JP5521698B2 - Anti-vibration rubber member, cross-linked product, anti-vibration rubber composition, conjugated diene rubber composition for anti-vibration rubber and production method thereof - Google Patents

Description

  The present invention comprises an anti-vibration rubber member having excellent anti-vibration properties, particularly dynamic magnification, and a crosslinked product of the anti-vibration rubber composition used for the anti-vibration rubber member, as well as the anti-vibration rubber composition and the anti-vibration rubber composition. The present invention relates to a conjugated diene rubber composition for vibration-proof rubber having excellent storage stability and a method for producing the same.

  Anti-vibration rubber members are used for the purpose of reducing vibration and noise generated from driving parts such as automobiles, vehicle engines, power transmission units, and motor rotations. The anti-vibration characteristics required for the anti-vibration rubber member include anti-vibration properties that suppress the influence of engine vibration on the vehicle body, and anti-vibration properties that suppress the noise caused by high engine rotation. Conventionally, natural rubber, or natural rubber and other conjugated diene rubbers have been used for these vibration-proof rubber members as raw rubber. However, in recent years, with higher output and higher grades of automobiles, the demand for improved ride comfort and quietness in the passenger compartment has increased, and anti-vibration rubbers with excellent vibration isolation characteristics, especially dynamic magnification, which is an index of sound insulation. There is a need for components.

  In order to meet these requirements, anti-vibration rubber compositions containing terminal-modified conjugated diene rubber and carbon black or silica as a reinforcing material have been studied. For example, Patent Document 1 discloses a vibration-proof rubber composition using a combination of a terminal-modified butadiene rubber whose molecular terminal is modified with lactam and a specific carbon black. In Patent Document 2, a conjugated diene polymer having an active end is reacted with a polyfunctional compound having 4 epoxy groups and 2 nitrogen-containing groups in one molecule, and the coupled polymer is 60 wt. An anti-vibration rubber composition containing a conjugated diene polymer containing more than 1% and silica or carbon black is disclosed. However, anti-vibration rubber members using these disclosed anti-vibration rubber compositions have insufficient anti-vibration properties, particularly sound-insulating properties, in response to the increasing demand for quietness in recent years.

  Patent Document 3 discloses that a conjugated diene polymer is reacted with a coupling agent such as tin tetrachloride and an amino group-containing alkoxysilane compound for the purpose of improving the wet grip property and wear resistance of the tire. Conjugated diene polymers are disclosed. In Patent Document 4, for the same purpose as Patent Document 3, a branched conjugated diene polymer having a structure in which three or more conjugated diene polymer chains are bonded via a specific polyorganosiloxane, and tin tetrachloride are disclosed. A conjugated diene rubber composition containing a specific amount of a conjugated diene polymer obtained by reacting a compound having a specific functional group in the molecule is disclosed. However, when the conjugated diene polymer disclosed in Patent Document 3 is to be used for a vibration-proof rubber member, the vibration-proof characteristics, particularly the sound-proof property, are insufficient to meet the increasing demand for quietness in recent years. Further, the conjugated diene rubber composition disclosed in Patent Document 4 has a problem that storage stability is poor and it is difficult to use the anti-vibration rubber member. In the field of anti-vibration rubber, unlike tires that process a large amount of raw rubber at a time, the amount of raw rubber used is small due to the small size of the parts, and it is common to store excess raw rubber bale. However, the conjugated diene rubber composition disclosed in Patent Document 4 is difficult to hold during storage of the veil and is difficult to handle because it flows.

  Further, Patent Document 5 uses a silicon compound having 5 or more specific halogen atoms or alkoxy groups for a conjugated diene polymer having an active end for the purpose of improving low heat generation and wear resistance of a tire. A conjugated diene polymer having a specific weight average molecular weight obtained by reacting a conventional coupling agent is disclosed. However, when this conjugated diene polymer is used as a vibration-proof rubber member, the vibration-proof property, particularly the sound-proof property, is insufficient to meet the increasing demand for quietness in recent years.

JP-A-8-269237 JP 2002-284932 A Japanese Patent Laid-Open No. 2004-18795 International Publication No. 2005/021637 Pamphlet International Publication No. 2007/114203 Pamphlet

  The object of the present invention is to provide anti-vibration rubber members excellent in dynamic ratio, which is an index of sound-proofing properties, and a crosslinked product of the anti-vibration rubber composition used for the anti-vibration rubber members, in response to a demand for anti-vibration properties, particularly silence. The object is to provide a composition for anti-vibration rubber. It is another object of the present invention to provide a conjugated diene rubber composition for vibration-proof rubber that is easy to handle for use as a vibration-proof rubber member and excellent in storage stability, and a method for producing the same.

The present inventors have made intensive studies to achieve the above object, a conjugated diene polymer having an active end (A), obtained by reacting a specific coupling agent, before Symbol conjugated diene polymer (A) coupled conjugated diene polymer (B) and the conjugated diene polymer (A), in one molecule, a reactive group that reacts with the active end of the conjugated diene polymer (A), and a functional group. is obtained by reacting a modifier having a group, you containing conjugated diene polymer functional group introduced at a molecular end (C), molecular weight as detected by gate helper permeation chromatography is specific numerical values by utilizing the reach to co auditors diene rubber composition vibration damping rubber member, it was found to achieve the above object.

Thus, according to the present invention, the coupling agent having 5 or more reactive groups that react with the active end of the conjugated diene polymer (A) in one molecule is added to the conjugated diene polymer (A) having an active end. the Ru obtained by reacting, before Symbol conjugated diene polymer (a) is a coupled co diene polymer (B) and the conjugated diene polymer (a), the conjugated diene polymer in a molecule a reactive group which reacts with the active terminal of the (a), you contain obtained by reacting a modifier having a functional group, a conjugated diene functional group at the molecular terminal has been introduced polymer (C), the ratio of the largest peak in the molecular weight as detected by gate helper permeation chromatography peak top molecular weight of (P-1) peak top molecular weight of the smallest peak of (MP-1) and the molecular weight (P-2) (MP- 2) (M -1 / MP-2) is not less than 3.5, and, (P-1) of, the area ratio to the total elution area of 10 to 55% anti-vibration rubber for conjugated diene rubber composition is provided .

Further, according to the present invention, the rubber composition further comprises a conjugated diene rubber composition for vibration-proof rubber and a conjugated diene rubber (D) other than the conjugated diene rubber composition for vibration-proof rubber as rubber components , with respect to 100 parts by weight of the rubber component. An anti-vibration rubber composition containing 10 to 150 parts by weight of silica is provided.

  Moreover, it is preferable that the said anti-vibration rubber composition contains a crosslinking agent.

  According to this invention, the crosslinked material formed by bridge | crosslinking the said composition for vibration-proof rubber is provided.

  According to the present invention, an anti-vibration rubber member using the cross-linked product is provided.

According to the present invention, a conjugated diene polymer having an active termini (A), 1 coupling agent having 5 or more reactive groups that react with the active terminal of the conjugated diene polymer in the molecule (A) and the the conjugated diene polymer (a), 1 wherein the molecule conjugated diene polymer and the reactive groups that react with the active terminal of the (a), Ru is reacted with the modifying agent having a functional group, detected by gel permeation chromatography Of the peak top molecular weight (MP-1) of the peak with the highest molecular weight (P-1) and the peak top molecular weight (MP-2) of the peak with the lowest molecular weight (P-2) (MP-1 / MP- 2) it is not less than 3.5, and, provided that (P-1) of the method of manufacturing a rubber vibration isolator for conjugated diene rubber composition area ratio is 10 to 55% of the total elution area.

  According to the present invention, a conjugated diene rubber composition for vibration-proof rubber that is easy to handle and excellent in storage stability can be obtained. Further, using the conjugated diene rubber composition for vibration-proof rubber, a cross-linked product of the composition for vibration-proof rubber excellent in dynamic magnification, which is an index of sound-proof property, with respect to a demand for vibration-proof properties, particularly quietness, and the cross-linked product A vibration-proof rubber member made of is obtained.

In the conjugated diene rubber composition for vibration-proof rubber of the present invention, the conjugated diene polymer (A) having an active terminal has 5 or more reactive groups that react with the active terminal of the conjugated diene polymer (A) in one molecule. Ru obtained by reacting a coupling agent having, before Symbol conjugated diene polymer (a) is a coupled conjugated diene polymer (B) and the conjugated diene polymer (a), it said in a molecule A conjugated diene polymer (C) having a functional group introduced at the molecular end, obtained by reacting a reactive group that reacts with the active end of the conjugated diene polymer (A) and a modifier having a functional group. contain, one or a peak top molecular weight of the peak top molecular weight of the largest peak in the molecular weight as detected by gate helper permeation chromatography (P-1) the smallest peak of (MP-1) and the molecular weight (P-2) MP-2) the ratio of (MP-1 / MP-2 ) is not less than 3.5, and wherein the area ratio is 10 to 55% of the total elution area of (P-1) .

  In the present invention, the conjugated diene polymer (A) having an active end means that at least one of the molecular ends of the conjugated diene polymer has activity. The conjugated diene polymer (A) having an active end preferably has one or more active ends in one molecule, and more preferably has one active end in one molecule.

  In the present invention, the conjugated diene polymer includes not only a polymer comprising only a conjugated diene monomer but also a copolymer of a conjugated diene monomer and a monomer copolymerizable therewith. Examples of the copolymerizable monomer include aromatic vinyl monomers.

  The conjugated diene monomer is not particularly limited. For example, 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2,3-dimethyl-1,3-butadiene, 2-chloro- 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and the like can be used. Among these, 1,3-butadiene and isoprene are preferably used, and 1,3-butadiene is more preferably used. These conjugated diene monomers can be used alone or in combination of two or more.

  The aromatic vinyl monomer is not particularly limited, and for example, styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4- Use ethyl styrene, 4-t-butyl styrene, 2,4-dimethyl styrene, 2,4-diisopropyl styrene, 5-t-butyl-2-methyl styrene, vinyl naphthalene, dimethylaminomethyl styrene, dimethylaminoethyl styrene, etc. be able to. Among these, styrene, α-methylstyrene, 4-methylstyrene are preferably used, styrene, α-methylstyrene is more preferably used, and styrene is particularly preferably used. These aromatic vinyl monomers can be used alone or in combination of two or more.

  The ratio of the conjugated diene monomer to the aromatic vinyl monomer (conjugated diene monomer / aromatic vinyl monomer) is in the range of (50 to 100% by weight) / (50 to 0% by weight). Preferably, it is in the range of (65-100% by weight) / (35-0% by weight), more preferably in the range of (80-100% by weight) / (20-0%). . When the ratio of the conjugated diene monomer to the aromatic vinyl monomer is in the above range, the vibration-proof rubber member obtained using the conjugated diene rubber composition for vibration-proof rubber has a loss factor that is an index of vibration-proof properties. Becomes larger and has excellent vibration-proofing characteristics. On the other hand, when the ratio of the aromatic vinyl monomer exceeds the above range, it becomes difficult to produce a conjugated diene rubber composition for vibration-proof rubber, and the vibration-proof rubber member finally obtained also has a poor dynamic magnification.

  The conjugated diene polymer can contain other monomer units other than the conjugated diene monomer and the aromatic vinyl monomer as desired, as long as the effects of the present invention are not impaired. Examples of other monomers include α, β-unsaturated nitriles such as acrylonitrile and methacrylonitrile; unsaturated carboxylic acids or acid anhydrides such as acrylic acid, methacrylic acid, and maleic anhydride; methyl methacrylate, acrylic Unsaturated carboxylic acid esters such as ethyl acrylate and butyl acrylate; Non-conjugated dienes such as 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, dicyclopentadiene, 5-ethylidene-2-norbornene; etc. Can be mentioned. The amount of these monomers used is preferably 10% by weight or less, more preferably 5% by weight or less, based on the total monomers.

  Polymerization of a monomer (mixture) containing a conjugated diene monomer or containing a conjugated diene monomer and an aromatic vinyl monomer includes bulk polymerization, emulsion polymerization, suspension polymerization, dispersion polymerization, Various polymerization methods such as solution polymerization can be selected as appropriate, but solution polymerization is preferred. The inert organic solvent used for solution polymerization is not particularly limited as long as it is usually used in solution polymerization and the polymerization reaction proceeds. For example, aliphatic hydrocarbons such as butane, pentane, hexane, and 2-butene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and cyclohexene; aromatic hydrocarbons such as benzene, toluene, and xylene; . The amount of the inert organic solvent used is such an amount that the monomer concentration is usually 1 to 50% by weight, preferably 10 to 40% by weight.

  In the polymerization, a polymerization initiator is preferably used. As a polymerization initiator, a monomer (mixture) containing a conjugated diene monomer or containing a conjugated diene monomer and an aromatic vinyl monomer is polymerized to give a conjugated diene weight having an active terminal. Any combination can be used without particular limitation as long as it can give the combination (A). For example, an organic alkali metal compound, an organic alkaline earth metal compound, or a polymerization initiator using a lanthanoid as a main catalyst is preferably used. Specific examples of the organic alkali metal compound include organic monolithium compounds such as n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium, and stilbenelithium; dilithiomethane, 1,4-dilithiobutane, 1, Organic polyvalent lithium compounds such as 4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene, 1,3,5-tris (lithiomethyl) benzene; organic sodium compounds such as sodium naphthalene; potassium naphthalene and the like Organic potassium compounds; and the like. In addition, the organic alkali metal compound includes a secondary amine such as dibutylamine, dihexylamine, dibenzylamine, pyrrolidine, hexamethyleneimine, heptamethyleneimine (preferably pyrrolidine, hexamethyleneimine, heptamethyleneimine) and the like. You may make it react and use as an organic alkali metal amide compound. These polymerization initiators can be used alone or in combination of two or more. Examples of organic alkaline earth metal compounds include di-n-butylmagnesium, di-n-hexylmagnesium, diethoxycalcium, calcium distearate, di-t-butoxystrontium, diethoxybarium, diisopropoxybarium, and diethyl. Examples include mercaptobarium, di-t-butoxybarium, diphenoxybarium, diethylaminobarium, barium distearate, and diketylbarium. As a polymerization initiator using a lanthanoid as a main catalyst, a lanthanoid salt consisting of a lanthanoid such as lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, and a carboxylic acid, a phosphorus-containing organic acid, etc. Examples thereof include polymerization initiators composed of promoters such as alkylaluminum compounds, organoaluminum hydride compounds, and organoaluminum halide compounds. Among these, an organic monolithium compound and an organic polyvalent lithium compound are preferably used, and an organic monolithium compound is more preferably used.

  The amount of the polymerization initiator used is usually in the range of 1 to 50 mmol, preferably 2 to 20 mmol, more preferably 4 to 15 mmol per 1000 g of the total amount of monomers.

  When polymerizing a monomer (mixture) containing a conjugated diene monomer or containing a conjugated diene monomer and an aromatic vinyl monomer, the polymerization temperature is usually −80 to + 150 ° C., preferably Is in the range of 0-100 ° C, more preferably 30-90 ° C.

  As the polymerization mode, any mode such as batch mode or continuous mode can be adopted, but the molecular weight distribution (Mw / Mn) can be kept small, and the vibration-proof rubber member finally obtained is excellent in dynamic magnification. A batch system is preferred in terms of points.

  When the conjugated diene polymer (A) having an active terminal has a conjugated diene monomer unit and an aromatic vinyl monomer unit, the bonding mode of the conjugated diene monomer unit and the aromatic vinyl monomer unit For example, various bonding modes such as a block shape, a tapered shape, and a random shape can be used. In addition, when the bonding mode of the conjugated diene monomer unit and the aromatic vinyl monomer unit is made random, the aromatic content relative to the total amount of the conjugated diene monomer and the aromatic vinyl monomer in the polymerization system. In order to prevent the ratio of the aromatic vinyl monomer from becoming too high, a conjugated diene monomer or a monomer mixture containing a conjugated diene monomer and an aromatic vinyl monomer is polymerized continuously or intermittently. It is preferable to supply the polymer into the system for polymerization.

  In order to adjust the vinyl bond content in the conjugated diene monomer unit in the conjugated diene polymer (A) having an active terminal, it is preferable to include a polar compound in the inert organic solvent during the polymerization. By containing the polar compound, the vinyl bond content in the conjugated diene monomer unit can be increased. Examples of the polar compound include ether compounds such as dibutyl ether, tetrahydrofuran and 2,2-di (tetrahydrofuryl) propane; tertiary amines such as tetramethylethylenediamine; phosphine compounds; Among these, ether compounds and tertiary amines are preferable, and 2,2-di (tetrahydrofuryl) propane and tetramethylethylenediamine are more preferable.

  The usage-amount of a polar compound is 0.01-100 mol normally with respect to 1 mol of polymerization initiators, Preferably it is the range of 0.01-30 mol, More preferably, it is the range of 0.01-10 mol. When the amount of the polar compound used is in the above range, it is easy to adjust the vinyl bond content in the conjugated diene monomer unit, and problems due to deactivation of the polymerization initiator hardly occur.

  In the conjugated diene polymer (A) having an active terminal, the vinyl bond amount in the conjugated diene monomer unit is preferably 5 to 80% by weight, more preferably 10 to 60% by weight. Particularly preferred is ˜40% by weight. When the vinyl bond content is in the above range, the vibration-proof rubber member obtained using the conjugated diene rubber composition for vibration-proof rubber has a large loss factor, which is an index of vibration-proof property, and has excellent vibration-proof characteristics. . On the other hand, when the vinyl bond amount is outside the above range, it becomes difficult to produce a conjugated diene rubber composition for vibration-proof rubber, and the vibration-proof rubber member finally obtained is inferior in dynamic magnification. In addition, when 1,3-butadiene is used as a monomer, in order to increase the vinyl bond content in the conjugated diene monomer unit portion of the conjugated diene polymer to 10% by weight or more, the polarity as described above is usually used. The use of compounds is preferred.

  The glass transition temperature (Tg) of the conjugated diene polymer (A) having an active end is preferably −110 to −10 ° C., more preferably −110 to −20 ° C., and particularly preferably −100 to −40 ° C. . When the glass transition temperature of the conjugated diene polymer (A) is within the above range, the vibration-proof rubber member obtained using the conjugated diene rubber composition for vibration-proof rubber has a large loss factor that is an index of vibration-proof properties. It is excellent in vibration-proof characteristics. On the other hand, when the glass transition temperature is out of the above range, it becomes difficult to produce a conjugated diene rubber composition for vibration-proof rubber, and the vibration-proof rubber member finally obtained is inferior in dynamic magnification.

Conjugated diene polymer (B) in the present invention, there is the upper Symbol conjugated diene polymer (A) is coupled to the conjugated diene polymer (A) having an active end, the in a molecule It can be obtained by reacting a coupling agent having 5 or more reactive groups that react with the active terminal of the conjugated diene polymer (A).

  The coupling agent is not particularly limited as long as it has 5 or more reactive groups that react with the active end of the conjugated diene polymer (A) in one molecule, but the number of reactive groups is 5 to 10 Are preferable, those having 6 to 9 reactive groups are more preferable, and those having 6 reactive groups are particularly preferable. When the number of reactive groups is in the above range or the above numerical value, the storage stability of the conjugated diene rubber composition for vibration-proof rubber and the dynamic ratio of the vibration-proof rubber member finally obtained are excellent.

The coupling agent used in the present invention is preferably a silicon compound represented by the general formula (I).

In general formula (I), X ¹ and X ² are each a halogen atom or an alkoxy group having 1 to 20 carbon atoms, and both X ¹ and X ² are preferably halogen atoms. In the compound represented by the general formula (I), the total number of halogen atoms and alkoxy groups having 1 to 20 carbon atoms is 5 or more. p and q are each an integer of 0 to 3. n is an integer of 0 to 20, and when n is 2 or more, the plurality of repeating units represented by -A ¹ -A ³ -A ^2- may be different from each other. When a plurality of X ¹ or X ² are present, they may be the same or different from each other, but X ¹ and X ² are both halogen atoms or both are carbon atoms It is preferable that it is a C1-C20 alkoxy group.

  Although a halogen atom is not specifically limited, For example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be mentioned. Among these, a chlorine atom is particularly preferable.

  1-10 are preferable and, as for carbon number of an alkoxy group, 1-6 are more preferable. Specific examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group, hexoxy group and the like. Among these, a methoxy group and an ethoxy group are preferable from the viewpoint of completing the reaction time with the polymer (A) having an active terminal in a short time.

R ¹ and R ² are each a monovalent hydrocarbon group having 1 to 20 carbon atoms. R ¹ and R ² may be the same or different from each other. When a plurality of R ¹ or R ² are present, they may be the same or different from each other. Specific examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, an alkyl group having 1 to 20 carbon atoms such as an n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-icosyl group; A cycloalkyl group having 5 or 6 carbon atoms such as a cyclopentyl group and a cyclohexyl group; an aralkyl group having 7 to 20 carbon atoms such as a benzyl group, a 2-phenylethyl group and a 3-phenylpropyl group; a phenyl group, a 1-naphthyl group, And aryl groups having 6 to 20 carbon atoms such as 2-naphthyl group. Among these, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and a methyl group or an ethyl group is particularly preferable. In addition, these alkyl groups, aralkyl groups, and aryl groups may have a substituent at any position.

In general formula (I), A ¹ and A ² are each a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms. A ¹ and A ² may be the same as or different from each other. When a plurality of A ¹ or A ² are present, they may be the same or different, respectively. Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms include linear alkylene groups having 1 to 20 carbon atoms such as methylene group, ethylene group and n-propylene group; and 3 to 20 carbon atoms such as isopropylene group. A branched alkylene group; a cycloalkylene group having 3 to 6 carbon atoms such as a cyclohexylene group; an alkylidene group having 2 to 20 carbon atoms such as an ethylidene group, an isopropylidene group, or a vinylidene group; Arylene groups; alkylarylene groups having 7 to 20 carbon atoms such as methylphenylene; arylalkylene groups having 7 to 20 carbon atoms such as phenylmethylene; and the like. A ¹ and A ² are preferably a single bond or a linear alkylene group having 1 to 20 carbon atoms, and more preferably a single bond or a linear alkylene group having 1 to 6 carbon atoms.

In the general formula (I), A ³ is a group represented by the following general formula (II), (III) or (IV). When a plurality of A ³ are present, they may be the same or different.

^{_{- (SiX 3 r R 3 2}} -r) m - (II)
(In the general formula (II), X ³ is a halogen atom or an alkoxy group having 1 to 20 carbon atoms. Specific examples of the halogen atom and the alkoxy group having 1 to 20 carbon atoms are exemplified for X ¹ and X ² . R ³ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include R ¹ and R ^1. It may be mentioned the same ones as those exemplified for ^2. of more of the X ³ or R ^3, when present, they each, the .r optionally be the same or different 0 It is an integer of 2, and m is an integer of 0 to 20. m is preferably an integer of 0 to 10, more preferably an integer of 1 to 3, and particularly preferably 1. If m is 2 or more, - ^(SiX _{3 r} ³ _2-r -.) A plurality of repeating units represented by may be of different ones Note ^that when ^{A 3} is represented by the general formula (II), (p + n × m × r + q) is 5 or more Is an integer.)

—NR ⁴ — (III)
(In General Formula (III), R ⁴ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include R ¹ and R ^2. And the same as those exemplified for A. When A ³ is represented by formula (III), (p + q) is 5 or 6.)

_{^{-N (-A 5 -SiX 5 s R}} 5 3-s) - (IV)
(In General Formula (IV), A ⁵ is a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms. Specific examples of the divalent hydrocarbon group having 1 to 20 carbon atoms include A ¹ And A ² may be the same as those exemplified for A ^2. X ⁵ is a halogen atom or an alkoxy group having 1 to 20 carbon atoms, as specific examples of the halogen atom and the alkoxy group having 1 to 20 carbon atoms. Can be the same as those exemplified for X ¹ and X ^2. R ⁵ is a monovalent hydrocarbon group having 1 to 20 carbon atoms. Examples of the hydrogen group include the same groups as those exemplified for R ¹ and R ^{2. When a} plurality of X ⁵ or R ⁵ are present, they may be the same or different. S is 0-3. Is a number. In the case ^{where A 3} is represented by the general formula (IV), (p + n × s + q) is an integer of 5 or more.)

^X 1, ^{X 2} in formula (I), general formula (II) in the ^{X 3,} the general formula (IV) in the ^{X 5} (alkoxy group a halogen atom and having 1 to 20 carbon atoms), a conjugated diene It is a reactive group in the coupling agent molecule that reacts with the active terminal of the polymer (A).

In general formula (I), when all of X ¹ and X ² are halogen atoms, A ³ is preferably represented by general formula (II). At this time, in general formula (II), it is preferable that all X ³ is a halogen atom. In this case, the coupling agent represented by the general formula (I) is a silicon halide compound.

  The halogen atoms contained in the compound represented by the general formula (I) may be the same or different, but from the viewpoint of facilitating the treatment of the salt by-produced by the coupling reaction, all halogen atoms Is particularly preferably a chlorine atom.

Examples of silicon compounds that can be suitably used as a coupling agent in the present invention include silicon halide compounds represented by the following general formula (V).
^{_{SiX 1 p R 1 3-p}} - (CH 2) k -SiX 2 3 (V)
In general formula (V), X ¹ and X ² are each a halogen atom, and when a plurality of X ¹ or X ² are present, they may be different halogen atoms. R ¹ is a monovalent hydrocarbon group having 1 to 20 carbon atoms. Especially, it is preferable that it is a C1-C20 alkyl group, and it is especially preferable that it is a methyl group or an ethyl group. k is an integer of 0 to 20, preferably an integer of 0 to 10, more preferably an integer of 0 to 6, and particularly preferably an integer of 0 to 2. p is 2 or 3, and is more preferably 3.

  Specific examples of the silicon halide compound represented by the general formula (V) include hexachlorodisilane, bis (trichlorosilyl) methane, 1,2-bis (trichlorosilyl) ethane, and 1,3-bis (trichlorosilyl) propane. 1,4-bis (trichlorosilyl) butane, 1,5-bis (trichlorosilyl) pentane, 1,6-bis (trichlorosilyl) hexane, and the like. Of these, hexachlorodisilane, 1,2-bis (trichlorosilyl) ethane or 1,6-bis (trichlorosilyl) hexane is preferably used, and 1,6-bis (trichlorosilyl) hexane is more preferably used. preferable. One of these silicon halide compounds may be used alone, or two or more thereof may be used in combination.

In general formula (I), when X ¹ and X ² are both alkoxy groups having 1 to 20 carbon atoms, in general formula (II), X ³ is an alkoxy group having 1 to 20 carbon atoms. It is preferable that it is C1-C10 alkoxy group. In general formula (IV), X ⁵ is preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an alkoxy group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. It is particularly preferred that In this case, the coupling agent represented by the general formula (I) is an alkoxysilane compound.

Specific examples of the group represented by the general formula (III): —NR ⁴ — include a methylimino group, an ethylimino group, a propylimino group, a phenylimino group, and a benzylimino group.

Specific examples of the group represented by the general formula (IV): —N (—A ⁵ —SiX ⁵ _s R ⁵ _3-s ) — include a trimethoxysilylpropylimino group and a triethoxysilylpropylimino group. be able to.

The alkoxysilane compound that can be used as a coupling agent in the present invention is preferably a compound represented by the following general formula (VI), (VII), or (VIII).
SiX ¹ _p R ¹ _3-p- A ⁶ -SiX ² ₃ (VI)
_{^{SiX 1 p R 1 3-p}} -A 7 -NR 4 -A 8 -SiX 2 3 (VII)
_{^{SiX 1 p 'R 1 3-}} p' -A 9 -N (-A 10 -SiX 5 s R 5 3-s) -A 11 -SiX 2 3 (VIII)

In the general formulas (VI), (VII) and (VIII), X ¹ , X ² and X ⁵ are each an alkoxy group having 1 to 20 carbon atoms, and a plurality of X ¹ , X ² or X ⁵ are When present, they may be the same or different, respectively. R ¹ and R ⁵ are each a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrocarbon group having 1 to 6 carbon atoms, and more preferably a hydrocarbon group having 1 to 3 carbon atoms. preferable. R ⁴ is a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrocarbon group having 1 to 10 carbon atoms. A ^{6 to} A ¹¹ are each a single bond, a polymethylene group having 1 to 20 carbon atoms ((CH ₂ ) _k ), an arylene group, or a cycloalkylene group. In A ^{6 to} A ¹¹ , the number k of methylene groups may be the same or different. k is preferably 1 to 8. p is 2 or 3, p ′ and s are each an integer of 0 to 3, and (p ′ + s) is an integer of 2 to 6.

  Specific examples of the alkoxysilane compound represented by the general formula (VI) include hexamethoxydisilane, hexaethoxydisilane, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis (trimethoxysilyl) ethane, Bis (triethoxysilyl) ethane, bis (trimethoxysilyl) propane, bis (triethoxysilyl) propane, bis (trimethoxysilyl) butane, bis (triethoxysilyl) butane, bis (trimethoxysilyl) heptane, bis ( Triethoxysilyl) heptane, bis (trimethoxysilyl) hexane, bis (triethoxysilyl) hexane, bis (trimethoxysilyl) benzene, bis (triethoxysilyl) benzene, bis (trimethoxysilyl) cyclohexane, bis (triethoxysilane) Lu) cyclohexane, bis (triethoxysilyl) benzene, bis (trimethoxysilyl) octane, bis (triethoxysilyl) octane, bis (trimethoxysilyl) nonane, bis (triethoxysilyl) nonane, bis (trimethoxysilyl) Ethylene, bis (triethoxysilyl) ethylene, bis (trimethoxysilylethyl) benzene, bis (triethoxysilylethyl) benzene, bis (3-trimethoxysilylpropyl) ethane, bis (3-triethoxysilylpropyl) ethane, etc. Can be shown.

  Specific examples of the alkoxysilane compound represented by the general formula (VII) include bis (3-trimethoxysilylpropyl) methylamine, bis (3-triethoxysilylpropyl) methylamine, and bis (3-trimethoxysilylpropyl). ) Ethylamine, bis (3-triethoxysilylpropyl) ethylamine, bis (3-trimethoxysilylpropyl) propylamine, bis (3-triethoxysilylpropyl) propylamine, bis (3-trimethoxysilylpropyl) butylamine, bis (3-triethoxysilylpropyl) butylamine, bis (3-trimethoxysilylpropyl) phenylamine, bis (3-triethoxysilylpropyl) phenylamine, bis (3-trimethoxysilylpropyl) benzylamine, bis (3- Triet Sisilylpropyl) benzylamine, bis (trimethoxysilylmethyl) methylamine, bis (triethoxysilylmethyl) methylamine, bis (2-trimethoxysilylethyl) methylamine, bis (2-triethoxysilylethyl) methylamine Bis (triethoxysilylmethyl) propylamine, bis (2-triethoxysilylethyl) propylamine, and the like.

  Specific examples of the alkoxysilane compound represented by the general formula (VIII) include tris (trimethoxysilylmethyl) amine, tris (2-triethoxysilylethyl) amine, tris (3-trimethoxysilylpropyl) amine, and tris. (3-triethoxysilylpropyl) amine and the like can be shown.

  In this invention, the coupling agent made to react with the conjugated diene polymer (A) which has an active terminal may be used individually by 1 type, and may use 2 or more types together.

The amount of the coupling agent to be reacted with the conjugated diene polymer (A) having an active end is the reaction of the coupling agent that reacts with the active end of the polymer (A) with respect to 1 mol of the polymerization initiator used for the polymerization. The number of moles of the sex group is usually set to 0.05 to 0.60 mol, preferably 0.07 to 0.35 mol, and more preferably 0.12 to 0.30 mol. When the amount of the coupling agent is in the range, and is excellent in dynamic magnification storage stability and ultimately obtained vibration damping rubber member of the rubber vibration isolator for conjugated diene rubber composition. On the other hand, when the usage-amount of a coupling agent is less than the said minimum, the conjugate which has the structure couple | bonded through the coupling agent with respect to the said polymer (A) unreacted with a coupling agent. The proportion of the diene polymer (B) is lowered, and as a result, the conjugated diene rubber composition for vibration-proof rubber is inferior in storage stability. Moreover, when the usage-amount of a coupling agent exceeds the said upper limit, it has the structure couple | bonded through the coupling agent with respect to the said polymer (A) which was unreacted with a coupling agent. The proportion of the conjugated diene polymer (B) increases, and as a result, the vibration-proof rubber member finally obtained is inferior in dynamic magnification.

  The method of reacting the conjugated diene polymer (A) having an active end with a coupling agent is not particularly limited, but the coupling is usually performed in a solution in which the conjugated diene polymer (A) having an active end is dissolved or dispersed. An agent may be added.

  When adding a coupling agent to a solution in which the conjugated diene polymer (A) having an active end is dissolved or dispersed, the coupling agent is dissolved in an inert organic solvent from the viewpoint of controlling the coupling reaction well. Alternatively, the solution obtained by dispersing is preferably added to a solution in which the conjugated diene polymer (A) having an active end is dissolved or dispersed in an inert organic solvent. The concentration of the coupling agent solution is preferably 1 to 50% by weight, and the inert organic solvent used for this is the same as that used for the polymerization of the monomer mixture. Can do.

  The conditions for reacting the conjugated diene polymer (A) having an active end with the coupling agent are not particularly limited, but the reaction temperature is usually −80 to + 150 ° C., preferably 0 to 100 ° C., more preferably 30. It is the range of -90 degreeC, and reaction time is 1-120 minutes normally, Preferably it is the range of 2-60 minutes.

  The timing of adding the coupling agent to the solution in which the conjugated diene polymer (A) having active ends is dissolved or dispersed is not particularly limited, but the conjugated diene polymer (A) having active ends because the polymerization reaction is not completed. ) Is dissolved or dispersed in a state that also contains a monomer, more specifically, a solution in which the conjugated diene polymer (A) having an active terminal is dissolved or dispersed is 100 ppm or more (more preferably It is preferable to add a coupling agent to the solution in a state of containing 300 to 50,000 ppm) monomer. By performing the addition of the coupling agent as described above, the side reaction between the conjugated diene polymer (A) having an active terminal and impurities contained in the polymerization system is suppressed, and the reaction is controlled well. Is possible.

In the present invention, at least the conjugated diene polymer portion of the conjugated diene rubber compositions coupling (A) is detected by gel permeation chromatography, the largest peak in the molecular weight in terms of polystyrene (P-1 ) Peak top molecular weight (MP-1) and peak top molecular weight (MP-2) of the lowest molecular weight peak (P-2) (MP-1 / MP-2) must be 3.5 or more. Yes, it is preferably 3.5 to 9.0, more preferably 3.5 to 6.0, and particularly preferably 4.0 to 6.0. When the peak top molecular weight ratio of (MP-1 / MP-2) is in the above range, the conjugated diene rubber composition for vibration proof rubber is excellent in storage stability, and the vibration proof rubber member finally obtained also has a dynamic magnification. It will be excellent.

  In the present invention, a conjugated diene polymer (A) having an active end is reacted with a coupling agent having 5 or more reactive groups that react with the active end of the conjugated diene polymer (A) in one molecule. , (MP-1 / MP-2) peak top molecular weight ratio can be 3.5 or more. As a result, the conjugated diene rubber composition for vibration proof rubber is excellent in storage stability, and the vibration proof rubber member finally obtained is also excellent in dynamic magnification.

In the present invention, the peak top molecular weight (MP-1) of the peak (P-1) having the largest molecular weight detected by gel permeation chromatography is the conjugated diene polymer (A) having an active end in one molecule. A conjugated diene having a structure bonded via a coupling agent, obtained by reacting a coupling agent having 5 or more reactive groups that react with the active end of the conjugated diene polymer (A) It refers to the peak top molecular weight of the peak having the highest molecular weight derived from the polymer (B) .

  (MP-1) is preferably 200,000 to 3,000,000, more preferably 500,000 to 2,000,000, and particularly preferably 750,000 to 1,500,000. When (MP-1) is in the above range, the conjugated diene rubber composition for vibration-proof rubber is excellent in storage stability, and the vibration-proof rubber member finally obtained is also excellent in dynamic magnification.

  In the present invention, the peak top molecular weight (MP-2) of the peak (P-2) having the smallest molecular weight detected by gel permeation chromatography refers to the conjugated diene polymer (A) having an active end in one molecule. When a coupling agent having 5 or more reactive groups that react with the active end of the conjugated diene polymer (A) is reacted with a conjugated diene polymer having an active end that has not reacted with the coupling agent ( A) or the peak top molecular weight of the lowest molecular weight peak derived from a conjugated diene polymer having a structure bonded via a coupling agent.

  (MP-2) is preferably 50,000 to 600,000, more preferably 100,000 to 450,000, and particularly preferably 150,000 to 350,000. When (MP-2) is in the above range, the conjugated diene rubber composition for vibration-proof rubber is excellent in storage stability, and the vibration-proof rubber member finally obtained is also excellent in dynamic magnification.

In the conjugated diene rubber composition for vibration-proof rubber of the present invention, the area ratio of the peak (P-1) having the largest molecular weight detected by gel permeation chromatography to the total elution area is usually 10 to 55%, preferably It is 10 to 35%, more preferably 15 to 30%. When the area ratio of (P-1) to the total elution area is in the above range, the conjugated diene rubber composition for vibration-proof rubber is excellent in storage stability, and the vibration-proof rubber member finally obtained is also excellent in dynamic magnification. It will be a thing. On the other hand, when the area ratio of (P-1) to the total elution area is less than the lower limit, the conjugated diene rubber composition for vibration-proof rubber is inferior in storage stability. Moreover, when the area ratio with respect to the total elution area of (P-1) exceeds the said upper limit, the vibration-proof rubber member finally obtained becomes inferior to a dynamic magnification.

According to the present invention, by adjusting the number of moles of the reactive group of the coupling agent that reacts with the active terminal of the conjugated diene polymer (A) to the above range with respect to 1 mole of the polymerization initiator used in the polymerization. Ri, it is possible to adjust the proportion against the total amount of Conjugate diene polymer (B), thereby the range of the area ratio from 10 to 55% relative to the total elution area (P-1) be able to. As a result, the conjugated diene rubber composition for vibration proof rubber is excellent in storage stability, and the vibration proof rubber member finally obtained is also excellent in dynamic magnification.

In the present invention, the conjugated diene rubber composition, the conjugated diene polymer having an active end (A), a reactive group which reacts with the active terminal of the conjugated diene polymer in a molecule (A), functional group is obtained by reacting a modifier having the bets, you containing conjugated diene polymer functional group introduced at a molecular end (C).

When the conjugated diene rubber composition contains the conjugated diene polymer (C) having a functional group introduced at the molecular end, the affinity between the conjugated diene rubber composition for vibration-proof rubber and silica can be improved. .

  The modifier used in the present invention is not particularly limited as long as it has a reactive group that reacts with the active terminal of the conjugated diene polymer (A) and a functional group in one molecule. Examples of the reactive group that reacts with the active terminal of the conjugated diene polymer (A) include an epoxy group, an alkoxyl group, a pyrrolidonyl group, an allyloxy group, a vinyl group, a halogenated silyl group, a carbonyl group, a thiocarbonyl group, and an aziridine group. Etc. Among these, an epoxy group, an alkoxyl group, and a pyrrolidonyl group are preferable, and an epoxy group and an alkoxyl group are more preferable. The functional group is preferably a functional group having an affinity for silica, and examples include a silicon-containing functional group, an amino group, and a hydroxyl group. These reactive groups and functional groups may be one kind or two or more kinds in one molecule.

  As the modifier, polyorganosiloxane or an alkoxysilane compound is preferable.

  When polyorganosiloxane is used as the modifier, the number of reactive groups is preferably 1 to 200, more preferably 20 to 150, and particularly preferably 30 to 120 in one molecule of polyorganosiloxane. . When the number of reactive groups is within the above range, the storage stability of the conjugated diene rubber composition for vibration-proof rubber and the dynamic ratio of the vibration-proof rubber member finally obtained are excellent.

Examples of the polyorganosiloxane suitably used as the modifier include polyorganosiloxanes represented by the general formula (IX), (X) or (XI).

(In the polyorganosiloxane of the above general formula (IX), R ^{1 to} R ⁸ are an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and these may be the same or different. X ¹ and X ⁴ are a reactive group that reacts with the active end of the conjugated diene polymer (A), or an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms. X ¹ and X ⁴ may be the same or different from each other, X ² is a reactive group that reacts with the active end of the conjugated diene polymer (A), and X ³ is 2 to 20 of a group containing repeating units of alkylene glycol, X ³ part may be of a group derived from a group containing repeating units of alkylene glycol 2 to 20 .m is an integer from 3 to 200, n is an integer from 0 to 200, k is It is an integer from 0 to 200.)

(In the polyorganosiloxane represented by the general formula (X), R ^{9 to} R ¹⁶ are alkyl groups having 1 to 6 carbon atoms or aryl groups having 6 to 12 carbon atoms, and these may be the same as each other. X ^{5 to} X ⁸ are reactive groups that react with the active end of the conjugated diene polymer (A).

(In the polyorganosiloxane represented by the general formula (XI), R ^{17 to} R ¹⁹ are an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and these may be the same as each other. X ^{9 to} X ¹¹ are reactive groups that react with the active terminal of the conjugated diene polymer (A), and s is an integer of 1 to 18.

In the polyorganosiloxane of the above general formula (IX), examples of the alkyl group having 1 to 6 carbon atoms constituting R ^{1 to} R ⁸ , X ¹ and X ⁴ include a methyl group, an ethyl group, an n-propyl group, Examples include isopropyl group, butyl group, pentyl group, hexyl group, cyclohexyl group and the like. Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group and a methylphenyl group. Among these alkyl groups and aryl groups, a methyl group is particularly preferable.

In the polyorganosiloxane of the general formula (IX), the reactive group that reacts with the active terminal of the conjugated diene polymer (A) constituting X ¹ , X ² and X ⁴ is an alkoxyl having 1 to 5 carbon atoms. C 4-12 groups containing a group, a hydrocarbon group containing a 2-pyrrolidonyl group, and an epoxy group are preferred.

  Examples of the alkoxyl group having 1 to 5 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group. Of these, a methoxy group is preferable.

Preferred examples of the hydrocarbon group containing a 2-pyrrolidonyl group include a group represented by general formula (XII).

  (In the formula, j is an integer of 2 to 10. In particular, j is preferably 2.)

The group having 4 to 12 carbon atoms and having an epoxy group is represented by the general formula (XIII).
General formula (XIII): ZY-E

  (In the above formula (XIII), Z is an alkylene group having 1 to 10 carbon atoms or an alkylarylene group having 7 to 10 carbon atoms, Y is a methylene group, a sulfur atom or an oxygen atom, and E has an epoxy group. A hydrocarbon group having 2 to 10 carbon atoms, of which Y is preferably an oxygen atom, more preferably Y is an oxygen atom, and E is a glycidyl group, and Z is a carbon number of 3 Particularly preferred are alkylene groups, Y is an oxygen atom, and E is a glycidyl group.)

In the polyorganosiloxane represented by the general formula (IX), when at least a part of X ¹ , X ² and X ⁴ is an alkoxyl group having 1 to 5 carbon atoms, the conjugated diene polymer (A) has a poly terminal at the active end. When the organosiloxane is reacted, the bond between the silicon atom and the oxygen atom of the alkoxyl group is cleaved, and the polymer chain is directly bonded to the silicon atom to form a single bond.

In the polyorganosiloxane represented by the general formula (IX), when at least part of X ¹ , X ² and X ⁴ is a hydrocarbon group containing a 2-pyrrolidonyl group, the active terminal of the conjugated diene polymer (A) When polyorganosiloxane is allowed to react, the carbon-oxygen bond of the carbonyl group constituting the 2-pyrrolidonyl group is cleaved to form a structure in which the polymer chain is bonded to the carbon atom.

In the polyorganosiloxane represented by the general formula (IX), when at least part of X ¹ , X ² and X ⁴ is a group having 4 to 12 carbon atoms containing an epoxy group, the conjugated diene polymer (A) When polyorganosiloxane is reacted with the active terminal, the carbon-oxygen bond constituting the epoxy ring is cleaved to form a structure in which a polymer chain is bonded to the carbon atom.

In the polyorganosiloxane represented by the general formula (IX), as X ¹ and X ⁴ , among the above, a group having 4 to 12 carbon atoms or an alkyl group having 1 to 6 carbon atoms containing an epoxy group is preferable, X ² is preferably a group having 4 to 12 carbon atoms containing an epoxy group.

In the polyorganosiloxane represented by the general formula (IX), X ³ , that is, a group containing 2 to 20 alkylene glycol repeating units is preferably a group represented by the following general formula (XIV).

  (In the above formula (XIV), t is an integer of 2 to 20, P is an alkylene group or alkylarylene group having 2 to 10 carbon atoms, R is a hydrogen atom or a methyl group, and Q is 1 carbon atom. 10 to an alkoxyl group or an aryloxy group, among which t is an integer of 2 to 8, P is an alkylene group having 3 carbon atoms, R is a hydrogen atom, and Q is a methoxy group. Some are preferred.)

  In the polyorganosiloxane represented by the general formula (IX), m is an integer of 3 to 200, preferably 20 to 150, more preferably 30 to 120. When this number is large, it becomes difficult to produce polyorganosiloxane itself.

  In the polyorganosiloxane represented by the general formula (IX), n is an integer of 0 to 200, preferably an integer of 0 to 150, more preferably an integer of 0 to 120. k is an integer of 0 to 200, preferably an integer of 0 to 150, more preferably an integer of 0 to 120. The total number of m, n, and k is preferably 400 or less, more preferably 300 or less, and particularly preferably 250 or less. When this number is large, it is difficult to produce polyorganosiloxane itself.

  In the polyorganosiloxane represented by the general formula (X) and the general formula (XI), an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an active terminal of the polymer (A) The reactive group which reacts is the same as that described for the polyorganosiloxane of the general formula (IX).

  Examples of the alkoxysilane compound that can be used as a modifier in the present invention include tetraalkoxysilane compounds such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetraphenoxysilane, and tetratoluoxysilane; methyl Trimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, ethyltriphenoxysilane, dimethyl Dimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, dimethyldiphenoxysilane, diethyldimethyl Alkylalkoxysilane compounds such as xylsilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldibutoxysilane, diethyldiphenoxysilane; 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 Aminoalkylalkoxysilane compounds such as N, N-bis (trimethylsilyl) aminoethylmethyldimethoxysilane and N, N-bis (trimethylsilyl) aminoethylmethyldiethoxysilane Alkenyl alcohols such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltributoxysilane, vinyltriphenoxysilane, allyltrimethoxysilane, octenyltrimethoxysilane, divinyldimethoxysilane, and styryltomethoxymethoxysilane Sixysilane compounds; arylalkoxysilane compounds such as phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltributoxysilane, phenyltriphenoxysilane; trimethoxychlorosilane, triethoxychlorosilane, tripropoxychlorosilane, tributoxy Chlorosilane, triphenoxychlorosilane, dimethoxydichlorosilane, dipropoxydichlorosilane, diphenoxy Halogenoalkoxysilane compounds such as dichlorodichlorosilane, methoxytrichlorosilane, ethoxytrichlorosilane, propoxytrichlorosilane and phenoxytrichlorosilane; halogenoalkylalkoxysilane compounds such as β-chloroethylmethyldimethoxysilane and γ-chloropropylmethyldimethoxysilane; β- And nitroalkylalkoxysilane compounds such as nitroethylmethyldimethoxysilane and γ-nitropropylmethyldimethoxysilane;

  In addition to the polyorganosiloxane and alkoxysilane compound described above, specific examples of the modifier that can be used in the present invention include, for example, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N-phenyl- N-substituted cyclic amides such as 2-pyrrolidone and N-methyl-ε-caprolactam; N-substituted cyclic ureas such as 1,3-dimethylethyleneurea and 1,3-diethyl-2-imidazolidinone; N-substituted aminoketones such as 4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone; aromatic isocyanates such as diphenylmethane diisocyanate and 2,4-tolylene diisocyanate; N, N-dimethyl N, N-disubstituted aminoalkylmethacrylates such as aminopropylmethacrylamide N-substituted aminoaldehydes such as 4-N, N-dimethylaminobenzaldehyde; N-substituted carbodiimides such as dicyclohexylcarbodiimide; Schiff bases such as N-ethylethylideneimine and N-methylbenzylideneimine; propylene oxide , Tetraglycidyl-1,3-bisaminomethylcyclohexane, epoxy group-containing compounds such as epoxidized polybutadiene; pyridyl group-containing vinyl compounds such as 4-vinylpyridine; tin tetrachloride, silicon tetrachloride, hexachlorosilane, bis (trichlorosilyl) ) Metal halide compounds such as methane, bis (trichlorosilyl) ethane, bis (trichlorosilyl) propane, bis (trichlorosilyl) hexane, bis (trichlorosilyl) nonane;

The amount of the modifier used is determined from the amount of the remaining active ends that did not react with the coupling agent among the conjugated diene polymers in which at least a part of the conjugated diene polymer (A) having active ends was coupled. Adjust as appropriate. It is preferable to add the modifier so that the number of moles of the reactive group of the modifier that reacts with the active terminal is 1.0 times the mole or more with respect to the number of moles of the remaining active terminal. It sets so that it may become 1.0-2.0 times mole, Most preferably, it is 1.0-1.2 times mole. If the amount of the modifier is in the range, by reacting the conjugated diene polymer (A) and the modifier having a residual active end that did not react with mosquito coupling agent, a higher silica-affinity, A conjugated diene polymer (C) having a functional group introduced at the molecular end is obtained. As a result, the storage stability of the conjugated diene rubber composition for vibration-proof rubber and the dynamic ratio of the vibration-proof rubber member finally obtained can be made excellent.

  A part of the conjugated diene polymer (C) having a modifying group introduced at the molecular end may be coupled via a modifying agent. As described above, there are usually many reactive groups in one molecule of polyorganosiloxane, but this is the case where polyorganosiloxane is used as a modifier by adjusting the amount of modifier used as described above. However, the peak top molecular weight (MP-3) of the peak (P-3) detected by gel permeation chromatography of the conjugated diene polymer (C) is the peak top molecular weight of the peak (P-1) having the largest molecular weight. It can be recognized between (MP-1) and the peak top molecular weight (MP-2) of the peak (P-2) having the smallest molecular weight. There may be a plurality of (P-3) between (P-1) and (P-2). Specifically, the peak top molecular weight ratio of (MP-3 / MP-2) is preferably in the range of 1.1 to 3.4. When the peak top molecular weight ratio of (MP-3 / MP-2) is in the above range, the conjugated diene rubber composition for vibration proof rubber is excellent in storage stability, and the vibration proof rubber member finally obtained also has a dynamic magnification. It will be excellent.

  In the present invention, the coupling reaction via the modifier can be controlled by the type of modifier added and the amount of modifier added. For example, by adding a modifier so that the number of moles of reactive groups of the modifier reacting with the active terminal is equal to or more than the number of moles of the remaining active terminal, The coupling reaction can be made difficult to occur.

  (MP-3) is preferably 90,000 to 2.1 million, more preferably 180,000 to 1,600,000, and particularly preferably 250,000 to 1,200,000. When (MP-3) is in the above range, the conjugated diene rubber composition for vibration-proof rubber is excellent in storage stability, and the vibration-proof rubber member finally obtained is also excellent in dynamic magnification.

  The method of reacting the conjugated diene polymer (A) having an active end with the modifier is not particularly limited, but the modifier is usually added to a solution in which the conjugated diene polymer (A) having an active end is dissolved or dispersed. What is necessary is just to add. In addition, when a modifier is added to a solution in which the conjugated diene polymer (A) having an active end is dissolved or dispersed, it is obtained by dissolving the modifier in an inert organic solvent from the viewpoint of controlling the reaction well. The resulting solution is preferably added to a solution in which the conjugated diene polymer (A) having an active end is dissolved or dispersed in an inert organic solvent. The concentration of the denaturing agent solution is preferably 1 to 50% by weight. Moreover, as an inert organic solvent used for this, the thing similar to what is used for superposition | polymerization of a monomer mixture can be used.

  The conditions for reacting the modifier with the conjugated diene polymer (A) having an active end are not particularly limited, but the reaction temperature is usually −80 to + 150 ° C., preferably 0 to 100 ° C., more preferably 30. It is the range of -90 degreeC, and reaction time is 1-120 minutes normally, Preferably it is the range of 2-60 minutes.

The order in which the coupling agent and the modifier are added to the conjugated diene polymer (A) having an active end is not particularly limited. Either one may be added first, and the coupling agent and the modifier may be added. If they are different, they may be performed simultaneously. However, after adding a coupling agent first, coupling at least a part of the conjugated diene polymer (A) to form a conjugated diene polymer (B), a modifier is added, and molecular terminals are added. It is preferable to produce a conjugated diene polymer (C) in which a modifying group is introduced. By carrying out in this order, a part of the conjugated diene polymer (A) having an active end can be reliably coupled with a coupling agent, and the intended conjugated diene rubber composition for vibration-proof rubber Is easier to obtain.

  On the other hand, when the modifying agent is added prior to the coupling agent, the amount of the modifying agent used is increased in order to reliably couple a part of the conjugated diene polymer (A) having an active end with the coupling agent. It is preferable to make it less than the amount used. Specifically, with respect to the number of moles of the active terminal of the polymer (A), the number of moles of the reactive group of the modifier that reacts with the active terminal is in the range of 0.40 to 0.95 times mole. It is preferable to add to 0.65, 0.93 times mole, more preferably 0.70 to 0.88 times mole.

  In the present invention, the coupling agent and the modifying agent are usually different compounds, but the same compound may be used as long as each condition is satisfied. However, in that case, the use amount that reacts with the conjugated diene polymer (A) is first added as a coupling agent, and then the use amount that reacts with the conjugated diene polymer (A) as a modifier. It is preferable to add them.

In the conjugated diene rubber composition for anti-vibration rubber of the present invention, a conjugated diene polymer (B) having a structure bonded through a coupling agent, and a modified group at the molecular end obtained through the modifier. Is preferably 0.10: 1 to 1.3: 1, and more preferably 0.10: 1 to 0.55: 1. It is particularly preferably 0.15: 1 to 0.45: 1. By being in such a range, the conjugated diene polymer (B ) having a structure in which the mechanical strength of the obtained conjugated diene rubber composition for vibration-proof rubber is bonded via a coupling agent having a high molecular weight. The conjugated diene rubber composition for vibration-proof rubber has a higher content per unit weight of the conjugated diene polymer (C) having a relatively low molecular weight and having a functional group introduced at the molecular end. The product has excellent storage stability, and the vibration-proof rubber member finally obtained also has excellent dynamic magnification.

  In addition, the conjugated diene rubber composition for vibration-proof rubber of the present invention may contain a polymer that has not reacted with either the coupling agent or the modifier, but the ratio is conjugated diene rubber composition for vibration-proof rubber. The total content is preferably 30% by weight or less, and more preferably 15% by weight or less.

  After reacting the conjugated diene polymer (A) having an active end with a coupling agent or a modifying agent, if desired, for example, an alcohol such as methanol or isopropanol or water is added to stop the reaction, thereby preventing vibration. A solution containing the conjugated diene rubber composition for rubber can be obtained. Then, if desired, after adding an anti-aging agent, a coagulation crumb stabilizer, a scale inhibitor, etc., the solvent is separated by direct drying or steam stripping to recover the desired conjugated diene rubber composition for vibration-proof rubber. . Before separating the solvent, the solution may be mixed with an extending oil, and the conjugated diene rubber composition for vibration-proof rubber may be recovered as an oil-extended rubber.

  As the extender oil used when recovering the conjugated diene rubber composition for anti-vibration rubber as an oil-extended rubber, those normally used in the rubber field can be used, and paraffinic, aromatic and naphthenic petroleum softeners. , Plant softeners such as castor oil and rapeseed oil, and fatty acids such as palmitic acid. When a petroleum softener is used, the polycyclic aromatic content is preferably less than 3% by weight. This content is measured by the method of IP346 (the testing method of THE INSTITUTE PETROLEUM, UK). These extending oils can be used singly or in combination of two or more. When using the extender oil, the content thereof is usually 5 to 60 parts by weight, preferably 10 to 40 parts by weight, more preferably 15 to 30 parts by weight with respect to 100 parts by weight of the conjugated diene rubber composition for vibration-proof rubber. It is.

  The weight average molecular weight of the conjugated diene rubber composition for vibration-proof rubber of the present invention obtained as described above is preferably 250,000 to 1,500,000, more preferably 300,000 to 1,000,000, and 350,000 to Particularly preferred is 650,000. When the weight average molecular weight of the conjugated diene rubber composition for vibration proof rubber is in the above range, the conjugated diene rubber composition for vibration proof rubber is excellent in storage stability, and the vibration proof rubber member finally obtained is also excellent in dynamic magnification. It becomes.

  Further, the molecular weight distribution represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the conjugated diene rubber composition for vibration-proof rubber of the present invention obtained as described above is preferably Is 1.2 to 3.0, more preferably 1.3 to 2.2, and particularly preferably 1.4 to 1.8. When (Mw / Mn) of the conjugated diene rubber composition for vibration-proof rubber is in the above range, the conjugated diene rubber composition for vibration-proof rubber is excellent in storage stability, and the vibration-proof rubber member finally obtained also has a dynamic magnification. It will be excellent.

  The anti-vibration rubber composition of the present invention comprises a conjugated diene rubber (D) other than the conjugated diene rubber composition for anti-vibration rubber and the conjugated diene rubber composition for anti-vibration rubber.

  Examples of the conjugated diene rubber (D) include natural rubber (NR), butadiene rubber (BR, may be polybutadiene rubber containing crystal fibers made of 1,2-polybutadiene polymer), isoprene rubber (IR). , Acrylonitrile-butadiene rubber (NBR), styrene-butadiene rubber (SBR), styrene-isoprene rubber, butadiene-isoprene rubber, styrene-isoprene-butadiene rubber, chloroprene rubber (CR), etc. Those other than the conjugated diene rubber composition. These can be used alone or in combination of two or more. Among these, natural rubber, butadiene rubber, isoprene rubber, and styrene-butadiene rubber are preferable, and natural rubber is more preferable. By containing natural rubber, the vibration-insulating rubber member using the vibration-insulating rubber composition of the present invention is excellent in sound proofing properties because of its excellent dynamic magnification.

  In the anti-vibration rubber composition, the ratio of the content of the conjugated diene rubber composition for anti-vibration rubber and the conjugated diene rubber (D) is as follows: (conjugated diene rubber composition for anti-vibration rubber / conjugated diene rubber (D)) 5 to 90% by weight) / (95 to 10% by weight), preferably (20 to 70% by weight) / (80 to 30% by weight), and more preferably (30 to 60% by weight). % By weight) / (70 to 40% by weight) is particularly preferable. When the ratio of the conjugated diene rubber composition for vibration proof rubber and the conjugated diene rubber (D) is in the above range, the vibration proof rubber member finally obtained is excellent in dynamic magnification.

  The anti-vibration rubber composition of the present invention can further contain butyl rubber (IIR) as the rubber component, and preferably contains halogenated butyl rubber. An anti-vibration rubber member using the anti-vibration rubber composition containing butyl rubber is excellent in soundproofing and anti-vibration properties because it has a large loss factor in addition to excellent dynamic magnification.

  When butyl rubber is contained, the content of butyl rubber in the total amount of rubber components contained in the vibration-proof rubber composition is preferably in the range of 5 to 60% by weight, and in the range of 10 to 40% by weight. More preferably, it is in the range of 15 to 30% by weight. When the content of butyl rubber is within the above range, the vibration-proof rubber member finally obtained is excellent in dynamic magnification and loss factor.

  The anti-vibration rubber composition of the present invention may be blended with other rubbers other than those described above, if desired, as long as the effects of the present invention are not impaired. Examples of other rubbers include ethylene-propylene rubber (EPM); ethylene-propylene-diene rubber (EPDM); polyurethane rubber; acrylic rubber; fluorine rubber; These can be used alone or in combination of two or more. The content of other rubber is preferably less than 50% by weight, more preferably 20% by weight or less, and more preferably 5% by weight or less, based on the total amount of rubber components contained in the vibration-proof rubber composition. Is particularly preferred.

  The anti-vibration rubber composition preferably contains a filler. The content of the filler is preferably 5 to 150 parts by weight, more preferably 10 to 90 parts by weight, with respect to 100 parts by weight of the total rubber components in the vibration-proof rubber composition. Part by weight is particularly preferred. When the content of the filler is in the above range, the vibration-proof rubber member finally obtained is excellent in dynamic magnification.

  Examples of the filler include, but are not limited to, silica, carbon black, calcium carbonate, clay, talc, aluminum hydroxide, and various metal oxides. Among these, silica is particularly preferable. By containing silica, the anti-vibration rubber member using the anti-vibration rubber composition of the present invention exhibits a particularly excellent dynamic magnification. Said filler can be used individually or in combination of 2 or more types.

The silica is not particularly limited, and examples thereof include dry method white carbon, wet method white carbon, colloidal silica, and precipitated silica. Among these, wet method white carbon mainly containing hydrous silicic acid is preferable. Alternatively, a carbon-silica dual phase filler in which silica is supported on the carbon black surface may be used. Nitrogen adsorption specific surface area of the silica (. As measured by the BET method according to ASTM D3037-81) is preferably 50 to 400 m ² / g, more preferably 80~220m ² / g, particularly preferably 100~180m ² / g. If the nitrogen adsorption specific surface area of silica is in the above range, the vibration-proof rubber member finally obtained is excellent in dynamic magnification.

  When silica is contained in the vibration proof rubber composition, the vibration proof property of the vibration proof rubber member finally obtained can be further improved by further containing a silane coupling agent. The silane coupling agent is not particularly limited. For example, vinyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane. , 3-octathio-1-propyl-triethoxysilane, bis (3- (triethoxysilyl) propyl) disulfide, bis (3- (triethoxysilyl) propyl) tetrasulfide, γ-trimethoxysilylpropyldimethylthiocarbamyl Examples thereof include tetrasulfide and γ-trimethoxysilylpropylbenzothiazyl tetrasulfide. Among these, from the viewpoint of avoiding scorch during kneading, those having 4 or less sulfur atoms contained in one molecule are preferable. The content of the silane coupling agent is preferably 0.1 to 30 parts by weight, more preferably 1 to 15 parts by weight with respect to 100 parts by weight of silica.

  Although it does not specifically limit as carbon black, For example, furnace black, acetylene black, thermal black, channel black, a graphite, a graphite fiber, fullerene etc. are mentioned. Of these, furnace black is preferable, and specific examples thereof include SAF, ISAF, HAF, MAF, FEF, GPF, and SRF.

The nitrogen adsorption specific surface area of carbon black is preferably 5 to 200 m ² / g, more preferably 20 to 100 m ² / g, and the dibutyl phthalate (DBP) adsorption amount is preferably 5 to 300 ml / 100 g, more preferably 50-160 ml / 100 g.

  The anti-vibration rubber composition of the present invention preferably contains a crosslinking agent. By containing the crosslinking agent, the vibration-proof rubber composition can be formed into a vibration-proof rubber member. Although it does not specifically limit as a crosslinking agent, For example, sulfur, halogenated halogen, an organic peroxide, a quinone dioxime, an organic polyvalent amine compound, the alkylphenol resin which has a methylol group etc. are mentioned. Among these, sulfur is preferably used. The content of the cross-linking agent is preferably 0.1 to 15 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the total rubber components in the vibration-proof rubber composition.

  In addition to the above components, the anti-vibration rubber composition includes a crosslinking accelerator, a scorch inhibitor, a crosslinking activator, an anti-aging agent, an activator, a process oil, a plasticizer, a lubricant, a tackifier and the like according to a conventional method. Each compounding agent can be contained.

  The crosslinking accelerator is not particularly limited, and examples thereof include N-cyclohexyl-2-benzothiazylsulfenamide, Nt-butyl-2-benzothiazolesulfenamide, N-oxyethylene-2-benzothiazolesulfuramide. Sulfenamide-based crosslinking accelerators such as phenamide, N-oxyethylene-2-benzothiazole sulfenamide, N, N′-diisopropyl-2-benzothiazole sulfenamide; diphenylguanidine, diortolylguanidine, orthotri Guanidine-based crosslinking accelerators such as rubiguanidine; thiourea-based crosslinking accelerators; thiazole-based crosslinking accelerators; thiuram-based crosslinking accelerators; dithiocarbamic acid-based crosslinking accelerators; xanthogenic acid-based crosslinking accelerators; Among these, sulfenamide-based crosslinking accelerators and guanidine-based crosslinking accelerators are preferable, and specifically, N-cyclohexyl-2-benzothiazylsulfenamide, Nt-butyl-2-benzothiazolesulfene. Amides and diphenylguanidine are more preferred. These can be used alone or in combination of two or more. The content of the crosslinking accelerator is preferably 0.1 to 15 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the total rubber components in the vibration-proof rubber composition.

  Examples of the scorch inhibitor include, but are not limited to, organic acids such as phthalic anhydride, salicylic acid, and benzoic acid; N- (cyclohexylthio) phthalimide; sulfonamide derivatives, and the like. These can be used alone or in combination of two or more. The content of the scorch inhibitor is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 2 parts by weight with respect to 100 parts by weight of the total rubber components in the vibration-proof rubber composition.

  Although it does not specifically limit as a crosslinking activator, For example, higher fatty acids, such as a stearic acid, zinc oxide, etc. can be used. These can be used alone or in combination of two or more. The content of the crosslinking activator is appropriately selected. The content of the higher fatty acid is preferably 0.05 to 15 parts by weight, more preferably 100 parts by weight of the total rubber component in the vibration-proof rubber composition. Is 0.5 to 5 parts by weight, and the content of zinc oxide is preferably 0.05 to 10 parts by weight, more preferably 0.1 parts per 100 parts by weight of the total rubber components in the vibration-proof rubber composition. 5 to 5 parts by weight.

  Although it does not specifically limit as an anti-aging agent, For example, Diphenylamine type | system | groups, such as 4,4 '-((alpha), (alpha) -dimethylbenzyl) diphenylamine; N-isopropyl-N'-phenyl-p-phenylenediamine, N-phenyl- Amine systems such as N ′-(1,3-dimethylbutyl) -p-phenylenediamine; amine-ketone systems such as 2,2,4-trimethyl-1,2-dihydroquinoline polymer; 2,2-methylenebis ( Phenolic compounds such as 4-methyl-6-tert-butylphenol can be used, and these can be used alone or in combination of two or more. Preferably it is 0.1-10 weight part with respect to 100 weight part of all the rubber components in a composition, More preferably, it is 0.1-5 weight part.

  Although it does not specifically limit as an activator, For example, diethylene glycol, polyethyleneglycol, a lecithin etc. can be used.

  As the process oil, the same oil as the extension oil mixed with the above-described conjugated diene rubber composition for vibration-proof rubber can be used. These can be used alone or in combination of two or more. The content of the process oil is preferably 1 to 40 parts by weight, more preferably 5 to 30 parts by weight with respect to 100 parts by weight of the total rubber components in the vibration-proof rubber composition.

  The plasticizer is not particularly limited, and examples thereof include phthalic acid derivatives such as dimethyl phthalate, dibutyl phthalate, and dioctyl phthalate; isophthalic acid derivatives such as dimethyl isophthalate; adipic acid derivatives such as dibutyl adipate;

  The lubricant is not particularly limited, and examples thereof include waxes such as paraffin wax; fatty acids; fatty acid metal salts; These can be used alone or in combination of two or more. The content of the lubricant is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the total rubber components in the vibration-proof rubber composition.

The tackifier is not particularly limited, and examples thereof include coumarone resins such as coumarone and indene resins; terpenes and phenol resins; petroleum hydrocarbon resins;

  In order to obtain a vibration-proof rubber composition from the conjugated diene rubber composition for vibration-proof rubber, each component may be kneaded according to a conventional method. For example, after kneading the compounding agent excluding the crosslinking agent and the crosslinking accelerator and the rubber component, the composition for vibration-proof rubber can be obtained by mixing the kneaded product with the crosslinking agent and the crosslinking accelerator. The kneading temperature of the compounding agent excluding the crosslinking agent and crosslinking accelerator and the rubber component of the conjugated diene rubber composition for vibration-proof rubber is preferably 80 to 200 ° C, more preferably 120 to 180 ° C, and the kneading time is Preferably, it is 30 seconds to 30 minutes. Mixing of the kneaded product with the crosslinking agent and crosslinking accelerator is usually performed at 100 ° C. or lower, preferably 80 ° C. or lower.

  A crosslinked product is obtained by crosslinking the vibration-proof rubber composition of the present invention. The method for crosslinking and molding the vibration-proof rubber composition is not particularly limited, and may be selected according to the shape and size of the crosslinked product. An anti-vibration rubber composition containing a crosslinking agent may be crosslinked at the same time as molding by filling a mold and heated. After pre-molding an anti-vibration rubber composition containing a crosslinking agent, It may be crosslinked by heating. The crosslinking temperature is preferably 120 to 200 ° C, more preferably 140 to 180 ° C, and the crosslinking time is usually 1 to 120 minutes.

  The cross-linked product of the present invention has excellent anti-vibration properties and is suitably used as an anti-vibration rubber member. The anti-vibration rubber member is not particularly limited. For example, it is used in railway vehicles, generators, electric motors, automobiles, houses, etc., and in particular, various mounts such as engine mounts and liquid-filled mounts, various bushes, dampers, and supports. It is suitably used for vibration-proof rubber members for automobiles such as rubber and bearings.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In addition, unless otherwise indicated, the part and% in each example are a basis of weight.

Various physical properties were evaluated according to the following methods.
[Weight Average Molecular Weight, (MP-1 / MP-2) Peak Top Molecular Weight Ratio and (P-1) Area Ratio to Total Elution Area]
A chart based on the molecular weight in terms of polystyrene was obtained by gel permeation chromatography, and the weight average molecular weight of the conjugated diene rubber composition for vibration-proof rubber was determined based on the chart. The ratio of the peak top molecular weight (MP-1) of the peak with the highest molecular weight (P-1) to the peak top molecular weight (MP-2) of the peak with the lowest molecular weight (P-2) (MP-1 / MP- 2) The area ratio with respect to the total elution area of (P-1) was calculated. Specifically, the measurement was performed by gel permeation chromatography under the following conditions.
Measuring instrument: HLC-8020 (manufactured by Tosoh Corporation)
Column: Four HM-H (manufactured by Tosoh Corporation) were connected in series.
Detector: Differential refractometer RI-8020 (manufactured by Tosoh Corporation)
Eluent: Tetrahydrofuran Column temperature: 40 ° C
[Styrene unit content and vinyl bond content of butadiene unit]
^It was measured by ¹ H-NMR.
[Glass-transition temperature]
Using a differential scanning calorimeter (Perkin Elmer), the temperature was raised from 23 ° C. to 120 ° C. (heating rate 100 ° C./min), held at 120 ° C. for 10 minutes, and cooled to −120 ° C. (cooling rate 100 ° C./min) Min), hold at −120 ° C. for 10 minutes, change the temperature of the measurement sample in the order of heating up to 23 ° C. (heating rate 10 ° C./min), and calculate the average value of the onset value twice as the measured value of the glass transition temperature. It was.
[Storage stability of conjugated diene rubber composition for anti-vibration rubber]
A conjugated diene rubber composition for vibration-proof rubber made into a 2 mm-thick test piece by press molding is punched out with a JIS No. 3 dumbbell. The time (seconds) from when the test piece was stretched to being cut was measured, and the average of three times was taken as the measured value. The measured value was 1 point for samples of less than 240 seconds, 2 points for samples of 240 seconds to less than 300 seconds, and 3 points of samples for 300 seconds or more. As for storage stability, 1 point is inferior, 2 points are good, and 3 points are excellent.
[Vibration-proof characteristics (dynamic magnification)]
Using a viscoelasticity measuring device EPLEXOR manufactured by GABO, the dynamic elastic modulus (E′-1) was measured under the conditions of initial strain 4.0%, dynamic strain 1.0%, 1 Hz, 25 ° C., and initial strain 4 The static elastic modulus (E′−2) is measured under the conditions of 0.0%, dynamic strain 0.5%, 10 Hz, 0 ° C., and (E′−2) / (E′−1) is set as the dynamic magnification. Asked. About this characteristic, the comparative example 7 was shown with respect to Examples 5-7 and Comparative Examples 7-9, and the comparative example 10 was shown with the index | exponent which set 100 as Example 8 and Comparative Examples 10-12. . The smaller this index is, the better the dynamic magnification is and the better the anti-vibration characteristics, particularly the soundproofing property.

[Example 1]
In an autoclave equipped with a stirrer, 4000 g of cyclohexane, 600 g of 1,3-butadiene and 0.08 mmol of tetramethylethylenediamine were charged in a nitrogen atmosphere, and then n-butyllithium was polymerized in cyclohexane and 1,3-butadiene. An amount necessary for inactivating the impurities to be inhibited was added, and 7.8 mmol of n-butyllithium was added for the polymerization reaction, and polymerization was started at 50 ° C. After 20 minutes from the start of polymerization, 400 g of 1,3-butadiene was continuously added over 30 minutes. The maximum temperature during the polymerization reaction was 75 ° C. After completion of the continuous addition, the polymerization reaction was continued for another 15 minutes, and after confirming that the polymerization conversion was in the range of 95% to 100%, coupling agent I (1,6-bis (trichlorosilyl) (Hexane) 0.35 mmol was added in the form of a 20% strength cyclohexane solution and reacted at 70 ° C. for 20 minutes. Next, 5.9 mmol of modifier II (N, N-bis (trimethylsilyl) -3-aminopropyltrimethoxysilane) was added in the form of a 20% strength xylene solution and reacted at 70 ° C. for 30 minutes. As a polymerization terminator, an amount of methanol corresponding to twice the mole of n-butyllithium used was added to obtain a solution containing a conjugated diene rubber composition for vibration-proof rubber. In this solution, (4,6-bis (octylthiomethyl) -o-cresol, trade name “Irganox 1520L”, manufactured by Ciba Specialty Chemicals Co., Ltd.) is used as an anti-aging agent, and a conjugated diene rubber composition for vibration-proof rubber. After adding 0.15 part to 100 parts of the rubber component, the solvent was removed by steam stripping and vacuum drying at 60 ° C. for 24 hours to obtain a solid conjugated diene rubber composition for vibration-proof rubber (B -1) was obtained. About (B-1), weight average molecular weight, styrene unit content, vinyl bond content of butadiene unit portion, peak top molecular weight ratio of glass transition temperature (MP-1 / MP-2), and (P-1) The area ratio to the total elution area was measured by the above method. Furthermore, the storage stability of the conjugated diene rubber composition (B-1) for vibration-proof rubber was also measured. These measurement results are shown in Table 1.

[Examples 2 to 4]
About the polymerization prescription component shown in Table 1, except changing a kind and quantity as shown in Table 1, operation similar to Example 1 is performed, and the solid conjugated diene rubber composition for vibration-proof rubbers (B-2) ) To (B-4) were obtained. Various measurement results are shown in Table 1.

[Comparative Examples 1-6]
About the polymerization prescription component shown in Table 1, except changing a kind and quantity as shown in Table 1, operation similar to Example 1 is performed, and the solid conjugated diene rubber composition for vibration-proof rubbers (BC-1) ) To (BC-6) were obtained. Various measurement results are shown in Table 1.

In Examples 2 and 4 and Comparative Examples 2 and 3, the structure of the polyorganosiloxane used as the modifier III is as shown in the following general formula (XV). The numerical values of m and k are average values.

[Example 5]
A Banbury mixer was charged with 50 parts of the conjugated diene rubber composition for vibration-proof rubber (B-1) obtained in Example 1 and 50 parts of natural rubber, and kneaded for 30 seconds at 80 ° C. as the starting temperature. Silica (trade name “Zeosil 1115MP”, manufactured by Rhodia, nitrogen adsorption specific surface area (BET method): 115 m ² / g), silane coupling agent (bis (3- ( Triethoxysilyl) propyl) tetrasulfide (trade name “Si69”, manufactured by Degussa) 2.6 parts was added, kneaded for 1.5 minutes at 80 ° C. as a starting temperature, and silica (trade name “Zeosil 1115MP”) 5 parts of carbon black (trade name "SEAST SO", manufactured by Tokai carbon Co., Ltd., nitrogen adsorption specific surface area (BET method): ^42m 2 / g) 5 parts, process oil Product name “Fukkor Eramik 30”, Shin Nippon Oil Co., Ltd. 5 parts, zinc oxide (Zinc Hua 1) 3 parts, stearic acid (trade name “SA-300”, Asahi Denka Kogyo Co., Ltd.) 2 parts, anti-aging Agent (N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine, trade name “NOCRACK 6C”, manufactured by Ouchi Shinsei Chemical Co., Ltd.) and wax (trade name “SUNNOCK”, large 2 parts, and then kneaded for 2.5 minutes starting at 130 ° C., and the anti-vibration rubber composition was discharged from the Banbury mixer. The composition temperature was 150 ° C. This anti-vibration rubber composition was cooled to room temperature (30 ° C.), kneaded again in a Banbury mixer at 80 ° C. for 3 minutes, and then Banbury Anti-vibration rubber composition from mixer At the end of kneading, the temperature of the anti-vibration rubber composition was 140 ° C. After confirming that the anti-vibration rubber composition was cooled to 100 ° C. or less, it was opened at 50 ° C. In a roll, the resulting anti-vibration rubber composition, 1.8 parts of sulfur as a crosslinking agent, and a crosslinking accelerator [Nt-butyl-2-benzothiazolylsulfenamide (trade name “Noxeller NS”) A mixture of 2.5 parts of Ouchi Shinsei Chemical Industry Co., Ltd.) and 1.2 parts of diphenylguanidine (trade name “Noxeller D”, produced by Ouchi Shinsei Chemical Industry Co., Ltd.)] The vibration isolator composition was taken out, and the anti-vibration rubber composition was press-crosslinked at 150 ° C. for 20 minutes to produce a test piece, and the anti-vibration property (dynamic magnification) of the test piece was evaluated. The results are shown in Table 2. This evaluation is based on the vibration isolating foam of Comparative Example 7. It represents crosslinked product of use compositions as an index based on the reference sample (index 100).

[Examples 6 and 7]
A test piece was prepared in the same manner as in Example 5 except that the type of the conjugated diene rubber composition for vibration-proof rubber to be used was changed as shown in Table 2. The test piece was subjected to vibration-proof characteristics (dynamic magnification). ) Was evaluated. Table 2 shows the results.

[Comparative Examples 7 to 9]
A test piece was prepared in the same manner as in Example 5 except that the type of the conjugated diene rubber composition for vibration-proof rubber used was changed as shown in Table 2, and the vibration-proof characteristics (dynamic magnification) of this test piece were Was evaluated. Table 2 shows the results.

[Example 8]
In a Banbury mixer, 40 parts of the conjugated diene rubber composition for vibration-proof rubber (B-4) obtained in Example 4, 40 parts of natural rubber and 20 parts of halogenated butyl rubber (trade name “Bromobutyl 2244”, manufactured by Nippon Butyl Co., Ltd.) The mixture was masticated for 30 seconds with 80 ° C. as the starting temperature, and then silica (trade name “Zeosil 1165MP”, manufactured by Rhodia, nitrogen adsorption specific surface area (BET method) with respect to a total of 100 parts of the rubber component. 165 m ² / g) 35 parts, 4 parts of silane coupling agent (bis (3- (triethoxysilyl) propyl) tetrasulfide, trade name “Si69”, manufactured by Degussa) are added, and the starting temperature is 80 ° C. After mixing for 1.5 minutes, silica (trade name “Zeosil 1165MP” 5 parts, carbon black (trade name “Seast SO”, Tokai Carbon Company Ltd., nitrogen adsorption specific surface area (BET method): ^42m 2 / g) 5 parts, process oil (trade name "Fukkoru Eramikku 30", manufactured by Nippon Oil Co., Ltd.), 5 parts of zinc oxide (zinc white No. 1) 3 parts , Stearic acid (trade name “SA-300”, manufactured by Asahi Denka Kogyo Co., Ltd.), antiaging agent (N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine, trade name “NOCRACK”) 6C ", manufactured by Ouchi Shinsei Chemical Co., Ltd.) and 2 parts of wax (trade name" Sannok ", manufactured by Ouchi New Chemical Co., Ltd.) are added and kneaded for 2.5 minutes, starting at 130 ° C. The anti-vibration rubber composition was discharged from the Banbury mixer, and the temperature of the anti-vibration rubber composition at the end of the kneading was 150 ° C. The anti-vibration rubber composition was allowed to reach room temperature (30 ° C.). Cool and reopen at 80 ° C in a Banbury mixer. After mixing for 3 minutes as the starting temperature, the anti-vibration rubber composition was discharged from the Banbury mixer, and the temperature of the anti-vibration rubber composition at the end of the kneading was 140 ° C. This anti-vibration rubber composition Was confirmed to be cooled to 100 ° C. or lower, and the obtained anti-vibration rubber composition, 1.7 parts of sulfur as a crosslinking agent, and a crosslinking accelerator [N- 1.7 parts of cyclohexyl-2-benzothiazolylsulfenamide (trade name “Noxeller CZ”, manufactured by Ouchi Shinsei Chemical Co., Ltd.) and diphenylguanidine (trade name “Noxeller D”, manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.) 0 Then, the sheet-like anti-vibration rubber composition was taken out, and the anti-vibration rubber composition was press-crosslinked at 160 ° C. for 20 minutes to prepare a test piece, About this specimen, anti-vibration characteristics (dynamic magnification) Evaluation was carried out. Table 3 shows the results. In addition, this evaluation is represented by the index | exponent which makes the crosslinked material of the composition for vibration-proof rubber of the comparative example 10 the reference | standard sample (index | index 100).

[Comparative Examples 10-12]
A test piece was prepared in the same manner as in Example 8 except that the type of the conjugated diene rubber composition for vibration-proof rubber used was changed as shown in Table 3, and the vibration-proof characteristics (dynamic magnification) of this test piece were Was evaluated. Table 3 shows the results.

  Table 1 shows the following. That is, the conjugated diene rubber composition for vibration-proof rubber of the present invention (Examples 1 to 4) obtained by using a specific coupling agent and using a specific modifier is specified in the present invention. Ratio of peak top molecular weight (MP-1) of peak (P-1) having the highest molecular weight detected by gel permeation chromatography to peak top molecular weight (MP-2) of peak (P-2) having the lowest molecular weight ( MP-1 / MP-2) was 3.5 or more, and the area ratio of (P-1) to the total elution area was in the range of 10 to 55%. As a result, the storage stability of the conjugated diene rubber composition for vibration-proof rubber was good or excellent and easy to handle. On the other hand, a specific coupling agent was not used, and the conjugated diene rubber composition for vibration-proof rubber (Comparative Example 2) in which the area ratio to the total elution area of (P-1) was less than the lower limit of the present invention, And storage of the conjugated diene rubber composition for vibration-proof rubber (Comparative Example 4) in which the area ratio of (P-1) to the total elution area was less than the lower limit of the present invention. Stability was inferior and difficult to handle.

  Table 2 shows the following. That is, the crosslinked product of the anti-vibration rubber composition containing the conjugated diene rubber composition for anti-vibration rubber of the present invention (Examples 1 to 3) has excellent anti-vibration properties (dynamic magnification) and is used as an anti-vibration rubber member. By using it, it became what was excellent in soundproofing (Examples 5-7). On the other hand, a specific coupling agent was not used, and the area ratio of (P-1) to the total elution area exceeded the upper limit of the present invention. Conjugated diene rubber composition for vibration-proof rubber (Comparative Example 1) A rubber composition comprising a cross-linked product of anti-vibration rubber and a specific coupling agent, wherein the area ratio of (P-1) to the total elution area exceeds the upper limit of the present invention The crosslinked product of the anti-vibration rubber composition containing the conjugated diene rubber composition (Comparative Example 3) is inferior in anti-vibration properties (dynamic magnification) and is insufficient for use in the anti-vibration rubber member (Comparison Examples 7, 9).

  Table 3 shows the following. That is, the crosslinked product of the composition for vibration-proof rubber including the conjugated diene rubber composition for vibration-proof rubber of the present invention (Example 4) has excellent vibration-proof characteristics (dynamic magnification) and is used for the vibration-proof rubber member. Thus, the soundproofing property was excellent (Example 8). On the other hand, a specific coupling agent was used, but the conjugated diene rubber composition for vibration-proof rubber (Comparative Example 4) in which the area ratio of (P-1) to the total elution area was less than the lower limit of the present invention. A crosslinked product of the composition for vibration-proof rubber and a specific coupling agent used, and the peak top molecular weight ratio of (MP-1 / MP-2) was less than 3.5. The crosslinked product of the anti-vibration rubber composition containing the conjugated diene rubber composition (Comparative Examples 5 and 6) is inferior in anti-vibration properties (dynamic magnification) and is insufficient for use in the anti-vibration rubber member ( Comparative Examples 10-12).

Claims (12)

The conjugated diene polymer (A) having an active end is obtained by reacting a coupling agent having 5 or more reactive groups that react with the active end of the conjugated diene polymer (A) in one molecule, The reactivity of the conjugated diene polymer (B) and the conjugated diene polymer (A) to which the conjugated diene polymer (A) is coupled reacts with the active terminal of the conjugated diene polymer (A) in one molecule. Conjugated diene rubber composition for anti-vibration rubber containing a conjugated diene polymer (C) having a functional group introduced at the molecular end, obtained by reacting a modifier having a group having a functional group having affinity with silica A thing,
Ratio of peak top molecular weight (MP-1) of peak (P-1) having the highest molecular weight detected by gel permeation chromatography to peak top molecular weight (MP-2) of peak (P-2) having the lowest molecular weight ( MP-1 / MP-2) is 3.5 or more, and the area ratio of (P-1) to the total elution area is 10 to 55%. Conjugated diene rubber for vibration-proof rubber Composition. The conjugated diene rubber composition for vibration-proof rubber according to claim 1, wherein the functional group having an affinity for silica is a silicon-containing functional group, an amino group or a hydroxyl group. The conjugated diene rubber composition for vibration-proof rubber according to claim 1 or 2, wherein the modifier is a polyorganosiloxane or an alkoxysilane compound. The conjugated diene rubber for vibration-proof rubber according to any one of claims 1 to 3, wherein the weight ratio of the conjugated diene polymer (B) to the conjugated diene polymer (C) is 0.10: 1 to 1.3: 1. Composition. The conjugated diene rubber composition for vibration-proof rubber according to any one of claims 1 to 4 and conjugated diene rubber (D) other than the conjugated diene rubber composition for vibration-proof rubber are contained as a rubber component, and 100 parts by weight of the rubber component An anti-vibration rubber composition containing 10 to 150 parts by weight of silica. Furthermore, the composition for vibration-proof rubbers of Claim 5 containing a crosslinking agent. A crosslinked product obtained by crosslinking the vibration-proof rubber composition according to claim 6 . An anti-vibration rubber member comprising the crosslinked product according to claim 7 . A conjugated diene polymer (A) having an active end, a coupling agent having 5 or more reactive groups that react with the active end of the conjugated diene polymer (A) in one molecule, and the conjugated diene in one molecule The conjugated diene rubber composition for vibration-proof rubber according to claim 1, wherein a modifier having a reactive group that reacts with an active terminal of the polymer (A) and a functional group having an affinity for silica are reacted. Production method. The method for producing a conjugated diene rubber composition for vibration-proof rubber according to claim 9 , wherein the coupling agent is reacted with the conjugated diene polymer (A) having an active end, and then the modifier is reacted. The method for producing a conjugated diene rubber composition for vibration-proof rubber according to claim 9 or 10, wherein the functional group having an affinity for silica is a silicon-containing functional group, an amino group or a hydroxyl group. The method for producing a conjugated diene rubber composition for vibration-proof rubber according to any one of claims 9 to 11, wherein the modifier is a polyorganosiloxane or an alkoxysilane compound.