JPH09137001A - Olefin-based thermoplastic elastomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the above composition moldable into products excellent in tensile strength, elongation at break and rubber elasticity, useful in automotive parts, etc., by (partly) crosslinking a blend of a crystalline polyolefin resin and a specific copolymer rubber. SOLUTION: This composition is obtained by partly or wholly crosslinking a blend of (A) 10-85pts. by wt. of a crystalline polyolefin resin and (B) 15-90pts. by wt. of an (ethylene/α-olefin) copolymer rubber (density=0.86-0.90g/cm<3> ; melt flow rate at 230 deg.C under a load of 2.16kg=0.01-20g/10min.; [η] at 135 deg.C in decaline=0.1-10dl/g) obtained by random copolymerization of (B1 ) ethylene and (B2 ) a 3-20C α-olefin with the molar ration of B1 /B2 =55/45-98/2 by use of a metallocene-based catalyst such as rac-dimethylsilylene-bis[1-(2-methyl-4- phenylindenyl)] zirconium dichloride of the formula (Me is methyl).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD OF THE INVENTION The present invention relates to an olefin-based thermoplastic elastomer composition, and more specifically, to tensile strength,
The present invention relates to a crosslinked olefin-based thermoplastic elastomer composition capable of providing a molded article excellent in elongation at break and rubber elasticity.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Olefin-based thermoplastic elastomers are widely used as energy-saving and resource-saving type elastomers, especially as substitutes for vulcanized rubber for automobile parts, industrial machine parts, electronic / electric equipment parts, building materials, etc. There is.

[0003] Olefin-based thermoplastic elastomers can be classified into crosslinked and non-crosslinked types. Non-crosslinking type thermoplastic elastomers have little variation in quality because they do not undergo a crosslinking reaction and are inexpensive to produce, but comparing the two in terms of performance, tensile strength, elongation at break, or rubber properties (for example, permanent In terms of elongation, compression set) and heat resistance, the crosslinkable olefinic thermoplastic elastomer is superior to the noncrosslinkable olefinic thermoplastic elastomer. This is because AY Coran et al. (Rubber Chemistry and Technology, 53 (1980),
It is widely known, as detailed in (Page 141).

Regarding the non-crosslinked or partially crosslinked olefinic thermoplastic elastomer, for example, JP-B-53-21021, JP-B-55-18448, JP-B-56-15741 and JP-B-56-15.
No. 742, JP-B-58-46138, JP-B-58-56575, JP-B-59-30376, JP-B-62-59139 and the like.

As described above, the olefin-based thermoplastic elastomer includes a non-crosslinking type thermoplastic elastomer and a crosslinking type thermoplastic elastomer. These thermoplastic elastomers are conventionally known vulcanized rubbers such as natural rubber. E
Compared with vulcanized rubber composed of PDM, SBR, NBR, CR, etc., it is superior in processability and cost,
In reality, the vulcanized rubber is inferior in terms of tensile properties such as tensile strength and elongation at break.

Therefore, it has been desired to develop an olefin-based thermoplastic elastomer composition capable of providing a molded product which is superior in tensile properties such as tensile strength and elongation at break to conventionally known vulcanized rubbers.

[0007]

It is an object of the present invention to solve the problems associated with the prior art as described above, and to provide a molded article which is superior to conventional vulcanized rubbers in tensile properties such as tensile strength and breaking elongation. It is an object of the present invention to provide a partially or completely crosslinked olefinic thermoplastic elastomer composition.

[0008]

SUMMARY OF THE INVENTION An olefinic thermoplastic elastomer composition according to the present invention comprises a crystalline polyolefin resin (A) 1.
0 to 85 parts by weight, ethylene and 3 to 20 carbon atoms
Partially or completely crosslinked with 15 to 90 parts by weight of ethylene / α-olefin copolymer rubber (B) consisting of α-olefin [the total amount of (A) and (B) is 100 parts by weight] A thermoplastic elastomer composition, wherein the ethylene / α-olefin copolymer rubber (B) contains ethylene in the presence of a metallocene catalyst.
Obtained by random copolymerization with an α-olefin having 3 to 20 carbon atoms, and (1) (a) a unit derived from ethylene and (b) 3 to 3 carbon atoms.
The unit derived from 20 α-olefins is 55/4
5 to 98/2 [(a) / (b)] in a molar ratio, (2) the density is 0.860 to 0.900 g / cm ³ , and (3) the melt flow rate (ASTM D 1238, 230 ℃, 2.16kg
(Load) is 0.01 to 20 g / 10 minutes, and (4) intrinsic viscosity [η] measured in decalin at 135 ° C.
Is 0.1 to 10 dl / g.

As the olefinic thermoplastic elastomer composition, the following compositions (1) and (2) are preferable. Olefin-based thermoplastic elastomer composition (1)
Is 10 to 85 parts by weight of the crystalline polyolefin resin (A) and 15 to 90 parts by weight of an ethylene / α-olefin copolymer rubber (B) consisting of ethylene and an α-olefin having 3 to 20 carbon atoms [(A And a total amount of (B) is 100 parts by weight], which is a partially or completely crosslinked thermoplastic elastomer composition, wherein the ethylene / α-olefin copolymer rubber (B) is In the presence of a metallocene catalyst, ethylene and 3 to 2 carbon atoms are included.
Obtained by random copolymerization with an α-olefin of 0, (1) (a) a unit derived from ethylene and (b) a carbon atom number of 3 to
The unit derived from 20 α-olefins is 55/4
5 to 98/2 [(a) / (b)] in a molar ratio, (2) the density is 0.860 to 0.900 g / cm ³ , and (3) the melt flow rate (ASTM D 1238, 230 ℃, 2.16kg
(Load) is 0.01 to 20 g / 10 minutes, and (4) intrinsic viscosity [η] measured in decalin at 135 ° C.
Is 0.1 to 10 dl / g, and (5) the intrinsic viscosity [η] measured in (4) above and the ethylene content of the same weight average molecular weight (by light scattering method) as 70 mol% Ratio of the linear ethylene / propylene copolymer of [η] _blank [η] ^* (= [η] /
[Η] _blank )] is a value exceeding 0.95.

Ethylene / α-olefin copolymer rubber (B) constituting the thermoplastic elastomer composition (1)
In addition to the above characteristics (1) to (5), is (6) T for Tαα in the ¹³ C-NMR spectrum.
The intensity ratio D (Tαβ / Tαα) of αβ is 0.5 or less, and (7) 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 the number of α-olefin / ethylene chains to the number of chains), (8) the glass transition temperature (Tg) determined by DSC is -5.
It is preferably 0 ° C. or lower.

The olefinic thermoplastic elastomer composition (2) is a crystalline polyolefin resin (A) 10
To 85 parts by weight and 15 to 90 parts by weight of ethylene / α-olefin copolymer rubber (B) consisting of ethylene and α-olefin having 3 to 20 carbon atoms [(A) and (B)]
Is 100 parts by weight] and a partially or completely crosslinked thermoplastic elastomer composition comprising the ethylene / α-olefin copolymer rubber (B).
Is obtained by randomly copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of a metallocene catalyst, and (1) (a) a unit derived from ethylene and (b) carbon. Number of atoms 3 ~
The unit derived from 20 α-olefins is 55/4
5 to 98/2 [(a) / (b)] in a molar ratio, (2) the density is 0.860 to 0.900 g / cm ³ , and (3) the melt flow rate (ASTM D 1238, 230 ℃, 2.16kg
(Load) is 0.01 to 20 g / 10 minutes, and (4) intrinsic viscosity [η] measured in decalin at 135 ° C.
Is 0.1 to 10 dl / g, and (5) the intrinsic viscosity [η] measured in (4) above and the ethylene content of the same weight average molecular weight (by light scattering method) as 70 mol% Ratio of the linear ethylene / propylene copolymer of [η] _blank [η] ^* (= [η] /
[Η] _blank )] is 0.2 to 0.95.

The olefinic thermoplastic elastomer composition according to the present invention comprises a crystalline polyolefin resin (A) 10
To 85 parts by weight, ethylene / α-olefin copolymer rubber (B) 15 to 90 parts by weight, and olefin rubber (C)
1 to 40 parts by weight and / or 1 to 40 parts by weight of the softening agent (D) [the total amount of the components (A), (B), (C) and (D) is 100 parts by weight]. Good. However, the ratio of the total amount of the components (A), (B), (C) and (D) to the total amount of the components (A), (B) and (C) is 60 to 100% by weight.

The olefinic thermoplastic elastomer composition according to the present invention can provide a molded article which is superior to conventional vulcanized rubbers in tensile properties such as tensile strength and elongation at break.

[0014]

DETAILED DESCRIPTION OF THE INVENTION The olefinic thermoplastic elastomer composition according to the present invention will be specifically described below.

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

Crystalline Polyolefin Resin (A) Examples of the crystalline polyolefin resin (A) used in the present invention include homopolymers or copolymers of α-olefin having 2 to 20 carbon atoms.

Specific examples of the above crystalline polyolefin resin include the following polymers or copolymers. (1) Ethylene homopolymer (manufacturing method may be either low pressure method or high pressure method) (2) Copolymerization of ethylene with 10 mol% or less of other α-olefin or vinyl monomer such as vinyl acetate or ethyl acrylate Polymer (3) Propylene homopolymer (4) Random copolymer of propylene and 10 mol% or less of other α-olefins (5) Block copolymerization of propylene and 30 mol% or less of other α-olefins Combined (6) 1-butene homopolymer (7) Random copolymer of 1-butene and other α-olefin at 10 mol% or less (8) 4-Methyl-1-pentene homopolymer (9) 4 -Methyl-1-pentene and other α up to 20 mol%
-Random copolymer with olefin As the α-olefin, specifically, ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-
Hexene, 1-octene and the like.

Among the above crystalline polyolefin resins, the propylene homopolymer and the propylene content are 5
A propylene / α-olefin copolymer of 0 mol% or more is particularly preferable.

The above crystalline polyolefin resins can be used alone or in combination. The crystalline polyolefin resin (A) used in the present invention has a melt flow rate (MFR; ASTMD).
1238, 230 ° C., 2.16 kg load), preferably 0.01 to 100 g / 10 minutes, more preferably 0.1.
It is in the range of 3 to 70 g / 10 minutes.

The crystallinity of the crystalline polyolefin resin determined by the X-ray method is usually 5 to 100%, preferably 20 to 80%. The crystalline polyolefin resin (A) as described above is 100 in total of the crystalline polyolefin resin (A), the ethylene / α-olefin copolymer rubber (B), the olefin rubber (C) and the softening agent (D). 10 to 85 parts by weight, preferably 10 to 75 parts by weight, more preferably 15 to 70 parts by weight.
Used in parts by weight. Since the olefin rubber (C) and the softener are optional components, these components may be 0 parts by weight.

When the crystalline polyolefin resin (A) is used in the above proportion, a thermoplastic elastomer composition having excellent moldability and capable of providing a molded product having excellent heat resistance can be obtained.

Ethylene / α-olefin copolymer rubber
(B) The ethylene / α-olefin copolymer rubber (B) used in the present invention comprises ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of a specific metallocene catalyst as described below. Can be obtained by random copolymerization.

The above-mentioned ethylene / α-olefin copolymer rubber (B) constituting the preferred olefinic thermoplastic elastomer composition (1) according to the present invention has a linear molecular structure, The ethylene / α-olefin copolymer rubber (B) constituting the preferred olefinic thermoplastic elastomer composition (2) according to the present invention has a long chain branched type molecular structure.

[Α-Olefin] The number of carbon atoms is 3 to 2
Examples of the α-olefin of 0 include propylene and 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, the α-olefin constituting the linear ethylene / α-olefin copolymer rubber is preferably an α-olefin having 4 to 10 carbon atoms,
Particularly, 1-butene, 1-hexene, 1-octene, 1-decene and the like are preferably used.

Further, as the α-olefin constituting the long chain branched ethylene / α-olefin copolymer rubber,
Α-Olefins having 3 to 10 carbon atoms are preferable, and propylene, 1-butene, 1-hexene, 1-octene and the like are particularly preferably used.

[Characteristics of Linear Ethylene / α-Olefin Copolymer Rubber (B)] The linear ethylene / α-olefin copolymer rubber (B) preferably used in the present invention is
It has the following characteristics. (1) Ethylene / α-olefin component ratio The ethylene / α-olefin copolymer rubber (B) used in the present invention comprises (a) a unit derived from ethylene and (b)
Α-olefins having 3 to 20 carbon atoms (hereinafter simply referred to as α-
Unit sometimes derived from olefin),
55/45 to 98/2, preferably 60/40 to 95 /
5, more preferably 60/40 to 90/10 [(a) /
It is contained in a molar ratio of (b)].

The ethylene / α-olefin copolymer rubber having such an ethylene component / α-olefin component ratio has excellent heat resistance. (2) Density The density of the ethylene / α-olefin copolymer rubber (B) is 0.860 to 0.900 g / cm ³ , preferably 0.862 to 0.885 g / cm ³ , and more preferably 0.862. Is about 0.880 g / cm ³ . When an ethylene / α-olefin copolymer rubber having a density in the above range is used, the resulting thermoplastic elastomer composition is easy to handle in pellets and can provide a molded article excellent in flexibility. it can. (3) Melt flow rate Melt flow rate of ethylene / α-olefin copolymer rubber (B) (MFR; ASTM D 1238, 230)
C, 2.16 kg load) is 0.01 to 20 g / 10
Min, preferably 0.2 to 10 g / 10 min, more preferably 0.2 to 5 g / 10 min. (4) Intrinsic viscosity [η] 135 of ethylene / α-olefin copolymer rubber (B)
The intrinsic viscosity [η] measured in decalin at
It is 10 dl / g, preferably 1.0 to 5 dl / g. (5) gη ^* value Jiita ^* values obtained from the intrinsic viscosity [eta] of linear ethylene · alpha-olefin copolymer rubber as described above (B) is greater 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 of the intrinsic viscosity [η]. The linear viscosity of a linear ethylene / propylene copolymer having the same weight average molecular weight (by light scattering method) as the α-olefin copolymer rubber (by light scattering method) and an ethylene content of 70 mol% is the limiting viscosity. From the linear ethylene / α-olefin copolymer rubber having the characteristics, it is possible to obtain a thermoplastic elastomer composition having excellent mechanical strength characteristics and heat resistance, and a molded product thereof.

Further, the linear ethylene / α-olefin copolymer rubber (B) preferably satisfies the following properties (6) to (8). (6) D value ¹³ C-of ethylene / α-olefin copolymer rubber (B)
The intensity (area) ratio D (Tαβ / Tαα) of Tαβ to Tαα in the NMR spectrum is preferably 0.5 or less, particularly 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

[0032]

Embedded image

The strength ratio D of the random copolymer rubber can be determined as follows. The ¹³ C-NMR spectrum of the random copolymer rubber was measured using, for example, a JEOL-GX270 NMR measuring 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 concretely by taking an ethylene / 1-butene copolymer rubber as an example. ¹³ C-N of this ethylene / 1-butene copolymer rubber
In the MR spectrum, the peak appearing at 39 to 40 ppm is Tαα, and the peak appearing at 31 to 32 ppm is T.
Belongs to αβ.

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, the ethylene-α-olefin is copolymerized with a specific Group IVB metallocene-based catalyst as described below, so that the strength ratio D is 0.5 or less. I got a polymer rubber,
For example, even if ethylene and 1-butene are copolymerized in the presence of a Group VB metallocene catalyst such as vanadium, an ethylene / 1-butene copolymer rubber having the strength ratio D of 0.5 or less is obtained. It is not possible. The same applies to α-olefins other than 1-butene. (7) B value Ethylene / α-olefin copolymer rubber (B) is ¹³ C
-The B value obtained from the NMR spectrum and the following equation is preferably 1.00 to 1.50.

B value = [P _OE ] / (2 · [P _E ] · [P _O ]) (In the formula, [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. The composition distribution of the copolymer rubber becomes wider as the B value becomes smaller than 1.00, and such a copolymer rubber has a higher strength when crosslinked, for example, as compared with a copolymer rubber having a narrower composition distribution. Properties may not be fully exhibited.

In the present invention, as described later,
By copolymerizing ethylene and α-olefin using a Group IVB metallocene catalyst, the above B value becomes 1.00.
Although a random copolymer rubber having a value of 1.50 is obtained,
For example, even if ethylene and α-olefin are copolymerized in the presence of a titanium-based nonmetallocene catalyst, an ethylene / α-olefin copolymer rubber having a B value in the above range cannot be obtained. (8) Glass transition temperature DSC of ethylene / α-olefin copolymer rubber (B)
Glass transition temperature (T measured by a differential scanning calorimeter)
g) is preferably -50 ° C or lower.

From the random copolymer rubber having a glass transition temperature (Tg) of −50 ° C. or lower, a thermoplastic elastomer composition having excellent low temperature flexibility can be obtained. [Characteristics of long-chain branched ethylene / α-olefin copolymer rubber (B)] On the other hand, long-chain branched ethylene / α-olefin copolymer rubber (B) preferably used in the present invention.
Has the following characteristics. (1) Ethylene / α-olefin component ratio The ethylene / α-olefin copolymer rubber (B) used in the present invention comprises (a) a unit derived from ethylene and (b)
Α-olefins having 3 to 20 carbon atoms (hereinafter simply referred to as α-
Unit derived from olefin) is 55/45 to 98/2, preferably 60/40 to 9
5/5, more preferably 60/40 to 90/10
It is contained in a molar ratio of [(a) / (b)]. (2) Density The density of the ethylene / α-olefin copolymer rubber (B) is 0.860 to 0.900 g / cm ³ , preferably 0.862 to 0.885 g / cm ³ , and more preferably 0.862. Is about 0.880 g / cm ³ . When an ethylene / α-olefin copolymer rubber having a density in the above range is used, the resulting thermoplastic elastomer composition is easy to handle in pellets and can provide a molded article excellent in flexibility. it can. (3) Melt flow rate Melt flow rate of ethylene / α-olefin copolymer rubber (B) (MFR; ASTM D 1238, 230)
C., 2.16 kg load) is 0.1 to 20 g / 10 minutes,
It is preferably in the range of 0.2 to 10 g / 10 minutes, more preferably 0.2 to 5 g / 10 minutes. (4) Intrinsic viscosity [η] 135 of ethylene / α-olefin copolymer rubber (B)
The intrinsic viscosity [η] measured in decalin at
It is 10 dl / g, preferably 1.0 to 5 dl / g. (5) gη ^* value of Jiita ^* value long-chain branched ethylene · alpha-olefin copolymer rubber (B) is 0.2 to 0.95, preferably 0.4 to 0.9, more preferably It is 0.5 to 0.85. This gη ^* value is obtained by the method described above.

When the gη ^* value of the ethylene / α-olefin copolymer rubber is 0.95 or less, it means that long chain branching is formed in the molecule. [Method for Preparing Ethylene / α-Olefin Copolymer Rubber (B)] The linear or long-chain branched ethylene / α-olefin copolymer rubber (B) as described above is a metallocene-based catalyst of a specific metallocene catalyst. In the presence of ethylene and 3 to 2 carbon atoms
It is produced by random copolymerization with 0 α-olefin.

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] First, as the metallocene compound [A] used in the preparation of the linear ethylene / α-olefin copolymer rubber (B), compounds represented by the following general formula [I] are mentioned. To be

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 that 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, the 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 the like, 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. Hei 4 (1994) represented by the following formula [A]
The metallocene compounds described in JP-A-268307 can be mentioned. The metallocene has the formula [A]:

[0060]

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

R ³ and R ^{4, which} may be the same 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 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, -
SiR ¹⁰ ₃ or —PR ¹⁰ ₂ group, where R ¹⁰ is a halogen atom, preferably a chlorine atom, or has 1 carbon atom.
Is an alkyl group having 10 to 10, preferably 1 to 3, or an aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms.

R ³ and R ⁴ are particularly preferably 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:

[0065]

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= BR¹¹, = AlR¹¹, -Ge-, -Sn
-, -O-, -S-, = SO, = SO _Two, = NR¹¹, =
CO, = PR¹¹ Or = P (O) R¹¹And that
When R¹¹, R¹²And R¹³Are the same but different
It may be a hydrogen atom, a halogen atom, or a carbon atom number 1 to
10, preferably 1 to 4 alkyl groups, more preferably
Is a methyl group, C1-C10 fluoroalkyl
Group, preferably CF_Three Group, having 6 to 10 carbon atoms, preferred
Or an aryl group having 6 to 8 and a fluoro group having 6 to 10 carbon atoms.
A lower aryl group, preferably a pentafluorophenyl group,
Alkoxy having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms
A group, particularly preferably a methoxy group, having 2 to 10 carbon atoms,
Preferably 2-4 alkenyl groups, 7-7 carbon atoms
0, preferably 7 to 10 arylalkyl groups, carbon source
Aryl alkeny having 8-40, preferably 8-12
Group or 7 to 40 carbon atoms, preferably 7 to 12 carbon atoms
An alkylaryl group of R or¹¹And R¹²Also
Is R¹¹And R¹³And are each the same as the atom to which they are bound.
They may be joined together 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.

[0070]

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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 a method for producing such a metallocene compound, a conventionally known method can be used (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.

[0074]

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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, particularly preferably a methyl, ethyl or propyl hydrocarbon group having 1 to 3 carbon atoms. 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.

[0081]

[Chemical 6]

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

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 the above 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 groups 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 groups,
A divalent silicon-containing group such as an alkyldisilirene group such as a tetraphenyl-1,2-disilirene group, an alkylaryldisilirene group, or an aryldisilirene group; a silicon-containing group of the above divalent silicon is replaced with germanium 2 A divalent germanium-containing group; a divalent tin-containing group substituent obtained by substituting tin for silicon in the divalent silicon-containing group, R ⁷
Is a halogen atom similar to R ¹ and R ² , a hydrocarbon group having 1 to 20 carbon atoms, and 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.

[0089]

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[0090]

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[0091]

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In the present invention, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal in the above compounds 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.

[0094]

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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.

[0097]

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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 , 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.

Further, 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 those in 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, by 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-mentioned 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.

[0106]

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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, a 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 and phenylethoxy. Examples thereof include an arylalkoxy group.

Specific examples of the sulfur-containing group include a substituent obtained by substituting the oxygen of the oxygen-containing group with sulfur, 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, rac-dimethylsilylene-bis (2,3,7-trimethyl-4-trimethylsiloxymethyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2,3,7-trimethyl-4-phenylethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,3,7-trimethyl-4
-Phenyldichloromethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,3,7-trimethyl-4-chloromethyl-1-indenyl) zirconium dichloride, rac-diethylsilylene-bis (2,3, 7-trimethyl-4-i-propyl-1-indenyl) zirconium dichloride, rac-di (i-propyl) silylene-bis (2,
3,7-trimethyl-4-i-propyl-1-indenyl) zirconium dichloride, rac-di (n-butyl) silylene-bis (2,3,7-trimethyl-4-i-propyl-1-indenyl) zirconium Dichloride, rac-di (cyclohexyl) silylene-bis (2,3,7-trimethyl-4-i-propyl-1-indenyl) zirconium dichloride, rac-methylphenylsilylene-bis (2,3,7-trimethyl-4 -i-propyl-1-
Indenyl) zirconium dichloride, rac-methylphenylsilylene-bis (2,3,7-trimethyl-4-t-butyl-1
-Indenyl) zirconium dichloride, rac-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, rac-di (p-chlorophenyl) silylene-bis (2,3,7-trimethyl-4-i-
Propyl-1-indenyl) zirconium dichloride, ra
c-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-phenyl) Sulfinato), rac-dimethylsilylene-bis (2-methyl-3-methyl-4-i-propyl-7)
-Methyl-1-indenyl) zirconium dichloride, ra
c-Dimethylsilylene-bis (2-ethyl-4-i-propyl-7
-Methyl-1-indenyl) zirconium dichloride, ra
c-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, ra
c-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, 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.

[0121]

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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 as 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 an alkyl group having 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.

[0125]

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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;

[0130]

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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.

Furthermore, 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,

[0133]

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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,

[0135]

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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.

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

The above metallocene compounds may be used in combination of two or more kinds. Next, the metallocene compound [A] used in the preparation of the long-chain branched ethylene / α-olefin copolymer rubber (B) preferably used in the present invention is a compound represented by the following general formula [V] Is mentioned.

[0140]

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

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

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

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

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

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

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

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

Specific examples of the sulfur-containing group include a substituent 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 sulfonates, trimethylbenzene sulfonates, triisobutylbenzene sulfonates, p-chlorobenzene sulfonates, pentafluorobenzene sulfonates, methylsulfinates, phenylsulfinates, benzenesulfinates , P-toluenesulfinate, trimethylbenzenesulfinate, pentafluorobenzenesulfinate, and other sulfinate groups.

Of these, X ¹ and X ² are preferably a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms. YY is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, -O. -, -C
O -, - S -, - SO -, - SO 2 -, - NR 7 -, -
^{P (R 7) -, -} P (O) (R 7) -, - BR 7 - or -AlR ⁷ - (provided that, R ⁷ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms , 1 carbon atom
To 20 halogenated hydrocarbon groups), and specifically,
Methylene, 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 ⁷ is the same halogen atom, hydrocarbon group having 1 to 20 carbon atoms, or halogenated hydrocarbon group having 1 to 20 carbon atoms as described above. Among them, Y is preferably a divalent silicon-containing group, a divalent germanium-containing group, more preferably a divalent silicon-containing group, and is preferably an alkylsilylene group, an alkylarylsilylene group, or an arylsilylene. Particularly preferred is a group.

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

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

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

In addition to the metallocene compound represented by the above general formula [V], a metallocene compound represented by the following general formula [VI] can be given. L ^a MX ₂ [VI] (M is a metal of Group IV or lanthanide series of the periodic table, L ^a is a derivative of a delocalized π-bonding group, and is bound to a metal M active site. (Given a geometric shape, X is independently a hydrogen atom, a halogen atom or a hydrocarbon group containing 20 or less carbon atoms, a silicon atom or a germanium atom, a silyl group or a germyl group.) Among the compounds represented by the formula [VI], specifically, the compound represented by the following formula [VII] is preferable.

[0156]

Embedded image

M is titanium, zirconium or hafnium, and X is the same as above. Cp is π in M
A substituted cyclopentadienyl group or a derivative thereof which is bonded and has a substituent Z.

Z is oxygen, sulfur, boron or an element of Group IVA of the periodic table, Y is a ligand containing nitrogen, phosphorus, oxygen or sulfur, and Z and Y form a condensed ring. You may.

Specific examples of the compound represented by the above formula [VII] include (dimethyl (t-butylamide))
(Tetramethyl-η ⁵ -cyclopentadienyl) silane)
Titanium dichloride, ((t-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl)
Titanium dichloride, (dibenzyl (t-butylamide)
(Tetramethyl-η ⁵ -cyclopentadienyl) silane)
Titanium dichloride, (dimethyl (t-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) silane) dibenzyl titanium, (dimethyl (t-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) silane) dimethyl Titanium, ((t-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl) dibenzyl titanium, ((methylamido) (tetramethyl-η ⁵ -cyclopentadienyl) -1, 2-ethanediyl) dineopentyl titanium, ((phenylphosphide) (tetramethyl-
η ⁵ -Cyclopentadienyl) methylene) diphenyl titanium, (dibenzyl (t-butylamide) (tetramethyl
-η ⁵ -cyclopentadienyl) silane) dibenzyl titanium, (dimethyl (benzylamido) (η ⁵ -cyclopentadienyl) silane) di (trimethylsilyl) titanium,
(Dimethyl (phenyl phosphide)-(tetramethyl-
η ⁵ -Cyclopentadienyl) silane) dibenzyl titanium, ((tetramethyl-η ⁵ -cyclopentadienyl)-
1,2-ethanediyl) dibenzyl titanium, (2-η ^5- (tetramethyl-cyclopentadienyl) -1-methyl-ethanolate (2-)) dibenzyl titanium, (2-η ^5- (tetramethyl- Cyclopentadienyl) -1-methyl-ethanolate (2-)) dimethyl titanium, (2-((4a, 4b, 8a, 9,9a-η)-
9H-fluoren-9-yl) cyclohexanolate (2-))
Examples include dimethyl titanium and (2-((4a, 4b, 8a, 9,9a-η) -9H-fluoren-9-yl) cyclohexanolate (2-)) dibenzyldititanium.

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

These compounds may be used alone or in combination of two or more. Among the metallocene compounds described above, the metallocene compound represented by the general formula [V] is preferably used in the preparation of the long-chain branched type ethylene / α-olefin copolymer rubber (B).

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

The conventionally known aluminoxane can be produced, for example, by the following method. (1) Compounds containing 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 (pentapentane 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 the borane compound, carborane complex compound and carborane anion salt include decaborane (14), 7,8-dicarbaundecaborane (13), 2,
7-dicarboundecaborane (13), undecahydride-7,8-dimethyl-7,8-dicarboundecaborane, dodecahydride-11-methyl-2,7-dicarboundecaborane, tri (n-butyl ) Ammonium 6-carbadecaborate (14), tri (n-butyl) ammonium 6-carbadecaborate (12), tri (n-butyl) ammonium
7-carboundecaborate (13), tri (n-butyl)
Ammonium 7,8-dicarboundecaborate (12),
Tri (n-butyl) ammonium 2,9-dicarboundecaborate (12), tri (n-butyl) ammonium dodecahydride-8-methyl-7,9-dicarboundecaborate, tri (n-butyl) ammoniumundeca Hydride 8-ethyl-7,9-dicarboundecaborate, tri (n-
Butyl) ammonium undeca hydride-8-butyl
-7,9-Dicarboundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-Dicarboundecaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7 , 8-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carboundecaborate, and the like.

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

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

(I) Compounds represented by R ⁵ _n Al (OR ⁶ ) _3-n , such as dimethylaluminum methoxide, diethylaluminum ethoxide and diisobutylaluminum methoxide.

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

(Iii) A compound represented by R ⁵ _n Al (OAlR ⁸ ₂ ) _3-n , 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, also R ⁵ ₃ A Of these
_{^{l, R 5 n Al (OR}} 6) 3-n, R 5 n Al (OAlR 8 2)
Preferred examples include an organoaluminum compound represented by _3-n , wherein R ⁵ is an isoalkyl group,
Particularly preferred are compounds where n = 2. These organoaluminum compounds can be used in combination of two or more.

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

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

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

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.

In the present invention, ethylene and 3 to 10 carbon atoms are used.
When copolymerizing with 20 α-olefins, the above metallocene compound [A] constituting the metallocene catalyst, the organoaluminum oxy compound [B], the compound [C] forming an ion pair, and the organoaluminum compound [ D]
May be separately supplied to the polymerization reactor, or the metallocene catalyst containing the metallocene compound [A] may be prepared in advance and then subjected to the 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 20 with α-olefin is usually 40 to 250.
° C, preferably 50 to 200 ° C, particularly preferably 60 to
At 160 ° C., atmospheric pressure to 100 kg / cm ^2, preferably atmospheric pressure to 50 kg / cm ^2, particularly preferably atmospheric pressure 30 kg / cm
It can be performed under the conditions of ² . The residence time (polymerization reaction time) is usually 0.1 to 4 hours, preferably 0.
2 to 2 hours.

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 copolymer rubber (B) can be obtained by the method as described above, and the molecular weight of the copolymer rubber (B) can be adjusted by changing the polymerization conditions such as the polymerization temperature. It can also be adjusted by controlling the amount of hydrogen (molecular weight modifier) used.

In the present invention, the ethylene / α-olefin copolymer rubber (B) is a crystalline polyolefin resin (A), an ethylene / α-olefin copolymer rubber (B), an olefin rubber (C) and 15 to 90 parts by weight, preferably 25 to 90 parts by weight, and more preferably 30 to 85 parts by weight based on 100 parts by weight of the total amount of the softening agent (D).
Used in parts by weight. As described above, since the olefin rubber (C) and the softening agent (D) are optional components, they may be 0 parts by weight. When the ethylene / α-olefin copolymer rubber (B) is used in the above proportion,
A thermoplastic elastomer composition having excellent moldability capable of providing a molded product having excellent tensile properties such as tensile strength and tensile elongation is obtained.

Olefin-based rubber (C) The olefin-based rubber (C) optionally used in the present invention is an amorphous random elastic copolymer having an α-olefin content of 2 to 20 carbon atoms of 50 mol% or more. Polymers may be mentioned. In addition, in the present invention, an olefin rubber (C) and a rubber other than the olefin rubber (C), such as styrene-
Butadiene rubber (SBR), nitrile rubber (NBR),
A diene rubber such as natural rubber (NR) or butyl rubber (IIR), or polyisobutylene rubber may be used in combination.

The above-mentioned amorphous random elastic copolymer having 2 to 20 carbon atoms and having an α-olefin content of 50 mol% or more includes α-olefin copolymers composed of two or more kinds of α-olefins, and 2 There is an α-olefin / non-conjugated diene copolymer composed of at least one α-olefin and a non-conjugated diene, and specific examples thereof include the following rubbers. (1) Ethylene / α-olefin copolymer rubber [ethylene / α-olefin (molar ratio) = about 90/10 to 50 /
50] (2) Ethylene / α-olefin / non-conjugated diene copolymer rubber [ethylene / α-olefin (molar ratio) = about 90
/ 10 to 50/50] (3) Propylene / α-olefin copolymer rubber [propylene / α-olefin (molar ratio) = about 90/10 to 5
0/50] (4) Butene / α-olefin copolymer rubber [butene /
α-olefin (molar ratio) = about 90/10 to 50/5
0] As the α-olefin, specifically, ethylene,
Propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene and the like can be mentioned.

Specific examples of the non-conjugated diene include dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene and ethylidene norbornene.

The iodine value of the ethylene / α-olefin / non-conjugated diene copolymer rubber of the above (2) in which such a non-conjugated diene is copolymerized is preferably 25 or less. Mooney viscosity of the copolymer rubber of the above (1) to (4) [ML
_{1 + 4} (100 ° C.)] is 10 to 250, especially 30
~ 150 is preferred.

In the present invention, the olefin rubber (C) includes a crystalline polyolefin resin (A), an ethylene / α-olefin copolymer rubber (B), an olefin rubber (C) and a softening agent (D). It is used in a proportion of 1 to 40 parts by weight, preferably 5 to 35 parts by weight, and more preferably 5 to 30 parts by weight, based on the total amount of 100 parts by weight. When the olefin rubber (C) is used in the above proportion,
A thermoplastic elastomer composition capable of providing a molded article having excellent flexibility is obtained.

Softener (D) As the softener (C) optionally used in the present invention, a softener usually used for rubber can be used.

Specifically, petroleum-based substances such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, and vaseline; coal tars such as coal tar and coal tar pitch; castor oil, linseed oil, rapeseed oil,
Fatty oils such as soybean oil and coconut oil; waxes such as tall oil, beeswax, carnauba wax and lanolin; fatty acids such as ricinoleic acid, palmitic acid, stearic acid, barium stearate and calcium stearate or metal salts thereof; petroleum resins, Synthetic polymeric substances such as coumarone indene resin and atactic polypropylene; ester plasticizers such as dioctyl phthalate, dioctyl adipate and dioctyl sebacate; other microcrystalline wax, sub (factice), liquid polybutadiene, modified liquid polybutadiene, liquid thiocol And so on.

In the present invention, the softening agent (D) is used in an amount of 1 to 40 parts by weight based on 100 parts by weight of the crystalline polyolefin resin (A) and the ethylene / α-olefin copolymer rubber (B). , Preferably 5 to 35 parts by weight, more preferably 5 to 30 parts by weight. When the softening agent (D) is used in the above proportion, a thermoplastic elastomer composition having excellent fluidity during molding can be obtained.

Other Components In the olefinic thermoplastic elastomer composition according to the present invention, if necessary, conventionally known heat stabilizer, weather resistance stabilizer, antiaging agent, antistatic agent, filler, colorant, Additives such as lubricants can be added within a range that does not impair the object of the present invention.

Examples of conventionally known heat stabilizers, weathering stabilizers, and antiaging agents include phenol-based, sulfite-based, phenylalkane-based, phosphite-based, and amine stabilizers.

Olefinic Thermoplastic Elastomer Composition In the olefinic thermoplastic elastomer composition of the present invention, the crystalline polyolefin resin (A), ethylene / α-olefin copolymer rubber (B), olefinic rubber (C ) And the total amount of the softening agent (D), that is, the ratio of the total amount of the polymer component, that is, the crystalline polyolefin resin (A), the ethylene / α-olefin copolymer rubber (B) and the olefin rubber (C) is It is 60 to 100% by weight.

Olefin-based thermoplastic elastomer composition
Preparation of the olefinic thermoplastic elastomer composition according to the present invention comprises the above-mentioned crystalline polyolefin resin (A), ethylene / α-olefin copolymer rubber (B), and, if necessary, olefinic rubber ( C) and / or the softening agent (D) can be prepared by blending them in the above-mentioned specific proportions and dynamically or thermally treating them in the presence of an organic peroxide to partially or completely crosslink them. .

Specific examples of the organic peroxide used in the present invention include dicumyl peroxide, di-tert-butyl peroxide and 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane. , 2,5-dimethyl-2,5-di- (tert-
Butylperoxy) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert
-Butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert- Examples thereof include butyl peroxybenzoate, tert-butyl perbenzoate, tert-butyl peroxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert-butyl cumyl peroxide.

Among these, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane and 2,5-dimethyl-2,5-di-in terms of odor and stability of scorch. (Tert-Butylperoxy) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene is preferred, and among them, 2,
Most preferred is 5-dimethyl-2,5-di- (tert-butylperoxy) hexane.

Such an organic peroxide is used as the whole cross-linked product, that is, the crystalline polyolefin resin (A), the ethylene / α-olefin copolymer rubber (B), the olefin rubber (C) and the softening agent ( Total amount of D) 100% by weight
With respect to 0.05 to 3% by weight, preferably 0.1 to 2
Used in percentages by weight.

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

By using the above compounds,
A uniform and mild crosslinking reaction can be expected. Particularly, in the present invention, divinylbenzene is most preferred. Divinylbenzene is easy to handle, has good compatibility with the crystalline polyolefin resin (A) and the olefin rubber (C), which are the main components of the above-mentioned substance to be crosslinked, and solubilizes the organic peroxide. Since it acts as a dispersant for organic peroxides, a cross-linking effect by heat treatment is uniform, and a thermoplastic elastomer composition having a good balance of fluidity and physical properties can be obtained.

The above-mentioned crosslinking aid or compound such as polyfunctional vinyl monomer is used as the whole object 1 to be cross-linked.
0.1 to 3% by weight, especially 0.3 to 100% by weight
It is preferably used in a proportion of 2% by weight.

The above-mentioned "dynamically heat-treating" means kneading each of the above components in a molten state. The dynamic heat treatment is carried out using a kneading device such as a mixing roll, an intensive mixer (for example, Banbury mixer, kneader), a single-screw or twin-screw extruder, and preferably in a non-open type kneading device. Further, the dynamic heat treatment is preferably performed in an atmosphere of an inert gas such as nitrogen.

The kneading should be performed with half the organic peroxide used.
It is desirable to carry out at a temperature such that the period is less than 1 minute. Kneading temperature
The temperature is usually 150 to 280 ° C, preferably 170 ° C to 2
40 ° C. Kneading time is usually 1 to 20 minutes, preferably
For 1 to 5 minutes. In addition, the shear added during kneading
The shearing force is usually 10 to 10,000 se at a shear rate.
c ^-1, Preferably 100 to 10,000 sec^-1Range
To be determined within.

As described above, the ethylene / α-olefin copolymer rubber (B), the olefin rubber (C), and the crystalline polyolefin resin (A) are partially or completely crosslinked to form an olefin heat. A plastic elastomer composition is obtained.

In the present invention, the fact that the thermoplastic elastomer composition is partially crosslinked means that the gel content measured by the following method is 10% by weight or more, preferably 20 to 9%.
7% by weight, particularly preferably 30 to 97% by weight. Further, the fact that the thermoplastic elastomer composition is completely crosslinked means that the gel content exceeds 97% by weight. [Measurement method of gel content] About 100 mg of a sample of the thermoplastic elastomer composition was weighed and 0.5 mm × 0.5 m
It is cut into m × 0.5 mm strips, and the strips obtained are then placed in 30 ml of cyclohexane in a closed container at 23 ° C.
Soak for 48 hours.

Next, this sample is taken out on a filter paper and dried at room temperature for 72 hours or more until a constant weight is obtained. The value obtained by subtracting the weight of the cyclohexane-insoluble component (fibrous filler, filler, pigment, etc.) other than the polymer component from the weight of this dry residue is defined as "corrected final weight (Y)".

On the other hand, a value obtained by subtracting the weight of a cyclohexane-soluble component other than the polymer component (for example, a softening agent) and the weight of a cyclohexane-insoluble component other than the polymer component (fibrous filler, filler, pigment, etc.) from the weight of the sample. Is the “corrected initial weight (X)”.

Here, the gel content (cyclohexane insoluble content) is calculated by the following formula. Gel content [% by weight] = [corrected final weight (Y) / corrected initial weight (X)] × 100

[0225]

The olefinic thermoplastic elastomer composition according to the present invention contains a crystalline polyolefin resin (A) and a specific ethylene / α-olefin copolymer rubber (B) in a specific ratio and is crosslinked. Therefore, it is possible to provide a molded product having excellent tensile properties such as tensile strength and elongation at break as compared with the conventional vulcanized rubber.

The present invention will be described below with reference to examples.
The present invention is not limited to these examples. The raw materials used in the production of the olefin-based thermoplastic elastomer in the examples are described below. Crystalline polyolefin resin (A) (A-1) Propylene-ethylene copolymer 1) Ethylene content: 3 mol% 2) MFR (ASTM D 1238-65T, 230 ° C, 2.16 kg load):
25 g / 10 min Olefin rubber (C) (C-1) Ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber 1) Ethylene content: 78 mol% 2) Iodine value: 8.2 3) Mooney Viscosity [ML _{1 + 4} (100 ° C)]: 62 (C-2) Butyl rubber 1) Unsaturation: 0.7 mol% 2) Mooney viscosity [ML _{1 + 8} (100 ° C)]: 55 (C-3 ) Ethylene / propylene copolymer rubber 1) Density: 0.868 g / cm ³ 2) Ethylene content: 81 mol% 3) MFR (ASTM D 1238-65T, 190 ° C, 2.16 kg load):
0.4 4) Intrinsic viscosity [η] measured in decalin at 135 ° C:
2.2 dl / g 4) Average molecular weight distribution (Mw / Mn): 2.19 5) Flow index (FI): 70 sec ^-1 softening agent (D) (D-1) mineral oil-based process oil manufactured by Idemitsu Kosan Co., Ltd., trade name PW-380 Note that the physical properties of the olefin-based thermoplastic elastomer compositions of Examples and Comparative Examples The measuring method is as follows.

[Measurement Method of Physical Properties] (1) Hardness: According to JIS K 6301, JIS A
Hardness was measured. (2) Tensile strength: 200 according to JIS K 6301
The tensile strength at break was measured at a tensile speed of mm / min. (3) Elongation at break: 200 according to JIS K 6301
The breaking elongation at the breaking point was measured at a tensile speed of mm / min.

[0228]

[Reference Example 1] [Preparation of catalyst solution] 51 g of rac-dimethylsilylene-bis- {1- (2-methyl-4-phenylindenyl)} zirconium dichloride represented by the formula below and a toluene solution of methylaluminoxane ( 1.57 liter of aluminum (1.1 mol / liter) and 2.76 liter of toluene were mixed by stirring for 30 minutes at room temperature in the dark to prepare a catalyst solution.

[0229]

Embedded image

Rac-Dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride [Polymer] Using a continuous solution polymerization apparatus, total pressure 6 kg / c
Copolymerization of ethylene and 1-octene was carried out at m-G and a polymerization temperature of 90 ° C. Then, the catalyst solution was continuously supplied at a rate of 0.02 mmol / h in terms of zirconium atom and 10 mmol / h of triisobutylaluminum, and ethylene was added to maintain a constant monomer composition during the polymerization.
1-octene and hydrogen were continuously supplied. (Gas composition (molar ratio): ethylene / 1-octene = 0.83, hydrogen / ethylene = 0.002) As described above, the ethylene / 1-octene copolymer rubber (B-1) contained 5 kg / hr. Obtained in quantity.

The obtained copolymer rubber had a molar ratio of ethylene-derived units to 1-octene-derived units (ethylene / 1-octene) of 83/17. This copolymer rubber has a density of 0.861 g / cm ³
The MFR is 0.4 g / 10 min, the intrinsic viscosity [η] measured in decalin at 135 ° C. is 2.0 dl / g, and the intensity ratio D value of Tαβ to Tαα in the ¹³ C-NMR spectrum is 0.01, B value is 1.1, glass transition temperature (Tg) is −65 ° C., g η
^* Value is 0.84, average molecular weight distribution (Mw / Mn)
Is 2.2 and the liquidity index (FI) is 125
It was sec ^-1 .

This liquidity index (FI) is 19
Shear stress at 0 ° C is 2.4 × 10 ⁶ dyne / cm ²
Is defined as the shear rate at which to reach. The fluidity index (FI) is determined by extruding the resin from the capillary while changing the shear rate and measuring the stress at that time. That is, the liquidity index (F
I) is a capillary flow characteristic tester manufactured by Toyo Seiki Seisakusho Co., Ltd. under a condition that the resin temperature is 190 ° C. and the shear stress range is about 5 × 10 ^{4 to} 3 × 10 ⁶ dyne / cm ^2. It was measured.

The results are shown in Table 1.

[0234]

[Reference Example 2] An ethylene / 1-butene copolymer rubber (B-2) was produced in the same manner as in Reference Example 1, except that the copolymerization reaction was carried out by changing the polymerization conditions.

The molar ratio of the units derived from ethylene and the units derived from 1-butene of these copolymer rubbers, iodine value, intrinsic viscosity [η], D value, B value, Tg, gη ^*
The values, Mw / Mn and FI are shown in Table 1.

[0236]

[Table 1]

[0237]

Example 1 Propylene-ethylene copolymer (A-1)
40 parts by weight of the pellets and 60 parts by weight of the pellets of ethylene / 1-octene random copolymer (B-1) were kneaded in a nitrogen atmosphere at 180 ° C. for 5 minutes, and then obtained. The kneaded product was passed through a roll to form a sheet, which was cut with a sheet cutter to produce square pellets.

Next, 100 parts by weight of the square pellets,
After 0.3 parts by weight of 2,5-di- (t-butylperoxy) hexane and 0.4 parts by weight of divinylbenzene were mixed by stirring with a Henschel mixer, the resulting mixture was mixed with L / D = 3.
The pellet of the thermoplastic elastomer composition was manufactured by extruding at 220 ° C. in a nitrogen atmosphere using a twin screw extruder having a screw diameter of 0 and a screw diameter of 50 mm.

Further, predetermined pellets were prepared from the pellets of the thermoplastic elastomer composition by an injection molding machine, and the physical properties thereof were measured according to the above measuring methods. Table 2 shows the results.

[0240]

[Example 2] In Example 1, except that 60 parts by weight of ethylene / 1-butene copolymer rubber (B-2) was used in place of the ethylene / 1-octene copolymer rubber (B-1). Pellets of the thermoplastic elastomer composition were produced in the same manner as in Example 1.

Then, test pieces were prepared from the pellets of the thermoplastic elastomer composition in the same manner as in Example 1, and the physical properties thereof were measured according to the above measuring methods. Table 2 shows the results.

[0242]

[Example 3] Propylene-ethylene copolymer (A-1)
20 parts by weight of pellets of ethylene / 1-octene copolymer rubber (B-1) 60 parts by weight of ethylene.
Pellets of the thermoplastic elastomer composition were produced in the same manner as in Example 1 using 20 parts by weight of propylene / 5-ethylidene-2-norbornene copolymer rubber (C-1).

Then, from the pellets of the thermoplastic elastomer composition, a test piece was prepared in the same manner as in Example 1, and its physical properties were measured according to the above measuring methods. Table 2 shows the results.

[0244]

Example 4 In Example 3, an ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber (C-
Pellets of the thermoplastic elastomer composition were produced in the same manner as in Example 1 except that 20 parts by weight of butyl rubber (C-2) was used instead of 1).

Then, from the pellets of this thermoplastic elastomer composition, a test piece was prepared in the same manner as in Example 1, and its physical properties were measured according to the above measuring methods. Table 2 shows the results.

[0246]

Example 5 Propylene / Ethylene Copolymer (A-1)
17 parts by weight of pellets, 50 parts by weight of ethylene / 1-octene copolymer rubber (B-1) pellets, 17 parts by weight of butyl rubber (C-2), and a mineral oil-based process oil (D
-1) 16 parts by weight was used to produce pellets of the thermoplastic elastomer composition in the same manner as in Example 1.

Then, from the pellets of the thermoplastic elastomer composition, a test piece was prepared in the same manner as in Example 1, and its physical properties were measured according to the above measuring methods. Table 2 shows the results.

[0248]

[Comparative Example 1] In Example 1, except that 60 parts by weight of ethylene / propylene copolymer rubber (C-3) was used in place of ethylene / 1-octene copolymer rubber (B-1).
Pellets of the thermoplastic elastomer composition were produced in the same manner as in Example 1.

Then, test pieces were prepared from the pellets of the thermoplastic elastomer composition in the same manner as in Example 1, and the physical properties thereof were measured according to the above measuring methods. Table 2 shows the results.

[0250]

[Comparative Example 2] In Example 3, except that 60 parts by weight of an ethylene / propylene copolymer rubber (C-3) was used in place of the ethylene / 1-octene copolymer rubber (B-1).
Pellets of the thermoplastic elastomer composition were produced in the same manner as in Example 1.

Then, a test piece was prepared from the pellet of the thermoplastic elastomer composition in the same manner as in Example 1, and the physical properties thereof were measured according to the above measuring methods. Table 2 shows the results.

[0252]

[Comparative Example 3] In Example 4, except that 60 parts by weight of an ethylene / propylene copolymer rubber (C-3) was used in place of the ethylene / 1-octene copolymer rubber (B-1).
Pellets of the thermoplastic elastomer composition were produced in the same manner as in Example 1.

Then, from the pellets of the thermoplastic elastomer composition, a test piece was prepared in the same manner as in Example 1, and its physical properties were measured according to the above measuring methods. Table 2 shows the results.

[0254]

[Comparative Example 4] In Example 5, except that 50 parts by weight of an ethylene / propylene copolymer rubber (C-3) was used instead of the ethylene / 1-octene copolymer rubber (B-1).
Pellets of the thermoplastic elastomer composition were produced in the same manner as in Example 1.

Then, test pieces were prepared from the pellets of the thermoplastic elastomer composition in the same manner as in Example 1, and the physical properties thereof were measured according to the above measuring methods. Table 2 shows the results.

[0256]

[Table 2]

[0257]

[Reference Example 3] [Preparation of ethylene / 1-octene copolymer rubber] (Preparation of catalyst solution) Bis (1,3-dimethylcyclopentadienyl) zirconium dichloride was added to a glass flask sufficiently purged with nitrogen. A catalyst solution was obtained by adding 5 mg and further adding 1.57 ml of a toluene solution of methylaminoxane (Al; 1.1 mol / liter) and 2.76 ml of toluene.

(Polymerization) 600 m of hexane was placed in a stainless steel autoclave having an internal volume of 2 liters, which was sufficiently replaced with nitrogen.
1 and 1-octene (400 ml) were inserted, and the temperature in the system was raised to 80 ° C. Subsequently, 1 mmol of triisobutylaluminum and 0.5 m of the catalyst solution prepared above
Polymerization was initiated by pressurizing 1 (0.001 mmol as Zr) with ethylene. Then, by continuously supplying only ethylene, the total pressure is 4.0 Kg / cm.
Polymerization was carried out at 90 ° C. for 30 minutes while keeping at ^2- G. After a small amount of ethanol was purged into the system to stop the polymerization, unreacted ethylene was purged. The polymer was deposited by pouring the obtained polymer into a large excess of methanol. The polymer was collected by filtration and dried under reduced pressure overnight to obtain a linear ethylene / 1-octene copolymer rubber (B-3).

The copolymer rubber (B
-3) has a molar ratio of ethylene-derived units to 1-octene-derived units (ethylene / 1-octene) of 9
0/10, the density is 0.885 g / cm ³ ,
MFR is 3.5 g / 10 min, intrinsic viscosity [η] measured in decalin at 135 ° C. is 1.5 dl / g, glass transition temperature (Tg) is −58 ° C., and X-ray diffraction method is used. The measured crystallinity is 14%, the average molecular weight distribution (Mw / Mn) determined by GPC is 2.5, the D value is 0.01 or less, the B value is 1.03, and gη ^*
The value was 1.00. These physical property values are shown in Table 3.

[0260]

Reference Example 4 In Reference Example 3, instead of 1-octene
Reference Example 3 except that 1-butene was used, and the polymerization pressure and the polymerization temperature were 20 Kg / cm ² -G and 110 ° C., respectively.
Polymerization was carried out in the same manner as above to obtain an ethylene / 1-butene copolymer rubber (B-4).

The resulting copolymer rubber (B-4) had a molar ratio of ethylene-derived units to 1-butene-derived units (ethylene / 1-butene) of 88/12 and a density of 0.886 g / cm ³ , MFR 3.5 g /
10 minutes, the intrinsic viscosity [η] measured in decalin at 135 ° C. is 1.5 dl / g, and the glass transition temperature (T
g) is -57 ° C, the crystallinity measured by X-ray diffraction is 10%, the average molecular weight distribution (Mw / Mn) determined by GPC is 2.2, and the D value is 0.01. The B value was 1.02 and the g η ^* value was 1.00. These physical property values are shown in Table 3.

[0262]

[Table 3]

[0263]

Example 6 In Example 1, 60 parts by weight of the ethylene / 1-octene copolymer rubber (B-3) prepared in Reference Example 3 was used instead of the ethylene / 1-octene copolymer rubber (B-1). Pellets of the thermoplastic elastomer composition were produced in the same manner as in Example 1 except that parts were used.

Then, from the pellets of the thermoplastic elastomer composition, a test piece was prepared in the same manner as in Example 1, and its physical properties were measured according to the above measuring methods. Table 4 shows the results.

[0265]

Example 7 In Example 1, 60 parts by weight of the ethylene / 1-butene copolymer rubber (B-4) prepared in Reference Example 4 was used instead of the ethylene / 1-octene copolymer rubber (B-1). Pellets of the thermoplastic elastomer composition were produced in the same manner as in Example 1 except that parts were used.

Then, test pieces were prepared from the pellets of the thermoplastic elastomer composition in the same manner as in Example 1, and the physical properties thereof were measured according to the above measuring methods. Table 4 shows the results.

[0267]

[Table 4]

Claims (5)

[Claims] 1. A crystalline polyolefin resin (A) 10-8.
An ethylene / α-olefin copolymer rubber (B) 1 comprising 5 parts by weight of ethylene and an α-olefin having 3 to 20 carbon atoms.
5 to 90 parts by weight [the total amount of ((A) and (B) is 100)
Parts by weight], wherein the ethylene / α-olefin copolymer rubber (B) is a partially or completely crosslinked thermoplastic elastomer composition, wherein the ethylene / α-olefin copolymer rubber (B) is mixed with ethylene in the presence of a metallocene catalyst. Obtained by random copolymerization with an α-olefin having 3 to 20 carbon atoms, and (1) (a) a unit derived from ethylene and (b) 3 to 3 carbon atoms.
The unit derived from 20 α-olefins is 55/4
5 to 98/2 [(a) / (b)] in a molar ratio, (2) the density is 0.860 to 0.900 g / cm ³ , and (3) the melt flow rate (ASTM D 1238, 230 ℃, 2.16kg
(Load) is 0.01 to 20 g / 10 minutes, and (4) intrinsic viscosity [η] measured in decalin at 135 ° C.
Is 0.1 to 10 dl / g, and the olefinic thermoplastic elastomer composition is characterized in that 2. Crystalline polyolefin resin (A) 10-8
An ethylene / α-olefin copolymer rubber (B) 1 comprising 5 parts by weight of ethylene and an α-olefin having 3 to 20 carbon atoms.
5 to 90 parts by weight [the total amount of ((A) and (B) is 100)
Parts by weight], wherein the ethylene / α-olefin copolymer rubber (B) is a partially or completely crosslinked thermoplastic elastomer composition, wherein the ethylene / α-olefin copolymer rubber (B) is mixed with ethylene in the presence of a metallocene catalyst. Obtained by random copolymerization with an α-olefin having 3 to 20 carbon atoms, and (1) (a) a unit derived from ethylene and (b) 3 to 3 carbon atoms.
The unit derived from 20 α-olefins is 55/4
5 to 98/2 [(a) / (b)] in a molar ratio, (2) the density is 0.860 to 0.900 g / cm ³ , and (3) the melt flow rate (ASTM D 1238, 230 ℃, 2.16kg
(Load) is 0.01 to 20 g / 10 minutes, and (4) intrinsic viscosity [η] measured in decalin at 135 ° C.
Is 0.1 to 10 dl / g, and (5) the intrinsic viscosity [η] measured in (4) above and the ethylene content of the same weight average molecular weight (by light scattering method) as 70 mol% Ratio of the linear ethylene / propylene copolymer of [η] _blank [η] ^* (= [η] /
[Η] _blank )] is a value exceeding 0.95, and the olefin-based thermoplastic elastomer composition according to claim 1. 3. The ethylene / α-olefin copolymer rubber (B) has (6) a T relative to Tαα in a ¹³ C-NMR spectrum.
The intensity ratio D (Tαβ / Tαα) of αβ is 0.5 or less, and (7) 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 the units derived from (b) α-olefin in the random copolymer rubber, and [P _OE ] is the total dyad chain in the random copolymer rubber. The ratio of α-olefin / ethylene chain number to the number), (8) the glass transition temperature (Tg) determined by DSC is -5.
It is 0 degreeC or less, The olefinic thermoplastic elastomer composition of Claim 2 characterized by the above-mentioned. 4. A crystalline polyolefin resin (A) 10-8.
An ethylene / α-olefin copolymer rubber (B) 1 comprising 5 parts by weight of ethylene and an α-olefin having 3 to 20 carbon atoms.
5 to 90 parts by weight [the total amount of ((A) and (B) is 100)
Parts by weight], wherein the ethylene / α-olefin copolymer rubber (B) is a partially or completely crosslinked thermoplastic elastomer composition, wherein the ethylene / α-olefin copolymer rubber (B) is mixed with ethylene in the presence of a metallocene catalyst. Obtained by random copolymerization with an α-olefin having 3 to 20 carbon atoms, and (1) (a) a unit derived from ethylene and (b) 3 to 3 carbon atoms.
The unit derived from 20 α-olefins is 55/4
5 to 98/2 [(a) / (b)] in a molar ratio, (2) the density is 0.860 to 0.900 g / cm ³ , and (3) the melt flow rate (ASTM D 1238, 230 ℃, 2.16kg
(Load) is 0.01 to 20 g / 10 minutes, and (4) intrinsic viscosity [η] measured in decalin at 135 ° C.
Is 0.1 to 10 dl / g, and (5) the intrinsic viscosity [η] measured in (4) above and the ethylene content of the same weight average molecular weight (by light scattering method) as 70 mol% Ratio of the linear ethylene / propylene copolymer of [η] _blank [η] ^* (= [η] /
[Η] _blank )] is 0.2 to 0.95, and the olefinic thermoplastic elastomer composition according to claim 1. 5. Crystalline polyolefin resin (A) 10-8
5 parts by weight, 15 to 90 parts by weight of ethylene / α-olefin copolymer rubber (B), and olefin rubber (C) 1
To 40 parts by weight and / or 1 to 40 parts by weight of the softening agent (D) [the total amount of components (A), (B), (C) and (D) is 100 parts by weight], and The ratio of the total amount of the components (A), (B), (C) and (D) to the total amount of the components (A), (B) and (C) is 60.
To 100% by weight, the olefinic thermoplastic elastomer composition according to any one of claims 1 to 4.