JPH0940819A - Vulcanizable rubber composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a vulcanizable rubber composition excellent in strength characteristics, heat-aging resistance, weatherability, ozone resistance and processability and useful as automobile parts, etc., by bringing the composition to contain a specific ethylene-olefin nonconjugated polyene copolymer. SOLUTION: This vulcanizable rubber composition comprises 5-95 pts.wt. (A) an ethylene.α-olefin nonconjugated polyene copolymer rubber consisting of (i) ethylene, (ii) a 3-20C α-olefin and (iii) nonconjugated polyene and 95-5 pts.wt. (B) an ethylene propylene copolymer rubber consisting of the component (i), (iv) propylene and, if needed, the component (iii). The component A is obtained by randomly copolymerizing the components (i), (ii) and (iii) in the presence of a metallocene catalyst, contains 40-95 mole % unit (a) derived from the component (i) and 60-5 unit derived from the component (ii) and is brought to have 1-50 iodine number, 0.1-10dl/g intrinsic viscosity (in decline at 135 deg.C) and 0.2-0.95 ratio of the intrinsic viscosity with a linear ethylene propylene copolymer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to strength characteristics, heat aging resistance,
The present invention relates to a vulcanizable rubber composition which can provide a vulcanized rubber excellent in weather resistance and ozone resistance, and is also excellent in processability (moldability).

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Ethylene / α-olefin rubbers such as ethylene / propylene copolymer rubber (EPR) and ethylene / propylene / diene copolymer rubber (EPDM) are unsaturated in the main chain of their molecular structure. Since it has no bond, it has superior heat aging resistance, weather resistance, and ozone resistance compared to the commonly used conjugated diene rubber, and is used for automobile parts, electric wire materials, electric / electronic parts, construction civil engineering materials, and industrial material parts. It is widely used for such purposes.

However, as the performance and functionality of parts have increased in recent years, further improvement in physical properties is required, and in order to complicate parts and reduce processing costs, workability is improved more than ever. It has been demanded.

Extrudability, which is one of the processability of EPDM,
In particular, the viscosity of the compound may be lowered in order to improve the extrusion amount and the extruded skin. However, if a large amount of oil is added or the molecular weight of EPDM is made extremely small in order to reduce the viscosity of the compound,
The resulting vulcanized rubber product has a low strength and is not practical. Also known is a method of broadening the molecular weight distribution and composition distribution to reduce the viscosity of the compound. The problem arises that the characteristics deteriorate.

On the other hand, in order to improve the shape retention when extruding EPDM, it is sufficient to increase the viscosity of the compound, but if the viscosity is increased, the extrusion amount of EPDM decreases,
There is a problem that the extruded skin becomes bad.

The present inventors can provide a vulcanized rubber having excellent strength characteristics, heat aging resistance, weather resistance and ozone resistance, and can be vulcanized with excellent processability (moldability). If a rubber composition consisting of a specific ethylene / α-olefin / non-conjugated polyene copolymer rubber and ethylene / propylene / non-conjugated polyene copolymer rubber is used, the above properties are excellent. It was found that a vulcanizable rubber composition was obtained, and the present invention was completed.

[0007]

It is an object of the present invention to solve the above problems associated with the prior art, and to provide a vulcanized rubber excellent in strength characteristics, heat aging resistance, weather resistance and ozone resistance. It is an object of the present invention to provide a vulcanizable rubber composition that can be processed and is excellent in processability (moldability).

[0008]

SUMMARY OF THE INVENTION A vulcanizable rubber composition according to the present invention comprises:
Ethylene, an α-olefin / non-conjugated polyene copolymer rubber (A) consisting of ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene, and ethylene consisting of ethylene, propylene and, if necessary, a non-conjugated polyene. -Propylene copolymer rubber (B) 5 / 95-95
A vulcanizable rubber composition containing a weight ratio [(A) / (B)] of / 5, wherein the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) is a metallocene catalyst. In the presence of ethylene, only one carbon-carbon double bond which can be polymerized by the catalyst among the carbon-carbon double bonds and ethylene, α-olefin having 3 to 20 carbon atoms is present in one molecule. Obtained by random copolymerization with a non-conjugated polyene, (1) (a) a unit derived from ethylene and (b) a carbon atom number 3
Units derived from .alpha.-olefin of 40 to 40 /
It is contained at a molar ratio of 60 to 95/5 [(a) / (b)], (2) has an iodine value of 1 to 50, and (3) has an intrinsic viscosity [η] measured in 135 ° C. decalin.
Is from 0.1 to 10 dl / g, and (4) the intrinsic viscosity [η] measured in (3) above and the ethylene content having the same weight average molecular weight (by light scattering method) as 70 are 70. Ratio of intrinsic viscosity [η] _blank of linear ethylene / propylene copolymer of mol% [gη ^* (= [η] /
[Η] _blank )] is 0.2 to 0.95.

The metallocene catalyst used for producing the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) preferably contains a metallocene compound represented by the following formula [I].

[0010]

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[Wherein M is a transition metal of Group IVB of the periodic table, R ¹ is a hydrocarbon group having 1 to 6 carbon atoms, and R ² , R ⁴ , R ⁵ and R ^{6 are} May be the same or different and each is a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 6 carbon atoms, R ³ is an aryl group having 6 to 16 carbon atoms, and this aryl group May be substituted with a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an organic silyl group.

X ¹ and X ² are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or 1 to 2 carbon atoms.
20 is a halogenated hydrocarbon group, an oxygen-containing group or a sulfur-containing group, and Y is a divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms. , A divalent silicon-containing group, a divalent germanium-containing group, -O-, -CO-, -S-, -SO-, -SO
^{_{2 -, - NR 7 -,}} - P (R 7) -, - P (O)
^{(R 7) -, - BR} 7 - or -AlR ⁷ - a.
(However, R ⁷ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms). As the ethylene / propylene copolymer rubber (B), the intrinsic viscosity [η] measured in a decalin solvent at 135 ° C.
Is preferably in the range of 0.1 to 10 dl / g, and the iodine value is preferably in the range of 0 to 50.

[0013]

DETAILED DESCRIPTION OF THE INVENTION The vulcanizable rubber composition according to the present invention will be specifically described below. The vulcanizable rubber composition according to the present invention contains an ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and an ethylene / propylene copolymer rubber (B).

Ethylene / α-olefin / non-conjugated polyene
Copolymer rubber (A) The ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) used in the present invention contains ethylene and α having 3 to 20 carbon atoms in the presence of a metallocene catalyst. -An olefin and a non-conjugated polyene in which only one carbon-carbon double bond of the carbon-carbon double bond that can be polymerized by the catalyst is present in one molecule (hereinafter sometimes referred to simply as non-conjugated polyene) ) And is copolymerized.

Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene,
1-decene, 1-undecene, 1-dodecene, 1-tridecene,
1-tetradecene, 1-pentadecene, 1-hexadecene, 1-
Heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene,
3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1- Hexene, 3-ethyl-1
-Hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene, and combinations thereof.

Of these, α-containing 3 to 10 carbon atoms
Olefin is preferred, especially propylene, 1-butene, 1-
Hexene, 1-octene and the like are preferably used. The above-mentioned non-conjugated polyene is a non-conjugated polyene in which only one carbon-carbon double bond which can be polymerized by a metallocene catalyst among carbon-carbon double bonds exists in one molecule. Such a non-conjugated polyene does not include a chain polyene having vinyl groups at both ends. When one of the two or more vinyl groups is a terminal vinyl group, the other vinyl group is preferably one having an internal olefin structure rather than a terminal.

Examples of such non-conjugated polyenes include aliphatic polyenes and alicyclic polyenes. As such an aliphatic polyene, specifically, 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4-ethyl-1,4
-Hexadiene, 3-methyl-1,5-hexadiene, 3,3-dimethyl-1,4-hexadiene, 5-methyl-1,4-heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1 , 5-heptadiene, 6-methyl-1,5-heptadiene, 5-ethyl-1,5
-Heptadiene, 1,6-octadiene, 4-methyl-1,4-octadiene, 5-methyl-1,4-octadiene, 4-ethyl-
1,4-octadiene, 5-ethyl-1,4-octadiene, 5-
Methyl-1,5-octadiene, 6-methyl-1,5-octadiene, 5-ethyl-1,5-octadiene, 6-ethyl-1,5-octadiene, 6-methyl-1,6-octadiene, 7- Methyl-1,6
-Octadiene, 6-ethyl-1,6-octadiene, 6-propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 4-methyl-1,4-nonadiene, 5-methyl-1,4 -Nonadiene, 4-ethyl-1,4-nonadiene, 5-ethyl-1,4-nonadiene, 5-methyl-1,5-nonadiene, 6-methyl-1,5-nonadiene, 5-ethyl-1,5 -Nonadiene, 6-ethyl-1,5-
Nonadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6
-Nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-
1,6-nonadiene, 7-methyl-1,7-nonadiene, 8-methyl-1,7-nonadiene, 7-ethyl-1,7-nonadiene, 5-methyl-1,4-decadiene, 5-ethyl- 1,4-decadiene, 5-
Methyl-1,5-decadiene, 6-methyl-1,5-decadiene,
5-ethyl-1,5-decadiene, 6-ethyl-1,5-decadiene, 6-methyl-1,6-decadiene, 6-ethyl-1,6-decadiene, 7-methyl-1,6-decadiene, 7-ethyl-1,6-decadiene, 7-methyl-1,7-decadiene, 8-methyl-1,7-decadiene, 7-ethyl-1,7-decadiene, 8-ethyl-1,7-
Decadiene, 8-methyl-1,8-decadiene, 9-methyl-1,8
-Decadiene, 8-ethyl-1,8-decadiene, 6-methyl-1,
Examples include 6-undecadiene and 9-methyl-1,8-undecadiene.

The alicyclic polyene is preferably a polyene composed of an alicyclic portion having one unsaturated bond and a chain portion having an internal olefin bond,
For example, 5-ethylidene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene and the like can be mentioned.

Further, trienes such as 2,3-diisopropylidene-5-norbornene and 2-ethylidene-3-isopropylidene-5-norbornene may be mentioned. Among these non-conjugated polyenes, 5-ethylidene-2-norbornene and 1,4-hexadiene are particularly preferable.

These non-conjugated polyenes can be used alone or in combination of two or more kinds. The ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) used in the present invention has the following characteristics. (1) Ethylene / α-olefin component ratio The ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) used in the present invention comprises (a) a unit derived from ethylene and (b) 3 carbon atoms. .About.20 .alpha.-olefin (hereinafter sometimes referred to simply as .alpha.-olefin) and 40/60 to 95/5, preferably 55/45 to 90/10 [(a) / (b )] In a molar ratio. (2) Iodine Value The iodine value of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) is 1 to 50, preferably 5 to 40.
It is.

Ethylene having an iodine value as described above
The α-olefin / non-conjugated polyene copolymer rubber has a high vulcanization rate and is capable of high-speed vulcanization. (3) Intrinsic viscosity [η] The intrinsic viscosity [η] of ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) measured in decalin at 135 ° C is 0.1 to 10 dl / g, preferably 0.5 ~
It is 7 dl / g, more preferably 0.9 to 5 dl / g. (4) gη ^* value The gη ^* value is the intrinsic viscosity [η] measured in (3) above,
Ethylene / α-olefin / non-conjugated polyene copolymer rubber having the intrinsic viscosity [η] of a linear ethylene / propylene copolymer having the same weight average molecular weight (by light scattering method) and an ethylene content of 70 mol% Intrinsic viscosity [η]
Defined as the ratio to _blank .

Gη ^* = [η] / [η] _blank The gη ^* value of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) used in the present invention is 0.2 to
It is 0.95, preferably 0.4 to 0.9, more preferably 0.5 to 0.85.

When the gη ^* value of the ethylene / α-olefin / non-conjugated polyene copolymer rubber is 0.95 or less, it means that long chain branching is formed in the molecule. Such an ethylene / α-olefin / non-conjugated polyene copolymer rubber has a low viscosity at a high shear rate during processing such as kneading and molding, and a viscosity at a low shear rate immediately after vulcanization after molding. Is low. Therefore, from the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) having the above-mentioned gη ^* value, it is excellent in processability such as kneading and molding, and also retains the shape immediately after vulcanization after molding. A rubber composition having excellent properties can be obtained.

When the gη ^* value of the ethylene / α-olefin / non-conjugated polyene copolymer rubber exceeds 0.95, the shape retention is insufficient, and when it is less than 0.2, the processability decreases. I have something to do.

The above-mentioned ethylene / α-olefin /
The non-conjugated polyene copolymer rubber (A) comprises ethylene and an α-containing 3 to 20 carbon atoms in the presence of a metallocene catalyst.
It can be obtained by randomly copolymerizing an olefin and a non-conjugated polyene.

The metallocene catalyst used in the present invention is
It contains a specific metallocene compound [A] as described below. The metallocene catalyst used in the present invention is not particularly limited except that it contains the metallocene compound [A]. For example, the metallocene compound [A] and the organoaluminum oxy compound [B] and / or the metallocene compound [A]. And a compound [C] which reacts with the compound to form an ion pair. Further, a metallocene compound [A], an organoaluminum oxy compound [B] and /
Alternatively, it may be formed from an organoaluminum compound [D] together with a compound [C] forming an ion pair.

The components used in forming the metallocene catalyst in the present invention will be described below. Metallocene Compound [A] In the present invention, as the metallocene compound [A], a compound represented by the following general formula [I] is used.

[0028]

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In the formula, M is a transition metal atom of Group IVB of the periodic table, specifically, titanium, zirconium,
Hafnium, particularly preferably zirconium. Substituent R ¹ R ¹ is a hydrocarbon group having 1 to 6 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec- Butyl group, tert
Examples include an alkyl group such as a butyl group, an n-pentyl group, a neopentyl group, an n-hexyl group, and a cyclohexyl group, and an alkenyl group such as a vinyl group and a propenyl group.

Of these, an alkyl group in which the carbon bonded to the indenyl group is primary is preferable, and the number of carbon atoms is 1
To 4 are preferred, and a methyl group and an ethyl group are particularly preferred.

The substituents R ² , R ⁴ , R ⁵ , R ^6, R ² , R ⁴ , R ⁵ and R ⁶ may be the same or different and are the same as hydrogen atom, halogen atom or R ¹ . It is a hydrocarbon group having 1 to 6 carbon atoms.

Here, the halogen atom is fluorine, chlorine, bromine or iodine. The substituent R ³ R ³ is an aryl group having 6 to 16 carbon atoms. The aryl group may be substituted with a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an organic silyl group.

Specific examples of the aryl group include phenyl group, α-naphthyl group, β-naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, acenaphthyl group, phenalenyl group, aceanthrylenyl group, tetrahydronaphthyl group, Examples thereof include an indanyl group and a biphenylyl group. Of these, phenyl group, naphthyl group,
Anthracenyl group and phenanthryl group are preferable.

Examples of the hydrocarbon group having 1 to 20 carbon atoms which is a substituent of the aryl group include, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group,
Alkyl groups such as cyclohexyl group, octyl group, nonyl group, dodecyl group, eicosyl group, norbornyl group, adamantyl group, alkenyl groups such as vinyl group, propenyl group, cyclohexenyl group, benzyl group, phenylethyl group, phenylpropyl group, etc. And the aryl groups exemplified above, and aryl groups such as tolyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, methylnaphthyl group and benzylphenyl group.

Examples of the organic silyl group include trimethylsilyl group, triethylsilyl group, triphenylsilyl group and the like. X ¹ and X ² X ¹ and X ² are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with halogen, an oxygen-containing group or a sulfur-containing group. Specifically, the same halogen atom and hydrocarbon group as described above can be mentioned.

Further, as the oxygen-containing group, specifically,
Alkoxy group such as hydroxy group, methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group, methylphenoxy group, dimethylphenoxy group, allyloxy group such as naphthoxy group, phenylmethoxy group, arylalkoxy group such as phenylethoxy group, etc. Can be mentioned.

As the sulfur-containing group, specifically, a substituent in which oxygen of the oxygen-containing group is replaced with sulfur, a methylsulfonate group, a trifluoromethanesulfonate group,
Phenyl sulfonate group, benzyl sulfonate group, p-toluene sulfonate group, trimethylbenzene sulfonate group, triisobutylbenzene sulfonate group, p-chlorobenzene sulfonate group, pentafluorobenzene sulfonate group Groups such as sulfonate group, methylsulfinate group, phenylsulfinate group, benzenesulfinate group, p-toluenesulfinate group, trimethylbenzenesulfinate group, pentafluorobenzenesulfinate group and other sulfinates group And so on.

Of these, X ¹ and X ² are preferably a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms. YY is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, -O. -, -C
O -, - S -, - SO -, - SO 2 -, - NR 7 -, -
^{P (R 7) -, -} P (O) (R 7) -, - BR 7 - or -AlR ⁷ - (provided that, R ⁷ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms , 1 carbon atom
To 20 halogenated hydrocarbon groups), and specifically,
Methylene group, dimethylmethylene group, 1,2-ethylene group, dimethyl-1,2-ethylene group, 1,3-trimethylene group, 1,4-tetramethylene group, 1,2-cyclohexylene group, 1,4- A divalent hydrocarbon group having 1 to 20 carbon atoms such as an alkylene group such as a cyclohexylene group, an arylalkylene group such as a diphenylmethylene group or a diphenyl-1,2-ethylene group; a carbon atom number 1 such as chloromethylene To a halogenated hydrocarbon group obtained by halogenating a divalent hydrocarbon group of 20; methylsilylene group, dimethylsilylene group, diethylsilylene group, di (n-propyl) silylene group, di (i-propyl) silylene group, di Alkylsilylene groups such as (cyclohexyl) silylene group, methylphenylsilylene group, diphenylsilylene group, di (p-tolyl) silylene group, di (p-chlorophenyl) silylene group, alkylaryl Silylsilyl group,
Arylsilylene group, tetramethyl-1,2-disilyl group,
A divalent silicon-containing group such as an alkyldisilyl group such as a tetraphenyl-1,2-disilyl group, an alkylaryldisilyl group or an aryldisilyl group; and 2 in which the silicon in the divalent silicon-containing group is replaced with germanium And a valent germanium-containing group.

R ⁷ is the same halogen atom, hydrocarbon group having 1 to 20 carbon atoms, or halogenated hydrocarbon group having 1 to 20 carbon atoms as described above. Among them, Y is preferably a divalent silicon-containing group, a divalent germanium-containing group, more preferably a divalent silicon-containing group, and is preferably an alkylsilylene group, an alkylarylsilylene group, or an arylsilylene. Particularly preferred is a group.

Specific examples of the metallocene compound represented by the above general formula [I] are shown below. rac-dimethyl silylene-
Bis (4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4-
Phenylindenyl) zirconium dichloride, rac-
Dimethylsilylene-bis (2-methyl-4- (α-naphthyl))
-1-Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (β-naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (1- Anthracenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (2-anthracenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- ( 9-anthracenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (9-phenanthryl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4) -(P-fluorophenyl) -1-
Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (pentafluorophenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (p-chlorophenyl)- 1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (m-chlorophenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (o-chlorophenyl) ) -1-Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (o, p-dichlorophenyl) phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4) -(P-
Bromophenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (p-
Tolyl) -1-indenyl) zirconium dichloride, ra
c-Dimethylsilylene-bis (2-methyl-4- (m-tolyl)
-1-Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (o-tolyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (o, o'-dimethylphenyl) -1-
Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (p-ethylphenyl) -1-
Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (pi-propylphenyl))
-1-Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (p-benzylphenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (p -Biphenyl)
-1-Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (m-biphenyl) -1-
Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (p-trimethylsilylenephenyl) -1-indenyl) zirconium dichloride, ra
c-Dimethylsilylene-bis (2-methyl-4- (m-trimethylsilylenephenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-phenyl-4)
-Phenyl-1-indenyl) zirconium dichloride,
rac-diethylsilylene-bis (2-methyl-4-phenyl-1)
-Indenyl) zirconium dichloride, rac-di- (i-
Propyl) silylene-bis (2-methyl-4-phenyl-1-
Indenyl) zirconium dichloride, rac-di- (n-butyl) silylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-dicyclohexylsilylene-bis (2-methyl-4-phenyl-1-) Indenyl) zirconium dichloride, rac-methylphenylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-diphenylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-di (p-tolyl) silylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-di (p-chlorophenyl) silylene-bis (2-
Methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-methylene-bis (2-methyl-4-phenyl-1)
-Indenyl) zirconium dichloride, rac-ethylene
-Bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylgermylene-bis (2-
Methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylstannylene-bis (2-methyl-4-)
Phenyl-1-indenyl) zirconium dichloride, ra
c-Dimethylsilylene-bis (2-methyl-4-phenyl-1-
Indenyl) zirconium dibromide, rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl)
Zirconium dimethyl, rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium methyl chloride, rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium chloride SO ₂ Me , Rac-Dimethylsilylene-bis (2-methyl-4-
Phenyl-1-indenyl) zirconium chloride OS
O ₂ Me, rac-dimethylsilylene-bis {1- (2-ethyl-
4-phenylindenyl)} zirconium dichloride, r
ac-Dimethylsilylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2-ethyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-Dimethylsilylene-bis {1- (2-ethyl-4- (2-methyl-1-
Naphthyl) indenyl) zirconium dichloride, ra
c-Dimethylsilylene-bis {1- (2-ethyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride, ra
c-dimethylsilylene-bis {1- (2-ethyl-4- (9-anthracenyl) indenyl)} zirconium dichloride,
rac-Dimethylsilylene-bis {1- (2-ethyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-Dimethylsilylene-bis {1- (2-ethyl-4- (o
-Methylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4-
(M-Methylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl
-4- (p-Methylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,3-dimethylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene- Screw {1-
(2-Ethyl-4- (2,4-dimethylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (2,5-dimethylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,4,6-trimethyl) Phenyl) indenyl)} zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2-ethyl-4- (o-chlorophenyl) indenyl)} zirconium dichloride, ra
c-dimethylsilylene-bis {1- (2-ethyl-4- (m-chlorophenyl) indenyl)} zirconium dichloride,
rac-Dimethylsilylene-bis {1- (2-ethyl-4- (p-chlorophenyl) indenyl)} zirconium dichloride, rac-Dimethylsilylene-bis {1- (2-ethyl-4-
(2,3-Dichlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,6-dichlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1 -
(2-Ethyl-4- (3,5-dichlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (2-bromophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (3-bromophenyl) indenyl)} zirconium Dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (4-bromophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (4-biphenylyl) ) Indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (4-trimethylsilylphenyl) indenyl)} zirconium dichloride, ra
c-Dimethylsilylene-bis {1- (2-n-propyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-propyl-4- (α-naphthyl) indenyl) )} Zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-propyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-propyl- 4- (2-methyl
-1-Naphtyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-propyl-4
-(5-Acenaphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-propyl-4- (9-anthracenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-
Propyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1-
(2-i-Propyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-
Propyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-
Propyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-
Propyl-4- (8-methyl-9-naphthyl) indenyl)}
Zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-propyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-i-propyl-4- (9-anthracenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-propyl-4- (9-phenanthryl) indenyl) } Zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2-s-butyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-s-butyl-4- (α-naphthyl) indenyl)} Zirconium dichloride, rac-dimethylsilylene-bis {1- (2-s-butyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-s-butyl-4- (2-Methyl-1-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-s-butyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-s-Butyl-4- (9-anthracenyl) indenyl)} zirconium dichloride, ra
c-Dimethylsilylene-bis {1- (2-s-butyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-Dimethylsilylene-bis {1- (2-n-pentyl-4)
-Phenylindenyl)} zirconium dichloride, ra
c-Dimethylsilylene-bis {1- (2-n-pentyl-4- (α-
Naphthyl) indenyl) zirconium dichloride, ra
c-Dimethylsilylene-bis {1- (2-n-butyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-butyl-4- (α-naphthyl))
Indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-butyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-butyl) -4- (2-Methyl-1-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-butyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2-n-butyl-4- (9-anthracenyl) indenyl)} zirconium dichloride,
rac-Dimethylsilylene-bis {1- (2-n-butyl-4- (9-
Phenanthryl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-butyl-4-
Phenylindenyl) zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2-i-butyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-butyl-4- (β-naphthyl)) Indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-butyl-4- (2-methyl-1)
-Naphthyl) indenyl)} zirconium dichloride,
rac-Dimethylsilylene-bis {1- (2-i-butyl-4- (5-
Acenaphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-butyl-4-
(9-anthracenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-butyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- ( 2-neopentyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-neopentyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-hexyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-hexyl
-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1- ( 2-ethyl
-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1- (2-ethyl-4- (9-anthracenyl) indenyl)} zirconium dichloride, rac-methylphenylsilylene-bis { 1-
(2-Ethyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1 -(2-
Ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2-ethyl-4- (9-anthracenyl) indenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1 -
(2-Ethyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2-ethyl-4- (4-biferrinyl) indenyl)}
Zirconium dichloride, rac-methylene-bis {1- (2-
Ethyl-4-phenylindenyl)} zirconium dichloride, rac-methylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-ethylene-bis {1- (2-ethyl -4-Phenylindenyl)} zirconium dichloride, rac-ethylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-ethylene-bis {1- (2-n- Propyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylgermyl-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylgermyl-bis {1- (2-ethyl-4-
(Α-Naphthyl) indenyl)} zirconium dichloride, rac-dimethylgermyl-bis {1- (2-n-propyl-4)
-Phenylindenyl)} zirconium dichloride and the like.

Further, compounds in which zirconium in the above compounds is replaced by titanium or hafnium can be also mentioned. In the present invention, the racemic form of the metallocene compound is usually used as the catalyst component, but R type or S type can also be used.

In the present invention, two or more kinds of the above metallocene compounds may be used in combination. Such metallocene compounds are available from the Journal of Organometallic Ch.
em.288 (1985), pp. 63-67, European Patent Application Publication No.
It can be manufactured according to the specification of Japanese Patent No. 0,320,762.

Organoaluminum Oxy Compound [B] The organoaluminum oxy compound [B] used in the present invention may be a conventionally known aluminoxane, and as exemplified in JP-A-2-78687. Benzene-insoluble organoaluminum oxy compound may be used.

The conventionally known aluminoxane can be produced, for example, by the following method. (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. A method of recovering a hydrocarbon solution by adding an organoaluminum compound such as trialkylaluminum to the hydrocarbon medium suspension and reacting the same. (2) A method in which water, ice or steam is allowed to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran to recover a hydrocarbon solution. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of organic metal component. The solvent or unreacted organoaluminum compound may be removed from the recovered aluminoxane solution by distillation, and then redissolved in the solvent.

Specific examples of the organoaluminum compound used in the production of aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec. -Trialkyl aluminum such as butyl aluminum, tri-tert-butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, and tridecyl aluminum; tricycloalkyl aluminum such as tricyclohexyl aluminum and tricyclooctyl aluminum; dimethyl aluminum chloride; Diethyl aluminum chloride,
Dialkylaluminum halides such as diethylaluminum bromide and diisobutylaluminum chloride; dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride; dialkylaluminum alkoxides such as dimethylaluminum methoxide and diethylaluminum ethoxide; dialkylaluminum aryloxy such as diethylaluminum phenoxide And the like.

Among these, trialkylaluminum and tricycloalkylaluminum are particularly preferable.
As the organoaluminum compound used for preparing the aluminoxane formulas _{(i-C 4 H 9)} x Al y (C
₅ H ₁₀ ) _z (where x, y and z are positive numbers, and z ≧
2x. ) Can also be used.

The above organoaluminum compounds may be used in combination of two or more kinds. Solvents used in the production of aluminoxane include, for example, benzene,
Aromatic hydrocarbons such as toluene, xylene, cumene and cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane, and fats such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane Petroleum fractions such as cyclic hydrocarbons, gasoline, kerosene, and gas oil; and hydrocarbon solvents such as the above-mentioned aromatic hydrocarbons, aliphatic hydrocarbons, and halides of alicyclic hydrocarbons, especially chlorinated compounds and brominated compounds. Can be

Further, ethers such as ethyl ether and tetrahydrofuran can be used. Of these solvents, aromatic hydrocarbons are particularly preferred. Reacts with metallocene compound [A] to form an ion pair
Compound [C] Examples of the compound [C] which forms an ion pair by reacting with the metallocene compound [A] used in the present invention include:
501950 gazette, special table 1-502036 gazette,
JP-A-3-179005, JP-A-3-179900
No. 6, JP-A-3-207703, JP-A-3-207703
The Lewis acid, the ionic compound, the borane compound, and the carborane compound described in 207704, US-547718, etc. can be mentioned.

As the Lewis acid, Mg-containing Lewis acid, A
Examples thereof include l-containing Lewis acids and B-containing Lewis acids, and among them, B-containing Lewis acids are preferable. As the Lewis acid containing a boron atom, specifically, compounds represented by the following general formula can be exemplified.

BR ¹ R ² R ³ (In the formula, R ¹ R ² and R ³ are each independently a phenyl group which may have a substituent such as a fluorine atom, a methyl group and a trifluoromethyl group. , Or a fluorine atom.) As the compound represented by the above general formula, specifically,
Trifluoroboron, triphenylboron, tris (4-
Fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl)
Boron, tris (pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron,
Examples include tris (3,5-dimethylphenyl) boron. Of these, tris (pentafluorophenyl) boron is particularly preferred.

The ionic compound used in the present invention is a salt composed of a cationic compound and an anionic compound. The anion functions to cationize the metallocene compound [A] by reacting with the metallocene compound [A] and to stabilize the transition metal cation species by forming an ion pair. Examples of such anions include an organic boron compound anion, an organic arsenic compound anion, and an organic aluminum compound anion, and an anion that is relatively bulky and stabilizes a transition metal cation species is preferable. Examples of the cation include a metal cation, an organometallic cation, a carbonium cation, a tripium cation, an oxonium cation, a sulfonium cation, a phosphonium cation, and an ammonium cation.
Specific examples include triphenylcarbenium cation, tributylammonium cation, N, N-dimethylammonium cation, ferrocenium cation, and the like.

In the present invention, an ionic compound having an organic boron compound anion is preferable. In particular,
Triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, trimethylammonium tetra (p-tolyl) boron, trimethylammonium tetra (o-tolyl) boron, Tributylammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o,
p-Dimethylphenyl) boron, tributylammonium tetra (m, m-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (o-tolyl) boron, tri ( n-Butyl) ammonium tetra (4-
Trialkyl-substituted ammonium salts such as fluorophenyl) boron, N, N-dimethylaniliniumtetra (phenyl) boron, N, N-diethylaniliniumtetra (phenyl) boron, N, N-2,4,6-pentamethyl N, N-dialkylanilinium salts such as anilinium tetra (phenyl) boron; dialkylammonium salts such as di (n-propyl) ammonium tetra (pentafluorophenyl) boron; dicyclohexylammonium tetra (phenyl) boron; triphenylphospho And triarylphosphonium salts such as ammonium tetra (phenyl) boron, tri (methylphenyl) phosphonium tetra (phenyl) boron, and tri (dimethylphenyl) phosphonium tetra (phenyl) boron.

In the present invention, as an ionic compound containing a boron atom, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentaphenyl) Fluorophenyl) borate can also be mentioned.

Further, the following ionic compounds containing a boron atom can be exemplified. (Note that the counter ion in the ionic compounds listed below is, but not limited to, tri (n-butyl) ammonium.) Salts of anions such as bis [tri (n-butyl) ammonium] nonaborate, bis (tri-n-butyl) ammonium [Tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl)
Ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachlorododecaborate, tri (n-butyl) ammonium-1-carbadecaborate, tri (n-butyl) ammonium-1-carboundecaborate , Tri (n-butyl) ammonium-1-carbadodecaborate, tri (n-butyl) ammonium-1-trimethylsilyl-1-carbadecaborate, tri (n-butyl) ammonium bromo-1-carbadodecaborate, etc. Include the following borane compounds and carborane compounds. These compounds are used as Lewis acids and ionic compounds.

Examples of salts of borane compounds, carborane complex compounds and carborane anions include decaborane (14), 7,8-dicarbaundecaborane (13), 2,
7-dicarboundecaborane (13), undecahydride-7,8-dimethyl-7,8-dicarboundecaborane, dodecahydride-11-methyl-2,7-dicarboundecaborane, tri (n-butyl ) Ammonium 6-carbadecaborate (14), tri (n-butyl) ammonium 6-carbadecaborate (12), tri (n-butyl) ammonium
7-carboundecaborate (13), tri (n-butyl)
Ammonium 7,8-dicarboundecaborate (12),
Tri (n-butyl) ammonium 2,9-dicarboundecaborate (12), tri (n-butyl) ammonium dodecahydride-8-methyl-7,9-dicarboundecaborate, tri (n-butyl) ammoniumundeca Hydride 8-ethyl-7,9-dicarboundecaborate, tri (n-
Butyl) ammonium undeca hydride-8-butyl
-7,9-Dicarboundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-Dicarboundecaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7 , 8-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carboundecaborate, and the like.

Examples of the carborane compound and carborane salts include 4-carbanonaborane (14) and 1,3-
Dicarbanonaborane (13), 6,9-dicarbadecaborane (14), dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodecahydride-1-methyl-1,3-
Dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane and the like.

Further, the following compounds can be exemplified. (Note that the counter ion in the ionic compounds listed below is tri (n-butyl) ammonium,
It is not limited to this. ) Salts of metal carboranes and metal borane anions such as tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (II
I), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) ferrate (ferrate) (III), tri (n-butyl) ammonium bis (undecahydride-7, 8-dicarboundecaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) nickelate (III), tri (n-butyl) ammonium bis (un) Decahydride-7,8-dicarboundecaborate) cubate (cuprate) (II
I), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) aurate (metal salt) (III), tri (n-butyl) ammonium bis (nonahydride-7,8- Dimethyl-7,8-dicarboundecaborate) ferrate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecaborate) chromate (chromate) ( III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarboundecaborate) cobaltate (III), tri (n-butyl)
Ammonium bis (dodecahydride dicarbadodecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) nickelate (III), tris [tri (n-butyl) ammonium] bis ( Undecahydride-7-carbaundecaborate) chromate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) manganate (I
V), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-cal) Bounce decaborate) nickelate (IV) and the like.

The above-mentioned compound [C] may be used in combination of two or more kinds. Organoaluminum compound [D] The organoaluminum compound [D] used in the present invention is:
For example, it can be represented by the following general formula (a).

R ⁵ _n AlX _3-n ... (a) (In the formula, R ⁵ is a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, and n is 1 to 1
3. In the above formula (a), R ⁵ is a hydrocarbon group having 1 to 12 carbon atoms, for example, an alkyl group, a cycloalkyl group or an aryl group, specifically, a methyl group, an ethyl group,
Examples include n-propyl group, isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group and tolyl group.

Specific examples of the organoaluminum compound include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum, and isoprenylaluminum. Alkenyl aluminum such as, dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride, diisobutyl aluminum chloride, dialkyl aluminum halides such as dimethyl aluminum bromide, methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, Ethyl aluminum Alkylaluminum sesquihalide such as Kiburomido, methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, alkyl aluminum dihalides such as ethyl aluminum dibromide, diethyl aluminum hydride, alkyl aluminum hydride such as diisobutylaluminum hydride and the like.

As the organoaluminum compound [D], a compound represented by the following formula (b) can also be used. During ^{_{R 5 n AlY 3-n ···}} (b) ( wherein, R ⁵ is the same as R ⁵ in the formula (a), Y is -OR ⁶ group, -OSiR ⁷ ₃ group, -OAlR ⁸ ₂
Group, -NR ⁹ ₂ group, -SiR ¹⁰ ₃ group or -N (R ¹¹⁾
A AlR ¹² ₂ group, n is 1~2, R ^6, R ^7,
R ⁸ and R ¹² are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, etc., and R ⁹ is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group, etc. And R ¹⁰ and R ¹¹ are a methyl group, an ethyl group or the like. ) Specific examples of such an organoaluminum compound include the following compounds.

(I) Compounds represented by R ⁵ _n Al (OR ⁶ ) _3-n , such as dimethyl aluminum methoxide, diethyl aluminum ethoxide and diisobutyl aluminum methoxide.

(Ii) A compound represented by R ⁵ _n Al (OSiR ⁷ ₃ ) _3-n , for example, (C ₂ H ₅ ) ₂ Al (OSi (C
H ₃ ) ₃ ), (iso-C ₄ H ₉ ) ₂ Al (OSi (C
_{H 3) 3), (iso} -C 4 H 9) 2 Al (OSi (C 2 H 5) 3)
Such.

(Iii) A compound represented by R ⁵ _n Al (OAlR ⁸ ₂ ) _3-n , such as (C ₂ H ₅ ) ₂ Al (OAl (C _{2
H 5) 2), (iso} -C 4 H 9) 2 Al (OAl (iso-C
₄ H _{9) 2),} etc..

(Iv) a compound represented by R ⁵ _n Al (NR ⁹ ₂ ) _3-n , such as (CH ₃ ) ₂ Al (N (C ₂ H ₅ ) ₂ ),
(C ₂ H ₅ ) ₂ Al (NH (CH ₃ )), (CH ₃ ) ₂ Al
_{(NH (C 2 H 5)} ), (C 2 H 5) 2 Al [N (Si (CH
₃ ) ₃ ) ₂ ], (iso-C ₄ H ₉ ) ₂ Al [N (Si (C
Such as H _{3) 3) 2].}

(V) A compound represented by R ⁵ _n Al (SiR ¹⁰ ₃ ) _3-n , for example, (iso-C ₄ H ₉ ) ₂ Al (Si (C
H ₃ ) ₃ ). In the present invention, also R ⁵ ₃ A Of these
_{^{l, R 5 n Al (OR}} 6) 3-n, R 5 n Al (OAlR 8 2)
Preferred examples include an organoaluminum compound represented by _3-n , wherein R ⁵ is an isoalkyl group,
Particularly preferred are compounds where n = 2. These organoaluminum compounds can be used in combination of two or more.

The specific metallocene catalyst used in the present invention contains the metallocene compound [A] as described above. For example, as described above, the metallocene compound [A] is used.
And an organic aluminum oxy compound [B]. It may be formed from a metallocene compound [A] and a compound [C] which reacts with the metallocene compound [A] to form an ion pair. Further, together with the metallocene compound [A], an organic aluminum oxy compound [B] is used. And a compound [C] which reacts with the metallocene compound [A] to form an ion pair. In these embodiments, it is particularly preferable to further use an organic aluminum compound [D] in combination.

In the present invention, the above metallocene compound [A]
Is generally used in an amount of about 0.00005 to 0.1 mmol, preferably about 0.0001 to 0.05 mmol, in terms of transition metal atoms per liter of polymerization volume.

Organoaluminum oxy compound [B]
Is usually about 1 to 10,000 moles, preferably 10 to 10 moles of aluminum atoms per mole of transition metal atom.
It can be used in an amount such that it is 5,000 mol.

The compound [C] which reacts with the metallocene compound [A] to form an ion pair has a boron atom in an amount of usually about 0.5 to 20 mol, preferably 1 to 1 mol of the transition metal atom. It is used in an amount such that it is 10 mol.

Further, the organoaluminum compound [D] is
It is usually about 0-1,000 mol, preferably about 0-500 mol, per 1 mol of boron atoms in the compound [C] forming an aluminum atom or an ion pair in the organic aluminum oxy compound [B]. Such amounts are used as needed.

Using the metallocene catalyst as described above,
Ethylene, an α-olefin having 3 to 20 carbon atoms,
By copolymerizing with a non-conjugated polyene, an ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) can be obtained with excellent polymerization activity.

Even if ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene are copolymerized by using a Group VB transition metal compound-based catalyst such as a vanadium-based catalyst, sufficient polymerization is possible. Copolymer rubber cannot be obtained because it is active.

In addition, when producing, for example, EPDM using a Group VB transition metal compound-based catalyst, the type of non-conjugated polyene is often limited to norbornene ring-containing polyenes such as ENB.

On the other hand, when the metallocene catalyst is used as in the present invention, the non-conjugated polyene is not limited to norbornene ring-containing polyenes, and various polyenes such as those mentioned above, such as 7-methyl-1,6. -Chain non-conjugated polyenes such as methyl octadiene (MOD) such as octadiene can also be copolymerized.

In the present invention, ethylene and 3 to 3 carbon atoms are used.
When the α-olefin of No. 20 and the non-conjugated polyene are copolymerized, the metallocene compound [A], the organoaluminum oxy compound [B], which constitute the metallocene catalyst,
The compound [C] forming the ion pair and the organoaluminum compound [D] may be separately supplied to the polymerization reactor, or a metallocene catalyst containing the metallocene compound [A] may be prepared in advance. May be subjected to a copolymerization reaction.

When preparing the metallocene catalyst,
A hydrocarbon solvent which is inert to the reaction with the catalyst component can be used. Specific examples of the inert hydrocarbon solvent include aliphatic solvents such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene. Hydrocarbon, cyclopentane, cyclohexane, alicyclic hydrocarbons such as methylcyclopentane, benzene, toluene, aromatic hydrocarbons such as xylene, ethylene chloride, chlorobenzene,
Halogenated hydrocarbons such as dichloromethane can be used. These hydrocarbon solvents can be used alone or in combination.

The metallocene compound [A], the organoaluminum oxy compound [B], the compound [C] forming an ion pair and the organoaluminum compound [D] are usually
Mixing contact can be performed at 100 to 200 ° C, preferably -70 to 100 ° C.

In the present invention, ethylene and 3 to 10 carbon atoms are used.
The copolymerization of an α-olefin of 20 and a non-conjugated polyene is usually carried out at 40 to 200 ° C, preferably 50 to 150 ° C,
Particularly preferably, at 60 to 120 ° C. and at atmospheric pressure to 100 kg /
cm ^2, preferably atmospheric pressure to 50 kg / cm ^2, particularly preferably be carried out under the conditions of atmospheric pressure 30 kg / cm ^2.

This copolymerization reaction can be carried out by various polymerization methods, but solution polymerization is preferred. At this time, the above-mentioned hydrocarbon solvent can be used as the polymerization solvent.

The copolymerization can be carried out by any of batch method, semi-continuous method and continuous method, but continuous method is preferred. Further, the polymerization can be carried out in two or more stages by changing the reaction conditions.

Further, ethylene / α-used in the present invention
The olefin / non-conjugated polyene copolymer rubber (A) can be obtained by the method as described above. The molecular weight of the copolymer rubber (A) can be adjusted by changing the polymerization conditions such as the polymerization temperature. It can also be controlled by controlling the amount of hydrogen (molecular weight modifier) used.

Ethylene / Propylene Copolymer Rubber (B) The ethylene / propylene copolymer rubber (B) used in the present invention is basically composed of ethylene and propylene, and further contains a non-conjugated polyene as a constituent component. You may contain a component.

The ethylene / propylene copolymer rubber (B) used in the present invention has a molar ratio of ethylene and propylene (ethylene / propylene) of 50/50 to 9
5/5, preferably 55/45 to 93/7, more preferably 60/40 to 91/9.

Specific examples of the non-conjugated polyene component include 1,4-hexadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene and 5-isopropenyl.
-2-norbornene, dicyclopentadiene and the like are mentioned, and among them, 5-ethylidene-2-norbornene and dicyclopentadiene are preferably used.

The content of these non-conjugated polyene components is
The iodine value is 1 to 50, preferably 4 to 40, more preferably 6 to 30, and the mol% is 0.1.
It is -10 mol%, preferably 0.5-7 mol%, more preferably 1-5 mol%.

The intrinsic viscosity [η] of the ethylene / propylene copolymer rubber (B) used in the present invention measured in a decalin solvent at 135 ° C. is 0.8 to 5 dl / g, preferably 0.9 to 4 dl. / G, more preferably 1.0 to 3d
1 / g. If the intrinsic viscosity [η] exceeds 5 dl / g, the processability of the obtained rubber composition tends to be poor,
On the other hand, when the intrinsic viscosity [η] is less than 0.8 dl / g, the strength and physical properties of the obtained rubber composition tend to deteriorate.

Vulcanizable Rubber Composition The vulcanizable rubber composition according to the present invention comprises the above-mentioned ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and ethylene / propylene copolymer rubber ( B) and are contained.

In the present invention, ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and ethylene /
The blending ratio with the propylene copolymer rubber (B) is 5/95 to 95/5 by weight ratio [(A) / (B)], preferably 10/90 to 95/5, more preferably 20/80. ~
It is 90/10.

The rubber composition according to the present invention contains SRF, G
PF, FEF, HAF, ISAF, SAF, FT, MT
Such as carbon black, rubber reinforcing agents such as finely divided silicic acid, and light calcium carbonate, heavy calcium carbonate,
You may mix | blend fillers, such as talc, clay, and silica. The type and blending amount of these rubber reinforcing agents and fillers can be appropriately selected depending on the application, but the blending amounts are usually ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and ethylene / The maximum amount is 300 parts by weight, preferably the maximum amount is 200 parts by weight, based on 100 parts by weight of the total amount of the propylene copolymer rubber (B).

The rubber composition according to the present invention can be used as it is in an unvulcanized state, but when it is used as a vulcanized product (vulcanized rubber), it can exhibit its characteristics most. When a vulcanized product is obtained from the rubber composition according to the present invention, the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and the ethylene / propylene copolymer are added depending on the intended use and performance of the vulcanized product. In addition to the united rubber (B), a rubber reinforcing agent,
Types of fillers and softeners and their amounts, vulcanizing agents,
Type of vulcanization compound such as vulcanization accelerator and vulcanization aid and its amount, antioxidant, processing aid type and its amount, and the step of producing a vulcanized product are appropriately selected. it can.

The total amount of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and the ethylene / propylene copolymer rubber (B) in the vulcanizate is the performance and intended use of the vulcanizate. Although it can be appropriately selected depending on the above, it is usually 20% by weight or more, preferably 25% by weight or more.

As the softening agent, a softening agent usually used for rubber can be used. Specifically, petroleum softeners such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, and petrolatum; coal tar,
Coal tar softeners such as coal tar pitch; Fat oil softeners such as castor oil, linseed oil, rapeseed oil and coconut oil; tall oil; sub; waxes such as beeswax, carnauba wax and lanolin; ricinoleic acid, palmitin Examples thereof include fatty acids and fatty acid salts such as acids, barium stearate, calcium stearate and zinc laurate; and synthetic polymer substances such as petroleum resin, atactic polypropylene and coumarone indene resin. Among them, a petroleum softener is preferably used, and particularly, a process oil is preferably used.

The blending amount of these softening agents can be appropriately selected depending on the use of the vulcanized product, but the blending amount is usually ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and ethylene / propylene. It is at most 150 parts by weight, preferably at most 100 parts by weight, based on 100 parts by weight of the total amount of the copolymer rubber (B).

In order to produce a vulcanized product from the rubber composition according to the present invention, an unvulcanized compounded rubber is once prepared and then this compounded rubber is prepared in the same manner as in the case of vulcanizing a general rubber. Vulcanization may be performed after molding into the intended shape.

As the vulcanization method, either a method of heating using a vulcanizing agent or a method of irradiating with an electron beam may be adopted. Examples of the vulcanizing agent used during vulcanization include sulfur compounds and organic peroxides. In particular, when a sulfur compound is used, the performance of the rubber composition according to the present invention can be best exhibited.

Specific examples of the sulfur compounds include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide and selenium dimethyldithiocarbamate. Of these, sulfur is preferably used.

Sulfur compounds include ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and ethylene /
It is used in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the total amount of the propylene copolymer rubber (B).

When a sulfur compound is used as a vulcanizing agent, it is preferable to use a vulcanization accelerator together. Specific examples of the vulcanization accelerator include N-cyclohexyl-2-benzothiazolesulfenamide, N-oxydiethylene
-2-Sulfenamide compounds such as benzothiazole sulfenamide and N, N-diisopropyl-2-benzothiazole sulfenamide; 2-mercaptobenzothiazole, 2- (2,4-dinitrophenyl) mercaptobenzothiazole, Thiazole compounds such as 2- (2,6-diethyl-4-morpholinothio) benzothiazole, dibenzothiazyl disulfide; diphenylguanidine, triphenylguanidine, diorsonitrile guanidine, orthonitrile biguanide, diphenylguanidine phthalate Guanidine compounds; acetaldehyde-aniline reaction products, butyraldehyde-aniline condensates, hexamethylenetetramine, aldehyde amines such as acetaldehyde ammonia, or aldehyde-ammonia compounds; 2-
Imidazoline compounds such as mercaptoimidazolines; thiourea compounds such as thiocarbanilide, diethylthiourea, dibutylthiourea, trimethylthiourea, diorsotolylthiourea; tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutyl Thiuram compounds such as thiuram disulfide and pentamethylene thiuram tetrasulfide; zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate,
Examples thereof include dithioate-based compounds such as sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, and tellurium dimethyldithiocarbamate; xanthate-based compounds such as zinc dibutylxanthate; compounds such as zinc white.

These vulcanization accelerators were added in an amount of 0.1 parts by weight based on 100 parts by weight of the total amount of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and the ethylene / propylene copolymer rubber (B). 1 to 20 parts by weight, preferably 0.2 to
Used in an amount of 10 parts by weight.

The organic peroxide may be any compound that is usually used for peroxide vulcanization of rubber. For example, dicumyl peroxide, di-t-butyl peroxide,
Di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butyl hydroperoxide, t-butylcumyl peroxide, benzoyl peroxide, 2,5-dimethyl-2,5-di (t-butyl Peroxin) hexyne-3,2,
5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-mono (t-butylperoxy)-
Hexane, α, α′-bis (t-butylperoxy-m-isopropyl) benzene and the like can be mentioned. Among them, dicumyl peroxide, di-t-butyl peroxide, di-
-T-Butylperoxy-3,3,5-trimethylcyclohexane is preferably used. These organic peroxides can be used alone or in combination of two or more.

The organic peroxide is 0.0003 to 0. 05 mol, preferably 0.00
It is used in the range of 1 to 0.03 mol, but it is desirable to appropriately determine the optimum amount according to the required physical property values.

When an organic peroxide is used as a vulcanizing agent, it is preferable to use a vulcanizing auxiliary together. Specific examples of vulcanization aids include sulfur; quinone dioxime compounds such as p-quinone dioxime; methacrylate compounds such as polyethylene glycol dimethacrylate; allyl compounds such as diallyl phthalate and triallyl cyanurate; Other examples include maleimide compounds; divinylbenzene and the like.

Such a vulcanization aid is used in an amount of 0.5 to 2 mol, preferably about equimolar, relative to 1 mol of the organic peroxide used. When an electron beam is used as a vulcanizing method without using a vulcanizing agent, 0.1 to 10 MeV, preferably 0.3 to
The absorbed dose of an electron beam having an energy of 2 MeV is 0.
Irradiation may be performed at 5 to 35 Mrad, preferably 0.5 to 10 Mrad.

The unvulcanized compounded rubber is prepared, for example, by the following method. That is, an ethylene / α-olefin / non-conjugated polyene copolymer rubber (A), an ethylene / propylene copolymer rubber (B), a filler, and a softening agent are mixed with an internal mixer such as a Banbury mixer, a kneader, or an intermix. 3 ~ at a temperature of 80-170 ℃
After kneading for 10 minutes, a roll such as an open roll is used to additionally mix a vulcanizing agent and, if necessary, a vulcanization accelerator or vulcanization aid, and a roll temperature of 40 to 80 ° C. for 5 to 3
After kneading for 0 minutes, dispensing is performed to prepare a ribbon-shaped or sheet-shaped compounded rubber.

The compounded rubber thus prepared is molded into an intended shape by an extruder, a calender roll, or a press. The vulcanized product can be obtained by heating at the temperature of 1 to 30 minutes or by irradiating with an electron beam by the method described above. In this vulcanization step, a mold may be used, or vulcanization may be performed without using a mold. When a mold is not used, the molding and vulcanization steps are usually carried out continuously. As a heating method in the vulcanization tank, a heating tank such as hot air, a fluidized bed of glass beads, UHF (ultra-high frequency electromagnetic wave), or steam can be used.
Of course, when vulcanization is performed by electron beam irradiation, compounded rubber containing no vulcanizing agent is used.

The vulcanized rubber molded and vulcanized as described above includes weather strips, door glass run channels, window frames, radiator hoses, brake parts, automobile industrial parts such as wiper blades, rubber rolls, belts, packings, hoses. Industrial rubber products such as, anode caps, electrical insulating materials such as grommets, construction gaskets, civil engineering materials such as civil engineering sheets, rubberized cloth, etc.

Further, in the case of producing a foam from the vulcanizable rubber composition according to the present invention, it can be produced by adding a foaming agent usually used for rubber and, if necessary, a foaming aid. .

As the foaming agent, a foaming agent generally used for foam-molding rubber can be widely used. Specifically, sodium bicarbonate, sodium carbonate,
Inorganic foaming agents such as ammonium bicarbonate, ammonium carbonate and ammonium nitrite, nitroso compounds such as N, N'-dimethyl-N, N'-dinitrosoterephthalamide, N, N'-dinitrosopentamethylenetetramine, azodicarbonamide , Azo compounds such as azobisisobutyronitrile, azocyclohexylnitrile, azodiaminobenzene, barium azodicarboxylate, benzenesulfonyl hydrazide, toluenesulfonyl hydrazide, p, p'-oxybis (benzenesulfonyl hydrazide), diphenyl sulfone-3 Examples thereof include sulfonyl hydrazide compounds such as 3,3′-disulfonyl hydrazide, azide compounds such as calcium azide, 4,4-diphenyldisulfonyl azide, and p-toluenesulphonyl azide.

Of these, nitroso compounds, azo compounds and azide compounds are preferable. The foaming agent is ethylene / α-olefin / non-conjugated polyene copolymer rubber (A)
Further, it can be used in an amount of 0.5 to 30 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the total amount of the ethylene / propylene copolymer rubber (B). From the rubber composition containing the foaming agent in such an amount, a foam having an apparent specific gravity of 0.03 to 0.8 g / cm ³ can be produced.

A foaming aid can be used together with the foaming agent. When the foaming aid is used in combination, the effects of lowering the decomposition temperature of the foaming agent, accelerating the decomposition, homogenizing the bubbles and the like can be obtained. Examples of such a foaming aid include organic acids such as salicylic acid, phthalic acid, stearic acid and oxalic acid, urea and derivatives thereof.

The foaming aid is ethylene / α-olefin /
Based on 100 parts by weight of the non-conjugated polyene copolymer rubber (A) and the ethylene / propylene copolymer rubber (B),
It can be used in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight.

The vulcanized foam obtained by heat-foaming a rubber compound containing the above-mentioned foaming agent and, if necessary, a foaming aid is used for heat insulating materials, cushioning materials, sealing materials and the like. You can

[0115]

The vulcanizable rubber composition according to the present invention is
In a molecule, ethylene, an α-olefin having 3 to 20 carbon atoms, and a carbon-carbon double bond which is polymerizable with the catalyst among the carbon-carbon double bonds prepared using a metallocene catalyst Is a random copolymer consisting of only one non-conjugated polyene present in, and the molar ratio of the unit derived from ethylene to the unit derived from an α-olefin having 3 to 20 carbon atoms, iodine value, and Ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) having a viscosity [η] and gη ^* within a specific range, and ethylene / propylene copolymer weight consisting of ethylene, propylene and, if necessary, non-conjugated polyene Since the compounded rubber (B) is contained in a specific ratio, it is possible to provide a vulcanized rubber having excellent strength characteristics, heat aging resistance, weather resistance, and ozone resistance. Further, this vulcanizable rubber composition is excellent in processability (moldability).

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In addition, ethylene and α in Examples and Comparative Examples
-The olefin / non-conjugated polyene copolymer rubber composition and the vulcanized rubber are evaluated and tested as follows. [1] Physical Property Test of Unvulcanized Rubber The physical property test of unvulcanized rubber was performed according to JIS K6300.

[2] Tensile test <Rubber sheet> A vulcanized rubber sheet was punched out and JIS K was used.
No. 3 dumbbell test piece described in 6301 was prepared, and the test piece was used in accordance with the method specified in JIS K 6301 Item 3 under the conditions of a measurement temperature of 25 ° C. and a pulling speed of 500 mm / min. A tensile test was performed to measure the stress at tensile break (T _B ) and the elongation at tensile break (E _B ). <Sponge Rubber> A vulcanized tubular sponge was punched out in the length direction with a No. 3 type dumbbell described in JIS K 6301 (1989) to obtain a test piece. Using this test piece, the measuring temperature was 25 ° C. and the pulling speed was 500 m according to the method specified in the same JIS K 6301 item 3.
Tensile test was carried out under the condition of m / min, and the stress at tensile break (T
_B ) and tensile elongation at break (E _B ) were measured. [3] Hardness test Hardness test in accordance with JIS K 6301 spring hardness; was measured (H _S JISA hardness).

[4] Evaluation of extrudability Using a extruder equipped with a circular die having a diameter of 3 mm (cylinder temperature 70 ° C., head temperature 80 ° C., die temperature 90 ° C.), compounded rubber was extruded at an extrusion speed of 30 m / min. The extruded skin was evaluated according to the following 5 grades. The amount of compounded rubber extruded in 10 seconds was taken as the extruded amount. <Five-step evaluation of extruded skin> 5 ・ ・ ・ Very smooth 4 ・ ・ ・ ・ ・ Slightly smooth 3 ・ ・ ・ Not smooth but not jagged 2 ・ ・ ・ Slightly jagged Yes 1 ・ ・ ・ Very jagged

[5] Measurement of specific gravity of sponge rubber 20 mm × 20 from the top of the vulcanized tubular sponge
mm test piece is punched out, and dirt on the surface is wiped off with alcohol. This test piece was attached to an automatic specific gravity meter [M-1 type manufactured by Toyo Seiki Seisaku-sho, Ltd.] in an atmosphere of 25 ° C., and specific gravity was measured from the difference in mass between air and pure water.

[6] Sponge rubber compression set test A vulcanized tubular sponge is cut into a length of 30 mm and attached to a compression device (device described in JIS K 6301). The test piece was compressed so that the height of the test piece was ½ of the height before the load was applied, and the mold and the mold were heat-treated in a gear oven at 70 ° C. for 200 hours. Then, the heat-treated test piece was taken out from the compression device, allowed to cool for 30 minutes, the height of the test piece was measured, and the compression set was calculated by the following formula. Compression set _{(%) = [(t O} -t 1) / (t O -t
₂ )] × 100 t _O : Height before test of test piece t ₁ : After heat treatment of test piece and removal from compression device 3
Height of test piece after being left to cool for 0 minutes t ₂ : Height of test piece attached to measurement mold

[7] Test of shape retention of sponge rubber The height and width of the cross section of the vulcanized tubular sponge were measured,
The ratio of this height to the width was defined as the shape retention rate. Shape retention rate [%] = (L / D) × 100 L: Height of tubular sponge D: Width of tubular sponge

[0122]

[Reference example 1]

[0123]

Embedded image

Rac-Dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride Zirconium compound and methylalumoxane are pre-contacted.
And preparation of catalyst solution A predetermined amount of the zirconium compound represented by the above formula and a toluene solution of methylalumoxane (1.2 milligram atom / ml in terms of aluminum atom) are stirred for 30 minutes at room temperature in the dark. The resulting mixture was mixed to prepare a toluene solution in which the zirconium compound and methylalumoxane were dissolved. The Zr concentration of this toluene solution is 0.002 mmol / ml, and the methylalumoxane concentration is 1.2 mg atom / ml in terms of aluminum atom. Then, to this toluene solution, hexane, which is 5 times the solution of toluene, is added under stirring to prepare a catalyst solution having the following Zr concentration and methylalumoxane concentration, which is used as a catalyst for polymerization reaction. Used as.

Zr concentration: 0.00033 mmol / ml
(= 0.33 mmol / l) Methylalumoxane concentration (converted to Al atom): 0.
20 mmol / ml (= 200 mmol / liter)

[0126] using a stainless steel polymerization vessel 15 liters of capacity, equipped with Polymerization stirring blade, and continuously ethylene, propylene, the copolymerization of 5-ethylidene-2-norbornene (hereinafter referred to as ENB), It was carried out in the presence of the above polymerization reaction catalyst.

That is, first, from the top of the polymerization vessel, into the polymerization vessel, 3.17 liters of dehydrated and purified hexane per hour, 0.03 liters per hour of the mixed solution of the above-mentioned zirconium compound and methylalumoxane, and a hexane solution of triisobutylaluminum were introduced. (Concentration 17 mmol / liter) 0.3 liter / hr, ENB in hexane (concentration 0.0
8 liter / liter) was continuously fed at 1.5 liter / hour.

Further, 220 liters of ethylene and 200 liters of propylene were continuously fed into the polymerization vessel from the upper portion of the polymerization vessel, respectively. This copolymerization reaction is
It was carried out at 65 ° C. and the average residence time was 1 hour (that is, 5 liters of polymerization scale).

Then, a small amount of methanol was added to the polymerization solution extracted from the lower part of the polymerization vessel to stop the polymerization reaction,
After separating the copolymer from the solvent by steam stripping, under conditions of 100 ° C. and reduced pressure (100 mmHg),
It was dried for 24 hours.

With the above operation, ethylene / propylene / E
82 g of NB copolymer rubber [copolymer rubber (A)] per hour
Was obtained in a quantity of.

The obtained copolymer had a molar ratio of ethylene-derived units to propylene-derived units (ethylene / propylene) of 67/33 and an iodine value of 1
2 (g-iodine / 100 g-polymer), 135
The intrinsic viscosity [η] measured in a decalin solvent at ℃ was 1.9.
dl / g. The gη ^* value was 0.69. Table 1 shows the results.

[0132]

[Reference Examples 2 to 7] An ethylene / α-olefin / non-conjugated polyene copolymer rubber [copolymer] was prepared in the same manner as in Reference Example 1 except that the copolymerization reaction was carried out under different polymerization conditions. Rubbers (B) to (G)] were produced.

Table 1 shows the molar ratio of units derived from ethylene and units derived from α-olefin, iodine value, intrinsic viscosity [η] and gη ^* value of these copolymer rubbers.

[0134]

[Reference Example 8] Using a 2-liter polymerization vessel equipped with a stirring blade, a copolymerization reaction of ethylene, propylene and 5-ethylidene-2-norbornene (ENB) was continuously carried out.

That is, from the upper part of the polymerization vessel into the polymerization vessel, EN
A hexane solution of B (concentration 18 g / liter) was added at an hourly rate of 0.
5 liters, 0.5 liters of a hexane solution of VO (OC ₂ H ₅ ) Cl ₂ (concentration 8 mmol / liter) as a catalyst, ethylaluminum sesquichloride [Al (C
₂ H ₅ ) _1.5 Cl _1.5 ] in a hexane solution (concentration: 64 mmol / l) at a rate of 0.5 liter / hour, and hexane at a rate of 0.5 liter / hour, respectively. Was continuously withdrawn so that the polymerization liquid of was always 1 liter.

Further, ethylene was supplied in an amount of 130 liters per hour, propylene was added in an amount of 170 liters per hour, and hydrogen was added in an amount of 60 liters per hour using a bubbling tube. The copolymerization reaction was carried out at a temperature of 20 ° C. by circulating a refrigerant in a jacket attached to the outside of the polymerization vessel.

When the copolymerization reaction was carried out under the above conditions,
A polymerization solution containing an ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber was obtained. Next, the obtained polymerization solution was decalcified with hydrochloric acid water, a large amount of methanol was added to precipitate the polymer, and the polymer was dried under reduced pressure at 100 ° C. for 24 hours.

Ethylene / propylene / 5-ethylidene-2-
Norbornene copolymer rubber [EPDM (A)] is 6 per hour
Obtained in an amount of 2 g. The obtained copolymer rubber has a molar ratio (ethylene / propylene) of units derived from ethylene and units derived from propylene of 69/31,
The iodine value was 12, and the intrinsic viscosity [η] measured in a 135 ° C. decalin solvent was 1.9 dl / g. Furthermore, the gη ^* value was 0.98.

As described above, it was found that when the vanadium-based catalyst was used, gη ^* showed a value close to 1, and long-chain branching was not formed.

[0140]

[Reference Example 9] An ethylene / propylene / ENB copolymer rubber [EPDM was prepared in the same manner as in Reference Example 8 except that the copolymerization reaction was carried out under different polymerization conditions.
(B)] was manufactured.

Table 1 shows the molar ratio of the units derived from ethylene and the units derived from propylene, the iodine value, the intrinsic viscosity [η] and the value of gη ^{* of} this copolymer rubber.

[0142]

[Table 1]

[0143]

Example 1 Ethylene / Propylene / ENB of Reference Example 1
80 parts by weight of copolymer rubber [copolymer rubber (A)], 20 parts by weight of EPDM (A) of Reference Example 1, 1 part by weight of stearic acid, 5 parts by weight of Zinc Hua No. 1, paraffin oil [trade name P -200, manufactured by Japan Energy Co., Ltd.] and 20 parts by weight of a filler and 100 parts by weight of a filler [trade name: Mistron Vapor Talc, manufactured by Nippon Mistron Co., Ltd.] by a Banbury mixer having a capacity of 1.7 liters (manufactured by Kobe Steel, Ltd.). Kneaded for 10 minutes.

Then, the kneaded material obtained as described above was mixed with 6 inch rolls (front roll temperature / back roll temperature = 6).
0 ° C./60° C.) and added to this kneaded product, 6.8 parts by weight of dicumyl peroxide (vulcanizing agent) and 3.5 parts of 4,4′-dibenzoylquinone dioxime (vulcanizing aid). By adding parts by weight, kneading and dispensing were performed to obtain a compounded rubber (rubber composition).

This compounded rubber was vulcanized by a press at 160 ° C. for 10 minutes to obtain a crosslinked rubber sheet having a thickness of 2 mm. Further, as a test piece for compression set, a right cylindrical test piece having a thickness of 12.7 mm and a diameter of 29 mm was obtained by vulcanizing the compounded rubber at 160 ° C. for 15 minutes.

Using the crosslinked rubber sheet and the test piece for compression set, the above-mentioned various physical property tests were conducted. Further, the extrudability was evaluated using the obtained compounded rubber. The results are shown in Table 2.

[0147]

Example 2 In Example 1, the copolymer rubber (A) and EPDM (A) were added in an amount of 60 parts by weight, respectively.
A crosslinked rubber sheet and a test piece for compression set were prepared in the same manner as in Example 1 except that the amount was 40 parts by weight, and the above-mentioned various physical property tests were conducted. Further, the extrudability was evaluated using the obtained compounded rubber. The results are shown in Table 2.

[0148]

Example 3 In Example 1, the ethylene / propylene / ENB copolymer rubber [copolymer rubber (B)] of Reference Example 2 was used in place of the copolymer rubber (A). A crosslinked rubber sheet and a test piece for compression set were prepared in the same manner as in Example 1 except that the compounding amounts of B) and EPDM (A) were 30 parts by weight and 70 parts by weight, respectively, and the various physical properties described above were prepared. The test was conducted. Further, the extrudability was evaluated using the obtained compounded rubber. The results are shown in Table 2.

[0149]

Example 4 The copolymer of Example 1 was replaced with the ethylene / 1-butene / ENB copolymer rubber [copolymer rubber (C)] of Reference Example 3 instead of the copolymer rubber (A). A crosslinked rubber sheet and a test piece for compression set were prepared in the same manner as in Example 1 except that the amounts of the rubber (C) and EPDM (A) compounded were 70 parts by weight and 30 parts by weight, respectively. Various physical property tests were conducted. Further, the extrudability was evaluated using the obtained compounded rubber. The results are shown in Table 2.

[0150]

Example 5 The copolymer of Example 1 was replaced with the ethylene / 1-octene / ENB copolymer rubber [copolymer rubber (D)] of Reference Example 4 instead of the copolymer rubber (A). A crosslinked rubber sheet and a test piece for compression set were prepared in the same manner as in Example 1 except that the amounts of the rubber (D) and EPDM (A) compounded were 70 parts by weight and 30 parts by weight, respectively. Various physical property tests were conducted. Further, the extrudability was evaluated using the obtained compounded rubber. The results are shown in Table 2.

[0151]

Comparative Example 1 In Example 1, the blending amounts of the copolymer rubber (A) and EPDM (A) were 0 parts by weight and 10 parts by weight, respectively.
A crosslinked rubber sheet and a test piece for compression set were prepared in the same manner as in Example 1 except that the amount was 0 part by weight, and various physical properties tests described above were performed. Further, the extrudability was evaluated using the obtained compounded rubber. The results are shown in Table 2.

[0152]

[Table 2]

[0153]

Example 6 Ethylene / Propylene / ENB of Reference Example 5
80 parts by weight of copolymer rubber [copolymer rubber (E)], 20 parts by weight of EPDM (B) of Reference Example 9, 70 parts by weight of paraffin oil [trade name Sunflex 2280, manufactured by Nippon San Oil Co., Ltd.] , SRF carbon black [Product name
Asahi 50HG, manufactured by Asahi Carbon Co., Ltd.] 90 parts by weight, stearic acid 2 parts by weight, dimethyl distearyl ammonium chloride 2 parts by weight, activated zinc white 5 parts by weight, and a volume of 1.7.
Liter Banbury mixer [Kobe Steel Co., Ltd.]
Was kneaded for 10 minutes.

Then, the kneaded material obtained as described above was mixed with 14 inch rolls (front roll temperature / back roll temperature =
50 (50 ° C / 50 ° C), and the kneaded product is further mixed with 1.5 parts by weight of sulfur (vulcanizing agent), 0.8 parts by weight of 2-mercaptobenzothiazole, and 2- (4'-morpholinodithio) benzothiazole. 1.2 parts by weight, dibutyldithiocarbamine-zinc zinc 2 parts by weight, ethylene urea 1 part by weight, p, p '
-Oxybis (benzenesulfonylhydrazide) 3.5
Parts by weight and 5 parts by weight of calcium oxide were added and kneaded to obtain a compounded rubber (rubber composition).

Next, this compounded rubber was extruded under the conditions of a die temperature of 80 ° C. and a cylinder temperature of 60 ° C. using a 50 mm extruder equipped with a tube-shaped die (inner diameter 10 m, wall thickness 1 mm) to form a tube. .

Next, the molded body obtained as described above was vulcanized in a hot air vulcanizing layer at 220 ° C. for 6 minutes to obtain a sponge rubber. Regarding the obtained sponge rubber,
Tensile test, specific gravity measurement, compression set test and shape retention test were conducted. The results are shown in Table 3.

[0157]

Example 7 In Example 6, the blending amounts of the copolymer rubber (E) and EPDM (B) were 60 parts by weight,
A sponge rubber was obtained in the same manner as in Example 6 except that the amount was 40 parts by weight. The obtained sponge rubber was subjected to a tensile test, a specific gravity measurement, a compression set test and a shape retention test. The results are shown in Table 3.

[0158]

Example 8 The copolymer of Example 6 was replaced with the ethylene / 1-butene / ENB copolymer rubber [copolymer rubber (F)] of Reference Example 6 instead of the copolymer rubber (E). A sponge rubber was obtained in the same manner as in Example 6 except that the amounts of the rubber (F) and EPDM (B) compounded were 30 parts by weight and 70 parts by weight, respectively. The obtained sponge rubber was subjected to a tensile test, a specific gravity measurement, a compression set test and a shape retention test. The results are shown in Table 3.

[0159]

[Example 9] In Example 6, the copolymer (F) of Reference Example 6 was used in place of the copolymer rubber (E), and the compounding amounts of the copolymer rubber (F) and EPDM (B) were respectively changed. 70
Sponge rubber was obtained in the same manner as in Example 6 except that 30 parts by weight and 30 parts by weight were used. The obtained sponge rubber was subjected to a tensile test, a specific gravity measurement, a compression set test and a shape retention test. The results are shown in Table 3.

[0160]

[Example 10] In Example 6, an ethylene / 1-octene / ENB copolymer rubber [copolymer rubber (G)] of Reference Example 7 was used instead of the copolymer (E). A sponge rubber was obtained in the same manner as in Example 6 except that the blending amounts of (G) and EPDM (B) were 70 parts by weight and 30 parts by weight, respectively. The obtained sponge rubber was subjected to a tensile test, a specific gravity measurement, a compression set test and a shape retention test. The results are shown in Table 3.

[0161]

Comparative Example 2 In Example 6, the blending amounts of the copolymer rubber (E) and EPDM (B) were 0 parts by weight and 10 parts by weight, respectively.
A sponge rubber was obtained in the same manner as in Example 6 except that the amount was 0 parts by weight. The obtained sponge rubber was subjected to a tensile test, a specific gravity measurement, a compression set test and a shape retention test. The results are shown in Table 3.

[0162]

[Table 3]

Front page continuation (72) Inventor Takashi Shirata 3 Chikusaigan, Ichihara-shi, Chiba Mitsui Oil Chemicals Co., Ltd. (72) Inventor Tetsuo Tojo 3 Chikusaigan, Ichihara-shi, Chiba Mitsui Oil Chemicals Incorporated (72) Inventor Toshiyuki Tsutsui 6-2 1-2 Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture Mitsui Petrochemical Co., Ltd. (72) Toshihiro Ane Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture 6-1-2, Mitsui Petrochemical Industry Co., Ltd.

Claims (4)

[Claims] 1. An ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) comprising ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene, and ethylene, propylene and, if necessary, a non-conjugated polyene. A vulcanizable rubber composition containing an ethylene / propylene copolymer rubber (B) comprising a conjugated polyene in a weight ratio [(A) / (B)] of 5/95 to 95/5, wherein the ethylene The α-olefin / non-conjugated polyene copolymer rubber (A) is a catalyst of ethylene, α-olefin having 3 to 20 carbon atoms, and carbon / carbon double bond in the presence of a metallocene catalyst. The carbon-carbon double bond that can be polymerized in (1) is obtained by random copolymerization with a non-conjugated polyene that is present in one molecule. (1) (a) A unit derived from ethylene and (b) 3 carbon atoms
A unit derived from an α-olefin of 20 to 60 at a molar ratio of 40/60 to 95/5 [(a) / (b)], (2) an iodine value of 1 to 50, and (3) ) Intrinsic viscosity [η] measured in decalin at 135 ° C
Is from 0.1 to 10 dl / g, and (4) the intrinsic viscosity [η] measured in (3) above and the ethylene content having the same weight average molecular weight (by light scattering method) as 70 are 70. Ratio of intrinsic viscosity [η] _blank of linear ethylene / propylene copolymer of mol% [gη ^* (= [η] /
[Η] _blank )] is 0.2 to 0.95. 2. The vulcanizable rubber composition according to claim 1, wherein the metallocene catalyst contains a metallocene compound represented by the following formula [I]: [In the formula, M is a transition metal of Group IVB of the periodic table, R ¹ is a hydrocarbon group having 1 to 6 carbon atoms, and R ² , R ⁴ , R ⁵ , and R ⁶ are respectively They may be the same or different and each is a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 6 carbon atoms, R ³ is an aryl group having 6 to 16 carbon atoms, and the aryl group is halogen. It may be substituted with an atom, a hydrocarbon group having 1 to 20 carbon atoms, or an organic silyl group. X ¹
And X ² is a hydrogen atom, a halogen atom, or a carbon atom of 1
To a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group, Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, or a carbon atom number. 1-20 divalent halogenated hydrocarbon groups, divalent silicon-containing groups, divalent germanium-containing groups, -O-, -C
O -, - S -, - SO -, - SO 2 -, - NR 7 -, -
^{P (R 7) -, -} P (O) (R 7) -, - BR 7 - or -AlR ⁷ - a. (However, R ⁷ is a hydrogen atom,
A halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and a halogenated hydrocarbon group having 1 to 20 carbon atoms). ] 3. The intrinsic viscosity [η] of the ethylene / propylene copolymer rubber (B) measured in a 135 ° C. decalin solvent is in the range of 0.1 to 10 dl / g. The vulcanizable rubber composition according to 1 or 2. 4. The content of non-conjugated polyene in the ethylene / propylene copolymer rubber (B) is 0 to 5 in terms of iodine value.
The vulcanizable rubber composition according to any one of claims 1 to 3, which is in a range of 0.