

  In the method for producing a hydrogenated conjugated diene polymer rubber according to this embodiment, after reacting at least one of a metal halogen compound and an organic acidic compound, known in the production of a hydrogenated diene polymer. The hydrogenated conjugated diene polymer rubber can be recovered by removing the solvent (for example, steam stripping) and drying.

  The method for reacting at least one of a metal halogen compound and an organic acidic compound with a hydrogenated diene polymer is not particularly limited. For example, the above compound is directly added to a solution containing the polymer. Or it can be made to react by adding in the state dissolved in the solution and mixing the mixture. In addition, after adding the said compound, it can also make it react by the steam stripping at the time of collect | recovering a polymer.

  Although there is no restriction | limiting in particular about the temperature at the time of this reaction, it is preferable that it is 10-150 degreeC, and it is still more preferable that it is 80-120 degreeC.

  In the method for producing a hydrogenated conjugated diene polymer rubber according to this embodiment, when a conjugated diene polymer is obtained using an initiator such as the organic alkali metal or organic alkaline earth metal described above, Organic alkali metal and organic alkaline earth metal as the initiator and organic alkali metal and organic alkaline earth metal as a hydrogenation catalyst activator added during hydrogenation to the conjugated diene polymer obtained. It is preferable to react the compound in such an amount that the total number of moles of halogen atoms and acidic groups is 0.5 to 10 times the total number of moles of the group. By comprising in this way, reaction with a compound is fully performed.

  For example, if the total number of moles of halogen atoms and acidic groups contained in the compound to be reacted is too small, the reaction between the hydrogenated diene polymer and the above compound is not sufficiently performed, the Mooney viscosity is high, and the shape stability is high. It is difficult to obtain a hydrogenated conjugated diene-based polymer rubber excellent in water resistance. Further, if the total number of moles of halogen atoms and acidic groups contained in the compound to be reacted exceeds 10 times, the amount of liberated hydrogen halide is increased, or the reactor is corroded to cause production problems. Or the vibration-proof property may be deteriorated due to remaining in the hydrogenated diene copolymer.

  In addition, when reacting only a metal halogen compound, it is preferable to react the metal halogen compound of the quantity which the number of moles of a halogen atom becomes 0.5 to 10 times, and when reacting only an organic acidic compound It is preferable to react an organic acidic compound in an amount such that the number of moles of the acidic group is 0.5 to 10 times.

  In the method for producing a hydrogenated conjugated diene polymer rubber of this embodiment, the ratio of the total number of moles of halogen atoms and acidic groups to the total number of moles of the organic group is 0.8 to 5.0. More preferably, it is particularly preferably 1.0 to 2.0.

[1-3A] Metal halide:
In the method for producing a hydrogenated conjugated diene polymer according to this embodiment, the metal halogen compound used for reacting with the hydrogenated diene polymer described above may be one that generates hydrogen halide by hydrolysis. preferable. By using such a metal halogen compound, the reaction between the hydrogenated diene polymer and the metal halogen compound can be favorably performed.

  In addition, the metal halide compound is at least one metal atom selected from the group consisting of silicon (Si), tin (Sn), aluminum (Al), zinc (Zn), titanium (Ti), and zirconium (Zr). It is preferable to use those containing.

  Specifically, for example, trimethylsilyl chloride, dimethyldichlorosilane, methyltrichlorosilane, silicon tetrachloride, methyldichlorosilane, tin tetrachloride, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, zinc chloride, titanium tetrachloride, Mention may be made of at least one compound selected from the group consisting of titanocene dichloride, zirconium tetrachloride and zirconocene dichloride.

[1-3B] Organic acidic compound:
In the method for producing a hydrogenated conjugated diene polymer of the present embodiment, the organic acidic compound used for reacting with the hydrogenated diene polymer described above is an organic compound having an acidic group. As such an organic acidic compound, at least one compound selected from the group consisting of an acidic phosphate compound, a carboxylic acid compound, and a sulfonic acid compound can be used.

  Specific examples of such organic acidic compounds include butyl phosphate, dibutyl phosphate, 2-ethylhexyl phosphate, bis (2-ethylhexyl) phosphate, tridecyl polyoxyethylene glycolate phosphate, bisphosphate. Mention may be made of at least one compound selected from the group consisting of (tridecyl polyoxyethylene glycolate), nonylphenyl polyoxyethylene glycolate phosphate, and bis (nonylphenyl polyoxyethylene glycolate) phosphate.

  Examples of the carboxylic acid compound include stearic acid, acetic acid, benzoic acid, maleic acid, propionic acid, oleic acid, lactic acid, and formic acid. Examples of the sulfonic acid compound include methanesulfonic acid and benzenesulfone. Examples include acid, p-toluenesulfonic acid, and dodecylbenzenesulfonic acid.

[2] Hydrogenated conjugated diene polymer rubber:
Next, an embodiment of the hydrogenated conjugated diene polymer rubber of the present invention will be described. The hydrogenated conjugated diene polymer rubber of the present embodiment is a hydrogenated conjugated diene polymer rubber obtained by the method for producing a hydrogenated conjugated diene polymer rubber described so far. Such hydrogenated conjugated diene polymer rubber has a high Mooney viscosity, excellent shape stability, and good processability.

The Mooney viscosity (ML _{1 + 4} , 125 ° C.) of the hydrogenated conjugated diene polymer rubber of this embodiment is preferably 35 to 150, and more preferably 40 to 120. If the Mooney viscosity (ML _{1 + 4} , 125 ° C.) is less than 35, rubber properties such as fracture properties tend to decrease. On the other hand, when the Mooney viscosity (ML _{1 + 4} , 125 ° C.) exceeds 150, workability is deteriorated and it may be difficult to knead with the compounding agent.

[3] Hydrogenated conjugated diene polymer rubber composition:
One embodiment of the hydrogenated conjugated diene polymer rubber composition of the present invention (hereinafter sometimes simply referred to as “rubber composition”) contains a rubber component and a filler. A hydrogenated conjugated diene polymer rubber composition comprising the hydrogenated conjugated diene polymer rubber of the present invention and containing 5 to 200 parts by mass of the filler with respect to 100 parts by mass of the rubber component. When the filler content relative to the rubber component is less than 5 parts by mass, the strength may not be sufficiently obtained. On the other hand, when the filler content exceeds 200 parts by mass, the vibration-proof characteristics deteriorate. Sometimes.

  Hereinafter, each component constituting the hydrogenated conjugated diene polymer rubber composition of the present embodiment will be described in more detail. Details will be described.

[3-1] Rubber component:
In the rubber composition of the present embodiment, as described above, the hydrogenated conjugated diene polymer rubber (hereinafter referred to as “the hydrogenated conjugated diene polymer rubber”), which is an embodiment of the present invention, is used as the rubber component. May be included).

  The rubber component may contain one kind of the hydrogenated conjugated diene polymer rubber or two or more kinds of the hydrogenated conjugated diene polymer rubber. In addition to the hydrogenated conjugated diene polymer rubber, other rubber components may be contained. Other rubber components include 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. Examples thereof include rubber, halogenated butyl rubber, and mixtures thereof.

  In addition, as a rubber component in the rubber composition of this embodiment, it is preferable to contain the above hydrogenated conjugated diene-based polymer rubber in an amount of 20% by mass or more, and 50% by mass or more based on the total rubber component. Is more preferable, and it is particularly preferable to include 80% by mass or more.

[3-2] Filler:
The rubber composition of this embodiment contains a filler in addition to the rubber component. In addition, this filler is a reinforcing agent used for a rubber composition.

  As described above, the filler content in the rubber composition of the present embodiment is 5 to 200 parts by mass with respect to 100 parts by mass of the hydrogenated conjugated diene polymer rubber as a rubber component. From the viewpoint of the effect of improving various physical properties, it is preferably 5 to 100 parts by mass, particularly preferably 5 to 70 parts by mass.

  In the rubber composition of the present embodiment, the filler is preferably at least one of silica and carbon black. Specific examples of carbon black include carbon blacks of various grades such as SRF, GPF, FEF, HAF, ISAF, and SAF.

  Carbon black having an iodine adsorption amount (IA) of 60 mg / g or more and a dibutyl phthalate oil absorption amount (DBP) of 80 ml / 100 g or more is preferable. By using carbon black, for example, the effect of improving the grip performance and fracture resistance of the rubber composition is increased. Note that HAF, ISAF, and SAF, which are excellent in wear resistance, are particularly preferable. Carbon black can be used individually or in combination of 2 or more types.

  Specific examples of silica include wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate and the like. Among these, wet silica is most preferable because it has the most remarkable effect of improving the fracture resistance, wet grip properties, and low rolling resistance. Silica can be used alone or in combination of two or more.

  When silica is contained as a filler in the rubber composition of the present embodiment, it is preferable to blend a silane coupling agent in order to further improve the reinforcing effect. 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-dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide 3-trimethoxysilylpropyl benzothiazolyl tetrasulfide, 3-triethoxysilylpropyl benzoyl tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis (3-di Ethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyltetrasulfur It de, can be given dimethoxymethylsilylpropyl benzothiazolyl tetrasulfide and the like.

  Of these, bis (3-triethoxysilylpropyl) polysulfide and 3-trimethoxysilylpropylbenzothiazyltetrasulfide are preferable from the viewpoint of reinforcing effect. In addition, these silane coupling agents can be used individually or in combination of 2 or more types.

  Although the compounding quantity of a silane coupling agent changes with kinds etc. of a silane coupling agent, it is preferable to set it as 1-20 mass% with respect to 100 mass% of silica, and it is still more preferable to set it as 3-15 mass%. . When it is less than 1% by mass, the effect as a coupling agent tends to be hardly exhibited. On the other hand, if it exceeds 20% by mass, the rubber component tends to be easily gelled.

  Various chemicals and additives that are usually used in the rubber industry can be added to the rubber composition of the present embodiment as desired, as long as the object of the present invention is not impaired. Examples of various chemicals and additives that can be added to the rubber composition of the present embodiment include vulcanizing agents, vulcanizing aids, processing aids, vulcanization accelerators, process oils, anti-aging agents, and scorch prevention. Agents, zinc white, stearic acid and the like.

  As the vulcanizing agent, sulfur is usually used, and the amount used is preferably 0.1 to 3 parts by mass, and 0.5 to 2 parts by mass with respect to 100 parts by mass of the raw rubber (rubber component). More preferably, it is part. As the vulcanization aid and processing aid, stearic acid is generally used, and the amount used is 0.5 to 5 parts by mass with respect to 100 parts by mass of the raw rubber (rubber component).

  Further, the vulcanization accelerator is not particularly limited, but preferably M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazylsulfenamide) and the like. A thiazole type vulcanization accelerator can be mentioned, The usage-amount is 0.1-5 mass parts normally with respect to 100 mass parts of raw rubbers (rubber component), and is 0.2-3 mass parts. Preferably there is.

  The rubber composition of the present invention can be produced by kneading using a kneader such as an open kneader including a roll and a closed kneader including a Banbury mixer.

[4] Rubber molded product:
Next, an embodiment of the rubber molded product of the present invention will be described. The rubber molded article of the present embodiment was obtained by crosslinking the hydrogenated conjugated diene polymer rubber composition of the present invention described above (hereinafter sometimes referred to as “the hydrogenated conjugated diene polymer rubber composition”). It consists of a crosslinked rubber composition. The rubber molded product of this embodiment is excellent in performance as a vibration-proof rubber.

  In order to produce a rubber molded article using the hydrogenated conjugated diene polymer rubber composition, first, a crosslinking agent (peroxide, etc.) and necessary for the hydrogenated conjugated diene polymer rubber composition are necessary. Depending on the case, a crosslinking aid (such as sulfur) is added to obtain a compounded rubber composition. The rubber molded product of this embodiment can be manufactured by crosslinking while molding the obtained compounded rubber composition into a predetermined shape.

  The rubber molded product of the present embodiment includes, for example, anti-vibration rubbers; various hoses such as diaphragms, rolls, radiator hoses, air hoses and hose covers; packings, gaskets, weather strips, O-rings, oil seals, etc. Seals; suitable as belts, linings, dust boots, etc. Especially as a rubber molded product of this embodiment, it uses suitably as a vibration-proof rubber.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In the examples and comparative examples, “parts” and “%” are based on mass unless otherwise specified. Moreover, the measuring method and evaluation method of various physical property values are shown below.

  [Vinyl bond content (%)]: Using infrared analysis, the total content of 1,2-vinyl bond and 3,4-vinyl bond was calculated by the Hampton method, and the vinyl bond content (%) did.

[Hydrogenation rate]: Carbon tetrachloride solution was used as a solvent, and calculation was carried out from a 270 MHz, ¹ H-NMR spectrum.

  [Peak molecular weight before denaturation reaction]: Reaction with polyfunctional monomer and silica of GPC curve obtained by using gel permeation chromatography (GPC) (HLC-8120GPC (trade name (manufactured by Tosoh Corporation))) It was calculated in terms of polystyrene from the retention time corresponding to the apex of the peak corresponding to the polymer portion excluding the possible compound and the polymer whose molecular weight was increased by the reaction with the coupling agent.

[Mooney viscosity (ML _{1 + 4} , 125 ° C.)]: Measured according to JIS K6300 using an L rotor under conditions of preheating 1 minute, rotor operating time 4 minutes, and temperature 125 ° C.

  [Cold flow (C / F)]: Cold flow (C / F) was measured by extruding the polymer through a 1/4 inch orifice at a pressure of 3.5 pounds per square inch and a temperature of 50 ° C. In order to obtain a steady state, the extrusion speed was measured after being left for 10 minutes, and the value was expressed in milligrams per minute (mg / min). The cold flow value indicates that the smaller the value, the better the shape stability (storage stability).

[Evaluation and measurement of properties of rubber composition]:
(I) [Mixed Mooney Viscosity]: Using a compounded rubber before vulcanization as a measurement sample, in accordance with JIS K6300, using an L rotor, preheating for 1 minute, rotor operating time of 4 minutes, temperature of 125 ° C. It was measured. Expressed as an index, the larger the value, the better the workability.

(Ii) [Tensile stress (tensile breaking strength (T _B ), tensile breaking elongation (E _B ))]: In accordance with JIS K6251, using a No. 3 type test piece, measuring temperature 23 ° C., tensile speed 500 mm / Measured under the condition of min (normal physical properties).

(Iii) “Static ratio”: For vulcanized rubber, a block-shaped test piece was prepared in accordance with JIS K6394, and the test piece was 70 Hz, dynamic strain 1%, and 0 at a temperature of 25 ° C. The dynamic elastic modulus at 1 Hz and dynamic strain of 10% was measured and obtained as a value calculated by the following formula. In addition, it shows that it is excellent in the anti-vibration characteristic, so that the static motion ratio is close to 1.
Formula: Static ratio = (Dynamic elastic modulus at 70 Hz) / (Dynamic elastic modulus at 0.1 Hz)

Example 1
Cyclohexane (28 kg), tetrahydrofuran (38.5 g), n-butyllithium (1.30 g) and 1,3-butadiene (2500 g) as initiators were added to a reaction vessel with an internal volume of 50 liters purged with nitrogen. Adiabatic polymerization was carried out from 50 ° C. to obtain a polymer (diene polymer).

  Thereafter, N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane (4.90 g) was added as a modifier in the system and reacted at 80 ° C. for 60 minutes. Next, hydrogen gas was supplied into the system at a pressure of 0.4 MPa-Gauge and stirred for 20 minutes, and the unreacted lithium at the end of the diene polymer was reacted with hydrogen to stop the modification reaction.

  Thus, a conjugated diene polymer in which a modifier is introduced at the polymerization active terminal (that is, a polymer in which an alkoxysilyl group and an optionally protected primary amino group are bonded to the diene polymer). ) The vinyl bond content of this conjugated diene polymer was 38%. Further, the peak molecular weight before the modification reaction of this conjugated diene polymer was 280,000.

  Thereafter, the hydrogen gas supply pressure was 0.7 MPa-Gauge, the reaction solution was 90 ° C., and a hydrogenation catalyst mainly composed of titanocene dichloride was added to carry out a hydrogenation reaction. When the hydrogen absorption in the modified diene polymer reached an integrated amount at which the desired hydrogenation rate was reached, the inside of the reaction vessel was purged with nitrogen. In this way, a hydrogenated diene polymer was obtained. The hydrogenated diene polymer had a hydrogenation rate of 91%. In this example, n-butyllithium (0.87 g) was added as a hydrogenation catalyst activator during hydrogenation.

  Silicon tetrachloride (2.26 g) is added as a metal halide to the resulting polymer solution containing the hydrogenated diene polymer, and then the solvent is removed by steam stripping, and the temperature is adjusted to 110 ° C. By drying with a hot roll, a hydrogenated conjugated diene polymer rubber (Example 1) was obtained. Various physical property values and the like of the obtained hydrogenated conjugated diene polymer rubber are shown in Table 1.

  In addition, 2.26 g of silicon tetrachloride is the total number of moles of chlorine atoms with respect to the total number of moles of organic groups contained in 2.17 g (initiator + hydrogen catalyst activator) of n-butyllithium (organic alkali metal). Is 2.29 times (Cl / Li molar ratio 2.29).

(Example 2)
A hydrogenated conjugated diene polymer rubber (Example 2) was obtained in the same manner as in Example 1 except that 3.14 g of silicon tetrachloride was added as the metal halide. Various physical property values and the like of the obtained hydrogenated conjugated diene polymer rubber are shown in Table 1.

(Example 3)
Cyclohexane (28 kg), tetrahydrofuran (52.3 g), n-butyllithium (1.60 g) and 1,3-butadiene (2500 g) are added to a reaction vessel having an internal volume of 50 liters purged with nitrogen, and insulated from 50 ° C. Polymerization was performed to obtain a polymer (diene polymer).

  Thereafter, N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane (6.32 g) was added as a modifier in the system and reacted at 80 ° C. for 60 minutes. Next, hydrogen gas was supplied into the system at a pressure of 0.4 MPa-Gauge and stirred for 20 minutes, and the unreacted lithium at the end of the diene polymer was reacted with hydrogen to stop the modification reaction. Thus, a conjugated diene polymer in which a modifier is introduced at the polymerization active terminal (that is, a polymer in which an alkoxysilyl group and an optionally protected primary amino group are bonded to the diene polymer). ) The vinyl bond content of this conjugated diene polymer was 40%. Moreover, the peak molecular weight before the modification reaction of this conjugated diene polymer was 230,000.

  Thereafter, the hydrogen gas supply pressure was 0.7 MPa-Gauge, the reaction solution was 90 ° C., and a hydrogenation catalyst mainly composed of titanocene dichloride was added to carry out a hydrogenation reaction. When the hydrogen absorption in the modified diene polymer reached an integrated amount at which the desired hydrogenation rate was reached, the inside of the reaction vessel was purged with nitrogen. In this way, a hydrogenated diene polymer was obtained. The hydrogenated diene polymer had a hydrogenation rate of 88%. In this example, n-butyllithium (0.87 g) was added as a hydrogenation catalyst activator during hydrogenation.

  Silicon tetrachloride (2.68 g) is added as a metal halide to the resulting polymer solution containing the hydrogenated diene polymer, and then the solvent is removed by steam stripping, and the temperature is adjusted to 110 ° C. By drying with a hot roll, a hydrogenated conjugated diene polymer rubber (Example 3) was obtained. Various physical property values and the like of the obtained hydrogenated conjugated diene polymer rubber are shown in Table 1. In addition, 2.52 g of silicon tetrachloride is the total number of moles of chlorine atoms relative to the total number of moles of organic groups contained in 2.47 g (initiator + hydrogen catalyst activator) of n-butyllithium (organic alkali metal). Is 2.29 times (Cl / Li molar ratio 2.29).

Example 4
Hydrogenation was carried out in the same manner as in Example 1 except that 2.42 g of butyl acid phosphate (trade name “JP-504”) manufactured by Johoku Chemical Industry Co., Ltd. was added as an organic acidic compound instead of the metal halide. A conjugated diene polymer rubber (Example 4) was obtained. Various physical property values and the like of the obtained hydrogenated conjugated diene polymer rubber are shown in Table 1.

(Example 5)
A hydrogenated conjugated diene polymer rubber (Example 5) was obtained in the same manner as in Example 1 except that 1.60 g of diethylaluminum chloride was added as the metal halide. Various physical property values and the like of the obtained hydrogenated conjugated diene polymer rubber are shown in Table 1.

(Example 6)
Cyclohexane (28 kg), tetrahydrofuran (51.1 g), n-butyllithium (1.30 g) and 1,3-butadiene (2500 g) as initiators were added to a 50-liter reaction vessel purged with nitrogen. Adiabatic polymerization was carried out from 50 ° C. to obtain a polymer (diene polymer).

  Thereafter, N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane (4.90 g) was added as a modifier in the system and reacted at 80 ° C. for 60 minutes. Next, hydrogen gas was supplied into the system at a pressure of 0.4 MPa-Gauge and stirred for 20 minutes, and the unreacted lithium at the end of the diene polymer was reacted with hydrogen to stop the modification reaction.

  Thus, a conjugated diene polymer in which a modifier is introduced at the polymerization active terminal (that is, a polymer in which an alkoxysilyl group and an optionally protected primary amino group are bonded to the diene polymer). ) The vinyl bond content of this conjugated diene polymer was 43%. Moreover, the peak molecular weight before the modification reaction of this conjugated diene polymer was 250,000.

  Thereafter, the hydrogen gas supply pressure was 0.7 MPa-Gauge, the reaction solution was 90 ° C., and a hydrogenation catalyst mainly composed of titanocene dichloride was added to carry out a hydrogenation reaction. When the hydrogen absorption in the modified diene polymer reached an integrated amount at which the desired hydrogenation rate was reached, the inside of the reaction vessel was purged with nitrogen. In this way, a hydrogenated diene polymer was obtained. The hydrogenated diene polymer had a hydrogenation rate of 84%. In this example, n-butyllithium (0.87 g) was added as a hydrogenation catalyst activator during hydrogenation.

  Silicon tetrachloride (2.26 g) is added as a metal halide to the resulting polymer solution containing the hydrogenated diene polymer, and then the solvent is removed by steam stripping, and the temperature is adjusted to 110 ° C. A hydrogenated conjugated diene polymer rubber (Example) was obtained by drying with a hot roll. Various physical property values and the like of the obtained hydrogenated conjugated diene polymer rubber are shown in Table 1.

(Example 7)
Cyclohexane (28 kg), tetrahydrofuran (19.6 g), n-butyllithium (1.30 g) and 1,3-butadiene (2500 g) as initiators were added to a reaction vessel with an internal volume of 50 liters purged with nitrogen. Adiabatic polymerization was carried out from 50 ° C. to obtain a polymer (diene polymer).

  Thereafter, N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane (4.90 g) was added as a modifier in the system and reacted at 80 ° C. for 60 minutes. Next, hydrogen gas was supplied into the system at a pressure of 0.4 MPa-Gauge and stirred for 20 minutes, and the unreacted lithium at the end of the diene polymer was reacted with hydrogen to stop the modification reaction.

  Thus, a conjugated diene polymer in which a modifier is introduced at the polymerization active terminal (that is, a polymer in which an alkoxysilyl group and an optionally protected primary amino group are bonded to the diene polymer). ) The vinyl bond content of this conjugated diene polymer was 34%. Further, the peak molecular weight of the conjugated diene polymer before the modification reaction was 260,000.

  Thereafter, the hydrogen gas supply pressure was 0.7 MPa-Gauge, the reaction solution was 90 ° C., and a hydrogenation catalyst mainly composed of titanocene dichloride was added to carry out a hydrogenation reaction. When the hydrogen absorption in the modified diene polymer reached an integrated amount at which the desired hydrogenation rate was reached, the inside of the reaction vessel was purged with nitrogen. In this way, a hydrogenated diene polymer was obtained. The hydrogenated diene polymer had a hydrogenation rate of 84%. In this example, n-butyllithium (0.87 g) was added as a hydrogenation catalyst activator during hydrogenation.

  Silicon tetrachloride (2.26 g) is added as a metal halide to the resulting polymer solution containing the hydrogenated diene polymer, and then the solvent is removed by steam stripping, and the temperature is adjusted to 110 ° C. A hydrogenated conjugated diene polymer rubber (Example) was obtained by drying with a hot roll. Various physical property values and the like of the obtained hydrogenated conjugated diene polymer rubber are shown in Table 1.

(Comparative Example 1)
As shown in Table 2, instead of the polymer (diene polymer) in Example 1, an ethylene / propylene / diene copolymer (EPDM, trade name “EP57”) manufactured by JSR was used, and hydrogen A polymer rubber (conjugated diene polymer rubber) was produced in the same manner as in Example 1 except that the addition and the reaction with the metal halogen compound were not performed. Table 2 shows various physical property values and the like of the obtained conjugated diene polymer rubber.

(Comparative Example 2)
A hydrogenated conjugated diene polymer rubber (Comparative Example 2) was obtained in the same manner as in Example 1 except that silicon tetrachloride was not used and the reaction with the metal halide was not performed. Table 2 shows various physical property values and the like of the obtained hydrogenated conjugated diene polymer rubber.

(Comparative Example 3)
A hydrogenated conjugated diene polymer rubber (Comparative Example 3) was obtained in the same manner as in Example 3 except that silicon tetrachloride was not used and the reaction with the metal halide was not performed. Table 2 shows various physical property values and the like of the obtained hydrogenated conjugated diene polymer rubber.

(Comparative Example 4)
A conjugated diene polymer rubber (Comparative Example 4) was obtained in the same manner as in Comparative Example 3 except that the conjugated diene polymer was not hydrogenated. Table 2 shows various physical property values and the like of the obtained conjugated diene polymer rubber.

(Preparation of rubber composition (vulcanized product))
Using the hydrogenated conjugated diene polymer rubber obtained in Examples 1 to 7 and the hydrogenated conjugated diene polymer rubber (conjugated diene polymer rubber) obtained in Comparative Examples 1 to 4, a rubber composition (added) Sulfur) was prepared. Table 3 shows the formulation of this rubber composition.

  A specific preparation method is as follows: 100 parts of hydrogenated conjugated diene polymer rubber (conjugated diene polymer rubber) immediately after drying, 5 parts of zinc white, 0.5 part of stearic acid, 30 parts of silica, coupling agent 3 parts, 5 parts of SRF carbon, and 40 parts of a softening agent were added, and a mixture was obtained by kneading at 150 ° C. for 5 minutes using a plastmill having a capacity of 250 ml. A rubber composition was obtained by adding 5 parts of a crosslinking agent and 0.2 part of a crosslinking aid to the obtained mixture and kneading with an open roll at 50 to 70 ° C. for 5 minutes.

In addition, A kneading was performed at 100 ° C. × 50 rpm for about 3 minutes, and the instrument temperature of the dump at that time was about 140 ° C., and the actual temperature was about 150 ° C. The kneading after adding sulfur and the vulcanization accelerator to the compounded rubber after Kneading (also referred to as “B kneading”) was performed at 70 ° C. × 60 rpm for 1 minute. Further, vulcanization was performed at 160 ° C. for 30 minutes. The rubber composition (vulcanized product) obtained was evaluated for processability, tensile strength at break (T _B ), tensile elongation at break (E _B ), and static ratio. The results are shown in Tables 4 and 5.

(result)
The hydrogenated conjugated diene polymer rubbers obtained in Examples 1 to 7 were compared with the hydrogenated conjugated diene polymer rubbers obtained in Comparative Examples 2 and 3 using the same hydrogenated diene polymer. The Mooney viscosity was high and the cold flow value was low (excellent shape stability). In addition, while the processability (mixed Mooney viscosity) was greatly improved (increased) for the obtained rubber composition, no particular change (decrease) was observed for other characteristics.

  Further, the rubber composition of this example has good vibration-proof characteristics (static ratio) as compared with the conjugated diene polymer rubber of Comparative Example 1 using a polymer other than the same Mooney viscosity and cold flow value. It turns out that it is.

  In addition, the rubber composition of Comparative Example 4 that was not hydrogenated was able to obtain the strength and elongation required as an anti-vibration rubber when compared with the rubber compositions of Example 3 and Comparative Example 3 that were hydrogenated. There was nothing.

  The method for producing a modified conjugated diene polymer of the present invention can provide a modified conjugated diene polymer having a high Mooney viscosity, excellent shape stability, and good processability. Therefore, the rubber composition containing the modified conjugated diene polymer obtained in the present invention includes, for example, tire applications such as tire treads, under treads, carcass, sidewalls, bead portions, vibration proof rubbers, antifouling materials, Although it can be used for applications such as belts, hoses and other industrial products, it is particularly suitably used as a vibration-proof rubber.

Claims (14)

A conjugated diene polymer having a vinyl bond content of a conjugated diene moiety of 20 to 70%, wherein an alkoxysilyl group and an optionally protected primary amino group are bonded to a polymer containing at least a conjugated diene unit. Then, hydrogenation is performed so that the hydrogenation rate of the conjugated diene part is 50% or more to obtain a hydrogenated diene polymer,
Water comprising a step of obtaining a hydrogenated conjugated diene polymer rubber by reacting the obtained hydrogenated diene polymer with at least one of a metal halogen compound and an organic compound having an acidic group. A process for producing a conjugated diene polymer rubber.   The method for producing a hydrogenated conjugated diene-based polymer rubber according to claim 1, wherein a homopolymer of a conjugated diene compound or a copolymer of a conjugated diene compound and an aromatic vinyl compound is used as the polymer containing the conjugated diene unit.   The method for producing a hydrogenated conjugated diene polymer rubber according to claim 1 or 2, wherein a metal halide that generates hydrogen halide by hydrolysis is used.   The metal halide compound includes at least one metal atom selected from the group consisting of silicon (Si), tin (Sn), aluminum (Al), zinc (Zn), titanium (Ti), and zirconium (Zr). The method for producing a hydrogenated conjugated diene-based polymer rubber according to any one of claims 1 to 3, wherein a material is used.   Examples of the metal halogen compounds include trimethylsilyl chloride, dimethyldichlorosilane, methyltrichlorosilane, silicon tetrachloride, methyldichlorosilane, tin tetrachloride, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, zinc chloride, titanium tetrachloride, and titanocene. The method for producing a hydrogenated conjugated diene polymer rubber according to any one of claims 1 to 4, wherein at least one compound selected from the group consisting of dichloride, zirconium tetrachloride, and zirconocene dichloride is used. The water according to any one of claims 1 to 5, wherein at least one compound selected from the group consisting of an acidic phosphate compound, a carboxylic acid compound, and a sulfonic acid compound is used as the organic compound having an acidic group. A process for producing a conjugated diene polymer rubber. Examples of the organic compound having an acidic group include butyl phosphate, dibutyl phosphate, 2-ethylhexyl phosphate, bis (2-ethylhexyl) phosphate, tridecyl polyoxyethylene glycolate phosphate, and bis (tridecyl polyoxy phosphate). 7. At least one compound selected from the group consisting of ethylene glycolate), nonylphenyl polyoxyethylene glycolate phosphate, and bis (nonylphenyl polyoxyethylene glycolate) phosphate is used. A method for producing a hydrogenated conjugated diene polymer rubber as described in the item. The method for producing a hydrogenated conjugated diene polymer rubber according to any one of claims 1 to 7, wherein a polymer obtained by the following reaction (I) is used as the conjugated diene polymer.
Reaction (I): An initiator containing at least one of an organic alkali metal and an organic alkaline earth metal is added to a hydrocarbon solvent containing a conjugated diene compound or a conjugated diene compound and an aromatic vinyl compound. A polymer is obtained by anionic polymerization, and at least one of a compound represented by the following general formula (1) and a compound represented by the following general formula (2) is reacted at the polymerization active terminal of the obtained polymer. Let

(However, in the general formula (1), ^{R 1} is an alkylene group having 1 to 12 carbon atoms, an alkyl group or an aryl group of ^{R 2} and ^{R 3} carbon atoms each independently 1 to ^{20, R} 4, R ⁵ and R ⁶ are each independently an alkyl group or aryl group having 1 to 20 carbon atoms, or two of them may be bonded to each other to form a ring containing a silicon atom to which they are bonded. Well, g is an integer from 1 to 2, and f is an integer from 1 to 10.)

(However, in General Formula (2), the definitions of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are the same as those in General Formula (1), and e is an integer of 1 to 2). is there.) In the step of reacting at least one of the metal halogen compound and the organic compound having an acidic group ,
An organic alkali metal and an organic alkaline earth metal as an initiator added to the hydrogenated diene polymer during polymerization of the conjugated diene polymer, an organic alkali metal as a hydrogen catalyst activator added during hydrogenation, and The total number of moles of halogen atoms in the metal halide compound and acidic groups in the organic compound having an acidic group is 0.5 to 10 times the total number of moles of organic groups contained in the organic alkaline earth metal. The method for producing a hydrogenated conjugated diene polymer rubber according to any one of claims 1 to 8, wherein a hydrogenated conjugated diene polymer rubber is obtained by reacting an amount of the compound.   A hydrogenated conjugated diene polymer rubber obtained by the method for producing a hydrogenated conjugated diene polymer rubber according to any one of claims 1 to 9. Containing a rubber component and a filler,
As the rubber component, at least the hydrogenated conjugated diene polymer rubber according to claim 10,
A hydrogenated conjugated diene polymer rubber composition containing 5 to 200 parts by mass of the filler with respect to 100 parts by mass of the rubber component. As the rubber component, including other rubber components other than the hydrogenated conjugated diene polymer rubber,
The hydrogenated conjugated diene polymer rubber composition according to claim 11, wherein the ratio of the mass of the hydrogenated conjugated diene polymer rubber to the total mass of the rubber component is 20% by mass or more.   The hydrogenated conjugated diene polymer rubber composition according to claim 11 or 12, wherein the filler is at least one of silica and carbon black.   A rubber molded article comprising a crosslinked rubber composition obtained by crosslinking the hydrogenated conjugated diene-based polymer rubber composition according to any one of claims 11 to 13.