JPH11349744A - Crosslinked thermoplastic elastomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a crosslinked thermoplastic elastomer composition including a polyolefin-based resin, consisting of complete olefin component alone containing no aromatic vinyl compound, such as styrene, and excellent in weatherability, mechanical strength, elastic recovery, flexibility and also recyclability. SOLUTION: This crosslinked thermoplastic elastomer composition is obtained by dynamically treating, with heat, a blend of (A) 5-95 wt.% of a polyolefin- based resin and (B) 95-5 wt.% of an olefin-based copolymer obtained by copolymerizing two or more kinds of olefins selected from ethylene, propylene and 4-20C α-olefins, wherein, the total number of carbons of the selected olefins is >=6.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a crosslinked thermoplastic elastomer composition. More specifically, the present invention comprises a polyolefin-based resin, is excellent in weather resistance, mechanical strength, elastic recovery and flexibility, and comprises only a complete olefin component not containing an aromatic vinyl compound such as styrene. And a crosslinked thermoplastic elastomer composition having excellent recyclability.

[0002]

2. Description of the Related Art An olefin-based thermoplastic elastomer composition comprises an olefin-based copolymer rubber and a polyolefin resin, and is obtained by dynamically curing a rubber portion by a known method. According to this method, a thermoplastic elastomer composition having excellent elastic recovery and mechanical strength without impairing the cold resistance, weather resistance, and chemical resistance of an ethylene-propylene (-non-conjugated diene) copolymer rubber is obtained. Is possible. However, olefinic thermoplastic elastomers are generally said to have poor flexibility and lack rubber-like properties. For this reason, mineral oil-based softeners are blended to provide flexibility, but the addition of a large amount of a softener reduces physical properties such as elastic recovery,
Adoption is constrained because it causes problems of dissolution of the softener. On the other hand, a method for providing a thermoplastic elastomer composition having excellent mechanical strength, elastic recovery and flexibility by blending a hydrogenated product of a conjugated diene-styrene copolymer with a polyolefin resin is disclosed in 286
No. 078 and the like. However, the hydrogenated product of the conjugated diene-styrene copolymer described above is expected to be improved because it contains styrene in its structure and thus does not always have sufficient weather resistance, especially ultraviolet light stability. Further, in view of the growing demand for recycling of polymer materials in recent years, and from the viewpoint of material development in consideration of environmental issues, it is desirable to use a material composed of only a complete olefin component not containing an aromatic vinyl compound such as styrene. The design is expected.

[0003]

Under such circumstances, the problem to be solved by the present invention is to contain a polyolefin-based resin, to have excellent weather resistance, mechanical strength, elastic recovery and flexibility, and to use styrene. It is an object of the present invention to provide a crosslinked thermoplastic elastomer composition which is excellent in recyclability because it comprises only a complete olefin component containing no such aromatic vinyl compound.

[0004]

That is, the present invention provides a method of dynamically heat-treating a mixture containing the following (a) 5 to 95% by weight and (b) 95 to 5% by weight in the presence of a crosslinking agent. The present invention relates to a crosslinked thermoplastic elastomer composition obtained as described above. (A): polyolefin resin (b): ethylene, propylene and α having 4 to 20 carbon atoms
-An olefin copolymer obtained by copolymerizing two or more olefins selected from the group consisting of olefins, wherein the total number of carbon atoms of the selected olefins is 6 or more.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The component (A) of the present invention is a polyolefin resin. Specific examples of (a) include polyethylene, polypropylene, poly-4-methyl-1-pentene, poly-1-butene and the like, and among them, polypropylene is preferred. The polypropylene is isotactic polypropylene or syndiotactic polypropylene, and may be a homo-type or a random type containing a comonomer, or a block type by multi-stage polymerization. The polypropylene may employ a gas-phase polymerization method, a bulk polymerization method, a solvent polymerization method, and optionally a multi-stage polymerization by combining them. Also, there is no particular limitation on the number average molecular weight of such a polymer,
Preferably, it is adjusted to 10,000 to 1,000,000. Further, two or more kinds of polyolefin resin resins may be used in combination. In addition, as (a), a corresponding commercial product can be used.

The component (b) of the present invention is at least two types of olefins selected from the group consisting of ethylene, propylene and α-olefins having 4 to 20 carbon atoms. An olefin copolymer obtained by copolymerizing two or more olefins having a total of 6 or more. It is necessary that the total number of carbon atoms of the selected olefin is 6 or more. When a combination of olefins having a total carbon number of less than 6 is selected, a molded article molded using the obtained crosslinked thermoplastic elastomer composition is inferior in flexibility.

The α-olefin having 4 to 20 carbon atoms includes linear and branched α-olefins. Specifically, the linear α-olefin includes 1-butene and 1-butene. 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,
Examples thereof include 1-octadecene, 1-nanodecene, and 1-eicosene. Examples of the branched α-olefin include 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, -Ethyl-1-hexene, 2,
2,4-trimethyl-1-pentene and the like are exemplified.

Specific examples of the combination of two or more selected olefins include ethylene / 1-butene, ethylene / 1-hexene, ethylene / 1-octene, and ethylene / 1-octene.
1-decene, ethylene / 1-octadecene, ethylene /
4-methyl-1-pentene, propylene / 1-butene,
Propylene / 1-hexene, propylene / 1-octene, propylene / 1-decene, propylene / 1-octadecene, propylene / 4-methyl-1-pentene, 1-
Butene / 1-hexene, 1-butene / 1-octene, 1
-Butene / 1-decene, 1-butene / 1-octadecene, 1-butene / 4-methyl-1-pentene, 1-hexene / 1-octene, 1-hexene / 1-decene, 1-
Hexene / 1-octadecene, 1-hexene / 4-methyl-1-pentene, 1-octene / 1-decene, 1-octene / 1-octadecene, 1-octene / 4-methyl-1-pentene, 1-decene / 1-octadecene, 1-
Decene / 4-methyl-1-pentene, 1-octadecene / 4-methyl-1-pentene, ethylene / propylene /
1-butene, ethylene / propylene / 1-hexene, ethylene / propylene / 1-octene, ethylene / propylene / 1-decene, ethylene / propylene / 1-octadecene, ethylene / propylene / 4-methyl-1-pentene, ethylene / 1-butene / 1-hexene, ethylene / 1-butene / 1-octene, ethylene / 1-butene /
1-decene, ethylene / 1-butene / 1-octadecene, ethylene / 1-butene / 4-methyl-1-pentene, ethylene / 1-hexene / 1-octene, ethylene / 1-hexene / 1-decene, ethylene / 1-hexene / 1-octadecene, ethylene / 1-hexene / 4-methyl-1-pentene, ethylene / 1-octene / 1-decene, ethylene / 1-octene / 1-octadecene, ethylene / 1-octene / 4 Methyl-1-pentene, ethylene / 1-decene / 1-octadecene, ethylene / 1
-Decene / 4-methyl-1-pentene, ethylene / 1-
Octadecene / 4-methyl-1-pentene, propylene / 1-butene / 1-hexene, propylene / 1-butene / 1-octene, propylene / 1-butene / 1-decene, propylene / 1-butene / 1-octadecene, Propylene / 1-butene / 4-methyl-1-pentene, propylene / 1-hexene / 1-octene, propylene / 1
-Hexene / 1-decene, propylene / 1-hexene /
1-octadecene, propylene / 1-hexene / 4-methyl-1-pentene, propylene / 1-octene / 1-
Decene, propylene / 1-octene / 1-octadecene, propylene / 1-octene / 4-methyl-1-pentene, propylene / 1-decene / 1-octadecene, propylene / 1-decene / 4-methyl-1-pentene, Propylene / 1-octadecene / 4-methyl-1-pentene, 1-butene / 1-hexene / 1-octene, 1-butene / 1-hexene / 1-decene, 1-butene / 1-hexene / 1-octadecene, 1-butene / 1-hexene / 4-methyl-1-pentene, 1-butene / 1-octene / 1-decene, 1-butene / 1-octene / 1-octadecene, 1-butene / 1-octene / 4- Methyl-1
-Pentene, 1-butene / 1-decene / 1-octadecene, 1-butene / 1-decene / 4-methyl-1-pentene, 1-butene / 1-octadecene / 4-methyl-1-
Pentene, ethylene / propylene / 1-butene / 1-hexene, ethylene / propylene / 1-butene / 1-octene, ethylene / propylene / 1-butene / 1-decene, ethylene / propylene / 1-butene / 1-octadecene, Ethylene / propylene / 1-butene / 4-methyl-1-pentene, ethylene / 1-butene / 1-hexene / 1-octene, ethylene / 1-butene / 1-hexene / 1-decene, ethylene / 1-butene / 1-hexene /
1-octadecene, ethylene / 1-butene / 1-hexene / 4-methyl-1-pentene, ethylene / propylene / 1-hexene / 1-octene, ethylene / propylene / 1-hexene / 1-decene, ethylene / propylene /
1-hexene / 1-octadecene, ethylene / propylene / 1-hexene / 4-methyl-1-pentene and the like.

(B) is at least two olefins selected from the group consisting of ethylene, propylene and α-olefins having 4 to 20 carbon atoms, wherein the total number of carbon atoms of the selected olefins is 6 or more. An olefin copolymer obtained by copolymerizing two or more olefins and a cyclic olefin is preferable. Here, the “two or more olefins” and the “cyclic olefin” have mutually different concepts.

Preferred cyclic olefins include cyclic monoolefins.
Olefins and cyclic polyenes can be mentioned. ring
Olefins have one or more rings of four or more carbon atoms.
To form at least one carbon-carbon double bond in the molecule
Cyclic compounds which may have various substituents including the above
You. Specific structures of such cyclic olefins include, for example,
For example, a compound represented by the following general formula [IV] or [V] is exemplified.
be able to.(In the formula, n1 to n5 represent an integer of 0 or more. C₁~ C_FifteenIs
Carbon atom, C₁~ C _TwoForms a polymerizable double bond
I have. R₁~ R₁₂And R₁₄~ R₁₇Is hydrogen atom, halogen
Atom, hydroxyl group, amino group and organic having 1 to 20 carbon atoms
Represents a substituent selected from the group consisting of groups. General formula [IV]
Is C_ThreeAnd C₆, C₈And C₁₁Are (C7) n and (C1
2) It can also be linked through n. R₉, R_TenAnd R
₁₁, R₁₂May form a ring via structural formula [IV].
The general formula [V] is R₁₃And select structural formula [VI] as
A structure can be formed. At this time, in structural formula [VI]
N4 and n5 in which the carbon number of the cyclic olefin is 4 or more
In this way, an integer greater than or equal to 0 is selected. )

Here, the substituent has 1 to 1 carbon atoms.
Specific examples of the organic group of 20 include a methyl group, an ethyl group,
Alkyl groups such as propyl group, butyl group, hexyl group, octyl group and dodecyl group; aryl groups such as phenyl group, tolyl group and naphthyl group; aralkyl groups such as benzyl group and phenethyl group; alkylidene groups such as methylidene group and ethylidene group Alkenyl groups such as vinyl group and allyl group; alkoxy groups such as methoxy group and ethoxy group; aryloxy groups such as phenoxy group; acyl groups such as acetyl group; alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group; An acyloxy group such as an oxy group; a (substituted) silyl group such as a trimethylsilyl group; and a part of the hydrogen atoms of the alkyl group, the aryl group, and the aralkyl group are halogen atoms, hydroxyl groups, amino groups, acyl groups, carboxyl groups, and alkoxy groups. Group, alkoxycarbonyl group, acyloxy group It can be mentioned (substituted) silyl group substituted with an alkylamino group or a cyano group group.

Specific examples of the cyclic olefin compound represented by the general formula [IV] include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, 1-methylnorbornene, -Methylnorbornene, 5,5,6-trimethylnorbornene, 5-phenylnorbornene,
-Benzylnorbornene, 5-ethylidenenorbornene, 5-vinylnorbornene, 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-methyl-1, 4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-
1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8, 8a-octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethylidene-1,4,5 8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano-1,2,3,4,4a, 5 8,8a-octahydronaphthalene, 1,5-dimethyl-1,4,5,8-
Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-cyclohexyl-1,4
5,8-Dimethano-1,2,3,4,4a, 5,8,8
a-octahydronaphthalene, 2,3-dichloro-1,
4,5,8-Dimethano-1,2,3,4,4a, 5
8,8a-octahydronaphthalene, 2-isobutyl-
1,4,5,8-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene, 1,2-dihydrodicyclopentadiene, 5-chloronorbornene,
5,5-dichloronorbornene, 5-fluoronorbornene, 5,5,6-trifluoro-6-trifluoromethylnorbornene, 5-chloromethylnorbornene, 5
-Methoxynorbornene, 5,6-dicarboxyl norbornene anhydrate, 5-dimethylaminonorbornene, 5-cyanonorbornene and the like can be exemplified. Examples of the cyclic olefin compound represented by the general formula [V] include cyclopentene, 3-methylcyclopentene,
-Methylcyclopentene, 3,4-dimethylcyclopentene, 3,5-dimethylcyclopentene, 3-chlorocyclopentene, cyclohexene, 3-methylcyclohexene, 4-methylcyclohexene, 3,4-dimethylcyclohexene, 3-chlorocyclohexene, Cycloheptene and the like can be exemplified.

Specific examples of the cyclic polyene compound having two carbon-carbon double bonds in the cyclic olefin molecule represented by the general formula [IV] include 5-ethylidene-2-norbornene and 5-methylene-2 -Norbornene, 5-isopropylidene-2-norbornene, 3-vinylcyclohexene, 4-vinylcyclohexene, 5-vinylnorbornene, 5-allylnorbornene, 5,6-diethylidene-2-norbornene, dicyclopentadiene, dimethylcyclopentadiene, 2,5-norbornadiene and the like can be exemplified. As the cyclic polyene compound represented by the general formula [V], 1,3-cyclopentadiene, 1,1,
3-cyclohexadiene, 1,4-cyclohexadiene, 5-ethyl-1,3-cyclohexadiene, 1,3
-Cycloheptadiene, 1,3-cyclooctadiene and the like.

The content of the cyclic olefin in (b) is
It is preferably 0.01 to 20 mol%, more preferably 0.1 to 0.2 mol%.
And preferably from 0.1 to 10 mol%, more preferably from 0.1 to 10 mol%.
Mol%, particularly preferably 0.15 to 5 mol%. When the content of the cyclic olefin is too low, the mechanical strength or elastic recovery of a molded article molded using the obtained crosslinked thermoplastic elastomer composition may be inferior, while the content of the cyclic olefin is excessive. In some cases, the balance between mechanical strength and flexibility of a molded article molded using the obtained crosslinked thermoplastic elastomer composition is poor. Propylene or ethylene and propylene can be contained as the olefin of (b).

The content of ethylene as the olefin in (b) is preferably 80 mol% or less, more preferably 70 mol% or less, from the viewpoint of the effect of improving the flexibility of the crosslinked thermoplastic elastomer composition. And more preferably at most 60 mol%, particularly preferably at most 50 mol%.
It is as follows. Outside this range, the olefin-based copolymer may contain crystals derived from ethylene, and the molded article molded from the obtained crosslinked thermoplastic elastomer composition may have poor flexibility. On the other hand, when low-temperature resistance is particularly required, the propylene content in (b) is preferably 90% or less, more preferably 80% or less, and still more preferably 70% or less. It is particularly preferably at most 60%, most preferably at most 50%. If the ratio is out of the range, the molded article molded using the obtained crosslinked thermoplastic elastomer composition may have poor low-temperature impact resistance.

(B) preferably satisfies the following relationship: [Y / (x + y)] ≧ 0.2 More preferably, [y / (x + y)] ≧ 0.3, more preferably, [y / (x + y)] ≧ 0.4, particularly preferably , [Y / (x + y)] ≧ 0.5. If the ratio is out of the above range, a molded article molded using the obtained crosslinked thermoplastic elastomer composition may have poor flexibility. In the above formula, x represents a molar content of ethylene in the copolymer, and y represents a carbon number of 4 to 2 in the copolymer.
Represents the sum of the molar contents of α-olefins of 0.

In (b), the intrinsic viscosity [η] of the tetralin solvent at a temperature of 135 ° C. is preferably 0.3 to 10, more preferably 0.5 to 7, and even more preferably 0.7 to 7. 5 If the intrinsic viscosity is too low,
In some cases, a molded article molded using the obtained crosslinked thermoplastic elastomer composition has poor mechanical strength. On the other hand, if the intrinsic viscosity is too high, the flexibility of a molded article formed using the obtained crosslinked thermoplastic elastomer composition may be poor. The intrinsic viscosity [η] is measured in tetralin at 135 ° C. using an Ubbelohde viscometer. Sample is 300m
g in 100 ml tetralin to prepare a 3 mg / ml solution. Further, the solution was を, ３, １ ／
And each is measured in a thermostatic oil bath at 135 ° C. (± 0.1 ° C.). The measurement is repeated three times at each concentration, and the obtained values are averaged and used.

(B) shows the molecular weight distribution (M) measured by gel permeation chromatography (GPC).
(w / Mn) is preferably 3 or less. When the molecular weight distribution is too wide, when the copolymer is used as a modifier, the resulting crosslinked thermoplastic elastomer composition may have poor flexibility. The molecular weight distribution is determined by gel permeation chromatography (GPC) (for example, Water).
s company, 150C / GPC device). The elution temperature is 140 ° C., and the column used is, for example, a product of Showa Denko
Odex Packed Column A-80M, the molecular weight standard substance is polystyrene (for example, manufactured by Tosoh Corporation,
Molecular weight 68-8,400,000). The obtained polystyrene-equivalent weight average molecular weight (Mw), number average molecular weight (Mn), and the ratio (Mw / Mn) are defined as a molecular weight distribution. The measurement sample was prepared by adding about 5 mg of polymer to 5 ml of o-
Dissolve in dichlorobenzene to a concentration of about 1 mg / ml. 400 μl of the obtained sample solution is injected, and the elution solvent flow rate is set to 1.0 ml / min, and detected by a refractive index detector.

(B) has neither a peak of 1 J / g or more based on melting of a crystal nor a peak of 1 J / g or more based on crystallization as measured by a differential scanning calorimeter (DSC). Is preferred. When such a peak is present, the flexibility of a molded article molded using the obtained crosslinked thermoplastic elastomer composition may be poor. The differential scanning calorimeter is, for example, DSC220 manufactured by Seiko Denshi Kogyo KK
C, 10 ° C./min for both the temperature rise and temperature fall processes
Measure at the speed of

(B) can be produced using a known Ziegler-Natta type catalyst or metallocene catalyst. It is preferable to use a metallocene catalyst from the viewpoint that a copolymer having a high molecular weight, a narrow molecular weight distribution, and a narrow composition distribution can be obtained. Examples of the metallocene catalyst include groups 4A to 6A of the periodic table having at least one cyclopentadienyl skeleton.
Group transition metal complexes. Specific examples of the metallocene catalyst include, for example, JP-A-9-12635.
And metallocene catalysts described in JP-A-9-151205.

In particular, (b) is propylene and / or carbon number
The sequence of 4 to 20 α-olefin side chains has an atactic structure
It is preferred that the Non-atactic structure
Is obtained when the copolymer is used as a modifier.
In some cases, the flexibility of the crosslinked thermoplastic elastomer composition is poor.
is there. The stereoregularity in the copolymer becomes an atactic structure
To do so, ethylene, propylene and C4-20
two or more olefins selected from the group consisting of α-olefins
A fin, the total number of carbon atoms of the selected olefin
Two or more olefins having at least 6;
The olefin in the form of the following (A), the following (B) and / or
Existence of olefin polymerization catalyst using the following (C)
Optimum production can be achieved by copolymerization below. (A): transition gold represented by the following general formulas [I] to [III]
At least one of the genus complexes(In the above general formulas [I] to [III], M¹Is
Represents a transition metal atom of Group 4 of the Periodic Table of the Elements, where A is an element
Indicates an atom belonging to Group 16 of the Periodic Table,
Shows the atoms of Group 14 of the Rule. Cp¹Is cyclopentadi
A group having an ene-type anion skeleton is shown. X¹, X^Two,
R¹, R^Two, R^Three, R^Four, R^FiveAnd R⁶Are each independently water
Element atom, halogen atom, alkyl group, aralkyl group,
Reel group, substituted silyl group, alkoxy group, aralkyl group
It represents a xy group, an aryloxy group or a disubstituted amino group.
X^ThreeRepresents an atom belonging to Group 16 of the periodic table of the elements. R¹, R
^Two, R^Three, R^Four, R^FiveAnd R⁶Are optionally linked to form a ring
You may. Two M¹, A, J, Cp¹, X¹, X^Two,
X^Three, R¹, R^Two, R^Three, R^Four, R^FiveAnd R⁶Are the same for each
Or different. (B): at least one selected from the following (B1) to (B3)
(B1) General formula E¹ _aAlZ_3-aOrganic aluminum indicated by
Compound (B2) General formula ｛-Al (E^Two) -O-｝_bIndicated by
Cyclic aluminoxane having a structure (B3) General formula E^Three｛-Al (E^Three) -O-｝_cAlE^Three
_TwoLinear aluminoxane having a structure represented by the following formula (provided that E¹, E^TwoAnd E^ThreeIs a hydrocarbon group
All E¹, All E ^TwoAnd all E^ThreeIs the same
Or different. Z is a hydrogen atom or a halogen atom
Represents a child, and all Z may be the same or different
No. a is a number satisfying 0 <a ≦ 3, b is an integer of 2 or more
And c represents an integer of 1 or more. (C): Boration of any of the following (C1) to (C3)
Compound (C1) General formula BQ¹Q^TwoQ^ThreeBoron compound represented by
Object, (C2) general formula G⁺(BQ¹Q^TwoQ^ThreeQ^Four)^-E represented by
Iodine compound, (C3) General formula (LH)⁺(BQ¹Q^TwoQ^ThreeQ^Four)^-In table
(Where B is a boron atom in a trivalent state, Q
¹~ Q^FourIs a halogen atom, hydrocarbon group, halogenated hydrocarbon
Group, substituted silyl group, alkoxy group or disubstituted amino group
And they may be the same or different.
G⁺Is an inorganic or organic cation, and L is a neutral Lewis
A base, (LH)⁺Is a Bronsted acid
You. )

Hereinafter, the above production method will be described in more detail. (A) The transition metal complex will be described. The transition metal complex (A) has the general formula [I], [II] or [II]
I]. In the general formulas [I], [II] or [III], the transition metal atom represented by M ¹ is the fourth metal in the periodic table of elements (IUPAC revised edition of inorganic chemical nomenclature 1989).
Represents a transition metal element of the group, such as a titanium atom, a zirconium atom, and a hafnium atom. Preferably it is a titanium atom or a zirconium atom.
Examples of the atoms of Group 16 of the periodic table of the element represented by A in Formulas [I], [II], and [III] include an oxygen atom, a sulfur atom, and a selenium atom.
Preferably it is an oxygen atom. Examples of atoms belonging to Group 14 of the periodic table of the element represented by J in the general formulas [I], [II] and [III] include a carbon atom, a silicon atom and a germanium atom, and preferably a carbon atom Or it is a silicon atom.

Examples of the group having a cyclopentadiene type anion skeleton represented by the substituent Cp ¹ include, for example, η
⁵ - (substituted) cyclopentadienyl group, eta ⁵ - (substituted) indenyl group, eta ⁵ - and the like (substituted) fluorenyl group. Specific examples include, for example, η ⁵ -cyclopentadienyl group, η ⁵ -methylcyclopentadienyl group, η ⁵
- dimethyl cyclopentadienyl group, eta ⁵ - trimethyl cyclopentadienyl group, eta ⁵ - tetramethylcyclopentadienyl group, eta ⁵ - Echirushikuro Bae Ntajieniru group, eta ^5-n-propyl cyclopentadienyl group, eta ⁵ −
Isopropyl cyclopentadienyl group, eta ^{5-n-butylcyclopentadienyl} group, eta ^{5-sec-butylcyclopentadienyl} group, eta ^{5-tert-Buchirushikuro} Bae Ntajieniru group, eta ^{5-n-Penchirushikuro} Bae Ntajieniru A group, η ⁵ -neopentylcyclopentadienyl group,
η ⁵ -n-hexylcyclopentadienyl group, η ⁵ -n-
Octylcyclopropane Bae Ntajieniru group, eta ⁵ - phenyl cycloalkyl Bae Ntajieniru group, eta ⁵ - Nafuchirushikuro Bae Ntajieniru group, eta ⁵ - trimethylsilylcyclopentadienyl Bae Ntajieniru group, eta ⁵ - triethylsilyl cycloalkyl Bae Ntajieniru group,
eta ^{5-tert-butyldimethylsilyl} cycloalkyl Bae Ntajieniru group, eta ⁵ - indenyl group, eta ⁵ - methylindenyl group, eta ⁵ - dimethyl indenyl group, eta ⁵ - ethyl indenyl group, eta ^5-n-propyl indenyl Nyl group, η ⁵ -isopropylindenyl group, η ⁵ -n-butylindenyl group, η ⁵
-Sec-butylindenyl group,? ⁵ -tert-butylindenyl group,? ^5- n-pentylindenyl group,? ⁵
-Neopentylindenyl group,? ^5- n-hexylindenyl group,? ^5- n-octylindenyl group,? ^5- n-
Decylindenyl group, η ⁵ -phenylindenyl group, η ⁵
- methylphenyl indenyl group, eta ⁵ - naphthyl indenyl group, eta ⁵ - trimethylsilyl indenyl group, eta ⁵ - triethylsilyl indenyl group, eta ^{5-tert-butyldimethylsilyl} indenyl group, eta ⁵ - tetrahydroindenyl group, eta ⁵ - fluorenyl group, eta ⁵ - methyl fluorenyl group, eta ⁵ - dimethyl fluorenyl group, eta ⁵ - ethyl fluorenyl group, eta ⁵ - diethyl fluorenyl group, eta ⁵ -n
- propyl fluorenyl group, eta ⁵ - di -n- propyl fluorenyl group, eta ⁵ - isopropyl fluorenyl group, eta ⁵
- diisopropyl fluorenyl group, eta ^{5-n-butyl-fluorenyl} group, eta ^{5-sec-butylfluorenyl} group,
η ⁵ -tert-butylfluorenyl group, η ⁵ -di-n-
Butylfluorenyl group, eta ⁵ - di -sec- butyl-fluorenyl group, eta ⁵ - di -tert- butyl-fluorenyl group, eta ^{5-n-pentyl-fluorenyl} group, eta ⁵ - Neopentyl fluorescens N-yl, η ⁵ -n-hexylfluorenyl, η ⁵ -n-octylfluorenyl, η ⁵ -n-decylfluorenyl, η ⁵ -n-dodecylfluorenyl, η ^5- phenyl fluorenyl group, eta ⁵ - di - phenyl fluorenyl group, eta ⁵ - methylphenyl fluorenyl group, eta ⁵ - naphthyl fluorenyl group, eta ⁵ - trimethylsilyl fluorenyl group, eta ⁵ - bis - trimethylsilyl fluorenyl group, eta ⁵ - triethylsilyl fluorenyl group, such as eta ^{5-tert-butyldimethylsilyl-fluorenyl} group and the like, preferably eta ⁵ - cyclopentadienyl group, eta ⁵ - Mechirushiku Pentadienyl, η ⁵ -
tert- butyl cyclopentadienyl group, eta ⁵ - fluorenyl group - tetramethylcyclopentadienyl group, eta ⁵ - indenyl group, or eta ^5.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
^{As the} halogen atom for ⁵ or R ⁶ , a fluorine atom,
Examples thereof include a chlorine atom, a bromine atom, and an iodine atom, preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom. Substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ ,
The alkyl group for R ⁵ or R ⁶ has 1 carbon atom.
To 20 alkyl groups, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, amyl, n -Hexyl group,
n-octyl group, n-decyl group, n-dodecyl group, n-
Examples thereof include a pentadecyl group and an n-eicosyl group, and more preferably a methyl group, an ethyl group, an isopropyl group, and a t-group.
tert-butyl or amyl. Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the alkyl group having 1 to 20 carbon atoms substituted with a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group and a dibromomethyl group. , Tribromomethyl, iodomethyl, diiodomethyl, triiodomethyl, fluoroethyl, difluoroethyl, trifluoroethyl, tetrafluoroethyl, pentafluoroethyl, chloroethyl, dichloroethyl, trichloroethyl , Tetrachloroethyl group, pentachloroethyl group, bromoethyl group, dibromoethyl group, tribromoethyl group, tetrabromoethyl group, pentabromoethyl group, perfluoropropyl group, perfluorobutyl group,
Perfluoropentyl group, perfluorohexyl group, perfluorooctyl group, perfluorododecyl group, perfluoropentadecyl group, perfluoroeicosyl group,
Perchloropropyl group, perchlorobutyl group, perchloropentyl group, perchlorohexyl group, perchlorooctyl group, perchlorododecyl group, perchloropentadecyl group, perchloroeicosyl group, perbromopropyl group,
Perbromobutyl, perbromopentyl, perbromohexyl, perbromooctyl, perbromododecyl, perbromopentadecyl, perbromoeicosyl and the like. All of these alkyl groups may be partially substituted with an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
The aralkyl group for ⁵ or R ⁶ has 7 carbon atoms.
~ 20 aralkyl groups are preferred, for example, benzyl, (2-methylphenyl) methyl, (3-methylphenyl) methyl, (4-methylphenyl) methyl,
(2,3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethyl Phenyl) methyl group, (4,6
-Dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) methyl group, (3,4 , 5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2,3,4,6-tetramethylphenyl) ) Methyl, (2,3,5,6-tetramethylphenyl) methyl, (pentamethylphenyl) methyl, (ethylphenyl) methyl, (n-propylphenyl) methyl,
(Isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl)
Methyl group, (n-hexylphenyl) methyl group, (n-
Octylphenyl) methyl group, (n-decylphenyl)
Methyl group, (n-dodecylphenyl) methyl group, (n-
Tetradecylphenyl) methyl group, naphthylmethyl group,
Examples include an anthracenylmethyl group, and more preferably a benzyl group. All of these aralkyl groups include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group and an aralkyloxy group such as a benzyloxy group. May be partially substituted.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
^{As the} aryl group for ⁵ or R ^6, C ^{6 to} C 6
Preferred are 20 aryl groups such as phenyl, 2
-Tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group,
2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,
3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group,
3,4,5-trimethylphenyl group, 2,3,4,5-
Tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-
Propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert
-Butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group, naphthyl group, Examples include an anthracenyl group, and more preferably a phenyl group. All of these aryl groups are a fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as an iodine atom, a methoxy group, an alkoxy group such as an ethoxy group,
An aryloxy group such as a phenoxy group or an aralkyloxy group such as a benzyloxy group may be partially substituted.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
The substituted silyl group represented by ⁵ or R ⁶ is a silyl group substituted by a hydrocarbon group, and examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. , Sec-butyl group, tert-
Examples thereof include an alkyl group having 1 to 10 carbon atoms such as a butyl group, an isobutyl group, an n-pentyl group, an n-hexyl group and a cyclohexyl group, and an aryl group such as a phenyl group. Examples of the substituted silyl group having 1 to 20 carbon atoms include mono-substituted silyl groups having 1 to 20 carbon atoms such as methylsilyl group, ethylsilyl group and phenylsilyl group, dimethylsilyl group, diethylsilyl group, diphenylsilyl group and the like. A disubstituted silyl group having 2 to 20 carbon atoms,
Trimethylsilyl group, triethylsilyl group, tri-n-
Propylsilyl group, triisopropylsilyl group, tri-
n-butylsilyl group, tri-sec-butylsilyl group,
Tri-tert-butylsilyl group, tri-isobutylsilyl group, tert-butyl-dimethylsilyl group, tri-
n-pentylsilyl group, tri-n-hexylsilyl group,
Examples thereof include a trisubstituted silyl group having 3 to 20 carbon atoms such as a tricyclohexylsilyl group and a triphenylsilyl group, and a trimethylsilyl group, a tert-butyldimethylsilyl group, or a triphenylsilyl group is preferable.
Any of these substituted silyl groups is a hydrocarbon group, a fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as an iodine atom, a methoxy group, an alkoxy group such as an ethoxy group,
An aryloxy group such as a phenoxy group or an aralkyloxy group such as a benzyloxy group may be partially substituted.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
The alkoxy group for ⁵ or R ⁶ has 1 carbon atom
~ 20 alkoxy groups are preferred, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-
Butoxy group, n-pentoxy group, neopentoxy group, n
-Hexoxy group, n-octoxy group, n-dodesoxy group, n-pentadeoxy group, n-icosoxy group and the like, and more preferably methoxy group, ethoxy group or tert-butoxy group. All of these alkoxy groups are a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group and an aralkyloxy group such as a benzyloxy group. May be partially substituted.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
The aralkyloxy group for ⁵ or R ⁶ is preferably an aralkyloxy group having 7 to 20 carbon atoms, for example, a benzyloxy group, a (2-methylphenyl) methoxy group, a (3-methylphenyl) methoxy group, a (4-methylphenyl) methoxy group. Methylphenyl) methoxy group, (2,3-dimethylphenyl)
Methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2
(6-dimethylphenyl) methoxy group, (3,4-dimethylphenyl) methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl)
A methoxy group, a (2,3,5-trimethylphenyl) methoxy group, a (2,3,6-trimethylphenyl) methoxy group, a (2,4,5-trimethylphenyl) methoxy group,
A (2,4,6-trimethylphenyl) methoxy group,
(3,4,5-trimethylphenyl) methoxy group,
(2,3,4,5-tetramethylphenyl) methoxy, (2,3,4,6-tetramethylphenyl) methoxy, (2,3,5,6-tetramethylphenyl) methoxy, (penta (Methylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n
-Butylphenyl) methoxy group, (sec-butylphenyl) methoxy group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-
Examples thereof include an (octylphenyl) methoxy group, a (n-decylphenyl) methoxy group, a (n-tetradecylphenyl) methoxy group, a naphthylmethoxy group, and an anthracenylmethoxy group, and more preferably a benzyloxy group. All of these aralkyloxy groups include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, and an aralkyloxy group such as a benzyloxy group. It may be partially substituted with a group or the like.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
^The aryloxy group for ⁵ or R ⁶ is preferably an aryloxy group having 6 to 20 carbon atoms, for example, phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 2,3- Dimethylphenoxy group, 2,4-dimethylphenoxy group, 2,5
-Dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2,3,4-trimethylphenoxy group,
2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 3,
4,5-trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2,3,5,6-tetramethylphenoxy group, pentamethylphenoxy Group, ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy Group, n-tetradecylphenoxy group, naphthoxy group, anthracenoxy group and the like. All of these aryloxy groups are halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group and aralkyloxy groups such as benzyloxy group. It may be partially substituted with a group or the like.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
^The disubstituted amino group in ⁵ or R ⁶ is an amino group substituted with two hydrocarbon groups, and examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group,
Isopropyl group, n-butyl group, sec-butyl group, t
tert-butyl group, isobutyl group, n-pentyl group, n
A hexyl group, a cyclohexyl group or the like having 1 to 1 carbon atoms
10 to 6 carbon atoms such as an alkyl group and a phenyl group
And an aralkyl group having 7 to 10 carbon atoms. Examples of such a disubstituted amino group substituted with a hydrocarbon group having 1 to 10 carbon atoms include a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a di-n-butylamino group, Di-sec-butylamino group, di-tert-butylamino group, di-isobutylamino group, tert-butylisopropylamino group, di-n-hexylamino group, di-n-octylamino group, di-n-decylamino Groups, a diphenylamino group, a bistrimethylsilylamino group, a bis-tert-butyldimethylsilylamino group and the like, and preferably a dimethylamino group or a diethylamino group. Each of these disubstituted amino groups is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyl group such as a benzyloxy group. Part may be substituted with an oxy group or the like. The substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be arbitrarily combined to form a ring. Preferred R ¹ includes an alkyl group, an aralkyl group, an aryl group and a substituted silyl group. Preferred X ¹ and X ² are each independently a halogen atom,
Examples thereof include an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group, and a disubstituted amino group, and more preferable examples include a halogen atom and an alkoxy group.

In the general formula [II] or [III], the atoms of Group 16 of the periodic table of the element represented by X ³ include:
For example, an oxygen atom, a sulfur atom, a selenium atom and the like can be mentioned, and an oxygen atom is preferable. Examples of the transition metal complex represented by the general formula [I] include methylene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy)
Titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (Cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl)
(3-tert-butyldimethylsilyl-5-methyl-
2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-trimethylsilyl-5
-Methyl-2-phenoxy) titanium dichloride,
Methylene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-t
tert-butyl-5-chloro-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-tert- Butyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-phenyl-2- Phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-
Trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-
Phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyl-5)
-Chloro-2-phenoxy) titanium dichloride,
Methylene (tert-butylcyclopentadienyl)
(3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3 -Tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-
Phenyl-2-phenoxy) titanium dichloride,
Methylene (tert-butylcyclopentadienyl)
(3-tert-butyldimethylsilyl-5-methyl-
2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-tert-butyl- 5-methoxy-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-te
rt-butyl-5-chloro-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3- tert-butyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-
Methyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-t
tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-trimethylsilyl-
5-methyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl)
(3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-
Chloro-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl)
(3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl -5-methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-
Phenyl-2-phenoxy) titanium dichloride,
Methylene (trimethylsilylcyclopentadienyl)
(3-tert-butyldimethylsilyl-5-methyl-
2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy- 2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-te
rt-butyl-5-chloro-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3,5-
Dimethyl-2-phenoxy) titanium dichloride,
Methylene (fluorenyl) (3-tert-butyl-2
-Phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl-5-methyl-2
-Phenoxy) titanium dichloride, methylene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-t
tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl-5- (Methoxy-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) Titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert-butyl-2)
-Phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-
Phenyl-2-phenoxy) titanium dichloride,
Isopropylidene (cyclopentadienyl) (3-te
rt-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) ( 3-tert
-Butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) ( 3,5-dimethyl-2-
Phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-t
tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert- Butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) ( 3-tert-butyl-
5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl)
(3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, isopropylidene (te
rt-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl)
(3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclo Pentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene ( tert-butylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2
-Phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-
tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (tert-
Butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (Tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert
-Butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert -Butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-trimethylsilyl-5-methyl-
2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-t
tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-
Chloro-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2- Phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-te
rt-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-
Butyldimethylsilyl-5-methyl-2-phenoxy)
Titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy-)
2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3
-Tert-butyl-5-chloro-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3
-Tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-t
tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl)
(3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-ter
t-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-trimethylsilyl-5-methyl-2-
Phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride , Diphenylmethylene (cyclopentadienyl)
(3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-butyl -5-methyl-2-
Phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) Titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-butyl-
5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3
-Tert-butyl-5-chloro-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3 -Tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-t
tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-tert- Butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) ( 3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titani Mujikuroraido, diphenylmethylene (tert- butylcyclopentadienyl) (3,5
-Dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (t
tert-butylcyclopentadienyl) (3-tert
-Butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (t
tert-butylcyclopentadienyl) (3-tert
-Butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (t
tert-butylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) Titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3,5-dimethyl-2) -Phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl)
(3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadiene) Enil)
(3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5)
-Methyl-2-phenoxy) titanium dichloride,
Diphenylmethylene (tetramethylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-tert
-Butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) ) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-
Phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-
tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-t
tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) ) (3-tert-butyl-5)
-Methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-chloro-2)
-Phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) ( 3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-tert-butyldimethylsilyl-5- Methyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, Enirumechiren (fluorenyl)
(3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-tert-butyl-5-chloro-2
-Phenoxy) titanium dichloride and the like, compounds obtained by changing titanium to zirconium or hafnium of these compounds, dibromide, diiodide, bis (dimethylamide), bis (diethylamide), di-n-butoxide, or diisopropoxy in dichloride (Cyclopentadienyl), (trimethylcyclopentadienyl), (trimethylcyclopentadienyl), (n-butylcyclopentadienyl),
(Tert-butyldimethylsilylcyclopentadienyl) or a compound changed to (indenyl), (3,5
-Dimethyl-2-phenoxy) to (2-phenoxy),
(3-methyl-2-phenoxy), (3,5-di-te)
rt-butyl-2-phenoxy), (3-phenyl-5
J in the general formula [I] such as a compound modified to -methyl-2-phenoxy), (3-tert-butyldimethylsilyl-2-phenoxy), or (3-trimethylsilyl-2-phenoxy) is a carbon atom. Transition metal complex, dimethylsilyl (cyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3-methyl-2
-Phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3,5-dimethyl-2-
Phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3-tert-butyl-2)
-Phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3-tert-butyl-
5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3,5
-Di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3-tert -Butyldimethylsilyl-5
-Methyl-2-phenoxy) titanium dichloride,
Dimethylsilyl (cyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, Dimethylsilyl (cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride, dimethylsilyl (Methylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) ) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-tert-butyl -
2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-tert-
Butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) ( 5-methyl-3-phenyl-
2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-tert-
Butyldimethylsilyl-5-methyl-2-phenoxy)
Titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-ter
t-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-tert-butyl-5-chloro-2-
Phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3,5-diamyl-
2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (n-
Butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (n
-Butylcyclopentadienyl) (3,5-dimethyl-
2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-ter
t-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-
Butylcyclopentadienyl) (3,5-di-tert
-Butyl-2-phenoxy) titanium dichloride,
Dimethylsilyl (n-butylcyclopentadienyl)
(5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl ( n-butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-
Butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) Titanium dichloride, dimethylsilyl (n-
Butylcyclopentadienyl) (3,5-diamyl-2
-Phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (Tert-butylcyclopentadienyl)
(3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (ter
t-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3,5-di-tert-butyl-2- Phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-tert-butyldimethyl Cyril-
5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) ( 3-te
rt-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-tert-butyl-5-
Chloro-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (2-phenoxy) titanium Dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (Tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-tert
-Butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadiene) Enyl) (5-methyl-
3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) ) (5-
Methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) )
(3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3,5-diamyl-2
-Phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopenta Dienyl)
(3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-tert -Butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-tert-butyldimethylsilyl-
5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-te
rt-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-
Chloro-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl)
(3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-ter
t-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3,5-di-
tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (5-methyl-
3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl)
(5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-tert-butyl -5-chloro-
2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3,5-diamyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (2-phenoxy) titanium dichloride,
Dimethylsilyl (fluorenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-tert-butyl-2- Phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride Dimethylsilyl (fluorenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-tert-butyldimethylsilyl-5
-Methyl-2-phenoxy) titanium dichloride,
Dimethylsilyl (fluorenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-tert
-Butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-
tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl)
(3,5-Diamyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (1-naphthoxy-2-yl) titanium dichloride and the like, and (cyclopentadienyl) of these compounds are (Dimethylcyclopentadienyl), (trimethylcyclopentadienyl), (ethylcyclopentadienyl), (n-propylcyclopentadienyl), (isopropylcyclopentadienyl), (sec-butylcyclopentadienyl) , (Isobutylcyclopentadienyl), (tert-butyldimethylsilylcyclopentadienyl), (phenylcyclopentadienyl),
(Methylindenyl) or a compound in which (phenylindenyl) is changed, (2-phenoxy) is converted to (3-phenyl-2-phenoxy), (3-trimethylsilyl-2-phenoxy), or (3-tert-butyldimethyl) A compound in which dimethylsilyl is changed to diethylsilyl, diphenylsilyl, or dimethoxysilyl, a compound in which titanium is replaced with zirconium,
Or a compound of the general formula [I] such as a compound in which hafnium has been changed, or a compound in which dichloride has been changed to dibromide, diiodide, bis (dimethylamide), bis (diethylamide), di-n-butoxide or diisopropoxide.
Wherein J is a group 14 atom of the periodic table of elements other than carbon atoms.

As the transition metal complex represented by the general formula [II], for example, μ-oxobis {isopropylidene (cyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene (cyclopentadiene) Enyl) (2-phenoxy) titanium methoxide}, μ-oxobis {isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene ( Cyclopentadienyl)
(3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide}, μ-oxobis {isopropylidene (methylcyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene (methyl) Cyclopentadienyl) (2-
Phenoxy) titanium methoxide {, μ-oxobis} isopropylidene (methylcyclopentadienyl)
(3-tert-butyl-5-methyl-2-phenoxy) titanium chloride {, μ-oxobis} isopropylidene (methylcyclopentadienyl) (3-te
rt-butyl-5-methyl-2-phenoxy) titanium methoxide, μ-oxobis {isopropylidene (tetramethylcyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene (tetramethylcyclo) Pentadienyl) (2
-Phenoxy) titanium methoxide {, μ-oxobis} isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene (tetramethyl) Cyclopentadienyl)
(3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide}, μ-oxobis {dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {dimethylsilylene (cyclopentane) Dienyl) (2-phenoxy) titanium methoxide {, μ-oxobis} dimethylsilylene (cyclopentadienyl) (3-tert-
Butyl-5-methyl-2-phenoxy) titanium chloride {, μ-oxobis} dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide {, μ-oxobis} Dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium chloride｝, μ-
Oxobis {dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium methoxide},
μ-oxobis {dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2)
-Phenoxy) titanium chloride｝, μ-oxobis ｛dimethylsilylene (methylcyclopentadienyl)
(3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide {, μ-oxobis} dimethylsilylene (tetramethylcyclopentadienyl) (2
-Phenoxy) titanium chloride {, μ-oxobis {dimethylsilylene (tetramethylcyclopentadienyl) (2-phenoxy) titanium methoxide}, μ
-Oxobis {dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride}, μ-oxobis {dimethylsilylene (tetramethylcyclopentadienyl) (3-tert -Butyl-5-methyl-2-
Phenoxy) titanium methoxide, and the like.

Examples of the transition metal complex represented by the general formula [III] include di-μ-oxobis {isopropylidene (cyclopentadienyl) (2-phenoxy) titanium} and di-μ-oxobis {isopropylidene ( Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium {, di-μ-oxobis} isopropylidene (methylcyclopentadienyl)
(2-phenoxy) titanium}, di-μ-oxobis {isopropylidene (methylcyclopentadienyl)
(3-tert-butyl-5-methyl-2-phenoxy) titanium}, di-μ-oxobis {isopropylidene (tetramethylcyclopentadienyl) (2-phenoxy) titanium}, di-μ-oxobis {isopropylidene (Tetramethylcyclopentadienyl) (3-
tert-butyl-5-methyl-2-phenoxy) titanium {, di-μ-oxobis {dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium}, di-μ-oxobis} dimethylsilylene (cyclopentadienyl) ) (3-tert-butyl-5-methyl-2-phenoxy) titanium}, di-μ-oxobis {dimethylsilylene (methylcyclopentadienyl)
(2-phenoxy) titanium}, di-μ-oxobis {dimethylsilylene (methylcyclopentadienyl)
(3-tert-butyl-5-methyl-2-phenoxy) titanium}, di-μ-oxobis {dimethylsilylene (tetramethylcyclopentadienyl) (2-phenoxy) titanium}, di-μ-oxobis {dimethylsilylene (Tetramethylcyclopentadienyl) (3-
tert-butyl-5-methyl-2-phenoxy) titanium}, and the like.

The transition metal complex represented by the general formula [I] can be produced, for example, by the method described in WO 97/03992. The transition metal complex represented by the general formula [II] or [III] can be produced by reacting the transition metal complex represented by the general formula [I] with one or two equivalents of water.

The aluminum compound (B) will be described. As the aluminum compound (B), the following (B1) to
One or more aluminum compounds selected from (B3). (B1) the general formula E ¹ _a AlZ organoaluminum compound represented by the _3-a (B2) general formula {-Al (E ²⁾ -O-} cyclic aluminoxane (B3) having a structure represented by _b the formula E ³ ｛-Al (E ³ ) -O-｝ _c AlE ³
Linear aluminoxane having a structure represented by ₂ (provided that E ¹ , E ² , and E ³ are each a hydrocarbon group, and all E ¹ , all E ^2, and all E ³ are the same; Z represents a hydrogen atom or a halogen atom, and all Z may be the same or different, a is a number satisfying 0 <a ≦ 3, and b is 2 or more. And c represents an integer of 1 or more.)

As the hydrocarbon group for E ¹ , E ² or E ³ , a hydrocarbon group having 1 to 8 carbon atoms is preferable, and an alkyl group is more preferable. Specific examples of the organoaluminum compound (B1) represented by the general formula E ¹ _a AlZ _3-a include:
Trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum and trihexylaluminum; dialkylaluminum chloride such as dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride and dihexylaluminum chloride; methyl Alkyl aluminum dichloride such as aluminum dichloride, ethyl aluminum dichloride, propyl aluminum dichloride, isobutyl aluminum dichloride, hexyl aluminum dichloride; dimethyl aluminum hydride;
Examples thereof include dialkylaluminum hydrides such as diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride, and dihexylaluminum hydride. Preferably, it is a trialkyl aluminum,
More preferably, it is triethylaluminum or triisobutylaluminum.

[0038] In the general formula {-Al (E ²⁾ -O-} cyclic aluminoxane having the structure represented by _b (B2), the general formula ^{E 3 {-Al (E 3)} -O-} c AlE 3 2 In a linear aluminoxane (B3) having the structure shown,
Specific examples of E ² and E ³ include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group,
Examples thereof include an alkyl group such as an isobutyl group, a normal pentyl group, and a neopentyl group. b is an integer of 2 or more, and c is an integer of 1 or more. Preferably, E ²
And E ³ is a methyl group or an isobutyl group, and b is 2
-40 and c are 1-40.

The above aluminoxane can be made by various methods. The method is not particularly limited, and may be made according to a known method. For example, a solution prepared by dissolving a trialkylaluminum (for example, trimethylaluminum or the like) in a suitable organic solvent (benzene or aliphatic hydrocarbon or the like) is brought into contact with water. In addition, a method in which a trialkylaluminum (for example, trimethylaluminum or the like) is brought into contact with a metal salt (for example, copper sulfate hydrate or the like) containing water of crystallization can be exemplified.

The (C) boron compound will be described. Examples of the boron compound (C) include (C1) a general formula BQ ¹
A boron compound represented by Q ² Q ³ , (C2) a general formula G ^{+
(BQ 1 Q 2 Q 3 Q} 4) - boron compound represented by, (C
3) Any of the boron compounds represented by the general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^— can be used.

General formula BQ¹Q^TwoQ^ThreeBoration represented by
In the compound (C1), B is boron in a trivalent valence state
Atom, Q¹~ Q^ThreeRepresents a halogen atom, a hydrocarbon group,
A hydrogenated hydrocarbon group, a substituted silyl group, an alkoxy group or
Disubstituted amino groups, which are the same or different
May be. Q¹~ Q^ThreeIs preferably a halogen atom,
A hydrocarbon group containing 1-20 carbon atoms, 1-20
Halogenated hydrocarbon groups containing carbon atoms, from 1 to 20 carbon atoms
Substituted silyl groups containing 1 to 20 carbon atoms
An alkoxy group or an amino containing 2 to 20 carbon atoms
And more preferred Q¹~ Q^ThreeIs a halogen atom, 1 to
A hydrocarbon group containing 20 carbon atoms, or 1-20
It is a halogenated hydrocarbon group containing a carbon atom. More preferred
Or Q ¹~ Q^FourIs at least one fluorine source
A fluorinated hydrocarbon group having 1 to 20 carbon atoms containing
And particularly preferably Q¹~ Q^FourIs at least 1 each
Fluorinated carbon atoms having 6 to 20 carbon atoms containing two fluorine atoms
It is a reel group.

Specific examples of compound (C1) include tris (pentafluorophenyl) borane, tris (2,3,
5,6-tetrafluorophenyl) borane, tris (2,3,4,5-tetrafluorophenyl) borane,
Tris (3,4,5-trifluorophenyl) borane,
Tris (2,3,4-trifluorophenyl) borane,
Phenylbis (pentafluorophenyl) borane and the like can be mentioned, and most preferred is tris (pentafluorophenyl) borane.

In the boron compound (C2) represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- , G ⁺ is an inorganic or organic cation, and B is boron in a trivalent valence state. an atom, Q ¹ to Q ⁴ are the same as Q ¹ to Q ³ in the above (C1).

The general formula ^{G + (BQ 1 Q 2 Q} 3 Q 4) - Examples of G ⁺ as an inorganic cation in the compound represented by, ferrocenium cation, alkyl-substituted ferrocenium cation, silver Examples of G ^{+ in} which a cation or the like is an organic cation include a triphenylmethyl cation. G ⁺ is preferably a carbenium cation, particularly preferably a triphenylmethyl cation. ^{(BQ 1 Q 2 Q 3 Q} 4) - as the tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluoro Phenyl) borate, tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,3,4-trifluorophenyl) borate, phenyltris (pentafluorophenyl) borate, tetrakis (3,5-bistriborate) Fluoromethylphenyl) borate and the like.

Specific examples of these combinations include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1'-dimethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, Phenylmethyltetrakis (pentafluorophenyl) borate,
Examples thereof include triphenylmethyltetrakis (3,5-bistrifluoromethylphenyl) borate, and most preferably triphenylmethyltetrakis (pentafluorophenyl) borate.

The formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q
^{4) -} In the boron compound represented (C3), L is a neutral Lewis base, (L-H) ⁺ is a Bronsted acid, B is boron atom in the trivalent valence state ,
Q ¹ to Q ⁴ are the same as Q ¹ to Q ³ in the above Lewis acid (C1).

The general formula ^{(L-H) + (BQ} 1 Q 2 Q 3 Q 4) - is a Brønsted acid in the compound represented by (L-
Specific examples of H) ⁺ include trialkyl-substituted ammonium, N, N-dialkylanilinium, dialkylammonium, triarylphosphonium, and the like.
As (BQ ¹ Q ² Q ³ Q ⁴ ) ^{-, the same} as those described above can be mentioned.

Specific combinations of these include triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri ( n-butyl) ammonium tetrakis (3,5-bistrifluoromethylphenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N N-2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate, N, N
-Dimethylanilinium tetrakis (3,5-bistrifluoromethylphenyl) borate, diisopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate,
Examples thereof include tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate and tri (dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate. Most preferably, tri (n-butyl) ammonium tetrakis (pentafluoro) is used. Phenyl) borate or N, N-
Dimethylanilinium tetrakis (pentafluorophenyl) borate.

In the copolymerization, an olefin polymerization catalyst comprising the transition metal complex (A) represented by the general formula [I] and the above (B) and / or the above (C) is used.
When an olefin polymerization catalyst comprising two components (A) and (B) is used, the cyclic aluminoxane (B2) and / or the linear aluminoxane (B3) may be used as (B).
Is preferred. Another preferred embodiment of the olefin polymerization catalyst is an olefin polymerization catalyst comprising the above (A), (B) and (C). In this case, the (B) may be the aforementioned (B1) ) Easy to use.

The amount of each component used is usually such that the molar ratio of (B) / (A) is from 0.1 to 10,000, preferably from 5 to 200.
It is desirable to use each component so that the molar ratio of 0, (C) / (A) is 0.01 to 100, preferably 0.5 to 10.

The concentration when each component is used in a solution state or a suspension state in a solvent is appropriately selected depending on conditions such as the performance of a device for supplying each component to the polymerization reactor. , Usually 0.01 to 500 μmol / g,
More preferably, 0.05 to 100 μmol / g, still more preferably, 0.05 to 50 μmol / g, (B)
Usually, in terms of Al atom, 0.01 to 10000 μmol /
g, more preferably 0.1 to 5000 μmol /
g, more preferably 0.1 to 2000 μmol / g,
(C) is usually from 0.01 to 500 μmol / g, preferably from 0.05 to 200 μmol / g, and more preferably from 0.05 to 100 μmol / g. desirable.

In order to produce (b), for example, aliphatic hydrocarbons such as butane, pentane, hexane, heptane and octane; aromatic hydrocarbons such as benzene and toluene;
Alternatively, solvent polymerization using a halogenated hydrocarbon such as methylene dichloride as a solvent, or slurry polymerization, gas-phase polymerization in a gaseous monomer, or the like is possible, and continuous polymerization or batch polymerization is also possible. . The polymerization temperature is
Although it can be in the range of −50 to 200 ° C., in particular, −20 to 200 ° C.
The temperature is preferably in the range of 100 ° C., and the polymerization pressure is from normal pressure to 60 k.
g / cm ² G is preferred. Generally, the polymerization time is appropriately determined depending on the type of the catalyst used and the reaction apparatus.
It can range from minutes to 20 hours. Further, a chain transfer agent such as hydrogen can be added to adjust the molecular weight of the polymer. Also, two or more kinds of the component (ii) may be used in combination.

The crosslinked thermoplastic elastomer composition of the present invention is obtained by dynamically heat-treating the above (A) from 5 to 95% by weight and (B) from 95 to 5% by weight in the presence of a crosslinking agent. It is a thermoplastic elastomer composition. The amount of each component used is (a) 5 to 95% by weight and (B) 95 to 5% by weight, preferably (A) 10 to 90% by weight and (B) 9
0 to 10% by weight. The total amount of (a) and (b) is 100% by weight. If (a) is too small, the resulting crosslinked thermoplastic elastomer composition will have poor mechanical strength, while if (a) is too large, the resulting crosslinked thermoplastic elastomer composition will have poor flexibility and elastic recovery. (B)
When the amount is too small, the obtained crosslinked thermoplastic elastomer composition is inferior in flexibility, while when the amount is too large, the obtained crosslinked thermoplastic elastomer composition has inferior mechanical strength.

The crosslinked thermoplastic elastomer composition of the present invention contains the following (A) in an amount of 5 to 95% by weight, (B) 95 to 5% by weight, and (A) and (B) in a total amount of 100 parts by weight. C) A mixture containing 10 to 900 parts by weight can be dynamically heat-treated in the presence of a crosslinking agent to obtain a crosslinked thermoplastic elastomer composition. (C): Ethylene-propylene (-non-conjugated diene) random copolymer rubber The ethylene-propylene (-non-conjugated diene) random copolymer rubber as the component (C) includes an ethylene-propylene random copolymer and ethylene. -A propylene-non-conjugated diene random copolymer.

The copolymer has a Mooney viscosity of ML _{1 + 4} 10
0 ° C. is 3 to 120, Mw / Mn is 1.3 to 10 (where Mw indicates a weight average molecular weight), and the ratio of ethylene / propylene / non-conjugated diene is 30 to 95/5 by weight ratio.
What is -70 / 0-8 is preferable. If the Mooney viscosity is too low, the strength of a molded article formed using the crosslinked thermoplastic elastomer composition obtained may be poor, while if the Mooney viscosity is too high, the molded article formed using the crosslinked thermoplastic elastomer composition obtained The flexibility of the product may be poor. If the Mw / Mn is too small, the processability of the obtained crosslinked thermoplastic elastomer composition may be poor. On the other hand, if the Mw / Mn is too large, the molded article molded using the obtained crosslinked thermoplastic elastomer composition may have The flexibility may be poor. In the ratio of ethylene / propylene / non-conjugated diene, if the amount of ethylene is too small, the strength of a molded article molded using the obtained crosslinked thermoplastic elastomer composition may be poor, while if the amount of ethylene is too large, the obtained crosslinkable The flexibility of a molded article molded using the thermoplastic elastomer composition may be inferior, and the flexibility of a molded article molded using the crosslinked thermoplastic elastomer composition obtained with too little propylene may be inferior. On the other hand, the strength of a molded article molded using the crosslinked thermoplastic elastomer composition obtained with an excessive amount of propylene may be inferior,
If the amount of the non-conjugated diene is excessive, the balance between the strength and the flexibility of a molded article molded using the obtained crosslinked thermoplastic elastomer composition may be poor.

The ethylene-propylene (-non-conjugated diene) random copolymer used in the present invention is obtained by, for example, copolymerizing ethylene with propylene or a non-conjugated diene using a Ziegler catalyst or the above-described metallocene catalyst. Obtained by Specific examples of the non-conjugated diene include dicyclopentadiene, tricyclopentadiene,
5-methyl-2,5-norbonadiene, 5-methylene-
2-norbornene, 5-ethylidene-2-norbornene, 5-isopropenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5- (1-butenyl) -2-norbornene, cyclooctadiene, vinylcyclohexene, , 5,9-Cyclododecatriene,
1,4-hexadiene, 1,6-octadiene, 1,7
-Octadiene, 1,8-nonadiene, 1,9-decadiene, 3,6-dimethyl-1,7-octadiene and the like. Preferably 5-ethylidene-2-norbornene,
Dicyclopentadiene. The copolymer may be modified with a functional group, an acid anhydride group, a carboxyl group,
It can be modified with an extruder or the like using an unsaturated compound having at least one functional group selected from a hydroxyl group, an amino group, an isocyanate group and an epoxy group. As (c), a corresponding commercially available product can be used.

The amount of (c) used is 10 to 900 parts by weight, preferably 30 to 500 parts by weight, per 100 parts by weight of the total amount of (a) and (b). If (c) is too small, the crosslinked thermoplastic elastomer composition obtained may have poor elastic recovery and flexibility, while if (c) is too large, the mechanical strength of the obtained crosslinked thermoplastic elastomer composition may be poor. May be inferior. The crosslinked thermoplastic elastomer composition of the present invention comprises the above (A), (B) and (C)
A mixture containing from 1 to 200 parts by weight of the following (d) per 100 parts by weight of the total amount of the above can be dynamically heat-treated in the presence of a crosslinking agent to obtain a crosslinked thermoplastic elastomer composition. (D): Mineral oil-based softener Examples of the mineral oil-based softener as the component (d) include naphthenic oil and paraffin-based mineral oil.

The amount of (d) used is 1 to 200 parts by weight, preferably 2 to 50 parts by weight, per 100 parts by weight of the total of (a), (b) and (c). If (d) is too small, the obtained crosslinked thermoplastic elastomer composition may be inferior in flexibility, while if (d) is too large, the obtained crosslinked thermoplastic elastomer composition may be inferior in mechanical strength. is there.

In the thermoplastic resin composition of the present invention, additives such as an antioxidant, an antistatic agent, a weathering agent, an ultraviolet absorber, a slip agent, a coloring agent, and a dispersant; Colorant or thermoplastic resin or polybutadiene, styrene-butadiene block copolymer rubber, styrene-butadiene-styrene block copolymer rubber, styrene-butadiene random copolymer rubber,
Partially hydrogenated styrene-butadiene-styrene block copolymer rubber, partially hydrogenated styrene-butadiene random copolymer rubber, styrene-isoprene block copolymer rubber, partially hydrogenated styrene-isoprene block copolymer rubber, acrylonitrile-butadiene Copolymer rubber, partially hydrogenated acrylonitrile-butadiene copolymer rubber, butyl rubber, chloroprene rubber, fluorine rubber, chlorosulfonated polyethylene, silicon rubber, urethane rubber, and the like can be appropriately compounded.

In the present invention, in addition to the above components, additional components such as antioxidants, antistatic agents, weathering agents, ultraviolet absorbers, slip agents, coloring agents, dispersants, carbon black And other rubbery polymers, thermoplastic resins, and the like. The crosslinked thermoplastic elastomer composition of the present invention is obtained by crosslinking (a) and (b), which are essential components, and (c) and (d), which are optional components, and an optional component which is optionally used. Is a crosslinked thermoplastic elastomer composition obtained by dynamic heat treatment in the presence of an agent.

As a method of dynamically heat-treating in the presence of a cross-linking agent, the following methods can be mentioned. Production method 11: (a) and (b), and components used as necessary ( C) and each component of (d) are kneaded at a temperature at which the component of (a) melts (usually 120 ° C to 200 ° C) until the components are uniformly mixed. 2: A crosslinking agent and, if necessary, a crosslinking assistant are added, and the temperature is set or raised to a temperature at which a crosslinking reaction occurs, and heat treatment is performed dynamically. Various additional components may be added during the steps 1 and 2 or after the completion of all the steps. Production method 2: 1: (a) and (b), and (c) and (d), which are optional components, each component of a crosslinking agent and optionally a crosslinking aid, The components are melted and kneaded at a temperature at which a crosslinking reaction does not occur (usually 120 to 170 ° C.) until the components are uniformly mixed. 2: The temperature is set or raised to a temperature at which a cross-linking agent reaction occurs, and heat treatment is performed dynamically. Various additional components are 1 and 2
May be added during the step or after the completion of all steps. In the production method 1 or 2, the production is divided into each stage, but it is not always necessary to take out the sample at the end of each stage, and they may be carried out continuously. Alternatively, a multi-stage kneading method may be adopted in which after kneading some components, the remaining components are added and kneading is continued. As a method for producing the crosslinked thermoplastic elastomer composition of the present invention, either Production Method 1 or 2 is preferred. Examples of the apparatus for producing the crosslinked thermoplastic elastomer composition of the present invention include a closed kneader such as a roll mill, a Banbury mixer, a pressure kneader, or a single-screw extruder or a twin-screw extruder which are usually used in the rubber and resin industries. Etc. are used, as long as the above manufacturing method can be applied,
There is no particular limitation.

As the cross-linking agent, a cross-linking agent usually used for vulcanizing an olefin rubber can be used. Among them, preferred are organic peroxides and phenolic resin-based crosslinking agents. Examples of the organic peroxide include dicumyl peroxide, di-tert-butyl peroxide,
2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl-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, tertiary butyl peroxybenzoate, tertiary butyl peroxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tertiary butyl peroxide and the like. Among these organic peroxides, an organic peroxide which starts to decompose after dispersing the rubber and resin components is preferable. For example, 2,5-dimethyl-2,5-di (tert-butylperoxy) -hexyne-
3,2,5-dimethyl-2,5-di (tert-butylperoxy) hexane and 1,3-bis (tert-butylperoxyisopropyl) benzene, and particularly 2,5-dimethyl-2 having a high decomposition temperature. , 5-Di (tert-butylperoxy) -hexyne-3 is most preferred. These organic peroxides are used in an amount of 0.02 to 1.5 parts by weight, preferably 0.02 to 1.5 parts by weight, based on 100 parts by weight of the total of (a) and (b).
5 to 1.0 parts by weight. When the amount of the organic peroxide is too small, the obtained crosslinked thermoplastic elastomer composition may have poor elastic recovery properties, whereas when the amount of the organic peroxide is too large, the obtained crosslinked thermoplastic elastomer composition has poor flexibility. There are cases.

In the present invention, if a suitable crosslinking aid is present together with the peroxide-based crosslinking agent, a uniform and mild crosslinking reaction can be expected. As a crosslinking aid, sulfur,
p-quinone dioxime, p, p'-dibenzoylquinone dioxime, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, diallyl phthalate , Tetraallyloxyethane, triallyl isocyanurate, N, N'-m-phenylenebismaleimide, maleic anhydride, divinylbenzene, zinc diacrylate, zinc dimethacrylate, and the like. Among them, N, N'-m-phenylenebismaleimide, p, p'-
It is preferable to use dibenzoylquinone dioxime, divinylbenzene, triallyl isocyanurate. Also, N, N'-m-phenylenebismaleimide alone can be used as a crosslinking agent. The amount of these crosslinking aids to be used is 0.05 to 3 parts by weight, preferably 0.2 to 2 parts by weight, based on 100 parts by weight of the total of (a) and (b). If the amount of the crosslinking aid is too small, the crosslinking efficiency of the dynamic crosslinking of the obtained crosslinked thermoplastic elastomer composition may be inferior to the crosslinking efficiency. Mechanical properties may be poor. Examples of the phenolic crosslinking agent include substances represented by the following general formula. Here, n is an integer of 0 to 10, X is a hydroxyl group, a halogenated alkyl group or a halogen atom, and R has a carbon number of 1 to 1.
5 is a saturated hydrocarbon group. The above-mentioned substances are generally used as rubber crosslinking agents, for example, as described in US Pat. Nos. 3,287,440 and 3,709,840. And this crosslinking agent is obtained by condensation polymerization of a substituted phenol and an aldehyde in an alkali catalyst. Other phenolic crosslinking agents include alkylphenol formaldehyde, brominated alkylphenol formaldehyde, and the like.
The amount of the phenolic crosslinking agent used is (b) component 100
The amount is preferably 0.5 to 15 parts by weight, more preferably 2 to 8 parts by weight based on parts by weight. If the amount of the crosslinking agent is too small, the elastic recovery of the obtained crosslinked thermoplastic elastomer composition may be poor, while if the amount of the crosslinking agent is too large, the flexibility of the obtained crosslinked thermoplastic elastomer composition may be poor. is there. The above-mentioned phenolic crosslinking agent can be used alone, but can also be used in combination with a crosslinking accelerator in order to adjust the crosslinking speed. Crosslinking accelerators include stannous chloride, ferric chloride metal halides, chlorinated polypropylene,
Organic halides such as butyl bromide rubber and chloroprene rubber can be used. It is more preferable to use a metal oxide such as zinc oxide or a dispersant such as stearic acid. As other crosslinking agents, sulfur and sulfur-based compounds, p-quinone, derivatives of p-quinonedioxime, bismaleimide compounds, epoxy compounds, silane compounds, amino resins and the like are used.

The crosslinked thermoplastic elastomer composition of the present invention can be used for a conventional vulcanized rubber or soft vinyl chloride-based resin, such as interior / exterior parts of automobiles, housing of weak electric parts, industrial parts, It can be used for waterproof sheet parts and the like.

[0065]

EXAMPLES The present invention will be described by way of examples. [I] Measurement method The measurement was performed as follows.

(1) Intrinsic viscosity [η] The viscosity was measured in tetralin at 135 ° C. using an Ubbelohde viscometer. For the sample, 300 mg was dissolved in 100 ml of tetralin to prepare a 3 mg / ml solution. The solution was further diluted to 1/2, 1/3, and 1/5, and each was diluted to 135 ° C.
(± 0.1 ° C.) in a constant temperature oil bath. The measurement was repeated three times at each concentration, and the obtained values were averaged and used. (2) Differential scanning calorimeter (DSC) measurement Differential scanning calorimeter (DSC220 manufactured by Seiko Instruments Inc.)
Using C), the measurement was performed at a rate of 10 ° C./min in both the temperature increasing and temperature decreasing processes. (3) Measurement of Each Monomer Unit Content in Copolymer (a) Preparation of Calibration Curve A mixture of propylene homopolymer and ethylene-1-butene copolymer at various mixing ratios was hot-pressed to a thickness of 0.1%. It was formed into a 05 mm film. Using an infrared spectrometer, a peak derived from propylene units (wave number 1150c
m ^-1 ) and a peak derived from a 1-butene unit (wave number 770 c
m ^-1 ), and the propylene and 1-butene unit content in the mixture was plotted against the absorbance. A regression line was determined from these plots and used as a calibration curve. In addition, propylene homopolymer and ethylene-
The mixture of 1-butene copolymers was dissolved in toluene, methanol was added, and the resulting precipitate was dried and used. (B) Measurement of propylene / 1-butene content The olefin copolymer was hot-pressed to form a film having a thickness of 0.05 mm, and then a peak derived from a propylene unit and a peak derived from a 1-butene unit were measured using an infrared spectrometer. The absorbance with respect to the peak was determined, and the propylene and 1-butene unit content in the olefin copolymer was calculated from the calibration curve obtained by the above method. (C) Measurement of the content of dicyclopentadiene (DCPD) The olefin copolymer was hot-pressed into a 0.5 mm-thick film, and then the infrared spectrometer was used to determine the dicyclopentadiene-derived (wave number 1611 cm ^{− 1} ) The peak transmittance was determined, and the content of dicyclopentadiene in the olefin copolymer was calculated.

[II] Preparation of polymerization catalyst (1) Synthesis of transition metal complex (dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride) ) Synthesis of 1-bromo-3-tert-butyl-5-methyl-2-phenol 20.1 g of 2-tert-butyl-4-methylphenol in a 500 ml four-necked flask equipped with a stirrer under a nitrogen atmosphere. 123 mmol) in 150 ml of toluene, followed by 25.9 ml of tert-butylamine.
(18.0 g, 246 mmol) was added. The solution was cooled to -70 ° C, and 10.5 ml of bromine (32.6 ml) was added thereto.
g, 204 mmol). This solution was kept at -70 ° C and stirred for 2 hours. Thereafter, the temperature was raised to room temperature, and 100 ml of 10% diluted hydrochloric acid was added each time, followed by washing three times. The organic layer obtained after washing is dried using anhydrous sodium sulfate, the solvent is removed using an evaporator, and then purified using a silica gel column, and 1-bromo-3-tert-butyl as a colorless oil is obtained. 18.4 g (75.7 mmol) of -5-methyl-2-phenol was obtained. The yield was 62%. (B) Synthesis of 1-bromo-3-tert-butyl-2-methoxy-5-methylbenzene 1-bromo- synthesized in the above (1) in a 100 ml four-necked flask equipped with a stirrer under a nitrogen atmosphere. 3-ter
13.9 g of t-butyl-5-methyl-2-phenol
(57.2 mmol) was dissolved in 40 ml of acetonitrile, followed by 3.8 g (67.9 mmol) of potassium hydroxide.
l) was added. Further, 17.8 ml of methyl iodide (4
0.6 g, 286 mmol) was added and stirring continued for 12 hours. Thereafter, the solvent was removed by an evaporator, and 40 ml of hexane was added to the residue to extract hexane-soluble components.
The extraction was repeated three times. The solvent was removed from the extract, and 1-bromo-3-tert-butyl- as a pale yellow oil was obtained.
13.8 g of 2-methoxy-5-methylbenzene (5
3.7 mmol). The yield was 94%. (C) Synthesis of (3-tert-butyl-2-methoxy-5-methylphenyl) chlorodimethylsilane tetrahydrofuran (31.5 ml), hexane (13
9 ml) and 1-bromo-3-t synthesized in (2) above.
To a solution of tert-butyl-2-methoxy-5-methylbenzene (45 g) was added at −40 ° C. a 1.6 mol / l hexane solution of n-butyllithium (115
ml) was added dropwise over 20 minutes. The obtained mixture was -4
After incubating at 0 ° C for 1 hour, tetrahydrofuran (3
1.5 ml) was added dropwise. Dichlorodimethylsilane (1
31 g) and hexane (306 ml) at −40 ° C., the mixture obtained above was added dropwise. The resulting mixture was allowed to warm to room temperature over 2 hours and then at room temperature for 1 hour.
Stir for 2 hours. The solvent and excess dichlorodimethylsilane were distilled off from the reaction mixture under reduced pressure, hexane-soluble components were extracted from the residue using hexane, and the solvent was distilled off from the resulting hexane solution to give a pale yellow oil. (3-te
41.9 g of rt-butyl-2-methoxy-5-methylphenyl) chlorodimethylsilane were obtained. The yield is 84
%Met. (D) Synthesis of (3-tert-butyl-2-methoxy-5-methylphenyl) dimethyl (tetramethylcyclopentadienyl) silane (3-tert-butyl-2-methoxy-5) synthesized in (c) above. -Methylphenyl) chlorodimethylsilane (5.24 g) and tetrahydrofuran (50 ml) were added to lithium tetramethylcyclopentadienyl (2.73 g) at −35 ° C. at room temperature for 2 hours. Then, the mixture was further stirred at room temperature for 10 hours. The solvent was distilled off from the obtained reaction mixture under reduced pressure, and the hexane-soluble component was extracted from the residue with hexane.The solvent was distilled off from the obtained hexane solution under reduced pressure to give a yellow oil. (3-tert-butyl-2-methoxy-5
-Methylphenyl) dimethyl (tetramethylcyclopentadienyl) silane 6.69 g was obtained. The yield is 97
%Met. (E) Synthesis of dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (3-tert-butyl-2-methoxy-) synthesized in (d) above. 5-methylphenyl) dimethyl (tetramethylcyclopentadienyl) silane (10.04 g), toluene (100 ml), and triethylamine (6.30 g)
A solution of 1.63 mol / l of n-butyllithium in hexane (19.0 m
l) was added dropwise, and then the temperature was raised to room temperature over 2 hours.
Further, the temperature was kept at room temperature for 12 hours. At 0 ° C under nitrogen atmosphere,
A solution of titanium tetrachloride (4.82 g) in toluene (50
ml), the mixture obtained above was added dropwise, and the mixture was heated to room temperature over 1 hour, and then heated and refluxed for 10 hours.
The reaction mixture was filtered, the solvent was distilled off from the filtrate, and the residue was recrystallized from a mixed solvent of toluene and hexane. Methyl-2-phenoxy) titanium dichloride (the following chemical formula) was converted to 3.4.
6 g were obtained. The yield was 27%. The spectrum data was as follows. ¹ H-NMR (CDCl ₃ ) δ 0.57 (s, 6
H), 1.41 (s, 9H), 2.15 (s, 6H),
2.34 (s, 6H), 2.38 (s, 3H), 7.1
5 (s, 1H), 7.18 (s, 1H) 13 C-NMR (CDCl 3) δ 1.25,14.4
8, 16.28, 22.47, 31.25, 36.2
9, 120.23, 130.62, 131.47, 13
3.86, 135.50, 137.37, 140.8
2, 142.28, 167.74 Mass spectrum (CI, m / e) 458

[III] Polymerization of Olefin-Based Copolymer (B) Example 1 Ethylene, propylene and 1-butene were continuously copolymerized using a 100 L SUS polymerization vessel equipped with stirring blades. That is, hexane was continuously supplied as a polymerization solvent at a rate of 83 L / hour from the lower part of the polymerization vessel. On the other hand, the polymerization liquid was continuously withdrawn from the upper part of the polymerization vessel such that the polymerization liquid in the polymerization vessel became 100 L. Dimethylsilyl (tetramethylcyclopentadienyl) (3-ter
t-butyl-5-methyl-2-phenoxy) titanium dichloride, triphenylmethyltetrakis (pentafluorophenyl) borate and triisobutylaluminum at a rate of 0.018 g / hr, 0.276 g / hr and 1.584 g / hr, respectively. To continuously feed into the polymerization vessel from the lower part of the polymerization vessel. The molecular weight was adjusted with hydrogen. The copolymerization reaction was carried out at 50 ° C. by circulating cooling water through a jacket attached outside the polymerization vessel.
A small amount of ethanol was added to the polymerization solution withdrawn from the polymerization vessel to stop the polymerization reaction, and after demonomerization and washing with water, the solvent was removed by steam in a large amount of water to remove the copolymer, and the pressure was reduced at 80 ° C day and night. Dried. By the above operation,
6.12 ethylene-propylene-1-butene copolymer
Obtained at a rate of Kg / hour. The conditions and results are shown in Table 1.

Example 2 Ethylene, propylene, 1-butene and dicyclopentadiene were continuously copolymerized using a 100 L SUS polymerization vessel equipped with stirring blades. That is, hexane was continuously supplied as a polymerization solvent at a rate of 83 L / hour from the lower part of the polymerization vessel. On the other hand, the polymerization liquid was continuously withdrawn from the upper part of the polymerization vessel such that the polymerization liquid in the polymerization vessel became 100 L. Dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-
2-phenoxy) titanium dichloride, triphenylmethyltetrakis (pentafluorophenyl) borate, and triisobutylaluminum at 0.045 each
g / hr, 0.827 g / hr and 2.376 g / hr were continuously fed from the lower part of the polymerization reactor into the polymerization reactor. The molecular weight was adjusted with hydrogen. The copolymerization reaction was carried out at 50 ° C. by circulating cooling water through a jacket attached outside the polymerization vessel. A small amount of ethanol was added to the polymerization solution withdrawn from the polymerization vessel to stop the polymerization reaction,
After removing the monomer and washing with water, the solvent was removed by steam in a large amount of water, and the copolymer was taken out and dried at 80 ° C. under reduced pressure day and night. By the above operation, ethylene-propylene-1
-Butene-dicyclopentadiene copolymer is 5.16K
g / h. The conditions and results are shown in Table 1.

[0070]

[Table 1]

* 1 DCPD: dicyclopentadiene * 2 (a): triisobutylaluminum * 3 (b): triphenylmethyltetrakis (pentafluorophenyl) borate * 4 (c): dimethylsilyl (tetramethylcyclopentadienyl) ) (3-tert-butyl-5-methyl-2)
-Phenoxy) titanium dichloride

[IV] Production of Crosslinked Thermoplastic Elastomer Composition The composition shown in Table 2 was mixed at a temperature of 200.degree. For 5 minutes. The composition was press-molded at 200 ° C., and the following tests were performed. Tensile test: 100% modulus (M100), tensile strength at break (TB) and tensile elongation at break (EB) were measured according to JIS K6251. Hardness: Hardness was measured with a JIS-A type hardness meter based on JIS K6253. Weather resistance: Using a sunshine weather meter (manufactured by Suga Test Instruments Co., Ltd., black panel temperature 63 ° C., with rain), the test piece was left in the tank for 240 hours. Next, the tensile strength (TB) was measured. The higher the TB retention, the better the weather resistance. Fluidity: The melt flow rate at 230 ° C. was measured according to JIS K7210. (Load 2.16 kg)

The following can be understood from the results. The crosslinked thermoplastic elastomer composition using the olefin copolymer of Example 3, which satisfies the conditions of the present invention, has excellent weather resistance.

[0074]

[Table 2] (B): Copolymer obtained in Example 2 Components other than (b): Dynalon 1320P (hydrogenated SBR manufactured by JSR) (a): MFR at 230 ° C. under 2.16 kg load was 14
(G / 10 min) Homopolypropylene (c): Esplene 305 (ethylene-propylene-non-conjugated diene copolymer rubber manufactured by Sumitomo Chemical Co., Ltd.) Antioxidant: Irganox 1010 (manufactured by Ciba Specialty Chemicals) PO: Perhexin 25B-40 (organic peroxide manufactured by NOF Corporation) BM: m-phenylenebismaleimide

[0075]

As described above, according to the present invention, a polyolefin resin is contained, excellent in weather resistance, mechanical strength, elastic recovery and flexibility, and completely free of an aromatic vinyl compound such as styrene. A crosslinked thermoplastic elastomer composition which was excellent in recyclability because it was composed only of an olefin component could be provided.

Claims (19)

[Claims] 1. The following (a): 5 to 95% by weight and (b)
A crosslinked thermoplastic elastomer composition obtained by dynamically heat-treating a mixture containing 95 to 5% by weight in the presence of a crosslinking agent. (A): polyolefin resin (b): ethylene, propylene and α having 4 to 20 carbon atoms
-An olefin copolymer obtained by copolymerizing two or more olefins selected from the group consisting of olefins, wherein the total number of carbon atoms of the selected olefins is 6 or more. 2. (B) is two or more olefins selected from the group consisting of ethylene, propylene and α-olefins having 4 to 20 carbon atoms, wherein the total number of carbon atoms of the selected olefins is The crosslinked thermoplastic elastomer composition according to claim 1, which is an olefin-based copolymer obtained by copolymerizing two or more olefins having 6 or more and a cyclic olefin. 3. The crosslinked thermoplastic elastomer composition according to claim 2, wherein the cyclic olefin is a cyclic monoolefin. 4. The crosslinked thermoplastic elastomer composition according to claim 2, wherein the cyclic olefin is a cyclic polyene. 5. The crosslinked thermoplastic elastomer composition according to claim 1, which contains propylene as the olefin of (b). 6. The crosslinked thermoplastic elastomer composition according to claim 1, which contains ethylene and propylene as the olefin (b). 7. The crosslinked thermoplastic elastomer composition according to claim 1, wherein the content of ethylene as the olefin of (b) is 80 mol% or less. 8. The crosslinked thermoplastic elastomer composition according to claim 1, wherein (b) satisfies the following relationship: [Y / (x + y)] ≧ 0.2 (x represents the ethylene content (mol%) in (b),
y represents the content (mol%) of the α-olefin having 4 to 20 carbon atoms in (b). ) 9. The crosslinked thermoplastic elastomer composition according to claim 1, wherein the intrinsic viscosity [η] of the tetralin solvent at (135) a temperature of 135 ° C. is 0.3 to 10. 10. The crosslinked thermoplastic elastomer composition according to claim 1, wherein the molecular weight distribution (Mw / Mn) measured by gel permeation chromatography (GPC) in (b) is 3 or less. 11. A differential scanning calorimeter (DS) for (b)
The crosslinked thermoplastic elastomer composition according to claim 1, which has neither a peak of 1 J / g or more based on melting of the crystal nor a peak of 1 J / g or more based on crystallization as measured in C). 12. (B) is the following (A) and (B)
And / or for olefin polymerization using the following (C)
In the presence of a catalyst, ethylene, propylene and carbon number 4-2
Two or more selected from the group consisting of
An olefin, wherein the number of carbon atoms of the selected olefin is
By copolymerizing two or more olefins having a total of 6 or more
The frame according to claim 1, which is an olefin-based copolymer obtained.
A bridge thermoplastic elastomer composition. (A): transition gold represented by the following general formulas [I] to [III]
At least one of the genus complexes(In the above general formulas [I] to [III], M¹Is
Represents a transition metal atom of Group 4 of the Periodic Table of the Elements, where A is an element
Indicates an atom belonging to Group 16 of the Periodic Table,
Shows the atoms of Group 14 of the Rule. Cp¹Is cyclopentadi
A group having an ene-type anion skeleton is shown. X¹, X^Two,
R¹, R^Two, R^Three, R^Four, R^FiveAnd R⁶Are each independently water
Element atom, halogen atom, alkyl group, aralkyl group,
Reel group, substituted silyl group, alkoxy group, aralkyl group
It represents a xy group, an aryloxy group or a disubstituted amino group.
X^ThreeRepresents an atom belonging to Group 16 of the periodic table of the elements. R¹, R
^Two, R^Three, R^Four, R^FiveAnd R⁶Are optionally linked to form a ring
You may. Two M¹, A, J, Cp¹, X¹, X^Two,
X^Three, R¹, R^Two, R^Three, R^Four, R^FiveAnd R⁶Are the same for each
Or different. (B): at least one selected from the following (B1) to (B3)
(B1) General formula E¹ _aAlZ_3-aOrganic aluminum indicated by
Compound (B2) General formula ｛-Al (E^Two) -O-｝_bIndicated by
Cyclic aluminoxane having a structure (B3) General formula E^Three｛-Al (E^Three) -O-｝_cAlE^Three
_TwoLinear aluminoxane having a structure represented by the following formula (provided that E¹, E^TwoAnd E^ThreeIs a hydrocarbon group
All E¹, All E ^TwoAnd all E^ThreeIs the same
Or different. Z is a hydrogen atom or a halogen atom
Represents a child, and all Z may be the same or different
No. a is a number satisfying 0 <a ≦ 3, b is an integer of 2 or more
And c represents an integer of 1 or more. (C): Boration of any of the following (C1) to (C3)
Compound (C1) General formula BQ¹Q^TwoQ^ThreeBoron compound represented by
Object, (C2) general formula G⁺(BQ¹Q^TwoQ^ThreeQ^Four)^-E represented by
Iodine compound, (C3) General formula (LH)⁺(BQ¹Q^TwoQ^ThreeQ^Four)^-In table
(Where B is a boron atom in a trivalent state, Q
¹~ Q^FourIs a halogen atom, hydrocarbon group, halogenated hydrocarbon
Group, substituted silyl group, alkoxy group or disubstituted amino group
And they may be the same or different.
G⁺Is an inorganic or organic cation, and L is a neutral Lewis
A base, (LH)⁺Is a Bronsted acid
You. ) 13. The crosslinked thermoplastic elastomer composition according to claim 12, wherein A in the general formula [I] is an oxygen atom. 14. The crosslinked thermoplastic elastomer composition according to claim 12, wherein R ¹ in the general formula [I] is an alkyl group, an aralkyl group, an aryl group or a substituted silyl group. 15. X ¹ and X ² in the general formula [I] are:
The crosslinked thermoplastic elastomer composition according to claim 12, which is independently a halogen atom, an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group, or a disubstituted amino group. 16. The crosslinked thermoplastic elastomer composition according to claim 12, wherein the compound (B) is triethylaluminum, triisobutylaluminum or methylaluminoxane. 17. The crosslinked thermoplastic elastomer composition according to claim 12, wherein the compound (C) is dimethylanilinium tetrakis (pentafluorophenyl) borate or triphenylmethyltetrakis (pentafluorophenyl) borate. 18. The method according to claim 1, wherein (a) is from 5 to 95% by weight.
And (b) 95 to 5% by weight, and a mixture containing (C) 10 to 900 parts by weight per 100 parts by weight of the total amount of (A) and (B) is dynamically heat-treated in the presence of a crosslinking agent. The resulting crosslinked thermoplastic elastomer composition. (C): ethylene-propylene (-non-conjugated diene) random copolymer rubber 19. The following items (d) and (2) per 100 parts by weight of the total of (a), (b) and (c) according to claim 18
A crosslinked thermoplastic elastomer composition obtained by dynamically heat-treating a mixture containing 00 parts by weight in the presence of a crosslinking agent. (D): Mineral oil softener