JP3512536B2 - Vulcanizable rubber composition - Google Patents

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 having excellent weather resistance and ozone resistance and also has excellent processability (moldability).

[0002]

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 the molecular structure. Because it does not have a bond, it has better heat aging resistance, weather resistance, and ozone resistance than general-purpose conjugated diene rubbers, and it is used for automobile parts, electric wire materials, electric / electronic parts, building civil engineering materials, and industrial material parts. Widely used for such purposes.

However, with the recent high performance and high functionality of parts, further improvement in physical properties is required. In order to complicate parts and reduce processing costs, further improvement in workability is required. It has been demanded.

[0004] Extrudability, one of the processability of EPDM,
In particular, in order to improve the extrusion amount and the extruded skin, the viscosity of the compound may be reduced. However, if a large amount of oil is blended or the molecular weight of EPDM is extremely reduced in order to reduce the viscosity of the compound,
There arises a problem that the strength of the obtained vulcanized rubber product becomes low and it is not practical. It is also known to reduce the viscosity of the compound by broadening the molecular weight distribution and composition distribution.However, if the molecular weight distribution and composition distribution are broadened, the resulting vulcanized rubber product may have a sticky surface or a low temperature. There is a problem that the characteristics are deteriorated.

On the other hand, in order to improve the shape retention when extruding EPDM, the viscosity of the compound may be increased, but when the viscosity is increased, the extrusion amount of EPDM decreases,
There is a problem that the extruded skin becomes worse.

The present inventors can provide a vulcanized rubber excellent in strength properties, heat aging resistance, weather resistance and ozone resistance, and can be vulcanized excellent in processability (moldability). Extensive research has been conducted to obtain a rubber composition. It has been found that a vulcanizable rubber composition can be obtained, and the present invention has been completed.

[0007]

An object of the present invention is to solve the problems associated with the prior art as described above, and to provide a vulcanized rubber having excellent strength properties, heat aging resistance, weather resistance and ozone resistance. It is an object of the present invention to provide a vulcanizable rubber composition which can be processed and has excellent processability (moldability).

[0008]

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

The metallocene catalyst used in 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 , R ⁶ 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, and R ³ is an aryl group having 6 to 16 carbon atoms, and the 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 each} represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 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. , Divalent silicon-containing group, 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). The intrinsic viscosity [η] of the ethylene / propylene copolymer rubber (B) 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 Hereinafter, the vulcanizable rubber composition according to the present invention will be described in detail. 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 polyether
Copolymer rubber (A) The ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) used in the present invention is prepared by adding ethylene and α-C 3-20 carbon atoms in the presence of a metallocene catalyst. -Non-conjugated polyene in which only one olefin and one carbon-carbon double bond polymerizable by the catalyst among carbon-carbon double bonds are present in one molecule (hereinafter sometimes simply referred to as non-conjugated polyene) ) Are 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-C 3-10
Olefins are preferred, especially propylene, 1-butene, 1-
Hexene, 1-octene and the like are preferably used. The non-conjugated polyene is a non-conjugated polyene in which, among carbon-carbon double bonds, only one carbon-carbon double bond polymerizable by a metallocene catalyst exists in one molecule. Such non-conjugated polyenes do not include linear polyenes having vinyl groups at both ends. When one of the two or more vinyl groups is a terminal vinyl group, the other vinyl group preferably has an internal olefin structure instead of a terminal.

Examples of such a non-conjugated polyene include an aliphatic polyene and an alicyclic polyene. Specific examples of such an aliphatic polyene include 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,
6-undecadiene, 9-methyl-1,8-undecadiene and the like.

The alicyclic polyene is preferably a polyene composed of an alicyclic moiety having one unsaturated bond and a chain having an internal olefinic 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 can be mentioned. Among these non-conjugated polyenes, 5-ethylidene-2-norbornene, 1,4-hexadiene and the like are particularly preferred.

These non-conjugated polyenes can be used alone or in combination of two or more. The ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) used in the present invention has the following properties. (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. And a unit derived from an α-olefin of from 20 to 20 (hereinafter, also referred to simply as an α-olefin) from 40/60 to 95/5, preferably 55/45 to 90/10 [(a) / (b )]]. (2) Iodine value The ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) has an iodine value of 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 can be vulcanized at high speed. (3) Intrinsic viscosity [η] The intrinsic viscosity [η] of the 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 gη ^* value is the intrinsic viscosity [η] measured in the above (3),
A linear ethylene / propylene copolymer having the same weight average molecular weight (by the light scattering method) and an ethylene content of 70 mol% as the ethylene / α-olefin / non-conjugated polyene copolymer rubber having the intrinsic viscosity [η] Intrinsic viscosity [η]
Defined as the ratio to _blank .

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

If the gη ^* value of the ethylene / α-olefin / non-conjugated polyene copolymer rubber is 0.95 or less, it indicates that a long-chain branch 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. Indicates a low characteristic. Therefore, from the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) having the above gη ^* value, the processability such as kneading and molding is excellent, and the shape retention after molding and immediately before vulcanization is maintained. 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 and the like become insufficient, while when it is less than 0.2, the processability decreases. Sometimes.

The ethylene / α-olefin /
Non-conjugated polyene copolymer rubber (A) is prepared by adding ethylene and α-C 3-20 in the presence of a metallocene catalyst.
It can be obtained by random copolymerization of an olefin and a non-conjugated polyene.

The metallocene catalyst used in the present invention is:
It contains the following specific metallocene compound [A]. 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], the organoaluminum oxy compound [B] and / or the metallocene compound [A] And a compound [C] that forms an ion pair by reacting with the compound [C]. Further, a metallocene compound [A], an organic aluminum oxy compound [B] and / or
Alternatively, it may be formed from an organic aluminum 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, a compound represented by the following general formula [I] is used as the metallocene compound [A].

[0028]

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

Of these, a primary alkyl group bonded to an indenyl group is preferred, and a C 1 -C 1 alkyl group is preferred.
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 , R ⁶ may be the same or different, and may be the same as a hydrogen atom, a 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. This aryl group may be substituted with a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an organic silyl group.

Examples of the aryl group include phenyl, α-naphthyl, β-naphthyl, anthracenyl, phenanthryl, pyrenyl, acenaphthyl, phenalenyl, aceanthrenyl, tetrahydronaphthyl, Examples include an indanyl group and a biphenylyl group. Of these, a phenyl group, a naphthyl group,
Anthracenyl and phenanthryl groups are preferred.

The hydrocarbon group having 1 to 20 carbon atoms which is a substituent of the aryl group includes, for example, methyl, ethyl, propyl, butyl, hexyl,
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 and cyclohexenyl group, benzyl group, phenylethyl group, phenylpropyl group, etc. And the aryl groups exemplified above, and aryl groups such as a tolyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a propylphenyl group, a methylnaphthyl group, and a benzylphenyl group.

The organic silyl group includes a trimethylsilyl group, a triethylsilyl group and a triphenylsilyl group. 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 by halogen, an oxygen-containing group or a sulfur-containing group. Specific examples include the same halogen atoms and hydrocarbon groups as described above.

Further, as the oxygen-containing group, specifically,
Hydroxy group, methoxy group, ethoxy group, propoxy group, alkoxy group such as butoxy, phenoxy group, methylphenoxy group, dimethylphenoxy group, aryloxy group such as naphthoxy group, phenylmethoxy group, arylalkoxy group such as phenylethoxy group and the like. No.

Examples of the sulfur-containing group include a substituent in which the oxygen of the oxygen-containing group is replaced with sulfur, a methylsulfonate group, a trifluoromethanesulfonate group,
Phenylsulfonate, benzylsulfonate, p-toluenesulfonate, trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, pentafluorobenzenesulfonate Sulfonate group such as sulfonate group, methyl sulfinate group, phenyl sulfinate group, benzene sulfinate group, p-toluene sulfinate group, trimethylbenzene sulfinate group, pentafluorobenzene sulfinate group, etc. And the like.

Of these, X ¹ and X ² are preferably a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Y Y 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), 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; Halogenated hydrocarbon group obtained by halogenating a divalent hydrocarbon group of from 20 to 20; methylsilylene group, dimethylsilylene group, diethylsilylene group, di (n-propyl) silylene group, di (i-propyl) silylene group, Alkylsilylene groups such as (cyclohexyl) silylene group, methylphenylsilylene group, diphenylsilylene group, di (p-tolyl) silylene group, di (p-chlorophenyl) silylene group, Ylsilylene 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; 2 in which the silicon of the divalent silicon-containing group is replaced with germanium And a monovalent germanium-containing group.

R ⁷ is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms as described above. Among these, 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-dimethylsilylene-
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-naphthyl) 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) デ 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-biferinyl) 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) デ 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.

Further, there may be mentioned compounds in which zirconium in the above compounds is replaced with titanium or hafnium. In the present invention, a racemate of the above metallocene compound is usually used as a catalyst component, but an R-type or S-type may also be used.

In the present invention, two or more of the above metallocene compounds can 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, or as disclosed in JP-A-2-78687. Benzene-insoluble organic aluminum oxy compounds.

A conventionally known aluminoxane can be produced, for example, by the following method. (1) Compounds containing water of adsorption or salts containing water of crystallization such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerous chloride A method of adding an organoaluminum compound such as trialkylaluminum to a suspension of a hydrocarbon medium of Example 1 and reacting the suspension to recover a hydrocarbon solution. (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 in which an organoaluminum compound such as trialkylaluminum is reacted 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 an organic metal component. Alternatively, 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, trin-butylaluminum, triisobutylaluminum, trisec Trialkylaluminum such as -butylaluminum, tritert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum; tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum; dimethylaluminum chloride; Diethylaluminum 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.

Of these, trialkyl aluminum and tricycloalkyl aluminum are particularly preferred.
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-mentioned organoaluminum compounds can 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 aromatic hydrocarbons, aliphatic hydrocarbons, and halides of alicyclic hydrocarbons, especially chlorinated compounds and bromide compounds. Can be

Further, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons are particularly preferred. Reacts with metallocene compound [A] to form an ion pair
Compound [C] The compound [C] which forms an ion pair by reacting with the metallocene compound [A] used in the present invention is described in
JP-A-501950, JP-T1-5020236,
JP-A-3-179005, JP-A-3-179900
No. 6, JP-A-3-207703, JP-A-3-207703
Examples thereof include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in US Pat. No. 207704 and US Pat.

Examples of the Lewis acid include a 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. Specific examples of the Lewis acid containing a boron atom include compounds represented by the following general formula.

BR ¹ R ² R ³ (wherein 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 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,
Tris (3,5-dimethylphenyl) boron and the like. Of these, tris (pentafluorophenyl) boron is particularly preferred.

The ionic compound used in the present invention is a salt comprising a cationic compound and an anionic compound. The anion functions to cationize the metallocene compound [A] by reacting with the metallocene compound [A], thereby stabilizing 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 organic metal cation, a carbonium cation, a tripium cation, an oxonium cation, a sulfonium cation, a phosphonium cation, and an ammonium cation.
Specifically, triphenylcarbenium cation, tributylammonium cation, N, N-dimethylammonium cation, ferrocenium cation and the like can be exemplified.

In the present invention, an ionic compound having an organic boron compound anion is preferred. 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, tributylammoniumtetra (m, m-dimethylphenyl) boron, tributylammoniumtetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammoniumtetra (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, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentane) are used as the ionic compound containing a boron atom. Fluorophenyl) borate can also be mentioned.

Further, the following ionic compounds containing a boron atom can also be exemplified. (Note that the counter ion in the ionic compounds listed below is, but is not limited to, tri (n-butyl) ammonium.) Salts of anions, for example, 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 borane compounds, carborane complex compounds and salts of carborane anions include decaborane (14), 7,8-dicarboundecaborane (13), 2,2
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 undecahydride-8-butyl
-7,9-Dicarboundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-Dicarboundecaborate, tri (n-butyl) ammoniumundecahydride-9-trimethylsilyl-7 , 8-dicarboundecaborate, tri (n-butyl) ammoniumundecahydride-4,6-dibromo-7-carboundecaborate, and the like.

Examples of the carborane compound and the salt of carborane include 4-carbanonaborane (14), 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. Metal salt of carborane and metal borane anion 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-carboundecaborate) 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 decarborate) nickelate (IV) and the like.

The above compound [C] can 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) (wherein, 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
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, and 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 such an organoaluminum compound include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum and tri-2-ethylhexylaluminum, and isoprenylaluminum. Alkenylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dialkylaluminum halide such as dimethylaluminum bromide, methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, etc. 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.

Further, 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 , for example, dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide and the like.

[0064] _{^{(ii) R 5 n Al (}} OSiR 7 3) a compound represented by _3-n, e.g., _{(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.

[0065] _{^{(iii) R 5 n Al (}} OAlR 8 2) 3-n compound represented by, for example, _{(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..

[0066] _{^{(iv) R 5 n Al (}} NR 9 2) a compound represented by _3-n, e.g., _{(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),} such as. 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)
Suitable examples include an organoaluminum compound represented by _3-n , wherein R ⁵ is an isoalkyl group,
Compounds where n = 2 are particularly preferred. These organoaluminum compounds can be used in combination of two or more.

The specific metallocene-based catalyst used in the present invention contains the above-mentioned metallocene compound [A]. For example, as described above, the metallocene compound [A]
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] may be used. And a compound [C] that reacts with the metallocene compound [A] to form an ion pair. In these embodiments, it is particularly preferable to further use an organoaluminum compound [D].

In the present invention, the 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.

The organic aluminum 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 of 5,000 mol.

The compound [C] which forms an ion pair by reacting with the metallocene compound [A] has a boron atom of usually about 0.5 to 20 mol, preferably 1 to 20 mol per mol of the transition metal atom. It is used in an amount to give 10 moles.

Further, the organoaluminum compound [D] is
It is usually about 0-1,000 mol, preferably about 0-500 mol, per 1 mol of boron atom 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 above-mentioned metallocene catalyst,
Ethylene, an α-olefin having 3 to 20 carbon atoms,
When copolymerized 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 using a Group VB transition metal compound-based catalyst such as a vanadium-based catalyst, sufficient polymerization can be achieved. Activity makes it impossible to obtain a copolymer rubber.

In the case of 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 a metallocene-based catalyst is used as in the present invention, the non-conjugated polyene is not limited to norbornene ring-containing polyenes, but various polyenes as described above, for example, 7-methyl-1,6- -Chain non-conjugated polyenes such as methyloctadiene (MOD) such as octadiene can also be copolymerized.

In the present invention, ethylene and C 3 -C
When the α-olefin of No. 20 and a non-conjugated polyene are copolymerized, the above-mentioned metallocene compound [A], organoaluminum oxy compound [B] constituting a 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.

In preparing the metallocene catalyst,
A hydrocarbon solvent which is inactive with the catalyst component can be used. Specific examples of the inert hydrocarbon solvent include 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 at -70 to 100 ° C.

In the present invention, ethylene and C 3 -C
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 is preferably carried out by solution polymerization. At this time, as the polymerization solvent, the above-mentioned hydrocarbon solvent can be used.

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

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

Ethylene / Propylene Copolymer Rubber (B) The ethylene / propylene copolymer rubber (B) used in the present invention is basically composed of ethylene and propylene. Components may be contained.

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

The non-conjugated polyene component specifically includes 1,4-hexadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, and 5-isopropenyl.
Examples thereof include 2-norbornene and dicyclopentadiene, 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, and more preferably 6 to 30.
-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. When the intrinsic viscosity [η] exceeds 5 dl / g, the processability of the obtained rubber composition tends to be inferior,
On the other hand, when the intrinsic viscosity [η] is less than 0.8 dl / g, the strength properties of the obtained rubber composition tend to decrease.

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).

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

The rubber composition according to the present invention contains SRF, G
PF, FEF, HAF, ISAF, SAF, FT, MT
Rubber reinforcing agents such as carbon black, finely divided silica, and light calcium carbonate, heavy calcium carbonate, etc.
Fillers such as talc, clay and silica may be blended. The types and amounts of these rubber reinforcing agents and fillers can be appropriately selected depending on the application, but the amounts are usually ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and ethylene / α-olefin. It is at most 300 parts by weight, preferably at most 200 parts by weight, based on 100 parts by weight in total with 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), its properties can be exhibited most. When a vulcanizate 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 may be used in accordance with the intended use and performance of the vulcanizate. In addition to the united rubber (B), a rubber reinforcing agent,
Fillers, types and amounts of softeners, vulcanizing agents,
Appropriate selection of the type and compounding amount of vulcanization accelerators, vulcanization aids and other compounds constituting the vulcanization system, the type of antioxidant and processing aids and their compounding amounts, and the process of producing the vulcanized product 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 vulcanized product depends on the intended performance and application of the vulcanized product. Can be appropriately selected according to the above, but 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, petrolatum; coal tar,
Coal tar softener such as coal tar pitch; fatty oil softener such as castor oil, linseed oil, rapeseed oil, coconut oil; tall oil; sub; waxes such as beeswax, carnauba wax, lanolin; ricinoleic acid, palmitin Fatty acids and fatty acid salts such as acids, barium stearate, calcium stearate, and zinc laurate; and synthetic high molecular substances such as petroleum resins, atactic polypropylene, and coumarone indene resins. Among them, a petroleum softener is preferably used, and particularly, a process oil is preferably used.

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

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

As the vulcanizing method, either a method of heating using a vulcanizing agent or a method of irradiating an electron beam may be adopted. Examples of the vulcanizing agent used for vulcanization include a sulfur compound and an organic peroxide. 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 compound include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, selenium dimethyldithiocarbamate and the like. Of these, sulfur is preferably used.

The sulfur compound is composed of ethylene / α-olefin / non-conjugated polyene copolymer rubber (A)
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 with the propylene copolymer rubber (B).

When a sulfur compound is used as a vulcanizing agent, it is preferable to use a vulcanization accelerator in combination. Specific examples of the vulcanization accelerator include N-cyclohexyl-2-benzothiazolesulfenamide, N-oxydiethylene
Sulfenamide compounds such as -2-benzothiazolesulfenamide, N, N-diisopropyl-2-benzothiazolesulfenamide; 2-mercaptobenzothiazole, 2- (2,4-dinitrophenyl) mercaptobenzothiazole, Thiazole compounds such as 2- (2,6-diethyl-4-morpholinothio) benzothiazole and dibenzothiazyldisulfide; diphenylguanidine, triphenylguanidine, diorthonitrileguanidine, orthonitrile biguanide, diphenylguanidine phthalate and the like Guanidine compound; aldehyde amine such as acetaldehyde-aniline reactant, butyraldehyde-aniline condensate, hexamethylenetetramine, acetaldehyde ammonia or aldehyde-ammonia compound;
Imidazoline compounds such as mercaptoimidazoline; thiourea compounds such as thiocarbanilide, diethylthiourea, dibutylthiourea, trimethylthiourea, diorthotolylthiourea; tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutyl Thiuram compounds such as thiuram disulfide, pentamethylenethiuram tetrasulfide; zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate,
Dithioacid salt compounds such as sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, and tellurium dimethyldithiocarbamate; xanthate compounds such as zinc dibutylxanthogenate; and compounds such as zinc white.

These vulcanization accelerators are used in an amount of 0.1 parts by weight based on 100 parts by weight of the total 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 which 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. Among them, dicumyl peroxide, di-t-butyl peroxide,
-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 used in an amount of 0.0003 to 0.1% based on 100 g of the total of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) and the ethylene / propylene copolymer rubber (B). 05 mol, preferably 0.00
Although it is used in the range of 1 to 0.03 mol, 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 aid in combination. Specific examples of the vulcanization aid 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 maleimide compounds; divinylbenzene and the like.

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

An unvulcanized compounded rubber is prepared, for example, by the following method. That is, ethylene / α-olefin / non-conjugated polyene copolymer rubber (A), ethylene / propylene copolymer rubber (B), filler, and softener are mixed by internal mixers such as Banbury mixer, kneader and intermix. 80 ~ 170 ℃ 3 ~
After kneading for 10 minutes, using a roll such as an open roll, a vulcanizing agent and, if necessary, a vulcanization accelerator or a vulcanization aid are further mixed, and a roll temperature of 40 to 80 ° C and 5 to 3 are applied.
After kneading for 0 minutes, the mixture is dispensed 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 a temperature of 1 to 30 minutes or by irradiating 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 steps of molding and vulcanization are usually performed continuously. As a heating method in the vulcanizing 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, a compounded rubber containing no compounding agent is used.

The vulcanized rubber molded and vulcanized as described above is used for automobile industrial parts such as weather strips, door glass run channels, window frames, radiator hoses, brake parts, wiper blades, rubber rolls, belts, packings, hoses. And the like, electrical insulating materials such as anode caps and grommets, construction gaskets, civil engineering construction materials such as civil engineering sheets, and rubber cloth.

Further, when a foam is produced from the vulcanizable rubber composition according to the present invention, the foam can be produced by blending a foaming agent usually used for rubber and, if necessary, a foaming aid. .

[0110] As the foaming agent, a foaming agent generally used for foaming rubber can be widely used. Specifically, sodium bicarbonate, sodium carbonate,
Inorganic blowing 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, benzenesulfonylhydrazide, toluenesulfonylhydrazide, p, p'-oxybis (benzenesulfonylhydrazide), diphenylsulfone-3 And azide compounds such as calcium azide, 4,4-diphenyldisulfonyl azide, and p-toluenesulfonyl azide.

Among these, nitroso compounds, azo compounds and azide compounds are preferred. The blowing agent is ethylene / α-olefin / non-conjugated polyene copolymer rubber (A)
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, there are effects such as lowering the decomposition temperature of the foaming agent, accelerating the decomposition, and making the bubbles uniform. 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.
For 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 heating and foaming a rubber compound containing the above-mentioned foaming agent and, if necessary, a foaming aid is used for applications such as heat insulating materials, cushioning materials and sealing materials. Can be.

[0115]

The vulcanizable rubber composition according to the present invention comprises:
Ethylene prepared using a metallocene catalyst, an α-olefin having 3 to 20 carbon atoms, and a carbon-carbon double bond polymerizable by the catalyst among carbon-carbon double bonds are contained in one molecule. Is a random copolymer comprising only one non-conjugated polyene and a molar ratio of a unit derived from ethylene to a unit derived from an α-olefin having 3 to 20 carbon atoms, an iodine value, and a limit. Ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) having viscosity [η] and gη ^* in specific ranges, and ethylene / propylene copolymer comprising ethylene, propylene and, if necessary, non-conjugated polyene Since the coalesced rubber (B) is contained in a specific ratio, a vulcanized rubber excellent in strength properties, heat aging resistance, weather resistance and ozone resistance can be provided. The vulcanizable rubber composition is excellent in processability (moldability).

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples. The ethylene and α in Examples and Comparative Examples
-The evaluation test method of the olefin / non-conjugated polyene copolymer rubber composition and the vulcanized rubber is as follows. [1] Physical property test of unvulcanized rubber The physical property test of the unvulcanized rubber was performed in accordance with JIS K 6300.

[2] Tensile test <Rubber sheet> A vulcanized rubber sheet was punched out and JIS K
No. 3 type dumbbell test piece described in No. 6301 was prepared, and the test piece was used at a measurement temperature of 25 ° C. and a tensile speed of 500 mm / min in accordance with the method specified in JIS K 6301, paragraph 3. A tensile test was performed to measure the stress at break (T _B ) and the elongation at break (E _B ). <Sponge rubber> A test piece was obtained by punching out the upper part of the vulcanized tubular sponge in the length direction with a No. 3 type dumbbell described in JIS K6301 (1989). Using this test piece, a measurement temperature of 25 ° C. and a tensile speed of 500 m were applied in accordance with the method specified in JIS K 6301, Paragraph 3.
m / min, a tensile test was performed, and the tensile stress at break (T
_B ) and the 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 The compounded rubber was extruded at an extrusion speed of 30 m / min using an extruder (cylinder temperature 70 ° C., head temperature 80 ° C., die temperature 90 ° C.) equipped with a circular die having a diameter of 3 mm. The extruded skin was evaluated according to the following five grades. The amount of the compounded rubber extruded for 10 seconds was defined as the amount of extrusion. <5 grades of extruded skin> 5 ······ Very smooth 4 ····· Slightly smooth 3 ······ Not smooth but not jagged 2 ····· Slightly jagged 1 ... very jagged

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

[6] Compression set test of sponge rubber The vulcanized tubular sponge is cut into a length of 30 mm in the length direction and attached to a compression device (a device described in JIS K6301). The test piece was compressed so that the height became 1/2 of the height before applying a load, and the mold was heat-treated in a gear oven at 70 ° C. for 200 hours. Next, the heat-treated test piece was taken out of 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 of test piece before test t ₁ : 3 after heat treatment of test piece and removal from compression apparatus
Height t ₂ of test piece after cooling for 0 minute: Height of test piece attached to measurement mold

[7] Test for maintaining shape of sponge rubber The height and width of the cross-section of the vulcanized tubular sponge were measured.
The ratio between the height and the width was defined as the shape retention. Shape retention [%] = (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 Pre-contact of zirconium compound with methylalumoxane
And Preparation of Catalyst Solution A predetermined amount of a zirconium compound represented by the above formula and a toluene solution of methylalumoxane (1.2 mg atom / ml in terms of aluminum atom) are stirred in a dark place at room temperature for 30 minutes. To prepare a toluene solution in which the zirconium compound and methylalumoxane were dissolved. The Zr concentration of this toluene solution was 0.002 mmol / ml, and the methylalumoxane concentration was 1.2 mg atom / ml in terms of aluminum atoms. Then, to this toluene solution, hexane, which is a 5-fold solution of toluene, was added with stirring to prepare a catalyst solution having a Zr concentration and a methylalumoxane concentration as described below. Used as

Zr concentration: 0.00033 mmol / ml
(= 0.33 mmol / liter) Methylalumoxane concentration (in terms of 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), The reaction was carried out in the presence of the above polymerization catalyst.

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

Further, from the upper part of the polymerization vessel, ethylene was continuously supplied to the polymerization vessel at a rate of 220 liters / hour, and propylene was supplied continuously at a rate of 200 liters / hour. This copolymerization reaction is
The reaction was carried out at 65 ° C. and an average residence time of 1 hour (ie, a polymerization scale of 5 liters).

Next, a small amount of methanol was added to the polymerization solution withdrawn 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)
Dry for 24 hours.

By the above operation, ethylene / propylene / E
82 g / h of NB copolymer rubber [Copolymer rubber (A)]
Was obtained.

The copolymer obtained had a molar ratio of units derived from ethylene to units derived from propylene (ethylene / propylene) of 67/33 and an iodine value of 1
2 (g-iodine / 100 g-polymer), 135
The intrinsic viscosity [η] measured in decalin solvent at ℃ is 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)].

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

[0134]

REFERENCE EXAMPLE 8 A copolymerization reaction of ethylene, propylene and 5-ethylidene-2-norbornene (ENB) was continuously performed using a 2-liter capacity polymerization vessel equipped with a stirring blade.

That is, EN was introduced into the polymerization vessel from the top of the polymerization vessel.
B in a hexane solution (concentration: 18 g / l) at a rate of 0.1 hour / hour.
5 liters, 0.5 liters / hour of a hexane solution (concentration: 8 mmol / liter) of VO (OC ₂ H ₅ ) Cl ₂ as a catalyst, ethyl aluminum sesquichloride [Al (C
₂ H ₅ ) _1.5 Cl _1.5 ] in a hexane solution (concentration 64 mmol / L) was supplied at a rate of 0.5 L / h, and hexane was further supplied at a rate of 0.5 L / h. Was continuously withdrawn so that the polymerization solution of 1 was always 1 liter.

Further, into this polymerization vessel, ethylene was supplied at a rate of 130 liters / hour, propylene was supplied at a rate of 170 liters / hour, and hydrogen was supplied at a rate of 60 liters / hour using a bubbling tube. The copolymerization reaction was carried out at a temperature of 20 ° C. by circulating a refrigerant through a jacket attached to the outside of the polymerization vessel.

When a 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 demineralized with hydrochloric acid, and then a large amount of methanol was added to precipitate a polymer, followed by drying 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 of units derived from ethylene to units derived from propylene (ethylene / propylene) of 69/31,
The iodine value was 12, and the intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. was 1.9 dl / g. Further, the gη ^* value was 0.98.

As described above, when the vanadium catalyst was used, gη ^* showed a value close to 1, indicating that no long-chain branch was 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)].

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

[0142]

[Table 1]

[0143]

Embodiment 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 8, 1 part by weight of stearic acid, 5 parts by weight of Zinc Hua No. 1, paraffinic oil [trade name P -200, manufactured by Japan Energy Co., Ltd.] and 20 parts by weight of a filler [trade name: Mythrone Vaportalc, manufactured by Nippon Mistron Co., Ltd.] were mixed with a 1.7 liter Banbury mixer [manufactured by Kobe Steel Ltd.]. Kneaded for 10 minutes.

Next, the kneaded material obtained as described above was placed on a 6-inch roll (front roll temperature / back roll temperature = 6).
(0 ° C./60° C.) and further added 6.8 parts by weight of dicumyl peroxide (vulcanizing agent) and 3.5 parts of 4,4′-dibenzoylquinone dioxime (vulcanizing aid) to the kneaded material. A part by weight was added, kneaded and fractionated 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. A test piece for compression set was obtained by vulcanizing a compound rubber at 160 ° C. for 15 minutes at a temperature of 160 ° C. for a test piece having a thickness of 12.7 mm and a diameter of 29 mm.

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

[0147]

Example 2 In Example 1, the amounts of the copolymer rubber (A) and EPDM (A) were changed to 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 various physical properties tests described above were performed. 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 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 B) and EPDM (A) were changed to 30 parts by weight and 70 parts by weight, respectively. The test was performed. 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 by the ethylene / 1-butene / ENB copolymer rubber [Copolymer Rubber (C)] of Reference Example 3 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 amounts of the rubber (C) and EPDM (A) were changed to 70 parts by weight and 30 parts by weight, respectively. Various physical properties tests were performed. 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 by 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) were changed to 70 parts by weight and 30 parts by weight, respectively. Various physical properties tests were performed. The extrudability was evaluated using the obtained compounded rubber. The results are shown in Table 2.

[0151]

Comparative Example 1 In Example 1, the amounts of the copolymer rubber (A) and EPDM (A) were changed to 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 parts by weight, and the various physical properties tests described above were performed. The extrudability was evaluated using the obtained compounded rubber. The results are shown in Table 2.

[0152]

[Table 2]

[0153]

Embodiment 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, and 70 parts by weight of paraffinic oil [trade name: Sunflex 2280, manufactured by Nippon Sun 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, capacity 1.7
Liter Banbury mixer [Kobe Steel, Ltd.]
And kneaded for 10 minutes.

Next, the kneaded material obtained as described above was placed on a 14-inch roll (front roll temperature / back roll temperature =
(50 ° C./50° C.), and further added 1.5 parts by weight of sulfur (vulcanizing agent), 0.8 parts by weight of 2-mercaptobenzothiazole, 2- (4′-morpholinodithio) benzothiazole 1.2 parts by weight, zinc dibutyldithiocarbaminesan 2 parts by weight, ethylene urea 1 part by weight, p, p '
-Oxybis (benzenesulfonyl hydrazide) 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 at a die temperature of 80 ° C. and a cylinder temperature of 60 ° C. using a 50 mm extruder equipped with a tube 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 vulcanized layer at 220 ° C. for 6 minutes to obtain a sponge rubber. About the obtained sponge rubber,
A tensile test, a specific gravity measurement, a compression set test and a shape retention test were performed. The results are shown in Table 3.

[0157]

Example 7 In Example 6, the amounts of the copolymer rubber (E) and EPDM (B) were changed to 60 parts by weight, respectively.
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 by 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) were changed to 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 rubber (F) of Reference Example 6 was used instead of the copolymer rubber (E), and the blending amounts of the copolymer rubber (F) and EPDM (B) were respectively adjusted. 70
A sponge rubber was obtained in the same manner as in Example 6, except that the amount was 30 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.

[0160]

EXAMPLE 10 The copolymer rubber of Example 6 was replaced by the ethylene / 1-octene / ENB copolymer rubber [copolymer rubber (G)] of Reference Example 7 in place of the copolymer (E). A sponge rubber was obtained in the same manner as in Example 6, except that the amounts of (G) and EPDM (B) were changed to 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 amounts of the copolymer rubber (E) and EPDM (B) were each 0 parts by weight,
A sponge rubber was obtained in the same manner as in Example 6, except that the amount was 0 part 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]

Continued on the front page (72) Inventor Takashi Shirata 3 Chigusa Coast, Ichihara-shi, Chiba Mitsui Oil Chemical Industry Co., Ltd. (72) Inventor Toshiyuki Tsutsui 1-2-1, Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture Inside (72) Inventor Toshihiro Aine 6-Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture No. 1-2 in Mitsui Petrochemical Industry Co., Ltd. (56) References JP-A-58-191705 (JP, A) JP-A-3-122146 (JP, A) JP-A-3-200854 (JP, A) ( 58) Field surveyed (Int.Cl. ⁷ , DB name) C08L 23/00-23/36 C08F 4/64-4/658

Claims (5)

(57) [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 optionally a non-conjugated polyene. A vulcanizable rubber composition comprising a conjugated polyene and an ethylene / propylene copolymer rubber (B) at a weight ratio of 5/95 to 95/5 [(A) / (B)]. The α-olefin / non-conjugated polyene copolymer rubber (A) is composed of ethylene, an α-olefin having 3 to 20 carbon atoms,
Among carbon-carbon double bonds, carbon-carbon double bonds polymerizable with a metallocene catalyst are obtained by random copolymerization of only one non-conjugated polyene in one molecule, and (1) (a) a unit derived from ethylene and (b) a unit derived from an α-olefin having 3 to 20 carbon atoms in a molar ratio of 40/60 to 95/5 [(a) / (b)]. (2) an iodine value of 1 to 50, and (3) an intrinsic viscosity [η] measured in decalin at 135 ° C.
Is 0.1 to 10 dl / g, and (4) the intrinsic viscosity [η] measured in the above (3) and the ethylene content having the same weight average molecular weight (according to the light scattering method) are the same. 70 mol% of the linear ethylene / propylene copolymer intrinsic viscosity [η] ratio to _blank [gη ^* (= [η] /
[Η] _blank )] is from 0.59 to 0.95. 2. The vulcanizable rubber composition according to claim 1, wherein the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) is obtained in the presence of a metallocene catalyst. object. 3. The vulcanizable rubber composition according to claim 1, wherein the metallocene-based catalyst contains a metallocene compound represented by the following formula [I]: [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 each May be the same or different and are 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 a halogen atom; It may be substituted by an 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, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group; 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 - is. (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). ] 4. An ethylene / propylene copolymer rubber (B) having an intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. in the range of 0.1 to 10 dl / g. The vulcanizable rubber composition according to any one of claims 1 to 3. 5. The non-conjugated polyene content in the ethylene / propylene copolymer rubber (B) is from 0 to 5 in iodine value.
The vulcanizable rubber composition according to any one of claims 1 to 4, which is in the range of 0.