JP3483173B2 - Olefin-based thermoplastic elastomer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an olefin-based thermoplastic elastomer composition, and more particularly, to tensile strength,
The present invention relates to an olefin-based thermoplastic elastomer composition capable of providing a molded article having excellent breaking elongation and rubber elasticity.

[0002]

BACKGROUND OF THE INVENTION Olefin-based thermoplastic elastomers are widely used as energy-saving and resource-saving elastomers, especially as substitutes for vulcanized rubber for automobile parts, industrial machine parts, electronic / electric equipment parts, building materials and the like. I have.

[0003] Olefin-based thermoplastic elastomers can be classified into crosslinked and non-crosslinked types. Non-crosslinked thermoplastic elastomers have less variation in quality because they do not involve a crosslinking reaction, and are inexpensive to manufacture. In terms of elongation, permanent compression set) and heat resistance, the crosslinked olefin-based thermoplastic elastomer is superior to the non-crosslinked olefin-based thermoplastic elastomer. This is described by AYCoran et al. (Rubber Chemistry and Technology, 53 (1980),
It is widely known, as described in detail on page 141).

Non-crosslinked or partially crosslinked olefinic thermoplastic elastomers are described, for example, in JP-B-53-21021, JP-B-55-18448, JP-B-56-155741, and JP-B-56-15.
742, JP-B-58-46138, JP-B-58-56575, JP-B-59-30376, JP-B-62-938, and JP-B-62-5913.
No. 9 and the like.

As described above, olefin-based thermoplastic elastomers include non-cross-linked thermoplastic elastomers and cross-linked thermoplastic elastomers. In the case of non-cross-linked thermoplastic elastomers, conventionally known non-cross-linked thermoplastic elastomers are used. Olefin-based thermoplastic elastomer composition capable of providing a molded article having excellent tensile strength, elongation at break, rubber-like properties (elongation, compression set, etc.), heat resistance, low-temperature properties, etc., as compared with thermoplastic elastomers In the case of a crosslinked thermoplastic elastomer, it is desirable to provide a molded article having better low-temperature properties, tensile strength, elongation at break, and rubber-like properties than conventionally known vulcanized rubbers. There is a demand for the appearance of an olefin-based thermoplastic elastomer composition that can be used.

[0006]

The object of the present invention is to provide a non-crosslinked type having a tensile strength, elongation at break, rubbery properties and heat resistance,
An olefin-based thermoplastic elastomer which is excellent in low-temperature properties and, in the case of a crosslinked type, can provide a molded article having better low-temperature properties, tensile strength, elongation at break and rubber properties than conventional vulcanized rubber. It is to provide a composition.

Another object of the present invention is to provide a molded article having excellent properties as described above.
Another object of the present invention is to provide a completely crosslinked olefinic thermoplastic elastomer composition.

[0008]

SUMMARY OF THE INVENTION An olefinic thermoplastic elastomer composition (1) according to the present invention comprises a crystalline polyolefin resin (A) in an amount of 10 to 60 parts by weight, ethylene, α of 3 to 20 carbon atoms. Ethylene / α comprising an olefin and a non-conjugated polyene (excluding a branched polyene compound represented by the following general formula (a)):
-Olefin / non-conjugated polyene copolymer rubber (B) 90
To 40 parts by weight [the total amount of (A) and (B) is 100 parts by weight], wherein the ethylene / α-olefin / non-conjugated polyene copolymer rubber is used. (B) is prepared by adding ethylene and C3 to C2 in the presence of a metallocene catalyst belonging to Group IVB of the periodic table.
A) a unit derived from ethylene and (b) a unit derived from an α-olefin having 3 to 20 carbon atoms, which is obtained by random copolymerizing an α-olefin of 0 and a non-conjugated polyene. (2) iodine value is 1 to 50, (3) limit measured in decalin at 135 ° C. Viscosity [η]
But, 0.1~10dl / g der is, measurements in (4) above (3)
Intrinsic viscosity [η] and the same weight average molecular weight (light
Linear chain having an ethylene content of 70 mol%
Intrinsic viscosity of ethylene / propylene copolymer [η] blank
[Gη * (= [η] / [η] blank )] is 0.95
It is characterized in that the value exceeds .

Embedded image [In the formula (A), n is an integer of 1 to 5, R ¹ is an alkyl group having 1 to 5 carbon atoms, and R ² and R ³ are each independently a hydrogen atom or a carbon atom number. 1 to 5 alkyl groups. ]

[0009]

The ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) constituting the thermoplastic elastomer composition (1) has the following properties (1) to (4). ) T to Tαα in ¹³ C-NMR spectrum
αβ intensity ratio D (Tαβ / Tαα) is 0.5 or less; (6) B value obtained from ¹³ C-NMR spectrum and the following formula is 1.00 to 1.50; B value = [P _OE ] / (2 · [P _E ] · [P _O ]) (where [P _E ] is the content mole fraction of the unit derived from (a) ethylene in the random copolymer rubber. ,
[P _O ] is the content mole fraction of units derived from (b) α-olefin in the random copolymer rubber, and [P _OE ]
Is the total dyad in random copolymer rubber
(7) The glass transition temperature (Tg) determined by DSC is -5.
The temperature is preferably 0 ° C. or lower.

Further, the olefin-based thermoplastic elastomer composition (2) according to the present invention comprises a crystalline polyolefin resin (A) in an amount of 10 to 60 parts by weight, ethylene, α of 3 to 20 carbon atoms. -
Olefin and non-conjugated polyene (excluding the branched polyene compound represented by the above general formula (A))
/ Α-olefin / non-conjugated polyene copolymer rubber (B) consisting of 90 to 40 parts by weight [the total amount of (A) and (B) is 100 parts by weight] A substance, wherein the ethylene
α-olefin / non-conjugated polyene copolymer rubber (B)
Is a carbon-carbon double bond polymerizable with the catalyst in the presence of ethylene, an α-olefin having 3 to 20 carbon atoms, and a carbon-carbon double bond in the presence of a metallocene catalyst belonging to Group IVB of the Periodic Table. The bond is obtained by random copolymerization of a non-conjugated polyene having only one bond in one molecule, and (1) (a) a unit derived from ethylene and (b) α- having 3 to 20 carbon atoms. A unit derived from an olefin in a molar ratio of 40/60 to 95/5 [(a) / (b)], (2) an iodine value of 1 to 50, and (3) decalin at 135 ° C. Intrinsic viscosity [η] measured by
(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 Ratio [gη ^* (= [η] / [η]) to the intrinsic viscosity [η] _{blank of} mol% linear ethylene / propylene copolymer
_blank )) is 0.2 to 0.95.

The olefin-based thermoplastic elastomer composition according to the present invention is used in an amount of 100 parts by weight based on the total amount of the above-mentioned crystalline polyolefin resin (A) and ethylene / α-olefin / non-conjugated polyene copolymer rubber (B). hand,
2 to 100 parts by weight of softener (C) and / or 2 to 5
It may contain 0 parts by weight of the inorganic filler (D).

The olefin-based thermoplastic elastomer composition according to the present invention has a low-temperature property even when it is not crosslinked.
A molded article having excellent tensile strength, elongation at break, rubbery properties and heat resistance can be provided. In addition, the olefin-based thermoplastic elastomer composition according to the present invention, particularly when partially or completely crosslinked, has lower temperature properties, tensile strength, elongation at break and rubber-like properties than conventional vulcanized rubber. It is possible to provide a molded article excellent in the above.

[0014]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the olefin-based thermoplastic elastomer composition according to the present invention will be described in detail.

The olefin-based thermoplastic elastomer composition according to the present invention is a non-crosslinked thermoplastic elastomer composition or a partially or completely crosslinked thermoplastic elastomer composition, and comprises a crystalline polyolefin resin (A). And an ethylene / α-olefin / non-conjugated polyene copolymer rubber (B).

Crystalline polyolefin resin (A) Crystalline polyolefin resin (A) used in the present invention
Consists of a crystalline high molecular weight solid product obtained by polymerizing one or more monoolefins by either the high-pressure method or the low-pressure method. Such resins include, for example, isotactic and syndiotactic monoolefin polymer resins. These representative resins are commercially available.

Suitable starting olefins for the crystalline polyolefin resin (A) include, specifically, ethylene,
Propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 2-methyl-1-propene, 3-methyl-1
-Pentene, 4-methyl-1-pentene, 5-methyl-1-hexene and the like. These olefins are used alone or in combination of two or more.

The polymerization mode may be random or block, and any polymerization mode may be adopted as long as a resinous material is obtained. These crystalline polyolefin resins may be used alone or in combination of two or more.

The crystalline polyolefin resin (A) used in the present invention is an MFR (ASTMD 1238-65).
T, 230 ° C.) is usually in the range of 0.01 to 100 g / 10 min, particularly preferably 0.05 to 50 g / 10 min.

The above crystalline polyolefin resin (A) comprises:
It has a role in improving the fluidity and heat resistance of the composition. In the present invention, the crystalline polyolefin resin (A) is 10 parts by weight based on 100 parts by weight of the total amount of the crystalline polyolefin resin (A) and the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B). parts to 60 parts by weight or less, preferably used in a ratio of 20 to 55 parts by weight.

When the crystalline polyolefin resin (A) is used in the above proportion, an olefin-based thermoplastic elastomer composition having excellent rubber elasticity and excellent molding can be obtained.

Ethylene / α-olefin / non-conjugated polyether
Copolymer rubber (B) The ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) used in the present invention is prepared by reacting ethylene and carbon atoms in the presence of a specific metallocene catalyst as described later. It can be obtained by random copolymerizing an α-olefin of Formulas 3 to 20 and a non-conjugated polyene.

[0023] mentioned above, ethylene constituting the present invention engaging Luo olefin-based thermoplastic elastomer composition (1)
α-olefin / non-conjugated polyene copolymer rubber (B)
Has a linear molecular structure, and is related to the present invention.
Luo olefin-based thermoplastic elastomer composition (2) constituting the ethylene-alpha-olefin-nonconjugated polyene copolymer rubber (B) has a molecular structure of the branched long chain.

[Α-Olefin] 3 to 2 carbon atoms
Examples of the α-olefin of 0 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,
Examples include 11-methyl-1-dodecene, 12-ethyl-1-tetradecene, and combinations thereof.

Among these, α-α constituting the linear ethylene / α-olefin / non-conjugated polyene copolymer rubber
As the olefin, an α-olefin having 4 to 10 carbon atoms is preferable, and 1-butene, 1-hexene, 1-octene, 1-decene and the like are particularly preferably used.

The α-olefin constituting the long-chain branched ethylene / α-olefin / non-conjugated polyene copolymer rubber is preferably an α-olefin having 3 to 10 carbon atoms, especially propylene, 1-olefin. Butene, 1-hexene,
1-octene and the like are preferably used.

[Non-conjugated polyene] linear ethylene / α
-Examples of the non-conjugated polyene constituting the olefin / non-conjugated polyene copolymer rubber include an aliphatic polyene and an alicyclic polyene.

As the aliphatic polyene, specifically, 1,
4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 1,6-octadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,13-tetradecadiene, 1, Five,
9-decatriene, 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, 3,4-dimethyl
-1,5-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, 3-methyl-1,6-heptadiene, 4- Methyl-1,6
-Heptadiene, 4,4-dimethyl-1,6-heptadiene, 4-
Ethyl-1,6-heptadiene, 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, etc. Aliphatic polyene, vinylcyclohexene, vinylnorbornene, ethylidene norbornene, dicyclopentadiene,
Cyclooctadiene, 2,5-norbornadiene, 1,4-divinylcyclohexane, 1,3-divinylcyclohexane, 1,
3-divinylcyclopentane, 1,5-divinylcyclooctane, 1-allyl-4-vinylcyclohexane, 1,4-diallylcyclohexane, 1-allyl-5-vinylcyclooctane,
1,5-diallylcyclooctane, 1-allyl-4-isopropenylcyclohexane, 1-isopropenyl-4-vinylcyclohexane, 1-isopropenyl-3-vinylcyclopentane and the like.

Specific examples of the aromatic polyene include divinylbenzene and vinylisopropenylbenzene. In the present invention, among these, non-conjugated polyenes having 7 or more carbon atoms are preferable. Ethylidene norbornene (ENB), dicyclopentadiene (DCPD) and the like are preferably used.

These non-conjugated polyenes can be used alone or in combination of two or more. The non-conjugated polyene constituting the long-chain branched ethylene / α-olefin / non-conjugated polyene copolymer rubber is one of carbon / carbon double bonds which can be polymerized with a metallocene catalyst.
It is a non-conjugated polyene having only one carbon double bond 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.

As the alicyclic polyene, a polyene composed of an alicyclic portion having one unsaturated bond and a chain portion having an internal olefin bond is preferable.
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. Note that
From the non-conjugated polyene used in the present invention,
Excluding the branched polyene compound represented by like this
Examples of such compounds include (1) 4-ethylidene-1,6
-Octadiene, (2) 7-methyl-4-ethylidene-1,6-
Octadiene, (3) 7-methyl-4-ethylidene-1,6-no
Nadiene, (4) 7-ethyl-4-ethylidene-1,6-nonazi
Ene, (5) 6,7-dimethyl-4-ethylidene-1,6-octa
Diene, (6) 6,7-dimethyl-4-ethylidene-1,6-nona
Diene, (7) 4-ethylidene-1,6-decadiene, (8)
7-methyl-4-ethylidene-1,6-decadiene, (9)
Tyl-6-propyl-4-ethylidene-1,6-octadiene,
(10) 4-ethylidene-1,7-nonadiene, (11) 8-methyl
-4-ethylidene-1,7-nonadiene (EMN), (12) 4-
Ethylidene-1,7-undecadiene, (13) 8-methyl-4-
Ethylidene-1,7-undecadiene, (14) 7,8-dimethyl
-4-ethylidene-1,7-nonadiene, (15) 7,8-dimethyl
-4-ethylidene-1,7-decadiene, (16) 7,8-dimethyl
-4-ethylidene-1,7-undecadiene, (17) 8-methyl-
7-ethyl-4-ethylidene-1,7-undecadiene, (1
8) 7,8-diethyl-4-ethylidene-1,7-decadiene, (1
9) 9-methyl-4-ethylidene-1,8-decadiene, (20)
8,9-dimethyl-4-ethylidene-1,8-decadiene, (21)
10-methyl-4-ethylidene-1,9-undecadiene, (2
2) 9,10-dimethyl-4-ethylidene-1,9-undecadier
, (23) 11-methyl-4-ethylidene-1,10-dodecadie
, (24) 10,11-dimethyl-4-ethylidene-1,10-dodeca
Diene and the like (Japanese Patent Application No. 07-146574).
In the specification of US Pat. ). [Linear ethyl
Les down-alpha-olefin-nonconjugated polyene copolymer rubber (B) Characteristics] linear preferably used in the present invention the ethylene-alpha-olefin-nonconjugated polyene copolymer rubber (B), the following It has such characteristics. (1) Ethylene / α-olefin component ratio Ethylene / α-olefin / non-conjugated polyene copolymer rubber used in the present invention (A)
Is obtained by combining (a) a unit derived from ethylene and (b) a unit derived from an α-olefin having 3 to 20 carbon atoms (hereinafter sometimes simply referred to as α-olefin) by 40/60.
To 95/5, preferably 40/60 to 90/10, particularly preferably 50/50 to 85/15 [(a) / (b)].

The ethylene / α-olefin / non-conjugated polyene copolymer rubber having such an ethylene component / α-olefin component ratio is excellent in both low-temperature flexibility and heat resistance. When the ethylene / α-olefin / non-conjugated polyene copolymer rubber has an ethylene / α-olefin component ratio of more than 95/5, the ethylene / α-olefin / non-conjugated polyene copolymer rubber exhibits physical properties and lowers low-temperature flexibility. If it is less than 40/60, the heat resistance tends to decrease. (2) Iodine Value The iodine value, which is an index of the amount of the non-conjugated polyene component of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B), is 1 to 50, preferably 1 to 30. (3) Intrinsic viscosity [η] The intrinsic viscosity [η] of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) measured in decalin at 135 ° C. is 0.1 to 10 dl / g, preferably 1.5-
7 dl / g. (4) gη ^* value Jiita ^* values obtained from the intrinsic viscosity [eta] of linear ethylene-alpha-olefin-nonconjugated polyene copolymer rubber as described above (B) is greater than 0.95 I have.

This gη ^* value is defined by the following equation. gη ^* = [η] / [η] _blank (where [η] is the intrinsic viscosity measured in the above (3), and [η] _blank is the ethylene • α- of the intrinsic viscosity [η]. (Intrinsic viscosity of a linear ethylene / propylene copolymer having the same weight average molecular weight (by light scattering method) as the olefin / non-conjugated polyene copolymer rubber and having an ethylene content of 70 mol%.) Linear ethylene / α-olefin / non-conjugated polyene copolymer rubber with excellent properties has excellent mechanical strength, weather resistance, ozone resistance, and excellent cold resistance (low temperature flexibility) and heat resistance. Also excellent thermoplastic elastomer compositions and molded articles thereof can be obtained.

Further, the linear ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) preferably satisfies the following properties (5) to (7). (5) D value Intensity (area) ratio of Tαβ to Tαα in ¹³ C-NMR spectrum of ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) D (Tαβ / Tαα)
Is desirably 0.5 or less, particularly preferably 0.3 or less.

The strength ratio D of the random copolymer rubber varies depending on the type of α-olefin constituting the random copolymer rubber. Here, Tαβ and Tαα in the ¹³ C-NMR spectrum are the peak intensities of CH _{2 in} the unit derived from α-olefin, respectively, and two types of CH ₂ having different positions with respect to the tertiary carbon as shown below. Means

[0039]

Embedded image

The strength ratio D of the random copolymer rubber can be determined as follows. The ¹³ C-NMR spectrum of the random copolymer rubber was measured using, for example, a JEOL-GX270 NMR measuring apparatus manufactured by JEOL Ltd. to obtain a hexachlorobutadiene / d having a sample concentration of 5% by weight.
A mixed solution of ₆ -benzene = 2/1 (volume ratio) was added to 67.8.
It is measured on the basis of d ₆ -benzene (128 ppm) at 25 ° C. and MHz.

The analysis of the ¹³ C-NMR spectrum is basically based on the proposal of Lindemann Adams (Analysis Chemistry 43,
p1245 (1971)), JCRandall (Review Macromolecular
Chemistry Physics, C29, 201 (1989)).

Here, the above-mentioned strength ratio D will be described more specifically by taking ethylene / 1-butene / 7-methyl-1,6-octadiene copolymer rubber as an example. This ethylene 1-
Butene-7-methyl-1,6-octadiene copolymer rubber ¹³
In the C-NMR spectrum, the peak appearing at 39 to 40 ppm is assigned to Tαα, and the peak appearing at 31 to 32 ppm is assigned to Tαβ.

The intensity ratio D is calculated from the integrated value (area) ratio of each peak portion. The intensity ratio D thus determined is generally the ratio of the occurrence of the 1,1 addition reaction of 1-butene followed by the 2,1 addition reaction, or the ratio of 1-butene of 2,1 addition.
It is considered to be a scale indicating the rate at which 1,2 addition reactions occur after addition reactions. Therefore, it is shown that the larger the value of the strength ratio D, the more irregular the bonding direction of α-olefin (1-butene). Conversely, the smaller the D value, the more α
-It indicates that the bonding direction of the olefin is regular. If the regularity is high, the molecular chains are easy to assemble, and the random copolymer rubber is preferable because it tends to have excellent strength and the like.

In the present invention, ethylene, α-olefin and non-conjugated polyene are copolymerized using a specific Group IVB metallocene catalyst as described later.
A random copolymer rubber having the above strength ratio D of 0.5 or less is obtained. For example, ethylene, 1-butene and 7-methyl-1,6 are used in the presence of a VB group metallocene catalyst such as vanadium. -Even if copolymerized with octadiene, the above-mentioned intensity ratio D is 0.5 or less, ethylene / 1-butene / 7-methyl-
No 1,6-octadiene copolymer rubber can be obtained. The same applies to α-olefins other than 1-butene. (6) B value For the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B), the B value determined from the ¹³ C-NMR spectrum and the following formula is desirably 1.00 to 1.50. .

B value = [P _OE ] / (2 · [P _E ] · [P _O ]) (where [P _E ] is the unit derived from (a) ethylene in the random copolymer rubber) Content mole fraction,
[P _O ] is the content mole fraction of units derived from (b) α-olefin in the random copolymer rubber, and [P _OE ]
Is the total dyad in random copolymer rubber
It is the ratio of the number of α-olefin / ethylene chains to the number of chains. The B value is an index indicating the distribution of ethylene and α-olefin in the copolymer rubber.
l (Macromolecules, 15, 353 (1982)), J. Ray (Macromolecules
olecules, 10,773 (1977)).

The larger the B value, the shorter the block chain of ethylene or α-olefin, the more uniform the distribution of ethylene and α-olefin, and the narrower the composition distribution of the copolymer rubber. I have. It should be noted that the composition distribution of the copolymer rubber becomes wider as the B value becomes smaller than 1.00. Properties may not be fully exhibited.

In the present invention, as will be described later,
By copolymerizing ethylene, an α-olefin and a non-conjugated polyene using a Group IVB metallocene catalyst, a random copolymer rubber having the above B value of 1.00 to 1.50 has been obtained. Even if ethylene, α-olefin and non-conjugated polyene are copolymerized in the presence of a titanium-based non-metallocene catalyst, an ethylene / α-olefin / non-conjugated polyene copolymer rubber having a B value in the above range can be obtained. It is not possible. (7) Glass transition temperature The glass transition temperature (Tg) of ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) measured by DSC (differential scanning calorimeter) may be -50 ° C or less. desirable.

From a random copolymer rubber having a glass transition temperature (Tg) of -50 ° C. or lower, a thermoplastic elastomer composition having excellent low-temperature flexibility can be obtained. The ethylene / α-olefin / non-conjugated polyene copolymer rubber used in the present invention, for example, a random copolymer rubber of ethylene, 1-butene, and ethylidene norbornene (ENB) is obtained by combining this random copolymer rubber with ethylene. ,
Copolymer rubber of ethylene, propylene and ENB (EP) having the same composition ratio of α-olefin and non-conjugated polyene
Glass transition temperature (Tg) of about 5 to 10 ° C compared to DM)
It is low and has excellent low-temperature characteristics.

[Long-chain branched ethylene / α-olefin /
Properties of Non-Conjugated Polyene Copolymer Rubber (B)] On the other hand, the long-chain branched ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) preferably used in the present invention has the following properties. Have. (1) Ethylene / α-olefin component ratio The ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) 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 (B) 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 (B) measured in decalin at 135 ° C. is 1.0 to 10 dl / g, preferably 1.0 to 10 dl / g. 1.2 ~
It is 6 dl / g, more preferably 1.5 to 5 dl / g. (4) gη ^* value of Jiita ^* value long-chain branched ethylene-alpha-olefin-nonconjugated polyene copolymer rubber (B) is 0.2-0.9
5, preferably 0.4 to 0.9, more preferably 0.
5 to 0.85. This gη ^* value is determined by the method described above.

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. [Method for Preparing Ethylene / α-Olefin / Non-Conjugated Polyene Copolymer Rubber (B)] The above-mentioned linear or long-chain branched ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) Is produced by randomly copolymerizing ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene in the presence of a specific metallocene catalyst.

The metallocene catalyst used in the present invention is:
It is not particularly limited except that it contains the metallocene compound [A]. For example, a compound that forms an ion pair by reacting with the metallocene compound [A] and the organoaluminum oxy compound [B] and / or the metallocene compound [A] [ C]. Further, it may be formed from a metallocene compound [A], an organic aluminum compound [D] together with an organic aluminum oxy compound [B] and / or a compound [C] forming an ion pair.

Hereinafter, each component used in forming the metallocene catalyst in the present invention will be described. Metallocene compound [A] First, as the metallocene compound [A] used in the preparation of the linear ethylene / α-olefin / non-conjugated polyene copolymer rubber (B), the following general formula [I]
The compound shown by these is mentioned.

MLx ... [I] In the formula [I], M is a transition metal selected from Group IVB of the periodic table, specifically, zirconium, titanium or hafnium, and x is an atom of the transition metal. Value.

L is a ligand which coordinates to the transition metal,
At least one of these ligands L is a ligand having a cyclopentadienyl skeleton, and the ligand having a cyclopentadienyl skeleton may have a substituent.

The ligand having a cyclopentadienyl skeleton includes, for example, cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group, n- or i-propylcyclopentadienyl group, n-,
i-, sec-, t-, butylcyclopentadienyl group, hexylcyclopentadienyl group, octylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl Group, pentamethylcyclopentadienyl group, methylethylcyclopentadienyl group, methylpropylcyclopentadienyl group, methylbutylcyclopentadienyl group, methylhexylcyclopentadienyl group, methylbenzylcyclopentadienyl group, Alkyl or cycloalkyl-substituted cyclopentadienyl groups such as ethylbutylcyclopentadienyl group, ethylhexylcyclopentadienyl group, methylcyclohexylcyclopentadienyl group, and further indenyl group, 4,5,6,7-tetrahydroindenyl Group, fluore And a nyl group.

These groups may be substituted with a halogen atom, a trialkylsilyl group or the like. Among these, an alkyl-substituted cyclopentadienyl group is particularly preferred.

When the compound represented by the formula [I] has two or more groups having a cyclopentadienyl skeleton as the ligand L, two of the groups having the cyclopentadienyl skeleton are It may be bonded via an alkylene group such as ethylene and propylene, a substituted alkylene group such as isopropylidene and diphenylmethylene, a silylene group or a substituted silylene group such as dimethylsilylene, diphenylsilylene and methylphenylsilylene.

L other than the ligand having a cyclopentadienyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms,
An alkoxy group, an aryloxy group, a halogen atom, a hydrogen atom or a sulfonic acid-containing group (—SO ₃ R ^a )
^Ra is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group, or an aryl group substituted with a halogen atom or an alkyl group. And the like.

The hydrocarbon group having 1 to 12 carbon atoms includes an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and the like. More specifically, methyl, ethyl, n-propyl, isopropyl, n Alkyl groups such as -butyl, isobutyl, sec-butyl, t-butyl, pentyl, hexyl, octyl, decyl, dodecyl, cycloalkyl groups such as cyclopentyl and cyclohexyl, aryl groups such as phenyl and tolyl, and aralkyl such as benzyl and neophyl Groups.

The alkoxy group includes methoxy, ethoxy, n-propoxy, isopropoxy,
Examples include an n-butoxy group, an isobutoxy group, a sec-butoxy group, a t-butoxy group, a pentoxy group, a hexoxy group, and an octoxy group.

Examples of the aryloxy group include a phenoxy group and the like. Examples of the sulfonic acid-containing group (—SO ₃ R ^a ) include a methanesulfonato group, a p-toluenesulfonato group,
Examples include a trifluoromethanesulfonato group and a p-chlorobenzenesulfonato group.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. When the valence of the transition metal is 4, for example, the metallocene compound represented by the above formula is more specifically represented by the following formula [II].

R ² _k R ³ _l R ⁴ _m R ⁵ _n M [II] In the formula [II], M is the above transition metal, and R ² is a group having a cyclopentadienyl skeleton (coordination) Child) and R ³ ,
R ⁴ and R ⁵ are independently the same as L except for a group having a cyclopentadienyl skeleton or a ligand having a cyclopentadienyl skeleton in the general formula [I]. k is an integer of 1 or more, and k + 1 + m + n = 4.

In the following, M is zirconium, and
A metallocene compound containing at least two ligands having a cyclopentadienyl skeleton is exemplified. Bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) methylzirconium monochloride, bis (cyclopentane Dienyl) zirconium phenoxymonochloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride,
Bis (n-propylcyclopentadienyl) zirconium dichloride, bis (isopropylcyclopentadienyl) zirconium dichloride, bis (t-butylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, Bis (sec-butylcyclopentadienyl) zirconium dichloride, bis (isobutylcyclopentadienyl) zirconium dichloride, bis (hexylcyclopentadienyl) zirconium dichloride, bis (octylcyclopentadienyl) zirconium dichloride, bis (indenyl) Zirconium dichloride, bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, bis (indenyl) zirconium dibromide, bis (cyclopentadienyl) zirconium Dimethyl, bis (cyclopentadienyl) zirconium methoxychloride, bis (cyclopentadienyl) zirconium ethoxychloride, bis (fluorenyl) zirconium dichloride, bis (cyclopentadienyl) zirconium bis (methanesulfonato), bis (cyclopentane Dienyl) zirconium bis (p-toluenesulfonato), bis (cyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (methylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (ethylcyclo Pentadienyl) zirconium bis (trifluoromethanesulfonato), bis (propylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (butylcyclopentadi Enil)
Zirconium bis (trifluoromethanesulfonato),
Bis (hexylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (1,3-dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (1-methyl-3-ethylcyclopentadi) (Enyl) zirconium bis (trifluoromethanesulfonato), bis (1-methyl-3-propylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (1-methyl-3-butylcyclopentadienyl) zirconium bis (Trifluoromethanesulfonato), bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-ethylcyclopentadienyl) zirconium dichloride,
Bis (1-methyl-3-propylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-butylcyclopentadienyl) zirconium dichloride, bis (1-
Methyl-3-hexylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-octylcyclopentadienyl) zirconium dichloride, bis (1-ethyl
-3-butylcyclopentadienyl) zirconium dichloride, bis (trimethylcyclopentadienyl) zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (methyl Examples thereof include benzylcyclopentadienyl) zirconium dichloride, bis (ethylhexylcyclopentadienyl) zirconium dichloride, and bis (methylcyclohexylcyclopentadienyl) zirconium dichloride.

A compound in which the above-mentioned 1,3-substituted cyclopentadienyl group is substituted by a 1,2-substituted cyclopentadienyl group can also be used in the present invention. In the above formula [II], at least two of R ² , R ³ , R ⁴ and R ⁵ , that is, R ² and R ³ are groups having a cyclopentadienyl skeleton (ligand).
Each group can also be exemplified by a bridge-type metallocene compound bonded via an alkylene group, a substituted alkylene group, a silylene group or a substituted silylene group. At this time, R ⁴ and R ⁵ are each independently the same as L except for the ligand having a cyclopentadienyl skeleton described in the formula [I].

Examples of such bridge type metallocene compounds include ethylene bis (indenyl) dimethyl zirconium, ethylene bis (indenyl) zirconium dichloride, ethylene bis (indenyl) zirconium bis (trifluoromethanesulfonate), and ethylene bis (indenyl) zirconium. Bis (methanesulfonato), ethylenebis (indenyl) zirconium bis (p-toluenesulfonato), ethylenebis (indenyl) zirconiumbis (p-chlorobenzenesulfonato), ethylenebis (4,5,6,7-tetrahydro Indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zirconium Dichloride, dimethylsilylenebis (cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (trimethylcyclopentadienyl) Zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconiumbis (trifluoromethanesulfonato), dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylenebis ( Cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, Methylphenylsilylenebis (indenyl) zirconium dichloride and the like can be mentioned.

Further, Japanese Patent Application Laid-Open No.
Metallocene compounds described in JP-A-268307. The metallocene has the formula [A]:

[0069]

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[In the formula [A], M ¹ is the IVB of the periodic table.
Group metals, specifically, for example, titanium, zirconium, and hafnium. R ¹ and R ² may be the same or different from each other, and represent a hydrogen atom, an alkyl group having 1 to 10, preferably 1 to 3 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms. An aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, 2 to 10 carbon atoms, preferably 2 to 4 carbon atoms.
An alkenyl group having 7 to 40 carbon atoms, preferably 7 to
10 arylalkyl groups, 7 to 40, preferably 7 to 12 alkylaryl groups, 8 to 8 carbon atoms
40, preferably 8 to 12 arylalkenyl groups, or halogen atoms, preferably chlorine atoms.

R ³ and R ⁴ may be the same or different from each other, and may be a hydrogen atom, a halogen atom, preferably a fluorine atom, a chlorine atom or a bromine atom, an optionally halogenated carbon atom having 1 to 10 carbon atoms, preferably 1 to 4 alkyl group, having 6 to 10 carbon atoms, preferably 6-8 aryl _{^{group, -NR 10 2, -SR 10,}} -OSiR 10 3, -
A SiR ¹⁰ ₃ or -PR ¹⁰ ₂ radical, where R ¹⁰ is a halogen atom, preferably a chlorine atom or a carbon atoms,
An alkyl group having 10 to 10, preferably 1 to 3, or an aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms.

R ³ and R ⁴ are particularly preferably a hydrogen atom. R ⁵ and R ^6, which may be the same or different from each other, preferably the same, R ⁵ and R
⁶ represents R ³ and R ³ provided that they are not hydrogen atoms.
^It has the meaning described for ⁴ . R ⁵ and R ⁶ are
Preferably 1 to 1 carbon atoms which may be halogenated
And an alkyl group of 4, specifically, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group or a trifluoromethyl group, and a methyl group is preferable.

R ⁷ is as follows:

[0074]

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= BR¹¹, = AlR¹¹, -Ge-, -Sn
-, -O-, -S-, = SO, = SO _Two, = NR¹¹, =
CO, = PR¹¹ Or = P (O) R¹¹And that
When R¹¹, R¹²And R¹³Are the same but different
Hydrogen atom, halogen atom, carbon atom number 1
10, preferably 1-4 alkyl groups, more preferably
Is a methyl group, a fluoroalkyl having 1 to 10 carbon atoms
Group, preferably CF_Three Group, 6-10 carbon atoms, preferred
Or an aryl group having 6 to 8 carbon atoms, a fluoro group having 6 to 10 carbon atoms.
A loaryl group, preferably a pentafluorophenyl group,
Alkoxy having 1 to 10, preferably 1 to 4 carbon atoms
A group, particularly preferably a methoxy group, having 2 to 10 carbon atoms,
Preferably 2-4 alkenyl groups, 7-4 carbon atoms
0, preferably 7 to 10 arylalkyl groups, carbon atoms
Arylalkenyl having 8 to 40, preferably 8 to 12 children
Group, or 7 to 40 carbon atoms, preferably 7 to 12 carbon atoms
Or an alkylaryl group of¹¹And R¹²Also
Is R¹¹And R¹³Are the atoms to which they are attached
It may form a ring around.

M ² is silicon, germanium or tin, preferably silicon or germanium. R ⁷ is = CR
^{11 R 12, = SiR 11 R} 12, = GeR 11 R 12, -O -, -
S -, = SO, it is preferred that = PR ¹¹ or = P (O) R ^11.

R ⁸ and R ⁹ may be the same or different and have the same meaning as described for R ¹¹ . m and n may be the same or different from each other and are 0, 1 or 2, preferably 0 or 1
And m + n is 0, 1 or 2, preferably 0 or 1.

Particularly preferred metallocene compounds satisfying the above conditions are shown in the following (i) to (iii).

[0079]

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[In the above formulas (i), (ii) and (iii),
M ¹ is Zr or Hf, R ¹ and R ² are a methyl group or a chlorine atom, R ⁵ and R ⁶ are a methyl group,
An ethyl group or a trifluoromethyl group, R ⁸ , R
^9, R ¹⁰ and R ¹² have the meaning given above. Among the compounds represented by the formulas (i), (ii) and (iii), the following compounds are particularly preferred.

Rac-ethylene (2-methyl-1-indenyl) ₂ -zirconium-dichloride, rac-dimethylsilylene (2-methyl-1-indenyl) ₂ -zirconium-
Dichloride, rac-dimethylsilylene (2-methyl-1
-Indenyl) ₂ -zirconium-dimethyl, rac-ethylene- (2-methyl-1-indenyl) ₂ -zirconium-
Dimethyl, rac-phenyl (methyl) silylene- (2-methyl-1-indenyl) ₂ -zirconium-dichloride, rac-diphenyl-silylene- (2-methyl-1-indenyl) ₂ -zirconium-dichloride, rac-methylethylene- ( 2-methyl-1-indenyl) ₂ -zirconium-dichloride, rac-dimethylsilylene- (2-ethyl-1-indenyl) ₂ -zirconium-dichloride.

The method for producing such a metallocene compound can be produced by a conventionally known method (for example, see JP-A-4-268307). In the present invention, a transition metal compound (metallocene compound) represented by the following formula [B] can also be used.

[0083]

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In the formula [B], M represents a transition metal atom belonging to Group IVB of the periodic table, and is specifically titanium, zirconium or hafnium. R ¹ and R ² each independently represent 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, a silicon-containing group, an oxygen-containing group, A containing group, a nitrogen-containing group or a phosphorus-containing group, and specifically, halogen atoms such as fluorine, chlorine, bromine, and iodine; methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, nonyl, dodecyl, eicosyl, Norbornyl, alkyl groups such as adamantyl, vinyl, propenyl, alkenyl groups such as cyclohexenyl, benzyl,
Phenylethyl, an arylalkyl group such as phenylpropyl, phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthracenyl, an aryl group such as phenanthryl; A hydrocarbon group; a halogenated hydrocarbon group in which a halogen atom is substituted for the hydrocarbon group; a monohydrocarbon-substituted silyl group such as methylsilyl and phenylsilyl, a dihydrocarbon-substituted silyl group such as dimethylsilyl and diphenylsilyl, trimethylsilyl, triethyl Trihydrocarbon-substituted silyls such as silyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, tolylsilyl, and trinaphthylsilyl , Hydrocarbon-substituted silyl ether groups of the silyl, silicon-substituted alkyl groups, such as trimethylsilylmethyl, silicon-containing substituents such as silicon-substituted aryl groups, such as trimethylsilyl phenyl such as trimethylsilyl ether; hydroxycarbonate groups, methoxy, ethoxy,
Oxygen-containing groups such as alkoxy groups such as propoxy and butoxy, allyloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy, and arylalkoxy groups such as phenylmethoxy and phenylethoxy;
A sulfur-containing group such as a substituent in which oxygen of the oxygen-containing group is substituted with sulfur; an amino group, an amino group such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, or dicyclohexylamino;
Phenylamino, diphenylamino, ditolylamino,
A nitrogen-containing group such as an arylamino group or an alkylarylamino group such as dinaphthylamino and methylphenylamino; and a phosphorus-containing group such as a phosphino group such as dimethylphosphino and diphenylphosphino.

Of these, R ¹ is preferably a hydrocarbon group, particularly preferably a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl and propyl. Also R ²
Is preferably hydrogen or a hydrocarbon group, particularly preferably hydrogen or a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl and propyl.

R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, a halogen atom, a C 1-20
And a halogenated hydrocarbon group having 1 to 20 carbon atoms, and among them, hydrogen, a hydrocarbon group or a halogenated hydrocarbon group is preferable. R ³ and R ⁴ , R ⁴
And R ^5, at least one pair of R ⁵ and R ⁶ may form an aromatic ring of a single together with the carbon atoms to which they are attached rings.

When there are two or more hydrocarbon groups or halogenated hydrocarbon groups other than the group forming an aromatic ring, these groups may be combined with each other to form a ring. When R ⁶ is a substituent other than an aromatic group, it is preferably a hydrogen atom.

Specific examples of the halogen atom, the hydrocarbon group having 1 to 20 carbon atoms and the halogenated hydrocarbon group having 1 to 20 carbon atoms include the same groups as those described above for R ¹ and R ² .

A ligand coordinating with M, including a monocyclic aromatic ring formed by combining at least one of R ³ and R ⁴ , R ⁴ and R ⁵ , and R ⁵ and R ⁶ with each other. Are as shown below.

[0090]

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Among these, the ligand represented by the above formula (1) is preferable. The aromatic ring may be substituted with a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms.

Examples of the halogen atom, the hydrocarbon group having 1 to 20 carbon atoms, and the halogenated hydrocarbon group having 1 to 20 carbon atoms to be substituted on the aromatic ring include the same groups as those described above for R ¹ and R ^2. Can be illustrated.

X ¹ and X ² each independently represent 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 group represented by R
The same halogen atom as that of ¹ and R ² , having 1 to 2 carbon atoms
Examples include a hydrocarbon group of 0, a halogenated hydrocarbon group having 1 to 20 carbon atoms, and an oxygen-containing group.

Examples of the sulfur-containing group include the same groups as those described above for R ¹ and R ² , and methylsulfonate, trifluoromethanesulfonate, phenylsulfonate, benzylsulfonate, p-toluenesulfonate and trimethylbenzenesulfonate. Sulfonate groups such as phonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, pentafluorobenzenesulfonate, methylsulfinate, phenylsulfinate, benzylsulfinate, p-toluenesulfinate , Trimethylbenzenesulfinate, pentafluorobenzenesulfinate and the like.

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,
Divalent tin-containing group, -O-, -CO-, -S-, -SO
_{-, - SO 2 -, -} NR 7 -, - P (R 7) -, - P
^{(O) (R 7) -} , - BR 7 - or -AlR ⁷ - [however, R ⁷ is a hydrogen atom, a halogen atom, 1 to carbon atoms
20 hydrocarbon groups and halogenated hydrocarbon groups having 1 to 20 carbon atoms], specifically, methylene, dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene, 1,3-
C 1-20 carbon atoms such as alkylene groups such as trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene and 1,4-cyclohexylene, and arylalkylene groups such as diphenylmethylene and diphenyl-1,2-ethylene A divalent hydrocarbon group of the above;
A halogenated hydrocarbon group obtained by halogenating a divalent hydrocarbon group of 0; methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methyl Alkylsilylene groups such as phenylsilylene, diphenylsilylene, di (p-tolyl) silylene, di (p-chlorophenyl) silylene, alkylarylsilylene groups, arylsilylene groups, tetramethyl-1,2-disilylene groups,
A divalent silicon-containing group such as an alkyldisilylene group such as a tetraphenyl-1,2-disilylene group, an alkylaryldisilylene group, or an aryldisilylene group; valent germanium-containing group; and the like divalent tin-containing group substituents replacing silicon of the divalent silicon-containing group to tin, 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, similar to the above R ¹ and R ² .

Of these, a divalent silicon-containing group, a divalent germanium-containing group, and a divalent tin-containing group are preferable, and a divalent silicon-containing group is more preferable.
Among them, an alkylsilylene group, an alkylarylsilylene group, and an arylsilylene group are particularly preferable.

Specific examples of the transition metal compound represented by the above formula [B] are shown below.

[0098]

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[0099]

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[0100]

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In the present invention, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal in the above compounds may be used. The transition metal compound is usually used as a catalyst component for olefin polymerization as a racemate, but may be of the R or S type.

Such an indene derivative ligand of a transition metal compound can be synthesized, for example, by the following reaction route using a conventional organic synthesis technique.

[0103]

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The transition metal compound used in the present invention can be synthesized from these indene derivatives by a known method, for example, a method described in JP-A-4-268307.

In the present invention, a transition metal compound (metallocene compound) represented by the following formula [C] can also be used.

[0106]

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In the formula [C], M, R ¹ , R ² , R ³ ,
As R ⁴ , R ⁵ and R ⁶ , those similar to the case of the formula [B] can be mentioned. R ³ , R ⁴ , R ⁵ and R ⁶
Among them, two groups including R ³ are preferably alkyl groups, and R ³ and R ⁵ , or R ³ and R ⁶ are preferably alkyl groups. This alkyl group is preferably a secondary or tertiary alkyl group. The alkyl group may be substituted with a halogen atom or a silicon-containing group.
^And the substituents exemplified for R ² .

Among the groups represented by R ³ , R ⁴ , R ⁵ and R ⁶ , groups other than the alkyl group are preferably hydrogen atoms. As a hydrocarbon group having 1 to 20 carbon atoms,
Methyl, ethyl, n-propyl, i-propyl, n-butyl,
i-butyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl,
Chain and cyclic alkyl groups such as dodecyl, eicosyl, norbornyl, and adamantyl; benzyl,
Examples include an arylalkyl group such as phenylethyl, phenylpropyl, and tolylmethyl, and may include a double bond or a triple bond.

Further, two groups selected from R ³ , R ⁴ , R ⁵ and R ⁶ may be bonded to each other to form a monocyclic or polycyclic ring other than an aromatic ring. As a halogen atom,
Specifically, the same groups as those for R ¹ and R ² can be exemplified.

X ¹ , X ² , Y and R ⁷ are the same as those in the above formula [B]. Hereinafter, specific examples of the metallocene compound (transition metal compound) represented by the above formula [C] will be shown.

Rac-dimethylsilylene-bis (4,7-dimethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,4,7-trimethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2,4,6-trimethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,5,6-trimethyl-1-indenyl) zirconium dichloride, rac-
Dimethylsilylene-bis (2,4,5,6-tetramethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,4,5,6,7-pentamethyl-1-indenyl)
Zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-n-propyl-7-methyl-1-indenyl)
Zirconium dichloride, rac-dimethylsilylene-bis (4-i-propyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl
-4-i-propyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl
-4-i-propyl-6-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl
-4-methyl-6-i-propyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl
-4-i-propyl-5-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl
-4,6-di (i-propyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4,6
-Di (i-propyl) -7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-i-butyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethyl Silylene-bis (2-methyl
-4-sec-butyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl
-4,6-di (sec-butyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-t
ert-butyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-
Cyclohexyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl
-4-benzyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4
-Phenylethyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-phenyldichloromethyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2-methyl-4-chloromethyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene
-Bis (2-methyl-4-trimethylsilylmethyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-trimethylsiloxymethyl-7-methyl-1-indenyl) zirconium dichloride , Rac-diethylsilylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium dichloride, rac-di (i-propyl) silylene-bis (2-methyl
-4-i-propyl-7-methyl-1-indenyl) zirconium dichloride, rac-di (n-butyl) silylene-bis (2-
Methyl-4-i-propyl-7-methyl-1-indenyl) zirconium dichloride, rac-di (cyclohexyl) silylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium dichloride, rac-methylphenylsilylene-bis (2-methyl-4-i-propyl-7-methyl-1
-Indenyl) zirconium dichloride, rac-diphenylsilylene-bis (2-methyl-4-i-propyl-7-methyl
-1-indenyl) zirconium dichloride, rac-diphenylsilylene-bis (2-methyl-4,6-di (i-propyl)-
1-indenyl) zirconium dichloride, rac-di (p-tolyl) silylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium dichloride, rac-di
(p-chlorophenyl) silylene-bis (2-methyl-4-i-
Propyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-i-
Propyl-7-methyl-1-indenyl) zirconium dibromide, rac-dimethylsilylene-bis (2-methyl-4-i-
Propyl-7-methyl-1-indenyl) zirconium dimethyl, rac-dimethylsilylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium methyl chloride, rac-dimethylsilylene-bis (2 -Methyl-4-i
-Propyl-7-methyl-1-indenyl) zirconium-
Bis (methanesulfonato), rac-dimethylsilylene-bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium-bis (p-phenylsulfinato),
rac-dimethylsilylene-bis (2-methyl-3-methyl-4-i
-Propyl-6-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-ethyl-4-i
-Propyl-6-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-phenyl-4
-i-Propyl-6-methyl-1-indenyl) zirconium dichloride.

In the present invention, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal in the above compounds may be used. The transition metal compound is usually used as a racemic compound, but it is also possible to use an R type or an S type.

Such an indene derivative ligand of a transition metal compound can be synthesized, for example, by the same reaction route as described above using a conventional organic synthesis technique. The transition metal compound (metallocene compound) represented by the above formula [C] can be synthesized from these indene derivatives by a known method, for example, a method described in JP-A-4-268307.

In the present invention, among the above-mentioned metallocene compounds, in particular, the following general formula [III] or [I
V] is preferably used. General formula [I
The metallocene compound represented by the formula [II] is a part of the compound represented by the above formula [C], and the metallocene compound represented by the general formula [IV] is a part of the compound represented by the above formula [B] It is.

[0115]

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In the formula, M is a transition metal atom belonging to Group IVB of the periodic table, and specifically, titanium, zirconium,
Hafnium, particularly preferably zirconium. R ¹¹ and R ¹² R ¹¹ and R ¹² represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, -Containing group or phosphorus-containing group, examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, Alkyl groups such as cyclohexyl, octyl, nonyl, dodecyl, iconosyl, norbornyl and adamantyl, vinyl, propenyl, alkenyl groups such as cyclohexenyl, benzyl,
Phenylethyl, arylalkyl groups such as phenylpropyl, phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, α- or β-naphthyl, methylnaphthyl, anthracenyl, phenanthryl, benzylphenyl, pyrenyl, acenaphthyl, And aryl groups such as phenalenyl, aceanthrenyl, tetrahydronaphthyl, indanyl, biphenylyl and the like.

These hydrocarbon groups include halogen atoms such as fluorine, chlorine, bromine and iodine, trimethylsilyl groups,
It may be substituted with an organic silyl group such as a triethylsilyl group and a triphenylsilyl group.

Specific examples of the oxygen-containing group include a hydroxy group, an alkoxy group such as methoxy, ethoxy, propoxy and butoxy, an allyloxy group such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy, and phenylmethoxy and phenylethoxy. And arylalkoxy groups.

Examples of the sulfur-containing group include substituents in which oxygen in the oxygen-containing group is replaced with sulfur, methylsulfonate, trifluoromethanesulfonate, phenylsulfonate, benzylsulfonate, p-toluene Sulfonate groups such as sulfonate, trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate and pentafluorobenzenesulfonate, methylsulfinate, phenylsulfinate, and benzylsulfinate , P-toluenesulfinate, trimethylbenzenesulfinate, pentafluorobenzenesulfinate and the like.

Examples of the nitrogen-containing group include an amino group, methylamino, dimethylamino, diethylamino,
Examples thereof include an alkylamino group such as dipropylamino, dibutylamino, and dicyclohexylamino; an arylamino group such as phenylamino, diphenylamino, ditolylamino, dinaphthylamino, and methylphenylamino; or an alkylarylamino group.

Examples of the phosphorus-containing group include a dimethylphosphino group and a diphenylphosphino group. R ¹¹ is preferably a hydrocarbon group among them, and particularly preferably a hydrocarbon group having 1 to 3 carbon atoms such as a methyl group, an ethyl group and a propyl group.

R ¹² is preferably a hydrogen atom or a hydrocarbon group, particularly preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms such as a methyl group, an ethyl group and a propyl group.

R ¹³ and R ¹⁴ R ¹³ and R ^{14 each} have 1 carbon atom as exemplified above.
-20 alkyl groups.

R ¹³ is preferably a secondary or tertiary alkyl group. R ¹⁴ may contain a double bond or a triple bond. X ¹ and X ² X ¹ and X ² represent 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, or an oxygen-containing group as exemplified above. Group or a sulfur-containing group, a halogen atom,
It is preferably 20 hydrocarbon groups.

[0125] Y Y is a divalent hydrocarbon group, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group , -O-, -C
O -, - S -, - SO -, - SO 2 -, - NR 15 -, -
^{P (R 15) -, -} P (O) (R 15) -, - BR 15 - or -AlR ¹⁵ - [however, R ¹⁵ 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, dimethylmethylene, 1,2-ethylene, dimethyl
Alkylene groups such as -1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene and 1,4-cyclohexylene, diphenylmethylene, diphenyl-1,2-
1 carbon atom such as an arylalkylene group such as ethylene
To 20 divalent hydrocarbon groups; halogenated hydrocarbon groups obtained by halogenating the above divalent hydrocarbon groups having 1 to 20 carbon atoms such as chloromethylene; methylsilylene, dimethylsilylene, diethylsilylene, di (n -Propyl) silylene,
Di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenylsilylene, diphenylsilylene,
Alkyl silylene groups such as di (p-tolyl) silylene and di (p-chlorophenyl) silylene, alkylarylsilylene groups, arylsilylene groups, and alkyl such as tetramethyl-1,2-disilyl and tetraphenyl-1,2-disilyl A divalent silicon-containing group such as a disilyl group, an alkylaryldisilyl group, and an aryldisilyl group; and a divalent germanium-containing group in which silicon of the above-described divalent silicon-containing group is substituted with germanium.

R ¹⁵ 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 [III] are shown below. rac-Dimethylsilylene-bis (2,7-dimethyl-4-ethyl-1-indenyl)
Zirconium dichloride, rac-dimethylsilylene-bis (2,7-dimethyl-4-n-propyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,7-
Dimethyl-4-i-propyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,7-dimethyl-4-n-butyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2, 7-dimethyl-4-sec
-Butyl-1-indenyl) zirconium dichloride, ra
c-Dimethylsilylene-bis (2,7-dimethyl-4-t-butyl
-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,7-dimethyl-4-n-pentyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,7-dimethyl-4-n -Hexyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2,7-dimethyl-4-cyclohexyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2,7-dimethyl-4-methylcyclohexyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,7-dimethyl-4-phenylethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene
-Bis (2,7-dimethyl-4-phenyldichloromethyl-1-
Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,7-dimethyl-4-chloromethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,7-dimethyl-4-trimethylsilylmethyl-1
-Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,7-dimethyl-4-trimethylsiloxymethyl-1-indenyl) zirconium dichloride, rac-
Diethylsilylene-bis (2,7-dimethyl-4-i-propyl
-1-indenyl) zirconium dichloride, rac-di (i-
Propyl) silylene-bis (2,7-dimethyl-4-i-propyl-1-indenyl) zirconium dichloride, rac-di (n-butyl) silylene-bis (2,7-dimethyl-4-i-propyl-1 -Indenyl) zirconium dichloride, rac-di (cyclohexyl) silylene-bis (2,7-dimethyl-4-i
-Propyl-1-indenyl) zirconium dichloride, r
ac-methylphenylsilylene-bis (2,7-dimethyl-4-i-
Propyl-1-indenyl) zirconium dichloride, r
ac-methylphenylsilylene-bis (2,7-dimethyl-4-t-
Butyl-1-indenyl) zirconium dichloride, rac
-Diphenylsilylene-bis (2,7-dimethyl-4-t-butyl-1-indenyl) zirconium dichloride, rac-diphenylsilylene-bis (2,7-dimethyl-4-i-propyl-1)
-Indenyl) zirconium dichloride, rac-diphenylsilylene-bis (2,7-dimethyl-4-ethyl-1-indenyl) zirconium dichloride, rac-di (p-tolyl) silylene-bis (2,7-dimethyl-4- i-propyl-1-indenyl) zirconium dichloride, rac-di (p-chlorophenyl) silylene-bis (2,7-dimethyl-4-i-propyl-1
-Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-i-propyl-7-ethyl-1
-Indenyl) zirconium dibromide rac-dimethylsilylene-bis (2,3,7-trimethyl-4-ethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,3,7-trimethyl-4-n -Propyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,3,7-trimethyl-4-i-propyl
-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,3,7-trimethyl-4-n-butyl-1-
Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,3,7-trimethyl-4-sec-butyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,3,7-trimethyl-4- t-butyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene
-Bis (2,3,7-trimethyl-4-n-pentyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2,3,7-trimethyl-4-n-hexyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2,3,7-trimethyl-4-cyclohexyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene
-Bis (2,3,7-trimethyl-4-methylcyclohexyl-1
-Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,3,7-trimethyl-4-trimethylsilylmethyl-1-indenyl) zirconium dichloride, ra
c-dimethylsilylene-bis (2,3,7-trimethyl-4-trimethylsiloxymethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,3,7-trimethyl-4-phenylethyl-1- Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,3,7-trimethyl-4-phenyldichloromethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,3,7-trimethyl-4 -Chloromethyl-1-indenyl)
Zirconium dichloride, rac-diethylsilylene-bis (2,3,7-trimethyl-4-i-propyl-1-indenyl) zirconium dichloride, rac-di (i-propyl) silylene
-Bis (2,3,7-trimethyl-4-i-propyl-1-indenyl) zirconium dichloride, rac-di (n-butyl) silylene-bis (2,3,7-trimethyl-4-i-propyl- 1-indenyl) zirconium dichloride, rac-di (cyclohexyl) silylene-bis (2,3,7-trimethyl-4-i-propyl-1-indenyl) zirconium dichloride, rac-methylphenylsilylene-bis (2,3, 7-trimethyl-4-i-propyl-1-indenyl) zirconium dichloride, rac-
Methylphenylsilylene-bis (2,3,7-trimethyl-4-t
-Butyl-1-indenyl) zirconium dichloride, ra
c-diphenylsilylene-bis (2,3,7-trimethyl-4-t-
Butyl-1-indenyl) zirconium dichloride, rac-
Diphenylsilylene-bis (2,3,7-trimethyl-4-i-propyl-1-indenyl) zirconium dichloride, rac-
Diphenylsilylene-bis (2,3,7-trimethyl-4-ethyl-1-indenyl) zirconium dichloride, rac-di (p-tolyl) silylene-bis (2,3,7-trimethyl-4-i-
Propyl-1-indenyl) zirconium dichloride, ra
c-Di (p-chlorophenyl) silylene-bis (2,3,7-trimethyl-4-i-propyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-i
-Propyl-7-methyl-1-indenyl) zirconium dimethyl, rac-dimethylsilylene-bis (2-methyl-4-i-
Propyl-7-methyl-1-indenyl) zirconium methyl chloride, rac-dimethylsilylene-bis (2-methyl-4
-i-Propyl-7-methyl-1-indenyl) zirconium
-Bis (methanesulfonato), rac-dimethylsilylene-
Bis (2-methyl-4-i-propyl-7-methyl-1-indenyl) zirconium-bis (p-phenylsulfinato),
rac-dimethylsilylene-bis (2-methyl-3-methyl-4-i
-Propyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-ethyl-4-i
-Propyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-phenyl-4
-i-propyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4
-i-propyl-7-methyl-1-indenyl) titanium dichloride, rac-dimethylsilylene-bis (2-methyl-4-i
-Propyl-7-methyl-1-indenyl) hafnium dichloride.

Of these, an i-propyl group at the 4-position, sec-
Compounds having a branched alkyl group such as a butyl group and a tert-butyl group are particularly preferred. In the present invention, usually, a racemic form of the transition metal compound is used as a catalyst component for olefin polymerization, but R-type or S-type can also be used.

The transition metal compound as described above can be prepared from an indene derivative by a known method, for example, as disclosed in
Can be synthesized by the method described in Japanese Patent Application Laid-open No. The compound represented by the following formula [IV] preferably used in the present invention is described in EP-549900 and Canada-20
No. 84017.

[0130]

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In the formula, M is a transition metal atom belonging to Group IVB of the periodic table, and specifically, titanium, zirconium,
Hafnium, particularly preferably zirconium. R ²¹ may be the same or different from each other, and may be a hydrogen atom, a halogen atom, preferably a fluorine atom or a chlorine atom, and an optionally halogenated carbon atom number of 1 to 1.
0, preferably 1-4 alkyl groups, 6-1 carbon atoms
0, preferably 6-8 aryl group, -NR _2, -S
R, —OSiR ₃ , —SiR ₃ or —PR ₂ groups (where R is a halogen atom, preferably a chlorine atom, an alkyl group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms or 6 to 10 carbon atoms; Preferably 6 to 8 aryl groups).

[0132] R ²² to R ²⁸ may be the same or different, have the same atom or group as R ^21, these R ²² to R
^At least two adjacent groups out of ²⁸ may form an aromatic ring or an aliphatic ring together with the atoms to which they are bonded.

X ³ and X ⁴ may be the same or different from each other, and include a hydrogen atom, a halogen atom, an OH group, an alkyl group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms, and 1 to 10 carbon atoms. Preferably 1 to 3 alkoxy groups, 6 to 10 carbon atoms, preferably 6 to 8 aryl groups, 6 to 10 carbon atoms, preferably 6 to 8 aryloxy groups, 2 to 10 carbon atoms, Preferably, it is an alkenyl group having 2 to 4 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, preferably 7 to 10 carbon atoms, and 7 to 40 carbon atoms.
It is a 12 alkylaryl group, an arylalkenyl group having 8 to 40 carbon atoms, preferably 8 to 12 carbon atoms.

[0134]

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-Sn-, -O-, -S-, = SO, = S
O ₂ , ＮＲNR ²⁹ , ＣＯCO, ＰＲPR ²⁹ or ＰP (O) R
²⁹ . However, R ²⁹ and R ³⁰ may be the same or different from each other, and include a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, particularly preferably a methyl group and 1 carbon atom. 10 to 10 fluoroalkyl group, preferably CF ₃ group, 6 to 10 carbon atom, preferably 6 to 8 aryl group, 6 to 10 carbon atom fluoroaryl group, preferably pentafluorophenyl group, 1-10, preferably 1-4 alkoxy groups, particularly preferably methoxy group, 2-1 carbon atom
0, preferably 2 to 4 alkenyl groups, 7 to 7 carbon atoms
It is an arylalkyl group having 40, preferably 7 to 10 carbon atoms, an arylalkenyl group having 8 to 40 carbon atoms, preferably 8 to 12 carbon atoms, and an arylalkyl group having 7 to 40 carbon atoms, preferably 7 to 12 carbon atoms.

R ²⁹ and R ³⁰ may form a ring together with the atoms to which they are bonded. M ² is silicon, germanium or tin.

The above-mentioned alkyl group is a linear or branched alkyl group, and the halogen (halogenated) is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, particularly preferably a fluorine atom or a chlorine atom. is there.

Among the compounds represented by the formula [IV], M is zirconium or hafnium,
R ²¹ is the same as each other and is an alkyl group having 1 to 4 carbon atoms, and R ^{22 to} R ²⁸ may be the same or different from each other and is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. X ³ and X ⁴ may be the same or different from each other, and are an alkyl group having 1 to 3 carbon atoms or a halogen atom;

[0139]

Embedded image

(M ² is silicon, R ²⁹ and R
³⁰ may be the same or different and are an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. ) Is preferably a compound which is, substituents R ²² and R ²⁸ are hydrogen atoms, R ²³ to R ²⁷ is more preferably a compound is an alkyl group or a hydrogen atom from 1 to 4 carbon atoms.

Further, M is zirconium, and R is
²¹ is the same alkyl group having 1 to 4 carbon atoms from each other, R ²² and R ²⁸ are hydrogen atoms, R ²³ to R
²⁷ may be the same or different, and has 1 to 4 carbon atoms.
X ³ and X ^3
4 is a chlorine atom,

[0142]

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(M ² is silicon, and R ²⁹ and R ³⁰
May be the same or different, and have 1 carbon atom
Or an alkyl group having 4 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. Is preferred, and in particular, M is zirconium, R ²¹ is a methyl group, and R ^{22 to} R ^22
28 is a hydrogen atom, X ³ and X ⁴ are chlorine atoms,

[0144]

Embedded image

(M ² is silicon, and R ²⁹ and R ³⁰
May be the same or different and each is a methyl group or a phenyl group). Several examples of such a metallocene compound represented by the formula [IV] are shown below.

Rac-dimethylsilylene-bis {1- (2-methyl-4,5-benzoindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4,5-
Acenaphthocyclopentadienyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2,3-6-trimethyl-4,5-benzoindenyl)} zirconium dichloride, rac-methylphenylsilylene-bis -(2-methyl-4,5-benzoindenyl)｝ zirconium dichloride, rac-methylphenylsilylene-bis ｛1- (2-methyl
-4,5-acenaphthocyclopentadienyl)｝ zirconium dichloride, rac-methylphenylsilylene-bis ｛1-
(4,5-benzoindenyl) zirconium dichloride,
rac-methylphenylsilylene-bis {1- (2,6-dimethyl)
-4,5-benzoindenyl)｝ zirconium dichloride,
rac-methylphenylsilylene-bis {1- (2,3-6-trimethyl-4,5-benzoindenyl)} 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 racemic metallocene compound represented by the formula [III] or [IV] is generally used as a catalyst component, but R-type or S-type may also be used.

The metallocene compounds as described above can be used in combination of two or more. Next, the metallocene compound [A] used for preparing the long-chain branched ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) preferably used in the present invention includes the following general formula [V] The compound shown by these is mentioned.

[0149]

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In the formula, M is a transition metal atom belonging to 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, and specifically, methyl, ethyl, n-propyl, isopropyl, n-
Examples thereof include alkyl groups such as butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl and cyclohexyl groups, and alkenyl groups such as vinyl and propenyl.

Of these, a primary alkyl group bonded to an indenyl group is preferred, and a C 1 -C 1 alkyl group is more 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 , and 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, cyclohexyl, octyl, nonyl, dodecyl, eicosyl, norbornyl, Alkyl groups such as adamantyl, vinyl, propenyl, alkenyl groups such as cyclohexenyl, benzyl, phenylethyl, arylalkyl groups such as phenylpropyl, the above exemplified aryl groups, and tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl,
And aryl groups such as propylphenyl, methylnaphthyl and benzylphenyl.

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

As the oxygen-containing group, specifically,
Examples include a hydroxy group, an alkoxy group such as methoxy, ethoxy, propoxy, and butoxy, an allyloxy group such as phenoxy, methylphenoxy, dimethylphenoxy, and naphthoxy, and an arylalkoxy group such as phenylmethoxy and phenylethoxy.

Examples of the sulfur-containing group include substituents in which the oxygen of the oxygen-containing group is replaced with sulfur, methylsulfonate, trifluoromethanesulfonate, phenylsulfonate, benzylsulfonate, p-toluene Sulfonate groups such as sulfonate, trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate and pentafluorobenzenesulfonate, methylsulfinate, phenylsulfinate, and benzylsulfinate , P-toluenesulfinate, trimethylbenzenesulfinate, pentafluorobenzenesulfinate and the like.

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, dimethylmethylene, 1,2-ethylene, dimethyl
Alkylene groups such as -1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene and 1,4-cyclohexylene, diphenylmethylene, diphenyl-1,2-
1 carbon atom such as an arylalkylene group such as ethylene
To 20 divalent hydrocarbon groups; halogenated hydrocarbon groups obtained by halogenating the above divalent hydrocarbon groups having 1 to 20 carbon atoms such as chloromethylene; methylsilylene, dimethylsilylene, diethylsilylene, di (n -Propyl) silylene,
Di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenylsilylene, diphenylsilylene,
Alkyl silylene groups such as di (p-tolyl) silylene and di (p-chlorophenyl) silylene, alkylarylsilylene groups, arylsilylene groups, and alkyl such as tetramethyl-1,2-disilyl and tetraphenyl-1,2-disilyl A divalent silicon-containing group such as a disilyl group, an alkylaryldisilyl group, and an aryldisilyl group; and a divalent germanium-containing group in which silicon of the above-described divalent silicon-containing group is substituted with germanium.

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 [V] 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, rac-
Dimethylsilylene-bis {1- (2-s-butyl-4- (9-phenanthryl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-pentyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-pentyl-4- (α-naphthyl) indenyl) )｝ Zirconium dichloride, rac-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-dimethylsilile -Bis {1- (2-n-butyl-4- (9-anthracenyl) indenyl)} zirconium dichloride, ra
c-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 metallocene compounds as described above 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.

Further, in addition to the metallocene compound represented by the above general formula [V], a metallocene compound represented by the following general formula [VI] can be mentioned. _{^{L a MX 2 ··· [VI]}} (M is a metal of the periodic table Group IV or the lanthanide series, L ^a is a derivative of a delocalized π bond group, bound to the metal M active site X is independently a hydrogen atom, a halogen atom or a hydrocarbon group containing up to 20 carbon atoms, a silicon atom or a germanium atom, a silyl group or a germyl group.) Among the compounds represented by Formula [VI], specifically, compounds represented by the following Formula [VII] are preferable.

[0165]

Embedded image

M is titanium, zirconium or hafnium, and X is the same as described above. Cp is π for M
A substituted cyclopentadienyl group having a substituent Z and a derivative thereof.

Z is oxygen, sulfur, boron or an element of group IVA of the periodic table, Y is a ligand containing nitrogen, phosphorus, oxygen or sulfur, and forms a condensed ring with Z and Y May be.

As the compound represented by the formula [VII], specifically, (dimethyl (t-butylamide))
(Tetramethyl-η ⁵ -cyclopentadienyl) silane
Titanium dichloride, ((t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl)
Titanium dichloride, (dibenzyl (t-butylamide)
(Tetramethyl-η ⁵ -cyclopentadienyl) silane
Titanium dichloride, (dimethyl (t-butylamido) (tetramethyl-eta ⁵ - cyclopentadienyl) silane) dibenzyl titanium, (dimethyl (t-butylamido) (tetramethyl-eta ⁵ - cyclopentadienyl) silane) dimethyl Titanium, ((t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl) dibenzyltitanium, ((methylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1, 2-ethanediyl) dineopentyl titanium, ((phenylphosphide) (tetramethyl-
η ⁵ -cyclopentadienyl) methylene) diphenyltitanium, (dibenzyl (t-butylamide) (tetramethyl
-η ⁵ -cyclopentadienyl) silane) dibenzyltitanium, (dimethyl (benzylamide) (η ⁵ -cyclopentadienyl) silane) di (trimethylsilyl) titanium,
(Dimethyl (phenyl phosphide)-(tetramethyl-
η ⁵ -cyclopentadienyl) silane) dibenzyltitanium, ((tetramethyl-η ⁵ -cyclopentadienyl)-
1,2-ethanediyl) dibenzyl titanium, (2-η ^5- (tetramethyl-cyclopentadienyl) -1-methyl-ethanolate (2-)) dibenzyl titanium, (2-η ^5- (tetramethyl- Cyclopentadienyl) -1-methyl-ethanolate (2-)) dimethyltitanium, (2-((4a, 4b, 8a, 9,9a-η)-
9H-fluoren-9-yl) cyclohexanolate (2-))
Dimethyltitanium, (2-((4a, 4b, 8a, 9,9a-η) -9H-fluoren-9-yl) cyclohexanolate (2-)) dibenzylziltitanium and the like can be mentioned.

In the present invention, two or more metallocene compounds represented by the above formula [VI] can be used in combination. In the above description, a titanium compound is exemplified as the metallocene compound, but a compound in which titanium is replaced with zirconium or hafnium can also be exemplified.

These compounds may be used alone or in combination of two or more. In preparing the long-chain branched ethylene / α-olefin / non-conjugated polyene copolymer rubber (B), among the above-mentioned metallocene compounds, the metallocene compound represented by the above general formula [V] is preferably used.

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.

Conventionally known aluminoxanes 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.

As the organoaluminum compound used in the production of aluminoxane, specifically, 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.

Among these, aluminum trialkyl and aluminum tricycloalkyl 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.

As the Lewis acid, 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 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,
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, as the ionic compound containing a boron atom, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentane) Fluorophenyl) borate can also be mentioned.

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 the borane compound, the carborane complex compound and the salt of the carborane anion include decaborane (14), 7,8-dicarboundecaborane (13),
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, tri-2-ethylhexylaluminum, and isoprenylaluminum. Alkenyl aluminum such as dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride, diisobutyl aluminum chloride, dialkyl aluminum halide 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 , for example, dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide and the like.

[0192] _{^{(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.

[0193] _{^{(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..

[0194] _{^{(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 catalyst used in the present invention contains the above 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 1 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, long-chain or long-chain branched ethylene / α-olefin /
A non-conjugated polyene copolymer rubber (B) can be obtained.

Even if ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene are copolymerized with a Group VB transition metal compound-based catalyst such as a vanadium-based catalyst, sufficient polymerization can be attained. Activity makes it impossible to obtain a copolymer rubber.

In the case of producing an ethylene / 1-butene / non-conjugated polyene copolymer rubber, EPDM or the like using a Group VB transition metal compound-based catalyst, the type of non-conjugated polyene may be ENB or the like. It is often limited to norbornene ring-containing polyenes.

On the other hand, when a metallocene catalyst is used as in the present invention, the non-conjugated polyene is not limited to the norbornene ring-containing polyenes, but may be any of the various polyenes described above, for example, 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 C 3 -C 3
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 above metallocene compound [A], organoaluminum oxy compound [B], compound [C] forming an ion pair and 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 3
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.

The 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.

[0211] The ethylene / α-
The olefin / non-conjugated polyene copolymer rubber (B) is obtained by the method described above, and the molecular weight of the copolymer rubber (B) 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.

In the present invention, the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) comprises a crystalline polyolefin resin (A) and an ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) Total amount of 100
90 to 40 parts by weight, preferably 80 to parts by weight,
Used in a proportion of 45 parts by weight.

Other Ingredients The olefin-based thermoplastic elastomer composition according to the present invention comprises a crystalline polyolefin resin (A) and an ethylene / α-olefin / non-conjugated polyene copolymer rubber (B).
Besides, a softener (C) and / or an inorganic filler (D)
Can be included.

As the softener (C) used in the present invention, a softener usually used for rubber can be used. Specifically, petroleum-based substances such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, petrolatum; coal tars such as coal tar and coal tar pitch; castor oil, linseed oil, rapeseed oil, soybean oil, Fatty oils such as coconut oil; waxes such as tall oil, beeswax, carnauba wax and lanolin; fatty acids such as ricinoleic acid, palmitic acid, stearic acid, barium stearate and calcium stearate or metal salts thereof;
Synthetic polymer substances such as coumarone indene resin and atactic polypropylene; ester plasticizers such as dioctyl phthalate, dioctyl adipate and dioctyl sebacate; other microcrystalline waxes, sub (factice), liquid polybutadiene, modified liquid polybutadiene, liquid thiocol And the like.

In the present invention, the softener (C) is used in combination with the crystalline polyolefin resin (A) and the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B).
200 parts by weight or less, preferably 2 to 100 parts by weight
100 parts by weight, more preferably 5 to 80 parts by weight. When the softener (C) is used in the above ratio, the obtained thermoplastic elastomer composition has excellent fluidity at the time of molding and does not lower the mechanical properties of the molded article. In the present invention, the use amount of the softener (C) is 2
When the amount exceeds 00 parts by weight, the heat resistance and heat aging resistance of the obtained thermoplastic elastomer composition tend to decrease.

Examples of the inorganic filler (D) used in the present invention include calcium carbonate, calcium silicate, clay, kaolin, talc, silica, diatomaceous earth,
Mica powder, asbestos, alumina, barium sulfate, aluminum sulfate, calcium sulfate, basic magnesium carbonate, molybdenum disulfide, graphite, glass fiber, glass sphere, shirasu balloon, basic magnesium sulfate whisker, calcium titanate whisker, aluminum borate whisker And the like.

In the present invention, the inorganic filler (D) is
Crystalline polyolefin resin (A) and ethylene α-
It is used in an amount of 100 parts by weight or less, preferably 2 to 50 parts by weight, based on 100 parts by weight of the total amount of the olefin / non-conjugated polyene copolymer rubber (B). In the present invention, when the amount of the inorganic filler (D) exceeds 100 parts by weight, the rubber elasticity of the obtained thermoplastic elastomer composition,
Moldability tends to decrease.

The olefin-based thermoplastic elastomer composition according to the present invention contains a crystalline polyolefin resin (A), an ethylene / α-olefin / non-conjugated polyene copolymer rubber (B), a softener (C) and In addition to the inorganic filler (D), ethylene-propylene copolymer rubber (E
PR), ethylene / propylene / non-conjugated diene copolymer rubber (EPDM).

Specific examples of the ethylene / propylene / non-conjugated diene copolymer rubber include ethylene / propylene / 5-
Ethylidene-2-norbornene copolymer rubber, ethylene
Propylene / dicyclopentadiene copolymer rubber and the like.

In the present invention, the above-mentioned ethylene / propylene copolymer rubber (EPR) and ethylene / propylene copolymer rubber (EPR)
Propylene / non-conjugated diene copolymer rubber (EPDM)
Is a crystalline polyolefin resin (A) and ethylene
It is preferably 10 to 200 parts by weight based on 100 parts by weight of the total amount of the α-olefin / non-conjugated polyene copolymer rubber (B).
It is desirable to use it in a ratio of 20 parts by weight, more preferably 20 to 150 parts by weight.

Further, in the present invention, a lubricant such as a heat-resistant stabilizer, an anti-aging agent, a weather-resistant stabilizer, an antistatic agent, a metal soap, a wax or the like, which is conventionally known, is added to the olefin-based thermoplastic elastomer. It can be added in a range that does not impair the purpose.

In the olefin-based thermoplastic elastomer composition according to the present invention, the non-crosslinked thermoplastic elastomer composition comprises the above-mentioned crystalline polyolefin resin (A),
After the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) is mixed with a softening agent (C) and / or an inorganic filler (D) which are blended as required, a dynamic heat treatment is performed. It is obtained by doing.

The partially or completely crosslinked olefin-based thermoplastic elastomer composition according to the present invention can be obtained by mixing the above-mentioned crystalline polyolefin resin (A) with an ethylene / α-olefin / non-conjugated polyene copolymer. A mixture of the coalesced rubber (B) and a softener (C) and / or an inorganic filler (D) blended as needed is dynamically mixed in the presence of an organic peroxide as described below. It is obtained by partial or complete crosslinking by heat treatment.

Here, “dynamically heat-treating” means kneading in a molten state. As the organic peroxide used in the present invention, specifically, dicumyl peroxide,
Di-tert-butyl peroxide, 2,5-dimethyl-2,5-di-
(Tert-butylperoxy) hexane, 2,5-dimethyl-2,
5-di- (tert-butylperoxy) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene,
1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-
Chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert-butylperbenzoate, tert-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert-butylcumyl peroxide, and the like.

Of these, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane and 2,5-dimethyl-2,5-di-, in terms of odor and scorch stability. (Tert-Butylperoxy) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene is preferred;
5-Dimethyl-2,5-di- (tert-butylperoxy) hexane is most preferred.

The organic peroxide is used in an amount of 100 parts by weight based on the total amount of the object to be treated, that is, the total amount of the crystalline polyolefin resin (A) and the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B). The amount is 0.02 to 3 parts by weight, preferably 0.05 to 1 part by weight. If the amount of the organic peroxide is less than the above range, the resulting thermoplastic elastomer composition has a low degree of crosslinking, and thus has insufficient heat resistance, tensile properties, elastic recovery, and rebound resilience. If the amount is more than the above range, the resulting thermoplastic elastomer composition may have an excessively high degree of cross-linking, resulting in a decrease in moldability.

In the present invention, sulfur, p-quinonedioxime, p,
Peroxy crosslinking aids such as p'-dibenzoylquinone dioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, trimethylolpropane-N, N'-m-phenylenedimaleimide, Or multifunctional methacrylate monomers such as divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate, vinyl butyrate, vinyl stearate, etc. Polyfunctional vinyl monomers can be included.

By using a compound as described above,
A uniform and mild crosslinking reaction can be expected. Particularly, in the present invention, divinylbenzene is most preferred. Divinylbenzene is easy to handle, and is a crystalline polyolefin resin (A) and an ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) which are the main components of the above-mentioned crosslinked product.
Has good compatibility with water and has the effect of solubilizing organic peroxides and acts as a dispersant for organic peroxides, so the crosslinking effect by heat treatment is uniform and the balance between fluidity and physical properties The obtained thermoplastic elastomer composition is obtained.

Compounds such as the above-mentioned cross-linking aids or polyfunctional vinyl monomers are used in the above-mentioned process.
2 parts by weight or less, preferably 0.3 part by weight,
It is used in such an amount that it becomes １1 part by weight.

In order to promote the decomposition of organic peroxides, tertiary amines such as triethylamine, tributylamine, 2,4,6-tri (dimethylamino) phenol, aluminum, cobalt, vanadium, copper, calcium , Zirconium, manganese, magnesium, lead, mercury and other naphthenates and other decomposition accelerators may be used.

The dynamic heat treatment in the present invention is preferably performed in a non-open type apparatus, and is preferably performed in an atmosphere of an inert gas such as nitrogen or carbon dioxide. The temperature of the heat treatment is in the range of from the melting point of the crystalline polyolefin resin (A) to 300 ° C, usually from 150 to 250 ° C, preferably from 170 to 225 ° C. The kneading time is usually 1
-20 minutes, preferably 1-10 minutes. The applied shearing force is 10 to 100,000 s in shear rate.
ec ^-1 , preferably in the range of 100 to 50,000 sec ^-1 .

As a kneading apparatus, a mixing roll, an intensive mixer (for example, a Banbury mixer, a kneader), a single-screw or twin-screw extruder can be used, but a non-open type apparatus is preferable.

According to the present invention, the crystalline polyolefin resin (A) and ethylene
A non-crosslinked olefinic thermoplastic elastomer composition comprising the α-olefin / non-conjugated polyene copolymer rubber (B) or a partially or completely crosslinked olefinic thermoplastic elastomer composition is obtained.

In the present invention, the fact that the thermoplastic elastomer composition is partially crosslinked means that the gel content measured by the following method is preferably 20% by weight or more and less than 99.5% by weight, particularly preferably 45% by weight or less. It means that it is within the range of 98% by weight. Further, the thermoplastic elastomer composition was completely crosslinked when the gel content was 99.5% by weight.
The above is the case. [Measurement Method of Gel Content] A 100 mg sample of the thermoplastic elastomer composition was sampled and 0.5 mm × 0.5 mm
A sample cut into × 0.5 mm strips is immersed in 30 ml of cyclohexane at 23 ° C. for 48 hours in a closed container, then the sample is taken out on a filter paper and dried at room temperature for at least 72 hours until a constant weight is obtained. I do.

From the weight of the dried residue, the weight of all cyclohexane-insoluble components (fibrous filler, filler, pigment, etc.) other than the polymer component and the weight of the crystalline polyolefin resin (A) in the sample before immersion in cyclohexane were determined. The subtracted value is referred to as “corrected final weight (Y)”.

On the other hand, the weight of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) in the sample is referred to as “corrected initial weight (X)”. Where the gel content is
It is obtained by the following equation.

Gel content [% by weight] = [corrected final weight (Y) / corrected initial weight (X)] × 100

[0238]

The olefin-based thermoplastic elastomer composition according to the present invention can be obtained by preparing an ethylene copolymer prepared by using [I] a crystalline polyolefin resin (A) and [II] a metallocene catalyst containing a specific metallocene compound. And a random copolymer consisting of an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene, and a unit derived from ethylene and a unit derived from an α-olefin having 3 to 20 carbon atoms. Ratio, iodine value and intrinsic viscosity [η]
Contains a specific range of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) in a specific ratio, so that even in the case of a non-cross-linked type, a conventionally known non-cross-linked type A molded article having excellent tensile strength, elongation at break, rubbery properties, heat resistance, and low-temperature properties can be provided as compared with olefin-based thermoplastic elastomers.

The olefin-based thermoplastic elastomer composition according to the present invention contains the above components (A) and (B) in a specific ratio, so that it is particularly partially or completely crosslinked. Can provide a molded article having better low-temperature properties, tensile strength, elongation at break, and rubber-like properties than conventional vulcanized rubber.

Hereinafter, the present invention will be described with reference to Examples.
The present invention is not limited to these examples. In addition, the measuring method of the physical property performed about the olefin-type thermoplastic elastomer composition of an Example and a comparative example is as follows.

[Measurement method of physical properties] (1) Tensile strength: 200 in accordance with JIS K6301
The tensile strength at break was measured at a tensile speed of mm / min. (2) Elongation at break: 200 in accordance with JIS K 6301
The breaking elongation at the breaking point was measured at a pulling speed of mm / min. (3) Permanent elongation: Measured according to JIS K6301. However, the retained length was a length corresponding to 100% elongation. (4) Heat Sag: A test piece (size 128 mm × 25 mm × 3 mm, length 128 m) is attached to a cantilever fixture.
The fixed part of m is 28 mm, and the measuring part is 100 mm)
Was held horizontally and allowed to stand at 90 ° C. for 1 hour, and the amount of deformation of the free end hanging down was measured with a caliper.

[0242]

[Reference Example 1]Preliminary contact between zirconium compounds and methylalumoxane
Preparation of catalyst solution

[0243]

Embedded image

A predetermined amount of a zirconium compound represented by the above formula and a toluene solution of methylalumoxane (1.2 mg / ml in terms of aluminum atoms) are stirred at room temperature in a dark place 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 0.004 mmol / ml, and the methylalumoxane concentration was 1.
2 milligram atoms / ml.

Next, to this toluene solution, hexane, which is a 5-fold solution of toluene, was added with stirring to prepare a catalyst solution having the following Zr concentration and methylalumoxane concentration. Used as a reaction catalyst.

Zr concentration: 0.00067 mmol / ml
(= 0.67 mmol / l) Methylalumoxane concentration (converted to Al atom): 0.1.
20 mmol / ml (= 200 mmol / l) using a stainless steel polymerization vessel 15 liters of capacity, equipped with Polymerization stirring blade, and continuously ethylene, 1-butene, 5-ethylidene-2-norbornene (hereinafter (Also referred to as ENB) in the presence of the above-mentioned polymerization reaction catalyst.

That is, first, 3.185 liters / hour of dehydrated and purified hexane was poured into the polymerization vessel from the top of the polymerization vessel.
0.67 l / h of the above catalyst solution, 0.3 l / h of a hexane solution of triisobutylaluminum (concentration: 17 mmol / l), 1.5 l / h of a hexane solution of ENB (concentration: 0.02 l / l) Each was fed continuously.

Further, 200 l / h of ethylene and 155 l / h of 1-butene were continuously supplied from the upper part of the polymerization reactor into the polymerization reactor. This copolymerization reaction is 8
The reaction was performed at 0 ° C. and the average residence time was 1 hour (that is, 5 liters of polymerization scale).

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.

As described above, ethylene / 1-butene
ENB copolymer rubber [Copolymer rubber (B-1)] was obtained in an amount of 250 g per hour. The resulting copolymer rubber has a molar ratio of units derived from ethylene to units derived from 1-butene (ethylene / 1-butene) of 79/21,
The iodine value based on ENB was 10.

[0251] Further, this copolymer rubber has an intrinsic viscosity measured at 135 ° C. in decalin [eta] is 2.7 dl / g, T for Tαα in ¹³ C-NMR spectrum
αβ intensity ratio D is less than 0.01, B value is 1.1, glass transition temperature (Tg) is −56 ° C., gη
^{* The} value was 0.98.

The results are shown in Table 1.

[0253]

REFERENCE EXAMPLES 2 AND 3 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-2) and (B-3)] were produced.

In these copolymer rubbers, the molar ratio of units derived from ethylene to units derived from α-olefin, iodine value, intrinsic viscosity [η], D value, B value, Tg, and gη ^* value Are shown in Table 1.

[0255]

Reference Example 4 In Reference Example 1, an ethylene / α-olefin / non-conjugated polyene copolymer rubber [copolymer rubber (B-4) was used in the same manner as in Reference Example 1 except that the following zirconium compound was used as a catalyst. )].

[0256]

Embedded image

Rac-Dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride The moles of units derived from ethylene and units derived from α-olefin of these copolymer rubbers Ratio, iodine value, intrinsic viscosity [η], D value, B value, Tg, and gη ^*
The values are shown in Table 1.

[0258]

[Table 1]

[Examples relating to non-crosslinked thermoplastic elastomer composition]

[0260]

Example 1 The ethylene / 1-butene / 5-ethylidene-2-norbornene copolymer rubber (B-
1) 50 parts by weight and MFR (ASTM D 1238-6)
5T, 230 ° C.) 11 g / 10 min, density 0.91 g
/ Cm ³ of propylene homopolymer (A-1) was kneaded with a Banbury mixer at 180 ° C. for 10 minutes, and the kneaded product was passed through an open roll and cut with a sheet cutter to form a square. A pellet was obtained.

Next, a predetermined test piece was prepared by injection molding using the square pellet, and its physical properties (tensile strength, elongation at break, permanent elongation, Heat Sag) were measured according to the above-mentioned measuring methods.

The results are shown in Table 2.

[0263]

Example 2 In Example 1, ethylene / 1-butene
5-ethylidene-2-norbornene copolymer rubber (B-1)
Instead of the ethylene / 1-octene obtained in Reference Example 2,
5-ethylidene-2-norbornene copolymer rubber (B-2)
An olefin-based thermoplastic elastomer composition was prepared and the physical properties were measured in the same manner as in Example 1 except for using.

The results are shown in Table 2.

[0265]

Example 3 In Example 1, ethylene / 1-butene
5-ethylidene-2-norbornene copolymer rubber (B-1)
Instead of ethylene / 1-butene / 5- obtained in Reference Example 3
An olefin-based thermoplastic elastomer composition was prepared in the same manner as in Example 1 except that the ethylidene-2-norbornene copolymer rubber (B-3) was used, and the physical properties were measured.

The results are shown in Table 2.

[0267]

[Example 4] In Example 1, ethylene / 1-butene
5-ethylidene-2-norbornene copolymer rubber (B-1)
In place of the ethylene / 1-butene / 5- obtained in Reference Example 4.
An olefin-based thermoplastic elastomer composition was prepared in the same manner as in Example 1 except that the ethylidene-2-norbornene copolymer rubber (B-4) was used, and the physical properties were measured.

The results are shown in Table 2.

[0269]

[0270]

[0271]

[Table 2]

[0272]

Example 5 In Example 1, ethylene / 1-butene
5-ethylidene-2-norbornene copolymer rubber (B-1)
An olefin-based thermoplastic elastomer composition was prepared in the same manner as in Example 1 except that the blending amounts of the propylene homopolymer (A-1) and the propylene homopolymer (A-1) were respectively 75 parts by weight and 25 parts by weight, and the physical properties were measured. did.

The results are shown in Table 3.

[0274]

[0275]

[0276]

[Table 3]

[0277]

[Embodiment 6] In Example 1, ethylene / 1-butene
5-ethylidene-2-norbornene copolymer rubber (B-1)
And a propylene homopolymer (A-1), and a mineral oil-based softener [PW-38 manufactured by Idemitsu Kosan Co., Ltd.]
0], 40 parts by weight, and 20 parts by weight of talc (trade name: ET-5, manufactured by Matsumura Sangyo Co., Ltd.) were prepared in the same manner as in Example 1 to prepare an olefin-based thermoplastic elastomer composition. Its physical properties were measured.

The results are shown in Table 4.

[0279]

[0280]

[0281]

[Table 4]

[Examples Related to Partially or Completely Crosslinked Thermoplastic Elastomer Composition]

[0283]

Example 7 The ethylene / 1-butene / 5-ethylidene-2-norbornene copolymer rubber (B-
1) An organic peroxide [2,5-dimethyl] was added to 50 parts by weight and 50 parts by weight of the propylene homopolymer (A-1) of Example 1.
-2,5-di- (tert-butylperoxy) hexyne-3]
0.2 parts by weight and divinylbenzene (DVB) 0.
After adding 3 parts by weight and thoroughly mixing in a Henschel mixer, the resulting mixture was mixed with a Banbury mixer for 1 hour.
After kneading at 80 ° C. for 10 minutes, the kneaded material was passed through an open roll and cut with a sheet cutter to obtain square pellets.

Next, a predetermined test piece was prepared by injection molding using the square pellet, and its physical properties were measured according to the above-mentioned measuring methods. Table 5 shows the results.

[0285]

[Embodiment 8] In Example 7, ethylene / 1-butene
5-ethylidene-2-norbornene copolymer rubber (B-1)
An olefin-based thermoplastic elastomer composition was prepared in the same manner as in Example 7, except that an ethylene / 1-octene / 5-ethylidene-2-norbornene copolymer rubber (B-2) was used instead of Its physical properties were measured.

The results are shown in Table 5.

[0287]

[Embodiment 9] In Example 7, ethylene / 1-butene
5-ethylidene-2-norbornene copolymer rubber (B-1)
An olefin-based thermoplastic elastomer composition was prepared in the same manner as in Example 7, except that an ethylene / 1-butene / 5-ethylidene-2-norbornene copolymer rubber (B-3) was used instead of Its physical properties were measured.

The results are shown in Table 5.

[0289]

[0290]

[0291]

[Table 5]

[0292]

Example 10 In Example 7, an ethylene / 1-butene / 5-ethylidene-2-norbornene copolymer rubber (B-
An olefin-based thermoplastic elastomer composition was prepared in the same manner as in Example 7, except that the blending amounts of 1) and the propylene homopolymer (A-1) were respectively 75 parts by weight and 25 parts by weight. Was measured.

The results are shown in Table 6.

[0294]

Example 11 In Example 10, an ethylene / 1-butene / 5-ethylidene-2-norbornene copolymer rubber (B-
Instead of 1), ethylene / 1-butene / 5-ethylidene-2
-An olefin-based thermoplastic elastomer composition was prepared in the same manner as in Example 10 except that the norbornene copolymer rubber (B-4) was used, and the physical properties were measured.

Table 6 shows the results.

[0296]

[0297]

[0298]

[Table 6]

[0299]

Example 12 In Example 7, an ethylene / 1-butene / 5-ethylidene-2-norbornene copolymer rubber (B-
In addition to 1) and propylene homopolymer (A-1),
Mineral oil-based softener [PW-3 manufactured by Idemitsu Kosan Co., Ltd.
80] 40 parts by weight, and talc [Matsumura Sangyo Co., Ltd.
[Trade name: ET-5] An olefin-based thermoplastic elastomer composition was prepared and the physical properties were measured in the same manner as in Example 7 except that 20 parts by weight was blended.

Table 7 shows the results.

[0301]

[0302]

[0303]

[Table 7]

Continuing on the front page (72) Inventor Kyoko Kobayashi 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 No. Mitsui Petrochemical Industry Co., Ltd. (72) Inventor Toshihiro Aine 1-2-1, Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Petrochemical Industry Co., Ltd. (56) References JP-A-4-114045 ( JP, A) JP-A-55-71738 (JP, A) JP-A-7-41617 (JP, A) JP-A-53-37754 (JP, A) JP-A-7-113025 (JP, A) Hei2-113045 (JP, A) Patent 3342604 (JP, B2) WO 94/006859 (WO, A1) WO 94/006858 (WO, A1) (58) Fields investigated (Int. Cl. ⁷ , DB) Name) C08L 1/00-101/16 C08F 210/00-210/18 C08F 4/64-4/69

Claims (6)

(57) [Claims] 1. A crystalline polyolefin resin (A) having an amount of 10 to 60 parts by weight, ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene (provided that the following general formula (A) 90 to 40 parts by weight of ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) [the total amount of (A) and (B) is 100 parts by weight Wherein the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) is in the presence of a Group IVB metallocene catalyst of the periodic table. It is obtained by random copolymerizing ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene, and (1) (a) a unit derived from ethylene and (b) 3 to 20 carbon atoms. Α-Oleph And a unit derived from the compound in a molar ratio of 40/60 to 95/5 [(a) / (b)], (2) an iodine value of 1 to 50, and (3) decalin at 135 ° C. Intrinsic viscosity [η] measured by
But, 0.1~10dl / g der is, measurements in (4) above (3)
Intrinsic viscosity [η] and the same weight average molecular weight (light
Linear chain having an ethylene content of 70 mol%
Intrinsic viscosity of ethylene / propylene copolymer [η] blank
[Gη * (= [η] / [η] blank )] is 0.95
An olefinic thermoplastic elastomer composition characterized by having a value exceeding : [In the formula (A), n is an integer of 1 to 5, R ¹ is an alkyl group having 1 to 5 carbon atoms, and R ² and R ³ are each independently a hydrogen atom or a carbon atom number. 1 to 5 alkyl groups]. Wherein said ethylene-alpha-olefin-nonconjugated polyene copolymer rubber (B) is, T for Tαα in (5) ¹³ C-NMR spectrum
αβ intensity ratio D (Tαβ / Tαα) is 0.5 or less; (6) B value obtained from ¹³ C-NMR spectrum and the following formula is 1.00 to 1.50; B value = [P _OE ] / (2 • [P _E ] • [P _o ]) (where [P _E ] is the content mole fraction of units derived from (a) ethylene in the random copolymer rubber. , [P _o ] is the content mole fraction of units derived from (b) α-olefin in the random copolymer rubber, and [P _OE ] is the total dyad in the random copolymer rubber. (7) The glass transition temperature (Tg) determined by DSC is -5.
The olefin-based thermoplastic elastomer composition according to claim 1 , wherein the temperature is 0C or lower. 3. An amount of from 10 to 60 parts by weight of a crystalline polyolefin resin (A), ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene (provided that the following general formula (A) 90 to 40 parts by weight of ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) [the total amount of (A) and (B) is 100 parts by weight Wherein the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) is in the presence of a Group IVB metallocene catalyst of the periodic table. Ethylene, an α-olefin having 3 to 20 carbon atoms,
Among carbon double bonds, a carbon-carbon double bond polymerizable by the catalyst is obtained by random copolymerization of a non-conjugated polyene having only one in one molecule, and (1) (a) 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)]; ) An iodine value of 1 to 50; (3) intrinsic viscosity [η] measured in 135 ° C decalin
(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 Ratio [gη ^* (= [η] / [η]) to the intrinsic viscosity [η] _{blank of} mol% linear ethylene / propylene copolymer
_blank )) is from 0.2 to 0.95; olefinic thermoplastic elastomer composition; [In the formula (A), n is an integer of 1 to 5, R ¹ is an alkyl group having 1 to 5 carbon atoms, and R ² and R ³ are each independently a hydrogen atom or a carbon atom number. 1 to 5 alkyl groups]. 4. A polystyrene resin (A) and an ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) having a total amount of 2 to 100 parts by weight based on 100 parts by weight.
The olefin-based thermoplastic elastomer composition according to any one of claims 1 to 3 , wherein the composition contains a softening agent (C) and / or 2 to 50 parts by weight of an inorganic filler (D). object. 5. The olefinic thermoplastic elastomer composition according to claim 3, wherein the olefinic thermoplastic elastomer composition is non-crosslinked. Wherein said olefinic thermoplastic elastomer composition is partially or completely olefinic thermoplastic elastomer composition according to any one of claims 1 to 4, characterized in that it is crosslinked.