JPWO2009060931A1 - Hydrogenated conjugated diene-based (co) polymer rubber and method for producing the same - Google Patents

Abstract

This is a hydrogenated conjugated diene-based (co) polymer rubber obtained by hydrogenating a copolymer that satisfies a predetermined condition and having a hydrogenation rate of a conjugated diene portion of 50% or more.

Description

  The present invention relates to a hydrogenated conjugated diene-based (co) polymer rubber, a production method thereof, a hydrogenated conjugated diene-based (co) polymer rubber composition, and a rubber molded product thereof.

  Conjugated diene rubbers typified by natural rubber have different properties depending on the structural unit, and various types have been developed depending on the application. For example, there are anti-vibration rubber (see, for example, Patent Document 1), rubber materials for tires, and the like.

  When conjugated diene rubber is used as a rubber material for tires, it is desirable that the conjugated diene rubber has excellent rolling resistance, wear resistance, and fracture characteristics in order to meet the recent demand for low fuel consumption for automobiles. . It is also desired that the steering stability is excellent.

  Polymerization of conjugated diene polymers obtained by anionic polymerization reactions using organolithium compounds as conjugated diene rubber compositions capable of producing rubber materials with excellent rolling resistance, wear resistance, fracture characteristics, handling stability, etc. A rubber composition in which an active terminal is modified with an alkoxysilane derivative containing a functional group that interacts with a filler is disclosed (for example, see Patent Document 2).

JP 2007-131807 A Japanese Patent Laid-Open No. 2004-18795

  However, the conventionally disclosed conjugated diene rubber composition may have a large cold flow value of the conjugated diene copolymer rubber before blending the filler, which has a practical problem. is there.

  The present invention has been made in view of such problems of the prior art, and the object of the present invention is to provide a hydrogenated conjugated diene-based (co) polymer rubber having a low cold flow value. is there. Another object of the present invention is to provide a method for producing a hydrogenated conjugated diene (co) polymer rubber having a small cold flow value. Furthermore, the subject of the present invention is to provide a hydrogenated conjugated diene-based (co) polymerized rubber composition capable of producing a rubber molded product having excellent processability, tensile breaking strength, tensile breaking elongation, and static / kinetic ratio. It is to provide. Moreover, the place made into the subject of this invention is providing the rubber molded product which is excellent in workability, tensile breaking strength, tensile breaking elongation, and static-motion ratio.

  As a result of intensive studies to achieve the above-described problems, the present inventors have found that the above-described problems can be achieved by adopting the following configuration, and have completed the present invention.

  That is, according to the present invention, there are provided the following hydrogenated conjugated diene (co) polymer rubber, a method for producing the same, a hydrogenated conjugated diene (co) polymer rubber composition, and a rubber molded product thereof.

[1] A hydrogenated conjugated diene-based (co) polymer rubber obtained by hydrogenating a copolymer satisfying the following conditions (A) to (D), wherein the hydrogenation rate of the conjugated diene moiety is 50% or more.
(A): (a-1) containing a conjugated diene unit.
(B): Vinyl bond content is 20 to 70%.
(C): (c-1) an optionally protected primary amino group-containing alkoxysilyl group, or (c-2) an optionally protected primary amino group and an alkoxysilyl group are bonded. Yes.
(D): having a structure coupled in (D1) or (D2) below.
(D1): (d-1) A coupling agent having a plurality of functional groups.
(D2): (d-1) a coupling agent having a plurality of functional groups and (d-2) a monomer having a plurality of functional groups.

  [2] The hydrogenated conjugated diene-based (co) polymerization according to [1], wherein the copolymer further includes at least one of (a-2) an aromatic vinyl unit and (a-3) other units. Rubber.

  [3] The above [1] or [2], wherein 1 kg of the copolymer contains 0.5 to 200 mmol of the primary amino group and 0.5 to 200 mmol of the alkoxysilyl group. ] The hydrogenated conjugated diene type | system | group (co) polymer rubber of description.

  [4] The hydrogenated conjugated diene system (co) according to any one of [1] to [3], wherein the structure of the copolymer is represented by the following general formula (1) or the following general formula (2): Polymerized rubber.

（前記一般式（１）中、Ｐは共重合体鎖を示し、Ｒ^１は炭素数１〜１２のアルキレン基を示し、Ｒ^２及びＲ^３は、相互に独立に、炭素数１〜２０のアルキル基又はアリール基を示し、ｎ、ｍ及びｋは、１又は２を示す（但し、ｎ＋ｍ＋ｋは、３又は４である。）。）

(In the general formula (1), P represents a copolymer chain, R ¹ represents an alkylene group having 1 to 12 carbon atoms, and R ² and R ³ independently of each other have 1 to 20 carbon atoms. Represents an alkyl group or an aryl group, and n, m and k represent 1 or 2 (provided that n + m + k is 3 or 4).

（前記一般式（２）中、Ｐは共重合体鎖を示し、Ｒ^１は炭素数１〜１２のアルキレン基を示し、Ｒ^２及びＲ^３は、相互に独立に、炭素数１〜２０のアルキル基又はアリール基を示し、ｊ及びｈは、１〜３の整数を示す（但し、ｊ＋ｈは、２〜４の整数である。）。）

(In the general formula (2), P represents a copolymer chain, R ¹ represents an alkylene group having 1 to 12 carbon atoms, and R ² and R ³ independently of each other have 1 to 20 carbon atoms. Represents an alkyl group or an aryl group, and j and h represent an integer of 1 to 3 (provided that j + h is an integer of 2 to 4).

  [5] The proportion of the (a-1) conjugated diene unit contained in the copolymer is 60 to 100 mass%, the proportion of the (a-2) aromatic vinyl unit is 0 to 40 mass%, a-3) Said [2]-[4] whose ratio of other units is 0-40 mass% (however, (a-1) + (a-2) + (a-3) = 100 mass%). The hydrogenated conjugated diene-based (co) polymer rubber according to any one of the above.

  [6] The above [1] to [5], wherein the proportion of the structural unit derived from the monomer having a plurality of (d-2) functional groups contained in the copolymer is 0.001 to 5% by mass. The hydrogenated conjugated diene-based (co) polymer rubber according to any one of the above.

  [7] The hydrogenated conjugated diene-based (co) polymer rubber according to any one of [1] to [6], wherein the coupling agent having a plurality of (d-1) functional groups is a silicon compound.

  [8] A conjugated diene monomer or a plurality of conjugated diene monomers and functional groups in a reaction system containing at least one of an organic alkali metal and an organic alkaline earth metal as a polymerization initiator in a hydrocarbon solvent. Even if it is protected by adding a monomer having an anionic polymerization reaction (1), adding a coupling agent having a plurality of functional groups (2), and adding a functional group modifier A hydrogenated conjugated diene system (co) comprising: a step (3) for obtaining a copolymer by bonding a good primary amino group-containing alkoxysilyl group; and a step (4) for adding hydrogen to the copolymer. A method for producing polymer rubber.

  [9] A conjugated diene monomer in a reaction system containing a reaction product of at least one of an organic alkali metal and an organic alkaline earth metal and a primary amine compound as a polymerization initiator in a hydrocarbon solvent, or A step (1) of adding an conjugated diene monomer and a monomer having a plurality of functional groups to perform an anionic polymerization reaction, a step (2) of adding a coupling agent having a plurality of functional groups, and a modification having a functional group A step (3) of adding an agent to bond an optionally protected primary amino group-containing alkoxysilyl group or alkoxysilyl group to obtain a copolymer, and a step of adding hydrogen to the copolymer (4) and a method for producing a hydrogenated conjugated diene-based (co) polymer rubber.

  [10] The hydrogenated conjugated diene according to [8] or [9], wherein in the step (1), at least one of an aromatic vinyl monomer and another monomer is further added to the reaction system. A method for producing a (co) polymer rubber.

  [11] The modifier having the functional group is an amino group-containing alkoxysilane compound whose structure is represented by the following general formula (3) or the following general formula (4). The method for producing a hydrogenated conjugated diene-based (co) polymer rubber according to any one of [8] to [10], further including a step (5) of decomposing.

（前記一般式（３）中、Ｒ^１は炭素数１〜１２のアルキレン基を示し、Ｒ^２及びＲ^３は、相互に独立に、炭素数１〜２０のアルキル基又はアリール基を示し、Ｒ^４、Ｒ^５及びＲ^６は、相互に独立に、炭素数１〜２０のアルキル基若しくはアリール基を示すか、又はそれらのうち２つが互いに結合して形成されるケイ素原子を含む環を示し、ｇは、１又は２を示し、ｆは、１〜１０の整数を示す。）

(In the general formula (3), ^{R 1} represents an alkylene group having 1 to 12 carbon atoms, ^{R 2} and ^{R 3,} independently of one another, an alkyl group or an aryl group having 1 to 20 carbon atoms, R ⁴ , R ⁵ and R ⁶ each independently represent a C 1-20 alkyl group or aryl group, or a ring containing a silicon atom formed by bonding two of them together, g represents 1 or 2, and f represents an integer of 1 to 10.)

（前記一般式（４）中、Ｒ^１は炭素数１〜１２のアルキレン基を示し、Ｒ^２及びＲ^３は、相互に独立に、炭素数１〜２０のアルキル基又はアリール基を示し、Ｒ^４、Ｒ^５及びＲ^６は、相互に独立に、炭素数１〜２０のアルキル基若しくはアリール基を示すか、又はそれらのうち２つが互いに結合して形成されるケイ素原子を含む環を示し、ｅは、２又は３を示す。）

(In the general formula (4), ^{R 1} represents an alkylene group having 1 to 12 carbon atoms, ^{R 2} and ^{R 3,} independently of one another, an alkyl group or an aryl group having 1 to 20 carbon atoms, R ⁴ , R ⁵ and R ⁶ each independently represent a C 1-20 alkyl group or aryl group, or a ring containing a silicon atom formed by bonding two of them together, e represents 2 or 3.)

  [12] The amino group-containing alkoxysilane compound comprises N, N-bis (trimethylsilyl) aminopropylmethyldimethoxysilane, N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane, and 1-trimethylsilyl-2,2- The method for producing a hydrogenated conjugated diene-based (co) polymer rubber according to [11], which is at least one selected from the group consisting of dimethoxy-1-aza-2-silacyclopentane.

  [13] The hydrogenated conjugated diene-based (co) polymer rubber according to any one of the above [1] to [7] and a filler, and 100 parts by mass of the hydrogenated conjugated diene-based (co) polymer rubber The hydrogenated conjugated diene-based (co) polymer rubber composition, wherein the filler content is 5 to 200 parts by mass.

  [14] The hydrogenated conjugated diene-based (co) polymer rubber composition according to [13], wherein the filler is at least one of silica and carbon black.

  [15] The hydrogenated conjugated diene-based (co) polymer rubber composition according to [13] or [14], further including another rubber component.

  [16] A rubber molded article comprising a crosslinked rubber composition obtained by crosslinking the hydrogenated conjugated diene-based (co) polymer rubber composition according to any one of [13] to [15].

  The hydrogenated conjugated diene-based (co) polymer rubber of the present invention has an effect that the cold flow value is small. Moreover, the method for producing a hydrogenated conjugated diene (co) polymer rubber of the present invention produces an effect that a hydrogenated conjugated diene (co) polymer rubber having a small cold flow value can be produced. Furthermore, the hydrogenated conjugated diene-based (co) polymer rubber composition of the present invention has the effect of being able to produce a rubber molded product having excellent processability, tensile breaking strength, tensile breaking elongation, and static / kinetic ratio. It is. In addition, the rubber molded product of the present invention has the effect of being excellent in workability, tensile breaking strength, tensile breaking elongation, and static / dynamic ratio.

  BEST MODE FOR CARRYING OUT THE INVENTION The best mode for carrying out the present invention will be described below, but the present invention is not limited to the following embodiment, and is based on the ordinary knowledge of those skilled in the art without departing from the gist of the present invention. It should be understood that modifications and improvements as appropriate to the following embodiments also fall within the scope of the present invention.

I Hydrogenated conjugated diene-based (co) polymer rubber The hydrogenated conjugated diene-based (co) polymer rubber of the present invention is obtained by hydrogenating a copolymer that satisfies the following conditions (A) to (D). It is.
(A): (a-1) containing a conjugated diene unit.
(B): Vinyl bond content is 20 to 70%.
(C): (c-1) an optionally protected primary amino group-containing alkoxysilyl group, or (c-2) an optionally protected primary amino group and an alkoxysilyl group are bonded. Yes.
(D): having a structure coupled in (D1) or (D2) below.
(D1): (d-1) A coupling agent having a plurality of functional groups.
(D2): (d-1) a coupling agent having a plurality of functional groups and (d-2) a monomer having a plurality of functional groups.

The hydrogenation rate of the conjugated diene portion of the hydrogenated conjugated diene-based (co) polymer rubber of the present invention is 50% or more, preferably more than 70%, and more preferably 72% or more. If the hydrogenation rate of the conjugated diene moiety is less than 50%, the heat resistance is low and may not be suitable for practical use. The upper limit of the hydrogenation rate is not particularly limited, but is substantially 93% or less. The hydrogenation rate can be calculated from a ¹ H-NMR spectrum using carbon tetrachloride as a heavy solvent.

As a physical property value of the hydrogenated conjugated diene-based (co) polymer rubber, the glass transition temperature is preferably −90 to 0 ° C., more preferably −80 to −40 ° C., and −70 to −50 ° C. It is particularly preferred. The weight average molecular weight is preferably 200,000 to 1,700,000, more preferably 200,000 to 1,000,000, and particularly preferably 200,000 to 600,000. . Furthermore, the coupling rate is preferably 5 to 60%, more preferably 5 to 50%, and particularly preferably 10 to 40%. The value of Mooney viscosity (ML _{1 + 4} , 125 ° C.) is preferably 35 to 150, more preferably 40 to 120, and particularly preferably 40 to 100. Furthermore, the cold flow value is preferably as small as possible. This is because the smaller the cold flow value, the better the shape stability (storage stability).

1 Copolymer The copolymer satisfies the conditions (A) to (D), and is preferably obtained by anionic polymerization of a monomer using a polymerization initiator in a hydrocarbon solvent. . More specifically, (a-1) a primary amino group-containing alkoxysilyl group containing a conjugated diene unit and having a vinyl bond content of 20 to 70% and (c-1) may be protected, Or (c-2) a primary amino group which may be protected and an alkoxysilyl group are bonded, and (d-1) a coupling agent having a plurality of functional groups, or (d-1) having a plurality of functional groups. It has a structure coupled with a coupling agent and (d-2) a monomer having a plurality of functional groups. In addition, it is preferable that a copolymer has a structure represented by General formula (1) or General formula (2).

In general formula (1), P represents a copolymer chain, R ¹ represents an alkylene group having 1 to 12 carbon atoms, and R ² and R ³ are each independently an alkyl group having 1 to 20 carbon atoms. Or an aryl group, n, m and k represent 1 or 2 (provided that n + m + k is 3 or 4).

In general formula (2), P represents a copolymer chain, R ¹ represents an alkylene group having 1 to 12 carbon atoms, and R ² and R ³ are each independently an alkyl group having 1 to 20 carbon atoms. Or an aryl group is shown, j and h show the integer of 1-3 (however, j + h is an integer of 2-4).

Examples of the alkylene group having 1 to 12 carbon atoms represented as R ¹ in the general formula (1) include a methylene group, an ethylene group, and a propylene group. Further, in the general formula (1), the alkyl group having 1 to 20 carbon atoms represented as ^{R 2} and ^{R 3,} for example, methyl group, ethyl group, propyl group. Furthermore, in the general formula (1), examples of the aryl group represented by R ² and R ³ include a phenyl group, a toluyl group, and a naphthyl group.

In the general formula (2), an alkylene group having 1 to 12 carbon atoms represented as ^{R 1,} the alkyl group or aryl group having 1 to 20 carbon atoms represented as ^{R 2} and ^{R 3,} for example, the general formula ( Among 1), there are those exemplified by an alkylene group having 1 to 12 carbon atoms represented by R ¹ , an alkyl group having 1 to 20 carbon atoms represented by R ² and R ³ , or an aryl group.

(1) Condition (A)
The copolymer preferably includes (a-1) a conjugated diene unit, and further includes at least one of (a-2) an aromatic vinyl unit and (a-3) other units.

(I) (a-1) Conjugated diene unit (a-1) The conjugated diene unit is a structural unit obtained by polymerizing a conjugated diene compound. Specific examples of the conjugated diene compound include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, 1,3-pentadiene, and mixtures thereof. Is mentioned.

  The proportion of the (a-1) conjugated diene unit contained in the copolymer is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, and 90 to 100% by mass. Particularly preferred. (A-1) When the ratio of the conjugated diene unit is less than 60% by mass, the vibration-proof property may be deteriorated.

(Ii) (a-2) Aromatic vinyl unit (a-2) The aromatic vinyl unit is a structural unit obtained by polymerizing an aromatic vinyl compound. Specific examples of the aromatic vinyl compound include styrene, tert-butyl styrene, α-methyl styrene, p-methyl styrene, p-ethyl styrene, divinyl benzene, 1,1-diphenyl styrene, vinyl naphthalene, and the like. Among these, it is preferable to use styrene.

  The proportion of the (a-2) aromatic vinyl unit contained in the copolymer is preferably 0 to 40% by mass, more preferably 0 to 35% by mass, and 0 to 30% by mass. It is particularly preferred. (A-2) When the ratio of the aromatic vinyl unit is more than 40% by mass, the dynamic characteristics may be deteriorated.

(Iii) (a-3) Other units (a-3) Other units other than conjugated diene compounds and aromatic vinyl compounds, other compounds that can be copolymerized with conjugated diene compounds and aromatic vinyl compounds Is a structural unit obtained by polymerizing Specific examples of the other compounds include acrylonitrile, methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, and the like.

  The proportion of (a-3) other units contained in the copolymer is preferably 0 to 40% by mass, more preferably 0 to 35% by mass, and 0 to 30% by mass. Is particularly preferred. (A-3) When the proportion of other units exceeds 40% by mass, the dynamic characteristics may be deteriorated.

(2) Condition (B)
The vinyl bond content of the copolymer (that is, the proportion of 1,2-bonds in the (a-1) conjugated diene unit) is 20 to 70%, preferably 25 to 50%, preferably 30 to 45. % Is more preferable. If the vinyl bond content is less than 20%, the low temperature characteristics may be deteriorated. On the other hand, if it exceeds 70%, the dynamic characteristics may deteriorate. The vinyl bond content can be calculated from the ¹ H-NMR spectrum.

(3) Condition (C)
In the copolymer, (c-1) an optionally protected primary amino group-containing alkoxysilyl group, or (c-2) an optionally protected primary amino group and an alkoxysilyl group are bonded. ing. That is, the primary amino group and the alkoxysilyl group are bonded as the same group or as independent groups. The amount of the primary amino group bonded to the copolymer is preferably 0.5 to 200 mmol, more preferably 1 to 100 mmol, and more preferably 2 to 50 mmol with respect to 1 kg of the copolymer. Particularly preferred. If the amount of the primary amino group is less than 0.5 mmol, it may be difficult to obtain the effect of binding the primary amino group. On the other hand, when the amount of the primary amino group is more than 200 mmol, the interaction with the filler such as carbon black and silica becomes too high, the blending viscosity is improved, and the workability may be deteriorated.

  Here, the amount of the primary amino group bonded to the copolymer can be calculated as follows. “Total amine number test method” conducted in accordance with JIS K7237 using a hydrogenated conjugated diene-based (co) polymer rubber that had been dissolved in a toluene solvent, precipitated with a large amount of methanol solution, and then dried as a sample. The amount of all amino groups bonded to the hydrogenated conjugated diene-based (co) polymer rubber is quantified. Next, by using the hydrogenated conjugated diene-based (co) polymerized rubber subjected to the same treatment as a sample, the secondary and third bonded to the hydrogenated conjugated diene-based (co) polymerized rubber by the “acetylacetone blocked method”. Quantify the amount of primary amino groups. It can be calculated by subtracting the amount of secondary and tertiary amino groups from the amount of total amino groups and dividing by the mass of the hydrogenated conjugated diene (co) polymer rubber used for the analysis.

  Further, the amount of the alkoxysilyl group bonded to the copolymer is preferably 0.5 to 200 mmol, more preferably 1 to 100 mmol, and more preferably 2 to 50 mmol with respect to 1 kg of the copolymer. It is particularly preferred. If the amount of the alkoxysilyl group is less than 0.5 mmol, it may be difficult to obtain the effect of bonding the alkoxysilyl group. On the other hand, when the amount of the alkoxysilyl group exceeds 200 mmol, the interaction with a filler such as carbon black or silica becomes too high, the blending viscosity is improved, and the workability may be deteriorated.

Here, the amount of the alkoxysilyl group bonded to the copolymer can be determined from the absorption amount of 1160 cm ⁻¹ due to the Si—C bond by infrared absorption spectrum measurement.

(I) (c-1) Primary amino group-containing alkoxysilyl group (c-1) The primary amino group-containing alkoxysilyl group contains an optionally protected primary amino group and alkoxyl group. Any group may be used as long as the silicon atom of the silyl group is bonded to the copolymer. Examples of the group that protects the amino group include a trimethylsilyl group.

  (C-1) The primary amino group-containing alkoxysilyl group is modified with a functional group, for example, by the method described in “II Hydrogenated Conjugated Diene (Co) polymer Rubber Production Method” described later. By using a primary amino group-containing alkoxysilane compound as an agent, it can be combined with a copolymer. As the primary amino group-containing alkoxysilane compound, it is preferable to use a primary amino group-containing alkoxysilane compound represented by the general formula (3) or the general formula (4). N, N-bis (trimethylsilyl) At least one selected from the group consisting of aminopropylmethyldimethoxysilane, N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane, and 1-trimethylsilyl-2,2-dimethoxy-1-aza-2-silacyclopentane. More preferably, seeds are used. In addition, a primary amino group containing alkoxysilane compound may be used individually by 1 type, and may be used in combination of 2 or more type.

In General Formula (3), R ¹ represents an alkylene group having 1 to 12 carbon atoms, R ² and R ³ each independently represent an alkyl group or an aryl group having 1 to 20 carbon atoms, R ⁴ , R ⁵ and R ⁶ each independently represent a C 1-20 alkyl group or aryl group, or a ring containing a silicon atom formed by bonding two of them together, g being 1 or 2 is shown, f shows the integer of 1-10.

In General Formula (4), R ¹ represents an alkylene group having 1 to 12 carbon atoms, R ² and R ³ each independently represent an alkyl group or aryl group having 1 to 20 carbon atoms, R ⁴ , R ⁵ and R ⁶ each independently represent a C 1-20 alkyl group or aryl group, or a ring containing a silicon atom formed by bonding two of them together, e being 2 or 3 is shown.

In the general formula (3), an alkylene group having 1 to 12 carbon atoms represented as ^{R 1,} the alkyl group or aryl group having 1 to 20 carbon atoms represented as R 2 to R ⁶ are, for example, the general formula ( Among 1), there are those exemplified by an alkylene group having 1 to 12 carbon atoms represented by R ¹ , an alkyl group having 1 to 20 carbon atoms represented by R ² and R ³ , or an aryl group. As the ring but two of them, represented as R ^4, R ⁵ and R ⁶ containing silicon atoms formed by bonding, it is preferably a 4- to 7-membered ring.

In the general formula (4), an alkylene group having 1 to 12 carbon atoms represented as ^{R 1,} the alkyl group or aryl group having 1 to 20 carbon atoms represented as R 2 to R ⁶ are, for example, the general formula ( Among 1), there are those exemplified by an alkylene group having 1 to 12 carbon atoms represented by R ¹ , an alkyl group having 1 to 20 carbon atoms represented by R ² and R ³ , or an aryl group. ^As the ring but two of them, represented as R 4, ^{R 5} and ^{R 6} containing silicon atoms formed by bonding, in the general formula ^(3), as R 4, ^{R 5} and ^{R 6} It is preferable that it is a 4-7 membered ring similarly to the ring containing the silicon atom formed when two of those represented mutually couple | bond together.

(Ii) (c-2) Primary amino group and alkoxysilyl group The primary amino group may be any group as long as an optionally protected primary amino group is bonded to the copolymer. Examples of the group that protects the amino group include a trimethylsilyl group.

(Primary amino group)
The primary amino group is, for example, a group described in “II Method for producing hydrogenated conjugated diene-based (co) polymer rubber” described later and at least one of an organic alkali metal and an organic alkaline earth metal. By using an amide compound as a polymerization initiator as a reaction product with a primary amine compound, it can be combined with a copolymer. Examples of the amide compound include a lithium amide compound represented by the general formula (5) or the general formula (6).

_{^{(R 4 R 5 R 6 Si}} ) 2 -N-R 1 -Li (5)
In general formula (5), R ¹ represents an alkylene group having 1 to 12 carbon atoms, and R ⁴ , R ^5, and R ⁶ independently represent an alkyl group or aryl group having 1 to 20 carbon atoms. Or a ring containing silicon atoms formed by bonding two of them together.

In General Formula (6), R ¹ represents an alkylene group having 1 to 12 carbon atoms, R ⁷ and R ⁸ each independently represent a hydrogen atom or an alkyl group or aryl group having 1 to 20 carbon atoms, d shows the integer of 1-7.

In the general formula (5), an alkylene group having 1 to 12 carbon atoms represented as ^{R 1,} the alkyl group or aryl group R 4, ^{R 5} and the carbon number of 1 to 20 represented as ^{R 6} is, for example, In general formula (1), there are those exemplified by an alkylene group having 1 to 12 carbon atoms represented by R ¹ , an alkyl group having 1 to 20 carbon atoms represented by R ² and R ³ , or an aryl group. ^As the ring but two of them, represented as R 4, ^{R 5} and ^{R 6} containing silicon atoms formed by bonding, in the general formula ^(3), as R 4, ^{R 5} and ^{R 6} It is preferable that it is a 4-7 membered ring similarly to the ring containing the silicon atom formed when two of those represented mutually couple | bond together.

In the general formula (6), an alkylene group having 1 to 12 carbon atoms represented as ^{R 1,} the alkyl group or aryl group having 1 to 20 carbon atoms represented as ^{R 7} and ^{R 8,} for example, the general formula ( Among 1), there are those exemplified by an alkylene group having 1 to 12 carbon atoms represented by R ¹ , an alkyl group having 1 to 20 carbon atoms represented by R ² and R ³ , or an aryl group.

(Alkoxysilyl group)
The alkoxysilyl group may be a group in which a silicon atom of a silyl group containing an alkoxyl group is bonded to a copolymer.

  The alkoxysilyl group is, for example, a primary amino group-containing alkoxysilane compound as a modifier having a functional group in the method described in “II Method for Producing Hydrogenated Conjugated Diene (Co) polymerized Rubber” described later. Alternatively, it can be combined with the copolymer by using an alkoxysilane compound. As the primary amino group-containing alkoxysilane compound, the aforementioned compounds are preferable. Moreover, as an alkoxysilane compound, there exists an alkoxysilane compound represented by General formula (7), for example.

In General Formula (7), R ² and R ³ each independently represent an alkyl group or aryl group having 1 to 20 carbon atoms, X represents a halogen atom, and c represents an integer of 0 to 2. , B represents an integer of 1 to 4 (provided that c + b is an integer of 2 to 4).

In the general formula (7), the alkyl group or aryl group having 1 to 20 carbon atoms represented as ^{R 2} and ^{R 3,} for example, in the general formula (1), the number of carbon atoms represented as ^{R 2} and ^{R 3} There are those exemplified with 1 to 20 alkyl groups or aryl groups.

(4) Condition (D)
The copolymer has a structure coupled with (D1) or (D2). Among them, it is preferable to have a structure coupled with (D2). This is because not only the cold flow value can be reduced, but also workability and physical properties can be improved.
(D1): (d-1) A coupling agent having a plurality of functional groups.
(D2): (d-1) a coupling agent having a plurality of functional groups and (d-2) a monomer having a plurality of functional groups.

(I) (D1)
The structure coupled with (D1) is a structure coupled with a coupling agent having a plurality of (d-1) functional groups. By having this structure, the value of cold flow can be reduced and the workability and physical properties can be improved. (D-1) Examples of the coupling agent having a plurality of functional groups include isocyanate compounds, isothiocyanate compounds, amide compounds, imide compounds, pyridyl-substituted ketone compounds, pyridyl-substituted vinyl compounds, silicon compounds, ester compounds, and ketones. Compounds and tin compounds. Among these, it is preferable to use a silicon compound. In addition, the coupling agent having a plurality of (d-1) functional groups may be the same as the primary amino group-containing alkoxysilane compound or alkoxysilane compound described in the above condition (C), It may be different.

  (D-1) The amount of the coupling agent having a plurality of functional groups used is preferably 0.01 to 1 mol, preferably 0.05 to 0.5 mol, per 1 g atom equivalent of alkali metal of the polymerization initiator. Is more preferable. If the amount used is less than 0.01 mol, the cold flow value may not be sufficiently reduced. On the other hand, if the amount used exceeds 1 mol, the physical properties may deteriorate, such as the generation of odor due to an increase in the amount of unreacted substances, and the speed of vulcanization being significantly increased.

(Ii) (D2)
The structure coupled in (D2) is a structure coupled with (d-1) a coupling agent having a plurality of functional groups and (d-2) a monomer having a plurality of functional groups. (D-1) As a coupling agent having a plurality of functional groups, for example, there is the coupling agent described above. Specific examples of the monomer (d-2) having a plurality of functional groups include divinylbenzene, diisopropenylbenzene, and trivinylbenzene. (D-2) The cold flow value can be further reduced by using a monomer having a plurality of functional groups.

  (D-1) It can be said that the usage-amount of the coupling agent which has multiple functional groups is the same as the usage-amount of the coupling agent mentioned above. Moreover, it is preferable that the ratio of the monomer which has multiple (d-2) functional groups contained in a copolymer is 0.001-5 mass%, and is 0.001-0.1 mass%. Is more preferable. (D-2) When the ratio of the monomer having a plurality of functional groups is less than 0.001% by mass, the improvement effect of reducing the cold flow value of the resulting hydrogenated conjugated diene (co) polymer rubber is poor. In addition, the physical properties of the hydrogenated conjugated diene (co) polymer rubber composition may deteriorate. On the other hand, when the ratio of the monomer having a plurality of (d-2) functional groups exceeds 5% by mass, the processability and physical properties of the resulting hydrogenated conjugated diene-based (co) polymer rubber composition may be deteriorated. is there.

(5) Other conditions The copolymer is preferably obtained by anionic polymerization of a monomer using a polymerization initiator in a hydrocarbon solvent. Examples of the hydrocarbon solvent used in the anionic polymerization reaction include pentane, hexane, heptane, methylcyclopentane, cyclohexane, benzene, toluene, xylene and the like. Among these, it is preferable to use cyclohexane and heptane.

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

  The polymerization initiator is a reaction product of at least one of an organic alkali metal and an organic alkaline earth metal, or at least one of an organic alkali metal and an organic alkaline earth metal, and a primary amine compound. More specifically, alkyl lithium such as n-butyl lithium, sec-butyl lithium and t-butyl lithium, alkylene dilithium such as 1,4-dilithiobutane, phenyl lithium, stilbene lithium, lithium naphthalene, sodium naphthalene and potassium naphthalene Organic alkali metals such as n-butylmagnesium, n-hexylmagnesium, ethoxybarium, isopropoxybarium, ethylmercaptobarium, t-butoxybarium, phenoxybarium, diethylaminobarium, and barium stearate It is done. The reaction product preferably uses an organic lithium compound as the organic alkali metal, and more preferably uses n-butyl lithium or sec-butyl lithium.

  The amount of the polymerization initiator used is 0.002 to 0.1 mmol in terms of alkali metal atoms or alkaline earth metal atoms with respect to 1 g of the total amount of the conjugated diene compound, aromatic vinyl compound, and other compounds. Is more preferable, and 0.005-0.03 mmol is more preferable.

2 Hydrogenation The method and reaction conditions for hydrogenating the copolymer are not particularly limited, and are usually carried out in the presence of a catalyst at 20 to 150 ° C., hydrogen pressure of 0.1 to 10 MPa, and 0.1 to 10 MPa. . The hydrogenation rate can be arbitrarily changed by changing conditions such as the amount of catalyst, hydrogen pressure, reaction time, and the like. Examples of the catalyst include compounds containing Ti, V, Co, Ni, Zr, Ru, Rh, Pd, Hf, Re, and Pt atoms. More specifically, metallocene compounds such as Ti, Co, Ni, Zr, Ru, Rh, Pd, Hf, Re, and Pt; metals such as Pd, Ni, Pt, Rh, and Ru are carbon, silica, alumina, and diatomaceous earth. Heterogeneous catalyst supported on a support such as earth; homogeneous Ziegler catalyst combining organic salt of metal element such as Co or Ni or acetylacetone salt and reducing agent such as organoaluminum; organometallic such as Ru or Rh Compound or complex: fullerenes occluded with hydrogen, carbon nanotubes, and the like.

  Among these, it is preferable to use a metallocene compound of Ti, Co, Ni, Zr, and Hf because a hydrogenation reaction can be performed in a homogeneous system in an inert organic solvent, and a metallocene compound of Ti, Zr, and Hf is used. It is more preferable to use, and since it is cheap and industrially useful, it is particularly preferable to use a catalyst prepared by reacting a titanocene compound and alkyl lithium. Examples of the catalyst prepared by reacting a titanocene compound with alkyllithium include, for example, JP-A-1-275605, JP-A-5-271326, JP-A-5-271325, JP-A-5-222115, JP-A-11-292924, JP-A-2000-37632, JP-A-59-133203, JP-A-63-5401, JP-A-62-2218403, JP-A-7-90017 And JP-A-43-19960 and JP-A-47-40473. In addition, these catalysts may be used individually by 1 type, and may be used in combination of 2 or more type.

II. Method for producing hydrogenated conjugated diene-based (co) polymer rubber One embodiment of a method for producing hydrogenated conjugated diene-based (co) polymer rubber (hereinafter referred to as “method (1)”) is a hydrocarbon solvent, Addition of conjugated diene monomer or conjugated diene monomer and monomer having multiple functional groups to the reaction system containing at least one of organic alkali metal and organic alkaline earth metal as a polymerization initiator A primary amino group-containing alkoxysilyl which may be protected by adding a functional group-containing modifier (1), a step (2) of adding a coupling agent having a plurality of functional groups, and a functional group-containing modifier A step (3) of obtaining a copolymer by bonding groups, and a step (4) of adding hydrogen to the copolymer. Moreover, when the primary amino group is protected, it is preferable to include the process (5) which performs deprotection.

  In another embodiment of the method for producing a hydrogenated conjugated diene-based (co) polymer rubber (hereinafter referred to as “method (2)”), at least one of an organic alkali metal and an organic alkaline earth metal is used in a hydrocarbon solvent. An anionic polymerization reaction by adding a conjugated diene monomer or a monomer having a plurality of conjugated diene monomers and functional groups to a reaction system containing a reaction product of any one of the primary amine compounds as a polymerization initiator A primary amino group-containing alkoxysilyl group which may be protected by adding a coupling agent having a plurality of functional groups, a step (2) of adding a coupling agent having a plurality of functional groups, and a modifier having a functional group Or a step (3) of obtaining a copolymer by bonding an alkoxysilyl group, and a step (4) of adding hydrogen to the copolymer. Moreover, when the primary amino group is protected, it is preferable to include the process (5) which performs deprotection.

1 Method (1)
In the method (1), the anionic polymer obtained in the step (1) is coupled in the step (2), and the primary amino group-containing alkoxysilyl group is bonded in the step (3). In this method, a coalescence is obtained and hydrogen is added to the copolymer obtained in the step (4). By carrying out by such a method, the primary amino group-containing alkoxysilyl group can be easily bonded to the copolymer in one reaction.

(1) Step (1)
In step (1), a conjugated diene monomer, or a conjugated diene monomer and a functional group in a reaction system containing at least one of an organic alkali metal and an organic alkaline earth metal as a polymerization initiator in a hydrocarbon solvent. In this step, an anionic polymerization reaction is performed by adding a monomer having a plurality of groups. In addition, it is preferable that this process (1) is a process which further adds at least any one of an aromatic vinyl monomer and another monomer in a reaction system, and performs an anionic polymerization reaction.

  “Conjugated diene monomer”, “monomer having a plurality of functional groups”, “aromatic vinyl monomer”, and “other monomer” are respectively “I hydrogenated conjugated diene series” It is the same as the “conjugated diene compound”, “(d-2) monomer having a plurality of functional groups”, “aromatic vinyl compound”, and “other compounds” described in “polymerized rubber”.

  The conditions for the anionic polymerization reaction are usually performed at a temperature of 0 to 120 ° C., and may be a constant temperature condition or an elevated temperature condition. The polymerization method may be a batch polymerization method or a continuous polymerization method.

(2) Step (2)
Step (2) is a step of adding a coupling agent having a plurality of functional groups, and before adding the coupling agent having a plurality of functional groups, at the same time as the addition, and at any time after the addition. It is preferable to further add a conjugated diene monomer. The “coupling agent having a plurality of functional groups” is the same as “(d-1) coupling agent having a plurality of functional groups” described in “I Hydrogenated conjugated diene-based (co) polymer rubber”. Say things. Further, the “conjugated diene monomer” added in step (2) may be the same as or different from the conjugated diene compound used in step (1).

(3) Process (3)
Step (3) is a step of adding a modifier having a functional group and bonding a primary amino group-containing alkoxysilyl group to obtain a copolymer. The “modifier having a functional group” referred to herein is the same as the “primary amino group-containing alkoxysilane compound” described in “I Hydrogenated Conjugated Diene (Co) polymer Rubber”. .

(4) Process (4)
Step (4) is a step of adding hydrogen to the copolymer. By performing this step, the conjugated diene moiety in the copolymer chain is hydrogenated. The conditions for hydrogenation are not particularly limited, and examples thereof include the method described in “I Hydrogenated conjugated diene-based (co) polymer rubber”.

(5) Step (5)
Step (5) is a step of deprotecting by hydrolysis when the primary amino group is protected. As a condition for the hydrolysis, water or acidic water of 2 times mol or more is used. Moreover, it is preferable that reaction temperature is 80-150 degreeC, and it is still more preferable that it is 90-120 degreeC. Furthermore, the reaction time is preferably 10 minutes or more, and more preferably 30 minutes or more. The upper limit of the reaction time is not particularly limited, but is substantially 300 minutes or less.

(6) Step (6)
Step (6) is a solvent removal step for isolating the hydrogenated conjugated diene-based (co) polymer rubber, and can be performed, for example, as follows. If necessary, add stabilizers etc. to the reaction solution after hydrogenation, hydrogenated conjugated diene-based (co) polymerization by the method used in ordinary solution polymerization methods, for example, direct drying method or steam stripping method Isolate the desired hydrogenated conjugated diene-based (co) polymer rubber by separating and cleaning the rubber and solvent and then drying using a vacuum dryer, hot air dryer, or roll. Can do. In addition, when a steam stripping method is used, it is possible to perform a process (5) and a process (6) simultaneously.

2 Method (2)
In the method (2), the anionic polymer obtained by the step (1) and bonded with the primary amino group which may be protected at the polymerization initiation terminal is coupled in the step (2). In this method, a primary amino group-containing alkoxysilyl group or alkoxysilyl group is bonded in step (3) to obtain a copolymer, and hydrogen is added to the copolymer obtained in step (4).

(1) Step (1)
In step (1), a conjugated diene monomer is contained in a reaction system containing a reaction product of at least one of an organic alkali metal and an organic alkaline earth metal and a primary amine compound as a polymerization initiator in a hydrocarbon solvent. Or an anionic polymerization reaction by adding a conjugated diene monomer and a monomer having a plurality of functional groups. In addition, it is preferable that this process (1) is a process which further adds at least any one of an aromatic vinyl monomer and another monomer in a reaction system, and performs an anionic polymerization reaction.

  “Conjugated diene monomer”, “monomer having a plurality of functional groups”, “aromatic vinyl monomer”, and “other monomer” are respectively “I hydrogenated conjugated diene series” It is the same as the “conjugated diene compound”, “(d-2) monomer having a plurality of functional groups”, “aromatic vinyl compound”, and “other compounds” described in “polymerized rubber”.

  The conditions for the anionic polymerization reaction are usually performed at a temperature of 0 to 120 ° C., and may be a constant temperature condition or an elevated temperature condition. The polymerization method may be a batch polymerization method or a continuous polymerization method.

(2) Step (2)
Step (2) is a step of adding a coupling agent having a plurality of functional groups, and before adding the coupling agent having a plurality of functional groups, at the same time as the addition, and at any time after the addition. It is preferable to further add a conjugated diene monomer. The “coupling agent having a plurality of functional groups” is the same as “(d-1) coupling agent having a plurality of functional groups” described in “I Hydrogenated conjugated diene-based (co) polymer rubber”. Say things. Further, the “conjugated diene monomer” added in step (2) may be the same as or different from the conjugated diene compound used in step (1).

(3) Process (3)
Step (3) is a step of adding a modifier having a functional group and bonding a primary amino group-containing alkoxysilyl group or alkoxysilyl group to obtain a copolymer. Here, the “modifier having a functional group” means “a primary amino group-containing alkoxysilane compound” or “alkoxysilane compound” described in “I hydrogenated conjugated diene-based (co) polymer rubber”. Means the same thing.

(4) Process (4)
Step (4) is a step of adding hydrogen to the copolymer. By performing this step, the conjugated diene moiety in the copolymer chain is hydrogenated. The conditions for hydrogenation are not particularly limited, and examples thereof include the method described in “I Hydrogenated conjugated diene-based (co) polymer rubber”.

(5) Step (5)
Step (5) is a step of hydrolyzing and deprotecting when the primary amino group is protected. As a condition for the hydrolysis, water or acidic water of 2 times mol or more is used. Moreover, it is preferable that reaction temperature is 80-150 degreeC, and it is still more preferable that it is 90-120 degreeC. Furthermore, the reaction time is preferably 10 minutes or more, and more preferably 30 minutes or more. The upper limit of the reaction time is not particularly limited, but is substantially 300 minutes or less.

(6) Step (6)
Step (6) is a solvent removal step for isolating the hydrogenated conjugated diene-based (co) polymer rubber, and can be performed, for example, as follows. If necessary, add stabilizers etc. to the reaction solution after hydrogenation, hydrogenated conjugated diene-based (co) polymerization by the method used in ordinary solution polymerization methods, for example, direct drying method or steam stripping method Isolate the desired hydrogenated conjugated diene-based (co) polymer rubber by separating and cleaning the rubber and solvent and then drying using a vacuum dryer, hot air dryer, or roll. Can do. In addition, when a steam stripping method is used, it is possible to perform a process (5) and a process (6) simultaneously.

III Hydrogenated conjugated diene (co) polymerized rubber composition The hydrogenated conjugated diene (co) polymerized rubber composition contains a hydrogenated conjugated diene (co) polymerized rubber and a filler. It is preferable to contain the rubber component. The filler content is usually 5 to 200 parts by weight, preferably 5 to 100 parts by weight, and preferably 5 to 70 parts by weight with respect to 100 parts by weight of the hydrogenated conjugated diene-based (co) polymer rubber. More preferably. By setting the content of the filler within the above range, it has an effect of reducing the static / dynamic ratio.

1 Hydrogenated conjugated diene (co) polymer rubber Hydrogenated conjugated diene (co) polymer rubber is described in “I Hydrogenated conjugated diene (co) polymer rubber”, and is contained alone. It may be included and may be contained in combination of two or more.

2 Filler Examples of the filler include silica, carbon black, glass fiber, glass powder, glass beads, mica, calcium carbonate, potassium titanate whisker, talc, clay, barium sulfate, glass flake, and fluorine resin. Among these, silica, carbon black, glass fiber, mica, potassium titanate whisker, talc, clay, barium sulfate, glass flake, and fluorine resin are preferably used, and at least one of silica and carbon black is further used. preferable.

  The use of silica is preferable from the viewpoint of the static / dynamic ratio. There are various types of silica such as wet method white carbon, dry method white carbon, and colloidal silica, and any of them can be used. Among these, it is preferable to use wet method white carbon mainly composed of hydrous silicic acid. The use of carbon black is preferable from the viewpoint of the strength of the hydrogenated conjugated diene-based (co) polymer rubber composition. There are various types of carbon black such as furnace black, acetylene black, thermal black, channel black, and graphite, and any of them can be used. Among these, furnace black is preferably used, and more specifically, SRF, GPF, FEF, HAF, ISAF, SAF, MT, and the like are more preferably used.

Further, the nitrogen adsorption specific surface area of carbon black measured by the BET method in accordance with ASTM D3037-81 is not particularly limited, but the tensile breaking strength of the hydrogenated conjugated diene-based (co) polymer rubber composition, etc. in order to sufficiently improve, it is preferably 5 to 200 m ² / g, further preferably from 50 to 150 m ² / g, particularly preferably 80~130m ² / g. The DBP adsorption amount is not particularly limited, but is preferably 5 to 300 mL / 100 g in order to sufficiently improve the strength and the like of the hydrogenated conjugated diene-based (co) polymer rubber composition. More preferably, it is -200mL / 100g, It is especially preferable that it is 80-160mL / 100g.

3 Other rubber components Other rubber components are rubber components other than hydrogenated conjugated diene-based (co) polymerized rubbers, and specifically, natural rubber, synthetic isoprene rubber, butadiene rubber, styrene / butadiene rubber, ethylene / Examples thereof include α-olefin copolymer rubber, ethylene / α-olefin / diene copolymer rubber, acrylonitrile / butadiene copolymer rubber, chloroprene rubber, halogenated butyl rubber, and mixtures thereof.

  The amount of the other rubber component contained in the hydrogenated conjugated diene-based (co) polymer rubber composition is preferably 80% by mass or less, more preferably 50% by mass or less, based on the total rubber component. It is preferably 20% by mass or less.

4 Amine compound In addition, the hydrogenated diene-based (co) polymer rubber composition may contain an amine compound as long as the properties thereof are not impaired. By containing an amine compound, the wettability of the filler can be improved, the dispersibility of the filler in the hydrogenated diene-based (co) polymer rubber composition can be improved, and the durability and vibration isolating performance can be improved. . In addition, an amine compound may be used individually by 1 type, and may be used in combination of 2 or more type.

  The amine compound should just contain an amino group. Further, the number of amino groups is not particularly limited, and may be monoamine, diamine, triamine, tetraamine, or polyamine. Furthermore, it does not specifically limit also about carbon number of an amine compound, Usually, it is 1-20, It is preferable that it is 1-15, It is more preferable that it is 3-15, It is 3-10 Is particularly preferred. Further, it may contain a functional group other than an amino group such as alkanolamine. Specific examples of the amine compound include 2-ethylhexylamine and triethanolamine.

  There is no limitation in particular also about content of an amine compound, It can be set as various ranges as needed. The content of the amine compound is usually 20 parts by mass or less, preferably 15 parts by mass or less, and preferably 10 parts by mass or less with respect to 100 parts by mass of the hydrogenated conjugated diene-based (co) polymer rubber. Is more preferably 0.01 to 10 parts by mass, particularly preferably 0.01 to 8 parts by mass, and most preferably 0.01 to 5 parts by mass.

IV Rubber Molded Article A rubber molded article is composed of a crosslinked rubber composition obtained by crosslinking a hydrogenated conjugated diene (co) polymer rubber composition. The crosslinking method may be a commonly used method, and is performed by adding a crosslinking agent. Moreover, unless the property is impaired, various additives can be appropriately added as necessary. Examples of such additives include reinforcing agents, rubber extending oils, fillers, crosslinking accelerators, and crosslinking activators.

  As crosslinking agents, organic peroxides such as dicumyl peroxide and di-t-butyl peroxide; sulfur such as powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur; sulfur monochloride, dichloride Sulfur halides such as sulfur; quinone dioximes such as p-quinone dioxime and p, p'-dibenzoylquinone dioxime; triethylenetetramine, hexamethylenediamine carbamate, 4,4'-methylenebis-o-chloroaniline, etc. Organic polyvalent amine compounds; alkylphenol resins having a methylol group, and the like can be used. In addition, a crosslinking agent may be used individually by 1 type, and may be used in combination of 2 or more type.

  The addition amount of the crosslinking agent is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the hydrogenated diene-based (co) polymer rubber composition. preferable. If the addition amount is within this range, properties such as the tensile strength at break can be sufficiently improved without impairing the properties of the crosslinked rubber composition.

  Examples of the crosslinking accelerator include N-cyclohexyl-2-benzothiazole sulfenamide, Nt-butyl-2-benzothiazole sulfenamide, N-oxyethylene-2-benzothiazole sulfenamide, N, N Sulfenamide-based crosslinking accelerators such as' -diisopropyl-2-benzothiazolesulfenamide; Guanidine-based crosslinking accelerators such as diphenylguanidine, diortolylguanidine, orthotolylbiguanidine; thiocarboanilide, diortolylthiourea Thiourea-based crosslinking accelerators such as ethylenethiourea, diethylthiourea and trimethylthiourea; 2-mercaptobenzothiazole, dibenzothiazyl disulfide, 2-mercaptobenzothiazole zinc salt, 2-mercaptobenzothiazole sodium Salt, 2-mercaptobenzothiazole cyclohexylamine salt, 2- (2,4-dinitrophenyl thio) thiazole crosslinking accelerators such as benzothiazole;

  Thiuram-based crosslinking accelerators such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, dipentamethylenethiuram tetrasulfide; sodium dimethyldithiocarbamate, sodium diethyldithiocarbamate, di-n-butyldithiocarbamine Sodium acetate, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate, zinc pentamethylenedithiocarbamate, zinc ethylphenyldithiocarbamate, tellurium diethyldithiocarbamate, selenium dimethyldithiocarbamate, selenium diethyldithiocarbamate, dimethyl Copper dithiocarbamate, iron dimethyldithiocarbamate, di Dithiocarbamic acid crosslinking accelerators such as diethylamine tildithiocarbamate, piperidine pentamethylenedithiocarbamate, pipecoline methylpentamethylenedithiocarbamate; xanthogenic crosslinking accelerators such as sodium isopropylxanthate, zinc isopropylxanthate, zinc butylxanthate . In addition, a crosslinking accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.

  The addition amount of the crosslinking accelerator is preferably 20 parts by mass or less and more preferably 10 parts by mass or less with respect to 100 parts by mass of the hydrogenated diene-based (co) polymer rubber composition. In addition, when an organic peroxide is used as a crosslinking agent, a small amount of sulfur can also be added as a crosslinking aid. As used herein, “small amount” means that it is preferably 1 to 5 parts by mass, more preferably 2 to 4 parts by mass with respect to 100 parts by mass of the organic peroxide.

  Examples of the crosslinking activator include higher fatty acids such as stearic acid and zinc oxide. As zinc oxide, one having a high surface activity and a number average particle diameter of 5 μm or less is preferable. Examples of such zinc oxide include active zinc white having a number average particle diameter of 0.05 to 0.2 μm, zinc white having 0.3 to 1 μm, and the like. Alternatively, zinc oxide surface-treated with an amine-based dispersant or wetting agent can be used. In addition, these crosslinking activators may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, the addition amount of a crosslinking activator can be suitably set with the kind etc.

  Examples of rubber extending oil include paraffinic process oil, aromatic process oil, and naphthenic process oil, which are petroleum-based blended oils. Among these, it is preferable to use paraffinic process oil. The amount of the rubber extending oil added is preferably 150 parts by mass or less, more preferably 100 parts by mass or less, with respect to 100 parts by mass of the hydrogenated diene-based (co) polymer rubber composition.

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

[Vinyl bond content (%) of copolymer]: 270 MHz, calculated from ¹ H-NMR spectrum.

[Hydrogenation rate (%)]: 270 MHz, calculated from ¹ H-NMR spectrum.

  [Glass transition temperature (° C.)]: Determined according to ASTM D3418.

  [Weight average molecular weight (Mw)]: Calculated in terms of polystyrene using gel permeation chromatography (GPC) (column: trade name “HLC-8120”, manufactured by Tosoh Corporation).

  [Coupling rate (%)]: Measured using gel permeation chromatography (GPC) (column: trade name “HLC-8120”, manufactured by Tosoh Corporation). It was calculated from the peak area ratio between the polymer and the copolymer with increased molecular weight after coupling. For copolymers having a unimodal molecular weight distribution, the coupling rate was calculated from the weight average molecular weight before coupling and the weight average molecular weight after coupling.

[Mooney viscosity (ML _{1 + 4} , 125 ° C.)]: Measured in accordance with JIS K6300 using an L rotor under conditions of a residual heat of 1 minute, a rotor operating time of 4 minutes, and a temperature of 125 ° C.

  [Amount of total amino groups (mmol / kg)]: JIS K7237 using a hydrogenated conjugated diene-based (co) polymer rubber that had been dissolved in a toluene solvent, precipitated with a large amount of methanol solution, and then dried, as a sample. The total amino group content in the hydrogenated conjugated diene-based (co) polymer rubber was quantified by the “total amine value test method” conducted in accordance with the above.

  [Amount of tertiary amino group (mmol / kg)]: A hydrogenated conjugated diene-based (co) polymer rubber that had been dissolved in a toluene solvent and precipitated with a large amount of methanol solution and then dried was used as a sample. The tertiary amino group content was quantified by the “acetylacetone blocked method”.

  [Amount of primary amino groups (mmol / kg)]: Subtract the amount of tertiary amino groups from the amount of all amino groups, and divide by the mass of the hydrogenated conjugated diene (co) polymer rubber used in the analysis. Calculated with

[Amount of alkoxyl group (mmol / kg)]: Determined by an absorption amount of 1160 cm ⁻¹ due to Si—C bond by infrared absorption spectrum measurement.

  [Cold flow (mg / min)]: Measured by extruding a hydrogenated conjugated diene-based (co) polymer through a 1/4 inch orifice at a pressure of 24.1 kPa and a temperature of 50 ° C. In order to obtain a steady state, the extrusion speed was measured after being left for 10 minutes, and the value was displayed in milligrams per minute.

[Kneadability]: The compounded rubber after kneading except for sulfur and a crosslinking accelerator was passed through a roll to form a sheet, and the gloss was visually observed. Evaluation was performed according to the following criteria.
◎: Extremely good ○: Good

  [Tensile rupture strength (MPa) and tensile rupture elongation (%)]: Based on JIS K6251 and using a No. 3 type test piece, measurement was performed at a measurement temperature of 23 ° C. and a tensile speed of 500 mm / min.

  [Dynamic elastic modulus]: Based on JIS K6394, using a block-shaped test piece, the dynamic elastic modulus at 70 Hz was measured under the conditions of dynamic strain of 1% and temperature of 25 ° C. Similarly, the dynamic elastic modulus at 0.1 Hz was measured under the conditions of a dynamic strain of 10% and a temperature of 25 ° C. In the measurement, a viscoelasticity measuring device (trade name “ARESS”) manufactured by Rheometric Co., Ltd. was used.

[Static motion ratio]: The static motion ratio was calculated by the following equation (8).
Static ratio = (dynamic elastic modulus at 70 Hz) / (dynamic elastic modulus at 0.1 Hz) (8)

(Synthesis Example 1)
Cyclohexane (27.5 kg), tetrahydrofuran (35.8 g), n-butyllithium (1.25 g), and butadiene (2500 g) are added to a reaction vessel with an internal volume of 50 L that is purged with nitrogen, and adiabatic polymerization is carried out from 50 ° C. went. When the polymerization conversion rate reached 99%, silicon tetrachloride (0.275 g) was added and reacted for 5 minutes, and then N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane (3.25 g) was added. In addition, a polymerization conversion reaction was carried out for 15 minutes to obtain a copolymer (A). The vinyl copolymer content of the obtained copolymer (A) was 38%.

(Synthesis Example 2)
Add cyclohexane (27.5 kg), tetrahydrofuran (35.8 g), n-butyllithium (1.25 g), divinylbenzene (0.25 g) and butadiene (2490 g) to a reaction vessel with an internal volume of 50 L purged with nitrogen. Then, adiabatic polymerization was carried out from 50 ° C. When the polymerization conversion reached 99%, butadiene (10 g) and silicon tetrachloride (0.275 g) were further added and reacted for 5 minutes, and then N, N-bis (trimethylsilyl) aminopropylmethyldiethoxy. Silane (4.50 g) was added and a polymerization conversion reaction was carried out for 15 minutes to obtain a copolymer (B). The vinyl copolymer content of the obtained copolymer (B) was 38%.

(Synthesis Example 3)
A copolymer (C) was obtained in the same manner as in Synthesis Example 2 except for the conditions shown in Table 1. The vinyl copolymer content of the obtained copolymer (C) was 38%.

(Synthesis Example 4)
Cyclohexane (27.5 kg), tetrahydrofuran (51.1 g), n-butyllithium (1.25 g) and butadiene (2500 g) are added to a reaction vessel having an internal volume of 50 L, which is purged with nitrogen, and adiabatic polymerization is carried out from 50 ° C. went. When the polymerization conversion rate reached 99%, silicon tetrachloride (0.275 g) was added and reacted for 5 minutes, and then N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane (3.25 g) was added. In addition, a polymerization conversion reaction was carried out for 15 minutes to obtain a copolymer (D). The vinyl copolymer content of the obtained copolymer (D) was 43%.

(Synthesis Example 5)
Add cyclohexane (27.5 kg), tetrahydrofuran (19.6 g), n-butyllithium (1.25 g), divinylbenzene (0.15 g) and butadiene (2500 g) to a reaction vessel with an internal volume of 50 L purged with nitrogen. Then, adiabatic polymerization was carried out from 50 ° C. When the polymerization conversion reached 99%, silicon tetrachloride (0.220 g) was further added and reacted for 5 minutes, and then N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane (4.92 g). ) Was added and a polymerization conversion reaction was carried out for 15 minutes to obtain a copolymer (E). The vinyl copolymer content of the obtained copolymer (E) was 34%.

(Synthesis Example 6)
Cyclohexane (27.5 kg), tetrahydrofuran (35.8 g), n-butyllithium (1.25 g), and butadiene (2500 g) are added to a reaction vessel with an internal volume of 50 L that is purged with nitrogen, and adiabatic polymerization is carried out from 50 ° C. went. When the polymerization conversion rate reached 99%, silicon tetrachloride (0.400 g) was added and reacted for 5 minutes to obtain a copolymer (F). The vinyl copolymer content of the obtained copolymer (F) was 38%.

(Synthesis Example 7)
A copolymer (G) was obtained in the same manner as in Synthesis Example 1 except for the conditions shown in Table 1. The vinyl copolymer content of the obtained copolymer (G) was 38%.

(Synthesis Example 8)
A copolymer (H) was obtained in the same manner as in Synthesis Example 1 except for the conditions shown in Table 1. The vinyl copolymer content of the obtained copolymer (H) was 38%.

Example 1
After the polymerization conversion reaction in Synthesis Example 1, the mixture was then stirred for 20 minutes while supplying hydrogen gas at a pressure of 0.4 MPa-Gauge to react with unreacted polymer terminal lithium to obtain lithium hydride. Hydrogenation was performed using a catalyst mainly composed of titanocene dichloride at a hydrogen gas supply pressure of 0.7 MPa-Gauge, a reaction temperature of 90 ° C. When the amount of hydrogen absorbed reaches the integrated amount that achieves the desired hydrogenation rate, the reaction temperature is brought to room temperature, the hydrogen pressure is returned to normal pressure, the reaction vessel is withdrawn from the reaction vessel, the reaction solution is stirred into water, and the solvent is steamed. Removal by stripping gave a hydrogenated conjugated diene-based (co) polymer rubber. The hydrogenated conjugated diene-based (co) polymer rubber obtained had a hydrogenation rate of 91%, a glass transition temperature of -62 ° C, a coupling rate of 32%, and a weight average molecular weight of 450,000. The Mooney viscosity was 65, the amount of primary amino groups was 3.1 mmol / kg, the amount of alkoxyl groups was 2.9 mmol / kg, and the cold flow value was 0.10 mg / min. It was.

(Examples 2-5, Comparative Examples 1-2)
A hydrogenated conjugated diene-based (co) polymer rubber was obtained in the same manner as in Example 1 except that the copolymer shown in Table 2 was used. Hydrogenation rate, glass transition temperature, coupling rate, weight average molecular weight, Mooney viscosity, amount of primary amino group, amount of alkoxyl group, cold flow of each hydrogenated conjugated diene-based (co) polymer rubber obtained The values are also shown in Table 2.

(Comparative Example 3)
As the copolymer, an ethylene / propylene / diene copolymer (trade name “EP57”, manufactured by JSR Corporation) was used. Table 2 shows the glass transition temperature, coupling rate, weight average molecular weight, Mooney viscosity, primary amino group amount, alkoxyl group amount and cold flow value of this copolymer.

(Comparative Example 4)
The hydrogenation rate, glass transition temperature, coupling rate, weight average molecular weight, Mooney viscosity, primary amino group amount, alkoxyl group amount, cold flow value of the copolymer (H) obtained in Synthesis Example 8 The results are also shown in Table 2.

(Example 6)
Using the hydrogenated conjugated diene (co) polymer rubber obtained in Example 1, a hydrogenated conjugated diene (co) polymer rubber composition was prepared according to the formulation shown in Table 3, and the crosslinked rubber composition was crosslinked The physical properties of the product were evaluated. The kneadability of the prepared crosslinked rubber composition was “◯”, the tensile strength at break was 11.4 MPa, the elongation at break was 387%, and the static to dynamic ratio was 1.32.

(Examples 7 to 10, Comparative Examples 5 to 6)
A crosslinked rubber composition was prepared in the same manner as in Example 6 except that the hydrogenated conjugated diene-based (co) polymer rubber shown in Table 4 was used. Table 4 shows the kneadability evaluation, tensile breaking strength, tensile breaking elongation, and static / dynamic ratio of each prepared crosslinked rubber composition.

(Comparative Examples 7-8)
A crosslinked rubber composition was prepared in the same manner as in Example 6 except that the copolymer shown in Table 4 was used instead of the hydrogenated conjugated diene-based (co) polymer rubber. Table 4 shows the kneadability evaluation, tensile breaking strength, tensile breaking elongation, and static / dynamic ratio of each prepared crosslinked rubber composition.

  As can be seen from Table 2, the hydrogenated conjugated diene-based (co) polymer rubber of the present invention has a good Mooney viscosity and a low cold flow value compared to the conventional conjugated diene-based (co) polymer rubber. It is. Further, as can be seen from Table 4, the crosslinked rubber composition prepared using the hydrogenated conjugated diene-based (co) polymer rubber of the present invention comprises a copolymer having the same Mooney viscosity and cold flow values. Compared to the crosslinked rubber composition, it has an excellent static / kinetic ratio. Therefore, when a crosslinked rubber composition obtained by crosslinking the hydrogenated conjugated diene-based (co) polymer rubber of the present invention is used, a rubber molded article having excellent processability, tensile breaking strength, tensile breaking elongation, and static ratio is produced. Can do.

  The hydrogenated conjugated diene polymer rubber of the present invention is capable of producing a rubber molded article excellent in vibration-proofing properties and elongation. Therefore, the rubber molded article of the present invention produced using this hydrogenated conjugated diene polymer rubber is excellent in vibration resistance and elongation and has a small cold flow value. For example, an engine mount, Anti-vibration rubbers such as muffler hangers; Various hoses such as diaphragms, rolls, radiator hoses, air hoses and hose covers; Seals such as packing, gaskets, weather strips, O-rings, oil seals; belts, linings, It can be suitably used as a dust boot or the like.

Claims (16)

A hydrogenated conjugated diene-based (co) polymer rubber obtained by hydrogenating a copolymer that satisfies the following conditions (A) to (D), wherein the hydrogenation rate of the conjugated diene moiety is 50% or more.
(A): (a-1) containing a conjugated diene unit.
(B): Vinyl bond content is 20 to 70%.
(C): (c-1) an optionally protected primary amino group-containing alkoxysilyl group, or (c-2) an optionally protected primary amino group and an alkoxysilyl group are bonded. Yes.
(D): having a structure coupled in (D1) or (D2) below.
(D1): (d-1) A coupling agent having a plurality of functional groups.
(D2): (d-1) a coupling agent having a plurality of functional groups and (d-2) a monomer having a plurality of functional groups.   The hydrogenated conjugated diene-based (co) polymer rubber according to claim 1, wherein the copolymer further comprises at least one of (a-2) an aromatic vinyl unit and (a-3) other units.   The hydrogenated product according to claim 1 or 2, wherein the amount of the primary amino group contained in 1 kg of the copolymer is 0.5 to 200 mmol, and the amount of the alkoxysilyl group is 0.5 to 200 mmol. Conjugated diene (co) polymer rubber. The hydrogenated conjugated diene-based (co) polymer rubber according to any one of claims 1 to 3, wherein the structure of the copolymer is represented by the following general formula (1) or the following general formula (2).

(In the general formula (1), P represents a copolymer chain, R ¹ represents an alkylene group having 1 to 12 carbon atoms, and R ² and R ³ independently of each other have 1 to 20 carbon atoms. Represents an alkyl group or an aryl group, and n, m and k represent 1 or 2 (provided that n + m + k is 3 or 4).

(In the general formula (2), P represents a copolymer chain, R ¹ represents an alkylene group having 1 to 12 carbon atoms, and R ² and R ³ independently of each other have 1 to 20 carbon atoms. Represents an alkyl group or an aryl group, and j and h represent an integer of 1 to 3 (provided that j + h is an integer of 2 to 4).   The proportion of the (a-1) conjugated diene unit contained in the copolymer is 60 to 100% by mass, the proportion of the (a-2) aromatic vinyl unit is 0 to 40% by mass, and (a-3) 5) The proportion of other units is 0 to 40% by mass (provided that (a-1) + (a-2) + (a-3) = 100% by mass). The hydrogenated conjugated diene-based (co) polymer rubber described.   The ratio of the structural unit derived from the monomer which has multiple said (d-2) functional groups contained in the said copolymer is 0.001-5 mass%, As described in any one of Claims 1-5. The hydrogenated conjugated diene-based (co) polymer rubber described.   The hydrogenated conjugated diene-based (co) polymer rubber according to any one of claims 1 to 6, wherein the (d-1) coupling agent having a plurality of functional groups is a silicon compound. In a hydrocarbon solvent, in a reaction system containing at least one of an organic alkali metal and an organic alkaline earth metal as a polymerization initiator, a conjugated diene monomer, or a monomer having a plurality of conjugated diene monomers and functional groups (1) performing an anionic polymerization reaction by adding a body;
Adding a coupling agent having a plurality of functional groups (2);
A step (3) of adding a modifier having a functional group and bonding a primary amino group-containing alkoxysilyl group which may be protected to obtain a copolymer;
A process for producing hydrogenated conjugated diene-based (co) polymer rubber, comprising a step (4) of adding hydrogen to the copolymer. In a hydrocarbon solvent, a reaction system containing a reaction product of at least one of an organic alkali metal and an organic alkaline earth metal and a primary amine compound as a polymerization initiator is used as a conjugated diene monomer or a conjugated diene monomer. A step (1) of performing an anionic polymerization reaction by adding a monomer having a monomer and a plurality of functional groups;
Adding a coupling agent having a plurality of functional groups (2);
A step (3) of adding a modifier having a functional group and bonding a primary amino group-containing alkoxysilyl group which may be protected, or an alkoxysilyl group to obtain a copolymer;
A method for producing a hydrogenated conjugated diene-based (co) polymer rubber comprising the step (4) of adding hydrogen to the copolymer.   The hydrogenated conjugated diene-based (co) polymer rubber according to claim 8 or 9, wherein in the step (1), at least one of an aromatic vinyl monomer and another monomer is further added to the reaction system. Manufacturing method. The modifier having the functional group is an amino group-containing alkoxysilane compound whose structure is represented by the following general formula (3) or the following general formula (4):
The method for producing a hydrogenated conjugated diene-based (co) polymer rubber according to any one of claims 8 to 10, further comprising a step (5) of performing hydrolysis after the step (4).

(In the general formula (3), ^{R 1} represents an alkylene group having 1 to 12 carbon atoms, ^{R 2} and ^{R 3,} independently of one another, an alkyl group or an aryl group having 1 to 20 carbon atoms, R ⁴ , R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group, or a ring containing a silicon atom formed by bonding two of them together. , G represents 1 or 2, and f represents an integer of 1 to 10.)

(In the general formula (4), R ¹ represents an alkylene group having 1 to 12 carbon atoms, R ² and R ³ each independently represent an alkyl group having 1 to 20 carbon atoms, or an aryl group, R ⁴ , R ⁵ and R ⁶ each independently represent an alkyl group or aryl group having 1 to 20 carbon atoms or a ring containing a silicon atom formed by bonding two of them together. E represents 2 or 3.)   The amino group-containing alkoxysilane compound is N, N-bis (trimethylsilyl) aminopropylmethyldimethoxysilane, N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane, and 1-trimethylsilyl-2,2-dimethoxy-1. The method for producing a hydrogenated conjugated diene-based (co) polymer rubber according to claim 11, which is at least one selected from the group consisting of -aza-2-silacyclopentane. Containing the hydrogenated conjugated diene-based (co) polymer rubber according to any one of claims 1 to 7 and a filler;
A hydrogenated conjugated diene-based (co) polymer rubber composition, wherein the filler content is 5 to 200 parts by mass with respect to 100 parts by mass of the hydrogenated conjugated diene-based (co) polymer rubber.   The hydrogenated conjugated diene-based (co) polymer rubber composition according to claim 13, wherein the filler is at least one of silica and carbon black.   The hydrogenated conjugated diene-based (co) polymer rubber composition according to claim 13 or 14, further comprising another rubber component.   A rubber molded article comprising a crosslinked rubber composition obtained by crosslinking the hydrogenated conjugated diene-based (co) polymer rubber composition according to any one of claims 13 to 15.