JPH0912801A - Crystalline plyolefin resin composition - Google Patents

Abstract

PURPOSE: To obtain a crystalline polyolefin resin composition having excellent low-temperature impact strength by mixing a crystalline polyolefin resin with an ethylene/α-olefin/nonconjugated polyene copolymer rubber having a specified iodine value and a specified intrinsic viscosity in a specified ratio. CONSTITUTION: An ethylene/3-20 C α-olefin/nonconjugated polyene copolymer rubber (e.g. ethylene/1-butene/dicyclopentadiene copolymer) having a molar ratio of ethylene units to α-olefin units of 40/60 to 95/5, an iodine value of 1-50 and an intrinsic viscosity of 0.1-10dl$/g (as measured in decalin at 135 deg.C) is obtained by using a catalyst containing a metallocene compound represented by the formula (M is a group IVB transition metal; R<11> and R<12> are each H, a halogen, a 1-20 C hydrocarbon group, an Si-containing group or the like; and Y is a 1-20 C bivalent hydrocarbon group or the like). 5-40 pts.wt. this copolymer is mixed with 95-60 pts.wt. crystalline polyolefin resin (e.g. crystalline PP) to obtain a crystalline polyolefin resin composition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a crystalline polyolefin resin composition, and more specifically, it is composed of a crystalline polyolefin resin and an ethylene copolymer rubber and is excellent in rigidity and heat resistance and has impact resistance, especially at low temperature. And a crystalline polyolefin resin composition capable of providing a molded article excellent in impact resistance.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION A molded product made of a polyolefin resin such as polyethylene or polypropylene has excellent rigidity and heat resistance and is therefore used in a wide variety of applications.

However, among the polyolefin resins, polypropylene has crystallinity and high glass transition temperature, so that the polypropylene molded article is inferior in impact resistance, particularly impact resistance at low temperature, and its use is limited. .

Therefore, in order to improve the impact resistance of a polypropylene molded body, conventionally, polypropylene has been blended with polyethylene, or a rubber-like substance such as polyisobutylene, polybutadiene, or an amorphous ethylene / propylene copolymer has been used. A compounding method was used to improve the impact resistance of the polypropylene molded body. Among these compounding agents, an amorphous or low crystalline ethylene / propylene random copolymer is often used.

However, in such a composition comprising an amorphous or low crystalline ethylene / propylene random copolymer and polypropylene, the amorphous or low crystalline ethylene / propylene random copolymer is
Since the effect of improving impact resistance is small, in order to improve the impact resistance of the polypropylene molded product, it is necessary to add a large amount of ethylene / propylene random copolymer to the polypropylene composition.

Therefore, when a large amount of an ethylene / propylene random copolymer is used, the impact resistance of a molded product made of this polypropylene composition is improved, but the rigidity and heat resistance originally possessed by polypropylene are large. There is a problem of decrease. On the other hand, if the amount of the ethylene / propylene random copolymer in the polypropylene composition is reduced to maintain the inherent rigidity and heat resistance of polypropylene, the impact resistance at low temperatures may not be sufficiently improved. Occurs.

The inventors of the present invention have earnestly studied to obtain a polypropylene resin composition which is excellent in rigidity, heat resistance and impact resistance, especially in low temperature. Crystalline polypropylene resin and specific ethylene / α-olefin /
By using a polypropylene resin composition comprising a non-conjugated polyene copolymer rubber, it was found that a molded article having excellent rigidity and heat resistance as well as impact resistance, particularly impact resistance at low temperature, can be obtained, and the present invention It came to completion.

[0008]

It is an object of the present invention to solve the problems associated with the prior art as described above, and to form a polyolefin having excellent rigidity and heat resistance as well as impact resistance, especially impact resistance at low temperature. An object of the present invention is to provide a crystalline polyolefin resin composition capable of obtaining a body, particularly a crystalline polypropylene resin composition.

[0009]

SUMMARY OF THE INVENTION The crystalline polyolefin resin composition according to the present invention is a crystalline polyolefin resin (A) 95-60.
5 to 40 parts by weight of ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) consisting of ethylene, α-olefin having 3 to 20 carbon atoms and non-conjugated polyene ([A] and (B And the total amount of 100) is 100 parts by weight].
-The olefin / non-conjugated polyene copolymer rubber (B) is
Obtained by randomly copolymerizing ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene in the presence of a metallocene catalyst, and (1) (a) a unit derived from ethylene and ( b) 3 to 3 carbon atoms
The units derived from 20 α-olefins are 40/6
It is contained at a molar ratio of 0 to 95/5 [(a) / (b)], (2) has an iodine value of 1 to 50, and (3) has an intrinsic viscosity [η] measured in 135 ° C decalin.
Is 0.1 to 10 dl / g.

The metallocene catalyst used for producing the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) may contain a metallocene compound represented by the following formula [III] or [IV]. preferable.

[0011]

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[In the formula, M is a transition metal of Group IVB of the periodic table, and R ¹¹ and R ¹² are hydrogen atoms, halogen atoms, and 1 to 2 carbon atoms which may be substituted with halogen.
0 hydrocarbon group, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group or phosphorus-containing group, R ¹³ and R ¹⁴ are each an alkyl group having 1 to 20 carbon atoms, and X ¹ And X ² are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group, and Y is a carbon atom A divalent hydrocarbon group of the formulas 1 to 20,
A divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, 2
Valent silicon-containing group, divalent germanium-containing group, -O
-, - CO -, - S -, - SO -, - SO 2 -, - NR
^{7 -, - P (R 7} ) -, - P (O) (R 7) -, - BR
⁷ - or -AlR ⁷ - it is. (However, R ⁷ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms.)]

[0013]

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[In the formula, M is a transition metal of Group IVB of the Periodic Table, and R ²¹ may be the same or different from each other, and is a hydrogen atom, a halogen atom or an optionally halogenated carbon atom. Alkyl group having 1 to 10 carbon atoms, 6 to
Aryl group, or -NR ₂ of 10, -SR, -OSi
R ₃ , —SiR ₃ or —PR ₂ (R is a halogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms), and R ^{22 to} R ²⁸ are as defined above. It is the same as R ²¹ , or adjacent R ^{22 to} R ²⁸ may form an aromatic ring or an aliphatic ring together with the atoms to which they are bonded, and X ³ and X ⁴ may be the same or different from each other. Hydrogen atom, halogen atom, O
H group, alkyl group having 1 to 10 carbon atoms, 1 carbon atom
Alkoxy group having 10 to 10 carbon atoms, aryl group having 6 to 10 carbon atoms, aryloxy group having 6 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, carbon atom An alkylaryl group having 7 to 40 carbon atoms, an arylalkenyl group having 8 to 40 carbon atoms,

[0015]

[Chemical 6]

-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, a fluoroalkyl group having 1 to 10 carbon atoms, and 6 carbon atoms. 10 to 10 aryl groups,
C6-C10 fluoroaryl group, C1-C10 alkoxy group, C2-C10 alkenyl group, C7-C40 arylalkyl group, C8-C40 aryl An alkenyl group or an alkylaryl group having 7 to 40 carbon atoms, or R
²⁹ and R ³⁰ may each form a ring with the atoms to which they are attached, and M ² is a silicon, germanium or tin atom. )] The ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) has, in addition to the characteristics (1) to (3), (4) T for Tαα in ¹³ C-NMR spectrum.
The intensity ratio D (Tαβ / Tαα) of αβ is 0.5 or less, and (5) the B value obtained from the ¹³ C-NMR spectrum and the following formula is 1.00 to 1.50; B value = [P _OE ] / (2 · [P _E ] · [P _O ]) (In the formula, [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 random copolymer rubber
The ratio of α-olefin / ethylene chain number to the chain number), (6) DSC glass transition temperature (Tg) is -5.
It is preferably 0 ° C. or lower.

[0017]

DETAILED DESCRIPTION OF THE INVENTION The crystalline polyolefin resin composition according to the present invention will be specifically described. The crystalline polyolefin resin composition according to the present invention contains 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. Examples of such resins include isotactic and syndiotactic monoolefin polymer resins. These representative resins are commercially available.

As a suitable raw material olefin of the crystalline polyolefin resin (A), specifically, ethylene,
Propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 3-methyl-1-butene, 2-methyl-1-
Examples include propene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, 3-methyl-1-hexene, vinylcyclopentene, vinylcyclohexane, vinylnorbornene and the like. These olefins are
They may be used alone or in combination of two or more.

In the present invention, propylene or a mixed olefin composed of propylene and another olefin is preferably used. That is, polypropylene is preferable as the crystalline polyolefin resin (A) used in the present invention.

Examples of the polypropylene include a propylene homopolymer and a propylene / α-olefin copolymer containing a constitutional unit derived from an α-olefin other than propylene in an amount of 10 mol% or less. Examples of the α-olefin constituting the propylene / α-olefin copolymer include the above-mentioned α-olefin.

The polymerization method for obtaining the crystalline polyolefin resin may be random type or block type, and any polymerization method may be adopted as long as a resinous material is obtained.
Crystalline polyolefin resin (A) used in the present invention
Is 230 ° C, 2.1 in accordance with ASTM-D1288.
Melt flow rate (MFR) measured under a load of 6 kg
Is usually 0.01 to 200 g / 10 minutes, preferably 0.
05-100g / 10 minutes, more preferably 0.1-1
It is preferably in the range of 00 g / 10 minutes.

These crystalline polyolefin resins may be used alone or in combination of two or more. In the present invention, the crystalline polyolefin resin (A) is 95 to 100 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). It is used in a proportion of 60 parts by weight, preferably 85 to 65 parts by weight.

Ethylene / α-olefin / non-conjugated polyene
Copolymer rubber (B) The ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) used in the present invention contains ethylene and carbon atoms in the presence of a specific metallocene catalyst as described below. It is obtained by randomly copolymerizing an α-olefin of the number 3 to 20 and a non-conjugated polyene.

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

Of these, α-containing 4 to 10 carbon atoms
Olefins are preferred, especially 1-butene, 1-hexene, 1-
Octene and 1-decene are preferably used. Also,
Examples of the non-conjugated polyene include aliphatic polyene and 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, vinyl norbornene, 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 can be mentioned.

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, such as methyl octadiene (MOD) such as 7-methyl-1,6-octadiene and 5-ethylidene-2-norbornene. Ethylidene norbornene (ENB) and dicyclopentadiene (DCPD) are preferably used.

These non-conjugated polyenes can be used alone or in combination of two or more. The ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) used in the present invention has the following characteristics. (1) Ethylene / α-olefin component ratio The ethylene / α-olefin / non-conjugated polyene copolymer rubber (A) used in the present invention comprises (a) a unit derived from ethylene and (b) 3 carbon atoms. Unit derived from an α-olefin (hereinafter, sometimes simply referred to as α-olefin) of 40 to 60 to 95/5, preferably 4
0/60 to 90/10, particularly preferably 50/50 to 8
It is contained in a molar ratio of 5/15 [(a) / (b)].

The ethylene / α-olefin / non-conjugated polyene copolymer rubber having such an ethylene component / α-olefin component ratio is excellent in low temperature flexibility, impact resistance at low temperature and heat resistance. There is. In addition, ethylene
When the olefin / non-conjugated polyene copolymer rubber has an ethylene / α-olefin component ratio of more than 95/5, the olefin / non-conjugated polyene copolymer rubber exhibits resin 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 5 to 40. (3) Intrinsic viscosity [η] The intrinsic viscosity [η] of ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) measured in decalin at 135 ° C is 0.1 to 10 dl / g, preferably 0.5 ~
It is 7 dl / g, more preferably 0.9 to 5 dl / g.

Further, ethylene / α used in the present invention
-The olefin / non-conjugated polyene copolymer rubber (B) is
It is preferable that the following properties (4) to (6) are satisfied. (4) D value The intensity (area) ratio of Tαβ to Tαα in the ¹³ C-NMR spectrum of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) D (Tαβ / Tαα)
Is preferably 0.5 or less, and particularly preferably 0.3 or less.

The strength ratio D value of the random copolymer rubber differs 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 units derived from α-olefins, respectively, and are the two types of CH ₂ having different positions with respect to the tertiary carbon as shown below. Means

[0033]

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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 device manufactured by JEOL Ltd., with a sample concentration of 5% by weight of hexachlorobutadiene / d.
A mixed solution of ₆ -benzene = 2/1 (volume ratio) was added to 67.8.
Measurement is carried out at 25 MHz and 25 MHz with d ₆ -benzene (128 ppm) standard.

Analysis of ¹³ C-NMR spectrum is basically carried out by Lindemann Adams (Analysis Chemistry 43,
p1245 (1971)), JCRandall (Review Macromolecular
Chemistry Physics, C29, 201 (1989)).

Here, the strength ratio D will be described more specifically by taking an 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 by the integrated value (area) ratio of each peak portion. The intensity ratio D thus obtained is generally a ratio of 1,2-addition reaction of 1-butene followed by 2,1 addition reaction, or 1-butene 2,1
It is considered to be a scale showing the ratio of 1,2 addition reaction following the addition reaction. Therefore, the larger the strength ratio D value, the more irregular the bonding direction of the α-olefin (1-butene). Conversely, the smaller the D value, the more α
-It is shown that the bonding direction of the olefin is regular, and if the regularity is high, the molecular chains are likely to aggregate, and the random copolymer rubber tends to have excellent strength and the like, which is preferable.

In the present invention, as described below, ethylene, α-olefin and non-conjugated polyene are copolymerized by using a specific Group IVB metallocene catalyst,
A random copolymer rubber having a strength ratio D of 0.5 or less has been obtained. For example, ethylene, 1-butene and 7-methyl-1,6 are added in the presence of a Group VB metallocene catalyst such as vanadium. -Ethylene / 1-butene / 7-methyl-with a strength ratio D of 0.5 or less even when it is copolymerized with octadiene
It is not possible to obtain 1,6-octadiene copolymer rubber. The same applies to α-olefins other than 1-butene. (5) B value The ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) preferably has a B value of 1.00 to 1.50, which is obtained from the ¹³ C-NMR spectrum and the following formula. .

B value = [P _OE ] / (2 · [P _E ] · [P _O ]) (where [P _E ] is a unit derived from (a) ethylene in the random copolymer rubber) Is the mole fraction contained,
[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 above B value, the shorter the blocky 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. There is. Note that the composition distribution of the copolymer rubber becomes wider as the B value becomes smaller than 1.00, and such a copolymer rubber is more vulcanized when compared with a copolymer rubber having a narrow composition distribution. Physical properties such as strength may not be sufficiently expressed.

In the present invention, as described later,
By copolymerizing ethylene, an α-olefin and a non-conjugated polyene using a Group IVB metallocene catalyst, a random copolymer rubber having a 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. (6) Glass transition temperature The glass transition temperature (Tg) of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) measured by DSC (differential scanning calorimeter) is -50 ° C or lower. desirable.

From the random copolymer rubber having a glass transition temperature (Tg) of −50 ° C. or lower, a crystalline polyolefin resin composition excellent in low temperature flexibility can be obtained.
It should be noted that ethylene / α-olefin /
A non-conjugated polyene copolymer rubber, for example, a random copolymer rubber of ethylene, 1-butene and ethylidene norbornene (ENB) has the same composition ratio of the random copolymer rubber, ethylene, α-olefin and non-conjugated polyene. The glass transition temperature (Tg) of the copolymer rubber (EPDM) of ethylene, propylene, and ENB is about 5 to 5.
It is 10 ° C. lower and has characteristics of low temperature characteristics, for example, excellent impact resistance at low temperatures.

The above-mentioned ethylene / α-olefin /
The gη ^* value obtained from the intrinsic viscosity [η] of the non-conjugated polyene copolymer rubber (B) is preferably more than 0.95.

This gη ^* value is defined by the following equation. gη ^* = [η] / [η] _blank (where [η] is the intrinsic viscosity measured in (3) above, and [η] _blank is the ethylene / α-of the intrinsic viscosity [η]. It is the intrinsic viscosity of a linear ethylene-propylene copolymer having the same weight average molecular weight (by light scattering method) as that of the olefin / non-conjugated polyene copolymer rubber and an ethylene content of 70 mol%.) As described above.・ Ethylene ・ α-olefin ・
From a non-conjugated polyene copolymer rubber, a crystalline polyolefin resin composition excellent in mechanical strength, weather resistance and ozone resistance, and also excellent in cold resistance (low temperature flexibility) and heat resistance and a molded product thereof are provided. Obtainable.

The above-mentioned specific ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) is prepared by adding ethylene and 3 carbon atoms in the presence of a specific metallocene catalyst.
It is produced by random copolymerization of .about.20 α-olefin and a non-conjugated polyene.

The metallocene catalyst used in the present invention is
There is no particular limitation 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 organoaluminum oxy compound [B] and / or an organoaluminum compound [D] together with a compound [C] forming an ion pair.

In the following, each component used in forming the metallocene catalyst in the present invention will be described. Metallocene Compound [A] As the metallocene compound [A] used in the present invention,
Examples thereof include compounds represented by the following general formula [I].

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

Examples of the ligand having a cyclopentadienyl skeleton include 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 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, indenyl group, 4,5,6,7-tetrahydroindenyl group Group, fluores And the like.

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 groups having a cyclopentadienyl skeleton among them 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,
Alkoxy group, aryloxy group, halogen atom, hydrogen atom or sulfonic acid-containing group (—SO ₃ ^Ra ) [wherein
^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.

Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group, and more specifically, methyl, ethyl, n-propyl, isopropyl, n. -Butyl, isobutyl, sec-butyl, t-butyl, pentyl, hexyl, octyl, decyl, dodecyl etc. alkyl groups, cyclopentyl, cyclohexyl etc. cycloalkyl groups, phenyl, tolyl etc. aryl groups, benzyl, neofil etc. aralkyl Groups.

As the alkoxy group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group,
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 examples of the sulfonic acid-containing group (--SO ₃ ^Ra ) 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 transition metal has a valence of 4, 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 above general formula [I]. k is an integer of 1 or more, and k + 1 + m + n = 4.

Below, M is zirconium, and
The 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 (cyclopenta 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) zirconi Dimethyl, bis (cyclopentadienyl) zirconium methoxy chloride, bis (cyclopentadienyl) zirconium ethoxy chloride, bis (fluorenyl) zirconium dichloride, bis (cyclopentadienyl) zirconium bis (methanesulfonato), bis (cyclopenta) 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 (butylcyclopentadiene) Enil)
Zirconium bis (trifluoromethanesulfonate),
Bis (hexylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (1,3-dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (1-methyl-3-ethylcyclopentadiene) 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 obtained by substituting the 1,3-position-substituted cyclopentadienyl group with a 1,2-position-substituted cyclopentadienyl group can also be used in the present invention. Further, 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 (ligands) having a cyclopentadienyl skeleton, and at least 2
The group can also be exemplified by a bridge-type metallocene compound in which an alkylene group, a substituted alkylene group, a silylene group, a substituted silylene group or the like is bonded. At this time, R ⁴ and R ⁵ are independently the same as L other than the ligand having the cyclopentadienyl skeleton described in the formula [I].

Examples of such bridge-type metallocene compounds are ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium bis (trifluoromethanesulfonate), ethylenebis (indenyl) zirconium. Bis (methanesulfonato), ethylenebis (indenyl) zirconium bis (p-toluenesulfonato), ethylenebis (indenyl) zirconium bis (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, dimethyl silylene bis (indenyl) zirconium dichloride, dimethyl silylene bis (indenyl) zirconium bis (trifluoromethanesulfonato), dimethyl silylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethyl silylene bis ( Cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, Methylphenylsilylenebis (indenyl) zirconium dichloride and the like can be mentioned.

Further, Japanese Patent Laid-Open No. 4-4100 shown by the following formula [A]
Metallocene compounds described in JP-A-268307. The metallocene has the formula [A]:

[0063]

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[In the formula [A], M ¹ is a metal of Group IVB of the Periodic Table, and specific examples thereof include titanium, zirconium and hafnium. R ¹ and R ² may be the same or different from each other, and are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms, and 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, an alkenyl group having 2 to 10 carbon atoms, preferably 2 to 4 carbon atoms, 7-40 carbon atoms, preferably 7-1
0 arylalkyl group, 7 to 40 carbon atoms, preferably 7 to 12 alkylaryl group, 8 to 4 carbon atoms
It is an arylalkenyl group having 0, preferably 8 to 12, or a halogen atom, preferably a chlorine atom.

R ³ and R ^{4, which} may be the same as or different from each other, are a hydrogen atom, a halogen atom, preferably a fluorine atom, a chlorine atom or a bromine atom, and an optionally halogenated carbon atom number of 1 to 10, 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, -Si
R ¹⁰ ₃ or —PR ¹⁰ ₂ group, wherein R ¹⁰ is a halogen atom, preferably a chlorine atom, or 1 to 1 carbon atoms.
It is 0, preferably an alkyl group having 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 hydrogen atoms. R ⁵ and R ⁶ may be the same or different from each other, and preferably the same, R ⁵ and R 6
⁶ is R ³ and R with the proviso that it is not a hydrogen atom.
^It has the meaning described for ⁴ . R ⁵ and R ⁶ are
Preferably 1 to 1 optionally halogenated carbon atoms
The 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, a trifluoromethyl group and the like can be mentioned, and a methyl group is preferable.

R ⁷ is the following:

[0068]

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= BR¹¹, = AlR¹¹, -Ge-, -Sn
-, -O-, -S-, = SO, = SO _Two, = NR¹¹, =
CO, = PR¹¹ Or = P (O) R¹¹And at that time
R¹¹, R ¹²And R¹³Are the same or different from each other
Also, hydrogen atom, halogen atom, carbon atom number 1 to 1
0, preferably 1-4 alkyl groups, more preferably
A methyl group, a fluoroalkyl group having 1 to 10 carbon atoms,
Preferably CF_Three A group having 6 to 10 carbon atoms, preferably
6-8 aryl group, C6-C10 fluoro group
Reel group, preferably pentafluorophenyl group, carbon
An alkoxy group having 1 to 10, preferably 1 to 4 atoms,
Is preferably a methoxy group, having 2 to 10 carbon atoms, preferably
Or 2 to 4 alkenyl groups, 7 to 40 carbon atoms, preferred
Specifically, it is an arylalkyl group having 7 to 10 carbon atoms.
40, preferably 8-12 arylalkenyl groups, or
Or an alkyl having 7 to 40, preferably 7 to 12 carbon atoms.
Is a aryl group or R¹¹And R¹²Or R¹¹When
R¹³And each with the atom to which they are bound
To form a ring.

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 from each other and have the same meaning as described for R ¹¹ . m and n may be the same as 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 (i) to (iii) below.

[0073]

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

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.

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

[0077]

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In the formula [B], M represents a transition metal atom of Group IVB of the periodic table, specifically titanium, zirconium or hafnium. R ¹ and R ² are each independently 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, or sulfur. A containing group, a nitrogen-containing group or a phosphorus-containing group, specifically, a halogen atom such as fluorine, chlorine, bromine or iodine; methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, nonyl, dodecyl, eicosyl, Norbornyl, adamantyl and other alkyl groups, vinyl, propenyl, cyclohexenyl and other alkenyl groups, benzyl,
C1-C20 arylalkyl groups such as phenylethyl, phenylpropyl, aryl groups such as phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthracenyl, phenanthryl, etc. Hydrocarbon group: Halogenated hydrocarbon group in which the above hydrocarbon group is substituted with a halogen atom; Monohydrocarbon-substituted silyl group such as methylsilyl and phenylsilyl, Dihydrocarbon-substituted silyl group such as dimethylsilyl and diphenylsilyl, trimethylsilyl, triethyl Trihydrocarbon-substituted silyl such as silyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyl, 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 alkylamino group such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, 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, and particularly preferably a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl or propyl. Also R ²
Is preferably hydrogen or a hydrocarbon group, and particularly preferably hydrogen or a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl or propyl.

R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, a halogen atom or a carbon atom number of 1 to 20.
And a halogenated hydrocarbon group having 1 to 20 carbon atoms, among which 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 kinds of hydrocarbon groups or halogenated hydrocarbon groups, the groups other than the group forming an aromatic ring may be bonded to 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 the above R ¹ and R ² .

As a ligand coordinated to M, which contains a monocyclic aromatic ring formed by bonding at least one set of R ³ and R ⁴ , R ⁴ and R ⁵ , and R ⁵ and R ⁶ to each other, The following may be mentioned.

[0084]

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Of these, those represented by the above formula (1) are 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.

As the halogen atom, the hydrocarbon group having 1 to 20 carbon atoms, and the halogenated hydrocarbon group having 1 to 20 carbon atoms, which are substituted on the aromatic ring, the same groups as the above R ¹ and R ² can be used. It can be illustrated.

X ¹ and X ² are each independently 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. Group, specifically R
Halogen atom similar to ¹ and R ² , ^{1 to 2} carbon atoms
Examples thereof include a hydrocarbon group having 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 for R ¹ and R ² , and methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, trimethylbenzene sulfonate. Sulfonate groups such as phonate, triisobutylbenzene sulfonate, p-chlorobenzene sulfonate, pentafluorobenzene sulfonate, methylsulfinate, phenylsulfinate, benzylsulfinate, p-toluenesulfinate , Trimethylbenzenesulfinate, pentafluorobenzenesulfinate, and other sulfinate groups.

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, halogenated hydrocarbon groups having 1 to 20 carbon atoms], specifically, methylene, dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene, 1,3-
1 to 20 carbon atoms such as alkylene groups such as trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene and 1,4-cyclohexylene, aryl alkylene groups such as diphenylmethylene and diphenyl-1,2-ethylene A divalent hydrocarbon group having 1 to 2 carbon atoms such as chloromethylene
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 Alkyl silylene groups such as phenyl silylene, diphenyl silylene, di (p-tolyl) silylene, di (p-chlorophenyl) silylene, alkylaryl silylene groups, aryl silylene groups, tetramethyl-1,2-disilylene, tetraphenyl-1, A divalent silicon-containing group such as an alkyl-di-silylene group such as 2-disililen, an alkylaryl-di-silylene group, an aryl-di-silylene group; a di-valent germanium-containing group obtained by substituting germanium for silicon in the above-mentioned di-valent silicon-containing group; A divalent tin-containing group in which silicon in the divalent silicon-containing group is replaced with tin. Group and the like, R ⁷ is,
The same halogen atom and carbon atom number 1 to R ¹ and R ² as described above.
It is a hydrocarbon group having 20 or a halogenated hydrocarbon group having 1 to 20 carbon atoms.

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,
Of these, 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.

[0092]

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[0093]

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[0094]

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

The indene derivative ligand of such a transition metal compound can be synthesized, for example, according to the following reaction route and using a conventional organic synthesis method.

[0097]

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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, the 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.

[0100]

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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 .

Of the groups represented by R ³ , R ⁴ , R ⁵ and R ⁶ , the groups other than the alkyl group are preferably hydrogen atoms. As the 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, adamantyl; benzyl,
Examples thereof include arylalkyl groups such as phenylethyl, phenylpropyl, tolylmethyl and the like, which may contain a double bond or a triple bond.

Two kinds of 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 the aromatic ring. As a halogen atom,
Specifically, the same groups as those for R ¹ and R ² can be exemplified.

Examples of X ¹ , X ² , Y and R ⁷ are the same as in the case of the above formula [B]. Specific examples of the metallocene compound (transition metal compound) represented by the above formula [C] are shown below.

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 in the above compounds is replaced with titanium metal or hafnium metal can be used. The transition metal compound is usually used as a racemic compound, but may be used in R-form or S-form.

The indene derivative ligand of such a transition metal compound can be synthesized, for example, according to the same reaction route as described above and using a usual organic synthesis method. 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 metallocene compounds, the following general formula [III] or [I]
The compound represented by V] is preferably used. General formula [I
The metallocene compound represented by the formula [II] is a part of the compound represented by the formula [C], and the metallocene compound represented by the general formula [IV] is a part of the compound represented by the formula [B]. Is.

[0109]

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

These hydrocarbon groups include halogen atoms such as fluorine, chlorine, bromine and iodine, trimethylsilyl group,
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, phenylmethoxy, phenylethoxy and the like. Examples thereof include an arylalkoxy group.

Specific examples of the sulfur-containing group include substituents obtained by substituting sulfur for oxygen in the oxygen-containing group, methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene. Sulfonate groups such as sulfonate, trimethylbenzene sulfonate, triisobutylbenzene sulfonate, p-chlorobenzene sulfonate, pentafluorobenzene sulfonate, methylsulfinate, phenylsulfinate, benzylsulfinate , P-toluenesulfinate, trimethylbenzenesulfinate, pentafluorobenzenesulfinate, and other sulfinate groups.

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

Specific 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.

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

R ¹³ and R ¹⁴ R ¹³ and R ¹⁴ have 1 carbon atom as exemplified above.
To 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 sulfur-containing group, a halogen atom,
It is preferably 20 hydrocarbon groups.

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 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, dimethyl methylene, 1,2-ethylene, dimethyl
-1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene, 1,4-cyclohexylene and other alkylene groups, diphenylmethylene, diphenyl-1,2-
1 carbon atom such as aryl alkylene group such as ethylene
A divalent hydrocarbon group having 20 to 20 carbon atoms; a halogenated hydrocarbon group obtained by halogenating the above divalent hydrocarbon group 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,
Alkylsilylene groups such as di (p-tolyl) silylene, di (p-chlorophenyl) silylene, alkylarylsilylene groups, arylsilylene groups, alkyl such as tetramethyl-1,2-disilyl, tetraphenyl-1,2-disilyl, etc. Examples thereof include a divalent silicon-containing group such as a disilyl group, an alkylaryldisilyl group, and an aryldisilyl group; and a divalent germanium-containing group obtained by substituting germanium for silicon in the above-mentioned divalent silicon-containing group.

R ¹⁵ is the same halogen atom, hydrocarbon group having 1 to 20 carbon atoms, or halogenated hydrocarbon group having 1 to 20 carbon atoms as described above. Among them, Y is preferably a divalent silicon-containing group, a divalent germanium-containing group, more preferably a divalent silicon-containing group, and is preferably an alkylsilylene group, an alkylarylsilylene group, or an arylsilylene. Particularly preferred is a group.

Specific examples of the metallocene compound represented by the above general formula [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) -Chlormethyl-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 and the like.

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

The transition metal compound as described above can be prepared by a known method from an indene derivative, for example, JP-A-4-268307.
Can be synthesized by the method described in Japanese Patent Application Laid-Open No. H10-260, 1988. The compound represented by the following formula [IV] preferably used in the present invention is EP-549900 and Canada-20.
No. 84017.

[0124]

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In the formula, M is a transition metal atom of Group IVB of the periodic table, specifically, titanium, zirconium,
Hafnium, particularly preferably zirconium. 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, preferably 1 to 3 carbon atoms, or 6 to 10 carbon atoms; Preferably 6 to 8 aryl groups).

R ^{22 to} R ^{28, which} may be the same or different, are the same atoms or groups as those of R ²¹ , and these R ^{22 to} R ²⁸ are the same.
^At least two adjacent groups out of ²⁸ may form an aromatic ring or an aliphatic ring together with their bonding atoms.

X ³ and X ⁴ may be the same or different from each other, and are a hydrogen atom, a halogen atom, an OH group, an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and 1 to 10 carbon atoms. , Preferably an alkoxy group having 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 2-4 alkenyl groups, 7-40 carbon atoms, preferably 7-10 arylalkyl groups, 7-40 carbon atoms, preferably 7-
A 12-alkylaryl group; and an arylalkenyl group having 8 to 40, preferably 8 to 12 carbon atoms.

[0128]

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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 atom 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 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;

[0133]

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(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 preferable, and the substituents R ²² and R ²⁸ are a hydrogen atom, and R ^{23 to} R ²⁷ are more preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.

Further, M is zirconium, and R
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,

[0136]

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(M ² is silicon, R ²⁹ and R ³⁰
May be the same or different, and have 1 carbon atom
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
²⁸ is a hydrogen atom, X ³ and X ⁴ are chlorine atoms,

[0138]

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(M ² is silicon, R ²⁹ and R ³⁰
May be the same or different and each is a methyl group or a phenyl group). Some examples of the 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
(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 and the like.

Further, a compound in which zirconium in the above compounds is replaced by titanium or hafnium can also be mentioned. In the present invention, the formula [III] or [I
The racemic metallocene compound represented by V] is preferably used as the catalyst component, but R type or S type can also be used.

The metallocene compounds as described above can be used in combination of two or more kinds. Organoaluminum oxy compound [B] The organoaluminum oxy compound [B] used in the present invention may be a conventionally known aluminoxane or a benzene-insoluble compound as exemplified in JP-A-2-78687. May be an organic aluminum oxy compound.

The conventionally known aluminoxane can be produced, for example, by the following method. (1) Compounds containing water of adsorption or salts containing water of crystallization, such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerous chloride A method of adding an organoaluminum compound such as a 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 of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

(Iii) A compound represented by R ⁵ _n Al (OAlR ⁸ ₂ ) _3-n , 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..

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

(V) A compound represented by R ⁵ _n Al (SiR ¹⁰ ₃ ) _3-n , for example, (iso-C ₄ H ₉ ) ₂ Al (Si (C
H ₃ ) ₃ ). In the present invention, among these, R ⁵ ₃ Al, R ⁵ _n Al (O
Preferred examples include the organoaluminum compounds represented by R ⁶ ) _3-n and R ⁵ _n Al (OAlR ⁸ ₂ ) _3-n , in which R ⁵ is an isoalkyl group and n = 2. 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] is used.
And an organic aluminum oxy compound [B]. It may be formed from a metallocene compound [A] and a compound [C] which reacts with the metallocene compound [A] to form an ion pair. Further, together with the metallocene compound [A], an organic aluminum oxy compound [B] is used. And a compound [C] which reacts with the metallocene compound [A] to form an ion pair. In these embodiments, it is particularly preferable to further use an organic aluminum compound [D] in combination.

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

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

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

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

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

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

Further, when producing ethylene / 1-butene / non-conjugated polyene copolymer rubber using a Group VB transition metal compound-based catalyst, the type of non-conjugated polyene is also a norbornene ring such as ENB. It is often limited to contained polyenes.

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

In the present invention, ethylene and 3 to 10 carbon atoms are used.
When the α-olefin of No. 20 and the non-conjugated polyene are copolymerized, the metallocene compound [A], the organoaluminum oxy compound [B], which constitute the metallocene catalyst,
The compound [C] forming the ion pair and the organoaluminum compound [D] may be separately supplied to the polymerization reactor, or a metallocene catalyst containing the metallocene compound [A] may be prepared in advance. May be subjected to a copolymerization reaction.

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

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

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

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

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

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

In the present invention, the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) is a crystalline polyolefin resin (A) and an ethylene / α-olefin / non-conjugated polyene copolymer rubber (B). The total amount of 100
5 to 40 parts by weight, preferably 15 to 3 parts by weight
Used in a proportion of 5 parts by weight.

Crystalline Polyolefin Resin Composition The crystalline polyolefin resin composition according to the present invention contains the crystalline polyolefin resin (A) and ethylene / α-olefin / non-conjugated polyene copolymer rubber (B). .

In addition to the crystalline polyolefin resin (A) and the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B), the crystalline polyolefin resin composition according to the present invention contains amorphous propylene / ethylene random. The total amount of the copolymer (C) of components (A) and (B) is
5 to 15 parts by weight, preferably 5-1 to 0 parts by weight
You may contain 0 weight part.

The amorphous propylene / ethylene random copolymer (C) contains a constitutional unit derived from ethylene in an amount of 30 to 60 mol%, preferably 35 to 45 mol%.

The crystalline polyolefin resin composition according to the present invention may optionally contain an inorganic filler in an amount of 5 to 20% by weight. As such an inorganic filler, specifically, calcium carbonate, calcium silicate, clay, carion, 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.

Further, the crystalline polyolefin resin composition according to the present invention contains a heat-resistant stabilizer such as an aromatic carboxylic acid aluminum salt, an aromatic phosphoric acid ester salt and dibenzylidene sorbitol within a range not impairing the object of the present invention. Nucleating agent; UV absorber; Lubricant; Antistatic agent; Flame retardant; Pigment;
Dye; Other polymers may be contained.

The crystalline polyolefin resin composition according to the present invention was kneaded by simultaneously or sequentially supplying the above components to a kneading device such as a Henschel mixer, a V-type blender, a tumbler blender, a ribbon blender or the like. After that, it can be obtained by melt-kneading with a single-screw extruder, a multi-screw extruder, a kneader, a Banbury mixer, or the like.

Among these melt-kneaders, when a device having excellent kneadability such as a multi-screw extruder, a kneader or a Banbury mixer is used, a high-quality crystalline polyolefin resin composition in which each component is uniformly dispersed is obtained. Obtainable.

[0191]

The crystalline polyolefin resin composition according to the present invention comprises: [I] a crystalline polyolefin resin (A);
[II] A random copolymer composed of ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene, which is prepared using a metallocene catalyst, and has a unit and a carbon derived from ethylene. An ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) having a molar ratio with a unit derived from an α-olefin having 3 to 20 atoms, an iodine value and an intrinsic viscosity [η] within a specific range. Since it is contained in a specific ratio, it is possible to provide a polyolefin molded article which is excellent in rigidity and heat resistance, as well as in impact resistance, especially at low temperature.

The present invention will be described below with reference to examples.
The present invention is not limited to these examples. In addition, the evaluation test method of the composition in an Example and a comparative example is as follows. (1) MFR MFR was measured according to ASTM D1238.

Conditions: 230 ° C., 2.16 kg (2) Bending elastic modulus (FM) A bending test was carried out in accordance with ASTM D790 to measure the bending elastic modulus (FM).

Specimen width: 12.7 mm, thickness: 6.
4 mm, length: 127 mm-span 100 mm-bending speed 2 mm / min (3) Izod impact strength (IZ) An Izod impact strength (IZ) was measured by performing an impact test according to ASTM D256.

-Temperature -30 ° C-Specimen width: 12.7 mm, thickness: 6.4 mm, length:
64mm ・ Notch is machined

[0196]

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

[0197]

Embedded image

Stirring a predetermined amount of the zirconium compound represented by the above formula and a toluene solution of methylalumoxane (1.2 milligram atom / ml in terms of aluminum atom) at room temperature in the dark for 30 minutes. Were mixed 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 1.10 in terms of aluminum atoms.
2 milligram atoms / ml.

Next, to this toluene solution was added hexane, which was 5 times the solution of toluene, with stirring to prepare a catalyst solution having the following Zr concentration and methylalumoxane concentration, which was polymerized. It was used as a reaction catalyst.

Zr concentration: 0.00067 mmol / ml
(= 0.67 mmol / l) Methylalumoxane concentration (in terms of Al atom): 0.
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, from the upper part of the polymerization vessel, into the polymerization vessel, dehydrated and purified hexane was added at 3.185 liter / hour,
0.67 l / h of the above catalyst solution, 0.3 l / h of a hexane solution of triisobutylaluminum (concentration 17 mmol / l), and 1.5 l / h of a hexane solution of ENB (concentration 0.02 l / l). Each was continuously fed.

Further, from the upper portion of the polymerization vessel, ethylene was continuously supplied to the polymerization vessel at 200 liters per hour, and 1-butene was 155 liters per hour, respectively. This copolymerization reaction is
The reaction was carried out at 0 ° C. and the average residence time was 1 hour (that is, 5 liters of polymerization scale).

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

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

Further, this copolymer rubber had an intrinsic viscosity [η] of 2.7 dl / g measured in decalin at 135 ° C., and had a T relative to Tαα in the ¹³ C-NMR spectrum.
The intensity ratio D of αβ is less than 0.01, the B value is 1.1, the glass transition temperature (Tg) is −56 ° C., and gη
^* Value was 0.98.

The results are shown in Table 1.

[0207]

[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), (B-3)] were produced.

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

[0209]

[Table 1]

[0210]

Example 1 75 parts by weight of a crystalline propylene homopolymer (A-1) having an MFR of 25 g / 10 minutes and a melting point (Tm) measured by DSC of 162 ° C., and ethylene obtained in Reference Example 1. Using 25 parts by weight of 1-butene / 5-ethylidene-2-norbornene copolymer rubber (B-1), an injection molding machine (resin temperature 200 ° C., mold temperature 40 ° C.) was used to prepare a crystalline polypropylene resin composition. ASTM test pieces for measuring flexural modulus and Izod impact strength were prepared and subjected to the above-mentioned bending test and impact test.

The results are shown in Table 2.

[0212]

Example 2 In Example 1, the ethylene / 1-butene / 5-ethylidene-2-norbornene copolymer rubber (B-2) obtained in Reference Example 2 was used in place of (B-1). A polypropylene resin composition was prepared in the same manner as in Example 1 except that it was used, and the physical properties thereof were measured.

The results are shown in Table 2.

[0214]

[Example 3] In Example 1, the ethylene / 1-octene / 5-ethylidene-2-norbornene copolymer rubber (B-3) obtained in Reference Example 3 was used in place of (B-1). A polypropylene resin composition was prepared in the same manner as in Example 1 except that it was used, and the physical properties thereof were measured.

The results are shown in Table 2.

[0216]

[Comparative Example 1] In Example 1, ethylene 1-butene
5-Ethylidene-2-norbornene copolymer rubber (B-1)
Instead of, ethylene content is 80 mol%, iodine value is 1
2, ethylene-propylene-5-ethylidene with an intrinsic viscosity [η] of 2.7 dl / g measured in decalin at 135 ° C
-2-A polypropylene resin composition was prepared in the same manner as in Example 1 except that the norbornene copolymer rubber (EPDM-1) was used, and the physical properties thereof were measured.

The results are shown in Table 2. Note that the above E
PDM-1 was prepared using a vanadium-based catalyst.

[0218]

[Table 2]

[0219]

Example 4 In Example 1, the compounding amounts of the crystalline propylene homopolymer (A-1) and the ethylene / 1-butene / 5-ethylidene-2-norbornene copolymer rubber (B-1) were each 60. Except that 20 parts by weight and 20 parts by weight of talc having an average particle size of 2.5 μm are blended.
A polypropylene resin composition was prepared in the same manner as in Example 1, and its physical properties were measured.

The results are shown in Table 3.

[0221]

[Comparative Example 2] In Example 4, ethylene 1-butene
5-Ethylidene-2-norbornene copolymer rubber (B-1)
A polypropylene resin composition was prepared in the same manner as in Example 4 except that EPDM-1 used in Comparative Example 1 was used instead of, and the physical properties thereof were measured.

The results are shown in Table 3.

[0223]

[Table 3]

[0224]

Example 5 In Example 1, ethylene / 1-butene
5-Ethylidene-2-norbornene copolymer rubber (B-1)
Amorphous propylene / ethylene random copolymer (C-1) having a blending amount of 15 parts by weight, an ethylene content of 41 mol% and an intrinsic viscosity [η] measured in 135 ° C. decalin of 3.0 dl / g. 10 parts by weight [11.1 parts by weight with respect to 100 parts by weight of the total amount of the components (A-1) and (B-1)] was blended in the same manner as in Example 1 to prepare a polypropylene resin composition. It was prepared and its physical properties were measured.

The results are shown in Table 4.

[0226]

[Comparative Example 3] In Example 5, ethylene 1-butene
5-Ethylidene-2-norbornene copolymer rubber (B-1)
A polypropylene resin composition was prepared in the same manner as in Example 5 except that EPDM-1 used in Comparative Example 1 was used instead of, and the physical properties thereof were measured.

The results are shown in Table 4.

[0228]

[Table 4]

[0229]

Example 6 In Example 1, instead of the crystalline propylene homopolymer (A-1), MFR was 15 g / 10 minutes,
A polypropylene resin composition was prepared in the same manner as in Example 1 except that the highly crystalline propylene homopolymer (A-2) having a melting point (Tm) measured by DSC of 167 ° C. was used.
Its physical properties were measured.

The results are shown in Table 5.

[0231]

Example 7 In Example 6, ethylene 1-butene
5-Ethylidene-2-norbornene copolymer rubber (B-1)
Of ethylene homopolymer (A-
3) [MFR (ASTM D 1238): 13 g / 10
Min, Density (ASTM D 1505): 0.965 g / c
[m ³ ] was added, and a polypropylene resin composition was prepared in the same manner as in Example 6, and the physical properties thereof were measured.

The results are shown in Table 5.

[0233]

[Example 8] In Example 1, instead of the crystalline propylene homopolymer (A-1), the MFR was 22 g / 10.
%, The content of the structural unit derived from ethylene is 8% by weight, the amount of the room temperature n-decane-soluble component is 11% by weight, and the room temperature n-
In the same manner as in Example 1 except that the propylene / ethylene block copolymer (A-4) having an intrinsic viscosity [η] measured in decalin-soluble portion of 135 ° C decalin of 2.9 dl / g was used. A polypropylene resin composition was prepared and its physical properties were measured.

The results are shown in Table 5.

[0235]

[Table 5]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor, Toshiyuki Tsutsui, No. 1-2, Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture, Mitsui Petrochemical Industries, Ltd. 6-1-2 Waki, Waki Town Mitsui Petrochemical Industry Co., Ltd.

Claims (5)

[Claims] 1. A crystalline polyolefin resin (A) 95-6.
0 parts by weight, ethylene, an α-olefin / non-conjugated polyene copolymer rubber (B) consisting of ethylene, an α-olefin having 3 to 20 carbon atoms and a non-conjugated polyene (B) 5 to 40 parts by weight [(A) and ( The total amount of B) is 100 parts by weight]
The ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) is a composition comprising: and ethylene and α having 3 to 20 carbon atoms in the presence of a metallocene catalyst. Obtained by random copolymerization of an olefin and a non-conjugated polyene, (1) (a) a unit derived from ethylene and (b) a carbon atom number of 3 to
The units derived from 20 α-olefins are 40/6
It is contained at a molar ratio of 0 to 95/5 [(a) / (b)], (2) has an iodine value of 1 to 50, and (3) has an intrinsic viscosity [η] measured in 135 ° C decalin.
Is 0.1-10 dl / g, The crystalline polyolefin resin composition characterized by the above-mentioned. 2. The metallocene catalyst has the following formula [III]:
Alternatively, the crystalline polyolefin resin composition according to claim 1, further comprising a metallocene compound represented by [IV]; [In the formula, M is a transition metal of Group IVB of the periodic table, and R ¹¹ and R ¹² are a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted by halogen. , A silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, R ¹³ and R ¹⁴ are each an alkyl group having 1 to 20 carbon atoms, and X ¹ and X ² are A hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group; Divalent hydrocarbon group, divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, divalent silicon-containing group, 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 - a. (However, R ⁷ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms.)], [In the formula, M is a transition metal of Group IVB of the Periodic Table, R ²¹ may be the same or different from each other, and each of them is a hydrogen atom, a halogen atom, or an optionally halogenated carbon atom having 1 to 1 carbon atoms. 10 alkyl group, aryl group, or -NR ₂ carbon atoms 6 to 10, -SR, -OSiR _3, -SiR
₃ or —PR ₂ groups (R is a halogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms), and R ^{22 to} R ²⁸ are the same as defined above for R ²¹ . And R ^{22 to} R ^{28 which} are present or adjacent to each other 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; Hydrogen atom, halogen atom, OH group, 1 to 1 carbon atoms
10 alkyl groups, 1 to 10 carbon atom alkoxy groups, 6 to 10 carbon atom aryl groups, 6 to 6 carbon atoms
10 aryloxy groups, alkenyl groups having 2 to 10 carbon atoms, arylalkyl groups having 7 to 40 carbon atoms, alkylaryl groups having 7 to 40 carbon atoms, 8 carbon atoms
~ 40 arylalkenyl groups; -Sn -, - O -, - S -, = SO, = SO 2, = NR
²⁹ , = CO, = PR ²⁹ or = P (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,
10 alkyl groups, fluoroalkyl group having 1 to 10 carbon atoms, aryl group having 6 to 10 carbon atoms, fluoroaryl group having 6 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, carbon number An alkenyl group having 2 to 10 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, and 8 carbon atoms
-40 arylalkenyl groups or 7-4 carbon atoms
0 may be an alkylaryl group, or R ²⁹ and R ³⁰ may each form a ring with the atoms to which they are attached, and M ² is a silicon, germanium or tin atom. )]. 3. The crystalline polyolefin resin composition according to claim 1 or 2, wherein the crystalline polyolefin resin (A) is a polypropylene resin. 4. The ethylene / α-olefin / non-conjugated polyene copolymer rubber (B) has (4) T relative to Tαα in ¹³ C-NMR spectrum.
The intensity ratio D (Tαβ / Tαα) of αβ is 0.5 or less, and (5) the B value obtained from the ¹³ C-NMR spectrum and the following formula is 1.00 to 1.50; B value = [P _OE ] / (2 · [P _E ] · [P _O ]) (In the formula, [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 random copolymer rubber
The ratio of α-olefin / ethylene chain number to the chain number), (6) DSC glass transition temperature (Tg) is -5.
It is 0 degreeC or less, The crystalline polyolefin resin composition in any one of Claims 1-3 characterized by the above-mentioned. 5. In addition to the crystalline polyolefin resin (A) and the ethylene / α-olefin / non-conjugated polyene copolymer rubber (B), an amorphous propylene / ethylene random copolymer (C) is used as a component ( The crystalline polyolefin resin composition according to any one of claims 1 to 4, which is contained in 5 to 15 parts by weight based on 100 parts by weight of the total amount of A) and (B).