JPH11302473A - Thermoplastic elastomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain thermoplastic elastomer compositions excellent in weatherability, strength, flexibility, clarity and heat resistance with no fear of a hygienic problem accompanied by elution of plasticizers and other problems of use and, at the same time, excellent in light stability, especially ultraviolet stability due to the absence of any aromatic vinyl compound and, in addition, excellent in recycling properties since the constituting components are composed solely of complete olefinic components. SOLUTION: Desired thermoplastic elastomer compositions comprises (A) 1-98 wt.% polypropylene; (B) 1-98 wt.% olefinic copolymer to be obtained by copolymerizing two or more olefins selected from ethylene, propylene and 4-20C α-olefins, the total carbon number of the selected two or more olefins being not less than 6; and (C) 1-98 wt.% poly-1-butene having a melting point, measured by a differential scanning calorimeter(DSC), of 30-130 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a thermoplastic elastomer composition. More specifically, the present invention relates to a thermoplastic elastomer composition having excellent weather resistance, strength, flexibility, transparency, heat resistance, and having no risk of causing hygiene or other use problems due to dissolution of a plasticizer. It is.

[0002]

2. Description of the Related Art Heretofore, many compositions have been proposed and put into practical use to obtain flexible and transparent molded products. For example, ethylene-acrylate copolymer, 1,2-polybutadiene, ethylene-vinyl acetate copolymer, ethylene-
Acrylic acid copolymer or metal salt of methacrylic acid copolymer is used as a flexible and transparent molded article, but has a problem that heat resistance is insufficient and softens at a temperature of 100 ° C or less. is there. On the other hand, styrene-based elastomers such as styrene-butadiene block copolymer and styrene-isoprene block copolymer have excellent flexibility, transparency, strength, and excellent low-temperature properties, but have insufficient heat resistance. Even at a temperature of 100 ° C. or lower, there is a problem that the shape cannot be maintained due to softening. In view of this, hydrogenated derivatives (hereinafter abbreviated as hydrogenated block copolymers) obtained by improving the styrene-based elastomer have been proposed, but they are excellent in flexibility, transparency, tensile strength and heat resistance. It is considerably improved as compared with the hydrogenated product, but it is still insufficient, and the flowability at the time of melting is abnormal and the moldability is poor.

Some proposals have been made on elastomer compositions using the above hydrogenated block copolymer. For example, JP-A-50-14742 and JP-A-52-65551 disclose elastomer compositions in which an olefin polymer and a hydrocarbon oil are blended with a hydrogenated block copolymer. These elastomer compositions maintain their shape even at a temperature of about 100 ° C.,
Also, it has good flexibility even at a low temperature of about −40 ° C., and is excellent in heat aging resistance, ozone resistance, light stability and moldability.

[0004] However, since these compositions contain a large amount of hydrocarbon oil, elution of hydrocarbon oil may be a problem in the fields of food packaging materials, medical devices and the like. Therefore, for the purpose of solving the above problem, a composition of a hydrogenated block copolymer containing no hydrocarbon oil has been proposed. For example, Japanese Patent Application Laid-Open No. 54-88950 discloses that a composition of an ABA-type hydrogenated block copolymer and a polypropylene-based resin is used as a softening agent to aid processability, or as a melt flow aid, polyethylene, ethylene acetic acid. There has been proposed a composition comprising a softening agent selected from a vinyl copolymer and an ethylene-propylene copolymer.

However, since these softeners have insufficient heat resistance per se, heat resistance can be obtained only in combination with a hydrogenated block copolymer having a specific structure, and the heat resistance is lowered. Therefore, the amount of the softening agent that can be used is limited, resulting in a problem that only a hard molded product is obtained, and the transparency is also insufficient.

JP-A-59-74153 proposes a composition comprising an ABA type hydrogenated block copolymer and a polypropylene resin, and further comprising an ethylene-acrylate copolymer. Since the ethylene-acrylate copolymer itself has good heat resistance and flexibility, a composition having flexibility and excellent heat resistance can be obtained. However, when using an ethylene-acrylate copolymer,
Due to the odor of the ethylene-acrylate copolymer, not only is its use restricted in the fields of food packaging materials, medical devices and the like, but also whitening and moisture absorption due to hot water occur. Also, even with this composition, excellent transparency like soft vinyl chloride cannot be obtained.

A molded article using a composition based on soft vinyl chloride is excellent in transparency, flexibility, heat resistance and 100%.
Since it can maintain its shape even at a temperature of at least ℃, it can be sterilized at high temperature, and is widely used in food packaging materials, medical devices and the like. However, a composition based on soft vinyl chloride usually contains a large amount of a plasticizer, so that the plasticizer is eluted, and there is a risk of causing hygiene and other problems in use. Further, the composition based on soft vinyl chloride has insufficient low-temperature properties, and the flexibility is significantly reduced at a temperature of 0 ° C. or lower. Therefore, when the molded product is subjected to freezing storage or the like, there is a possibility that a problem such as breakage due to impact of the molded product may occur.
In addition, harmful gas may be generated during incineration.

Further, a method for providing a thermoplastic elastomer composition having excellent strength, flexibility, transparency and heat resistance by blending a hydrogenated product of a conjugated diene-styrene copolymer with a polyolefin resin such as polypropylene. Is disclosed in JP-A-7-53799. 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.

[0009]

Under these circumstances, the problems to be solved by the present invention are weather resistance, strength, flexibility,
Excellent transparency, heat resistance, no risk of hygiene and other problems associated with dissolution of plasticizer, and no aromatic vinyl compound such as styrene, so it has excellent light stability, especially UV stability Further, the present invention is intended to provide a thermoplastic elastomer composition having excellent recyclability since the constituent components are composed of a complete olefin component.

[0010]

That is, the present invention provides a thermoplastic elastomer composition containing the following (a) 1 to 98% by weight, (b) 1 to 98% by weight and (c) 1 to 98% by weight. It is related to. (A): polypropylene (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. (C): The melting point measured by a differential scanning calorimeter (DSC) is 3
Poly-1-butene at 0 to 130 ° C.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The component (A) of the present invention is polypropylene. The polypropylene of the present invention is an isotactic polypropylene or a 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 can employ a gas-phase polymerization method, a bulk polymerization method, a solvent polymerization method and optionally a multi-stage polymerization by combining them, and the number average molecular weight of such a polymer is not particularly limited, but is preferably used. Is adjusted to 10,000 to 1,000,000.
As (A), a corresponding commercially available 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. As (b), those included in the category of (a) are excluded. It is necessary that the total number of carbon atoms of the selected olefin is 6 or more. Total carbon number is 6
When a combination of olefins less than the above is selected, the flexibility of a molded article molded using the obtained thermoplastic elastomer composition is inferior.

The α-olefin having 4 to 20 carbon atoms includes linear and branched α-olefins. Specifically, examples of the linear α-olefin include 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 combinations of two or more selected olefins include ethylene / 1-butene, ethylene / 1-hexene, ethylene / 1-octene, ethylene / 1
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.

(Ii) 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 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 and cyclic polyenes.

The cyclic olefin has four or more carbon atoms.
Form one or more rings and at least carbon-carbon
Rings optionally having various substituents containing one or more double bonds
Compound. The specific structure of such a cyclic olefin and
For example, a compound represented by the following general formula [IV] or [V]
Things can be exemplified.(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, 4-methylcyclopentene, 3,4-dimethylcyclopentene, 3,5-dimethylcyclopentene, 3-chlorocyclopentene and cyclohexene. Examples thereof include xen, 3-methylcyclohexene, 4-methylcyclohexene, 3,4-dimethylcyclohexene, 3-chlorocyclohexene, and cycloheptene.

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, 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 cyclic polyene compounds represented by the general formula [V], 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 5-ethyl-1,3-cyclohexadiene, Examples include 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%. If the content of the cyclic olefin is too low, the heat resistance of a molded article molded using the thermoplastic elastomer composition obtained may be poor, while the thermoplastic elastomer composition obtained if the content of the cyclic olefin is too high In some cases, the balance between the strength and the flexibility of a molded article molded using the article may be poor.

The olefin (b) may contain propylene or ethylene and propylene. The content of ethylene as the olefin of (b) is preferably 80 mol% or less, more preferably 70 mol% or less, from the viewpoint of the flexibility and the transparency improving effect of the thermoplastic elastomer composition. Yes, more preferably 60 mol%
Or less, particularly preferably 50 mol% or less. Outside the range, the olefin-based copolymer may contain crystals derived from ethylene, and the flexibility and transparency of a molded article molded from the obtained thermoplastic elastomer composition may be poor. 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. Preferably it is at most 60%, most preferably at most 50%. If the ratio is out of the range, the molded article molded using the obtained 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 outside the above range, a molded article molded using the obtained thermoplastic elastomer composition may be poor in whitening resistance. In the above formula, x represents the molar content of ethylene in the copolymer, and y represents 4 to 20 carbon atoms in the copolymer.
Represents the total molar content of α-olefins.

In (b), the intrinsic viscosity [η] of the tetralin solvent at a temperature of 135 ° C. is preferably from 0.3 to 10, more preferably from 0.5 to 7, and further preferably from 0.7 to 7. 5 If the intrinsic viscosity is too low,
A molded article molded using the obtained thermoplastic elastomer composition may have poor heat resistance. On the other hand, if the intrinsic viscosity is too high, the flexibility of a molded article molded from the obtained thermoplastic elastomer composition may be poor. The intrinsic viscosity [η] is measured in tetralin at 135 ° C. using an Ubbelohde viscometer. The sample is 300mg 100m
Dissolve in 1 tetralin to prepare a 3 mg / ml solution. Further dilute the solution to 1/2, 1/3, 1/5,
Each is measured in a constant temperature 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. If the molecular weight distribution is too wide, when the copolymer is used as a modifier, the resulting thermoplastic elastomer composition may have poor flexibility. The molecular weight distribution is measured by gel permeation chromatography (GPC) (for example, 150C / GPC apparatus manufactured by Waters). Elution temperature is 1
At 40 ° C., the column used is, for example, Show
ex Packed ColumnA-80M, polystyrene (for example, molecular weight 68-8, 400,000, manufactured by Tosoh Corporation) is used as a molecular weight standard substance. 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 is prepared by dissolving about 5 mg of a polymer in 5 ml of o-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 the crystal nor a peak of 1 J / g or more based on crystallization as measured by a differential scanning calorimeter (DSC). Is preferred. When it has such a peak, the flexibility of a molded article molded using the obtained thermoplastic elastomer composition may be poor. The differential scanning calorimeter uses, for example, DSC220C manufactured by Seiko Denshi Kogyo Co., Ltd., and performs measurement at a rate of 10 ° C./min in both the temperature rising and temperature decreasing processes.

(B) can be produced using a known Ziegler-Natta type catalyst or a 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.

Particularly, (b) is propylene and / or carbon
The sequence of α-olefin side chains of Formulas 4 to 20 is atactic
It is preferably a structure. Non-atactic structure
In this case, when the copolymer is used as a modifier,
Transparency and flexibility of thermoplastic elastomer composition
There are cases. Atactic tacticity in the copolymer
To make the structure, ethylene, propylene and carbon number 4 ~
Two or more selected from the group consisting of 20 α-olefins
Wherein the carbon number of the selected olefin is
The total of 6 or more, two or more olefins,
(A) and the following (B) and / or (C)
Copolymerization in the presence of an olefin polymerization catalyst
It can be more optimally manufactured. (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.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
The alkyl group for ⁵ or R ⁶ has 1 to 1 carbon atoms.
Preferred are 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. Examples of Group 16 atoms in the periodic table of the element represented by X ³ in Formula [II] or [III] include, for example, an oxygen atom, a sulfur atom, and a selenium atom, and are preferably an oxygen atom.

The transition metal complex represented by the general formula [I] includes, for example, methylene (cyclopentadienyl)
(3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-t
tert-butyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-ter
t-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-tert-butyl-5-chloro-2- Phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3,5
-Dimethyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-t
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-butyldimethyl Silyl-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 (t
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 (te
rt-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-tert-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-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 -T
tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert-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-t
tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-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-ter
t-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-yl) Phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert-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-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 (tert-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 (te
rt-butylcyclopentadienyl) (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 (tetramethylcyclopentadiene) Enil) (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-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-tert-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-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert- 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-te
rt-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-butyl Dimethylsilyl-
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-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) titanium dichloride, diphenylmethylene (tert
-Butylcyclopentadienyl) (3,5-dimethyl-
2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl)
(3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-
Methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyldimethyl Silyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (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-te
rt-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 (tetramethylcyclopentadienyl) (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-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, diphenylmethylene (fluorenyl) (3-te
rt-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, etc., and titanium of these compounds is zirconium or hafnium The compound in which dichloride was changed to dibromide, diiodide, bis (dimethylamide), bis (diethylamide), di-n-butoxide or diisopropoxide, and (cyclopentadienyl) was changed to (dimethylcyclopentadiene) Enyl), (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.

Examples of the transition metal complex represented by the general formula [II] include μ-oxobis {isopropylidene (cyclopentadienyl) (2-phenoxy) titanium chloride} and 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 (B) aluminum compound 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 trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum and trihexylaluminum; Dialkylaluminum chlorides such as dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, dihexylaluminum chloride; alkylaluminum dichlorides such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, hexylaluminum dichloride Dimethylal Examples thereof include dialkylaluminum hydrides such as minium hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride, and dihexylaluminum hydride. Preferably, it is a trialkylaluminum, and more preferably, triethylaluminum or triisobutylaluminum.

[0047] 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.

The 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 the 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. And Q ^{1 to} Q ⁴ are the same as Q ^{1 to} Q ³ in (C1) above.

[0053] 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 combinations of these 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).

[0056] 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.

As specific combinations of these, 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 0.1 to 10000, preferably 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. When each component is used in a solution state or a suspension state in a solvent, the concentration is appropriately selected depending on conditions such as the performance of an apparatus for supplying each component to the polymerization reactor. .01-500 μmol
/ G, more preferably 0.05 to 100 μmol /
g, more preferably 0.05 to 50 μmol / g,
(B) is usually 0.01 to 10,000 in terms of Al atom.
μmol / g, more preferably 0.1-5000 μm
mol / g, more preferably 0.1 to 2000 μmo
1 / g, (C) is usually 0.01 to 500 μmol / g
And more preferably, 0.05 to 200 μmol / g,
More preferably, it is desirable to use each component so as to be in the range of 0.05 to 100 μmol / g. In order to produce (b), for example, an aliphatic hydrocarbon such as butane, pentane, hexane, heptane and octane, an aromatic hydrocarbon such as benzene and toluene, or a halogenated hydrocarbon such as methylene dichloride is used as a solvent. Solvent polymerization, slurry polymerization, gas phase polymerization in a gaseous monomer, and the like are possible, and both continuous polymerization and batch polymerization are possible. The polymerization temperature is -50 ° C to 200 ° C
-20 ° C to 100 ° C, and the polymerization pressure is preferably normal pressure to 60 kg / cm ² G. The polymerization time is generally appropriately determined depending on the type of the catalyst to be used and the reactor, but can range from 1 minute to 20 hours. Further, a chain transfer agent such as hydrogen can be added to adjust the molecular weight of the polymer.

The component (c) of the present invention is poly-1-butene having a melting point of 30 to 130 ° C. measured by a differential scanning calorimeter (DSC). As (c), those included in the above categories (a) or (b) are excluded.
(C) is a Ziegler-Natta type catalyst by a known technique,
Or a poly-1-butene homopolymer resin or a poly-1-butene copolymer resin synthesized using a metallocene catalyst, and having a melting point of 30 to 130 ° C. measured by a differential scanning calorimeter (DSC). The temperature is more preferably 40 to 130 ° C, particularly preferably 50 to 130 ° C. If the melting point is too low, the heat resistance and strength of a molded article molded using the obtained thermoplastic elastomer composition may be poor. The differential scanning calorimeter uses, for example, DSC220C manufactured by Seiko Denshi Kogyo Co., Ltd., and performs measurement at a rate of 10 ° C./min in both the temperature rising and temperature decreasing processes. Poly
The 1-butene copolymer resin is obtained by copolymerizing 1-butene and ethylene or an α-olefin having 3 to 8 carbon atoms, and propylene is preferably used as the α-olefin.
Examples include 1-hexene and 1-octene. The proportion of these α-olefins is not more than 50% by weight, preferably 0.5 to 40% by weight, particularly preferably 1 to 30% by weight. As (c), a commercially available poly-1-butene having a melting point of 30 to 130 ° C. can be used.

The thermoplastic elastomer composition of the present invention comprises:
A thermoplastic elastomer composition containing (A) 1 to 98% by weight, (B) 1 to 98% by weight and (C) 1 to 98% by weight, preferably (A) 10 to 90% by weight;
A thermoplastic elastomer composition containing (b) 5 to 95% by weight and (c) 10 to 90% by weight. In addition,
The total amount of (a) to (c) is 100% by weight. If the amount of (a) is too small, the heat resistance and strength of the molded article molded using the thermoplastic elastomer composition obtained are remarkably reduced, which is inconvenient for practical use. The flexibility and transparency of a molded article molded using the thermoplastic elastomer composition obtained are inferior and inconvenient. (B)
If the amount is too small, the molded article molded using the thermoplastic elastomer composition obtained is inferior in flexibility and transparency, which is inconvenient for practical use. However, the heat resistance and strength of the molded article formed by using this method are inferior, which is inconvenient. If (c) is too small, the heat resistance, strength and transparency of a molded article molded using the thermoplastic elastomer composition obtained are inferior, which is inconvenient for practical use, while (c) is obtained if it is excessive. The flexibility and transparency of a molded article molded using the thermoplastic elastomer composition are inferior and are inconvenient.

In the thermoplastic elastomer composition of the present invention, in addition to an antioxidant as an additional component, an antistatic agent,
Additives such as weathering agents, ultraviolet absorbers, slip agents, coloring agents, dispersants, glass fibers, carbon fibers, metal fibers, glass beads, asbestos, mica, calcium carbonate, potassium titanate whiskers, talc, aramid fibers, sulfuric acid Fillers such as barium, glass flakes and fluororesins, or other rubbery polymers or thermoplastic resins can be appropriately compounded. If necessary, the thermoplastic elastomer composition of the present invention may be subjected to crosslinking such as sulfur crosslinking, peroxide crosslinking, metal ion crosslinking, and silane crosslinking by a conventionally known method. In order to obtain the thermoplastic elastomer composition of the present invention, the components described above are mixed with a usual kneading apparatus, for example, a rubber mill, a Brabender mixer, a Banbury mixer, a pressure kneader, a ruder, a twin-screw extruder, or the like. And knead it. The kneading device may be any of a closed type and an open type, but a closed type device which can be replaced with an inert gas is preferable. The kneading temperature is a temperature at which all of the mixed components are melted, and is usually 160 to 250 ° C.
And preferably at 180 to 240 ° C. The kneading time depends on the type and amount of the constituent components mixed and the type of the kneading device, and is therefore not generally discussed.However, when using a kneading device such as a pressure kneader or a Banbury mixer, it is usually , About 3 to 10 minutes. In the kneading step, each component may be kneaded at a time. Alternatively, after kneading some components, the remaining components are added to continue kneading. A kneading method can also be adopted. The thermoplastic elastomer composition of the present invention can be applied to various molding methods such as injection molding, sheet extrusion molding, vacuum molding, hollow molding, press molding, profile extrusion molding, and foam molding to obtain various molded products.

[0063]

EXAMPLES The present invention will be described by way of examples. [I] Measurement method The measurement was performed as follows. (1) Intrinsic viscosity [η] This was carried out 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-tert
-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. It was continuously fed into the polymerization reactor from the lower part of 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, 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,
6.12K ethylene-propylene-1-butene copolymer
g / h. 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- as a catalyst
Phenoxy) titanium dichloride, triphenylmethyltetrakis (pentafluorophenyl) borate,
0.045 g of triisobutylaluminum /
It was continuously fed from the lower part of the polymerization vessel into the polymerization vessel at a rate of 0.827 g / hour and 2.376 g / hour. Also,
Molecular weight control was performed 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, an ethylene-propylene-1-butene-dicyclopentadiene copolymer was obtained at a rate of 5.16 kg / hour. The conditions and results are shown in Table 1.

[0067]

[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 Thermoplastic Elastomer Composition The compositions shown in Table 2 were mixed at a temperature of 200 ° C. and a screw rotation speed of 100 rpm using a biaxial batch kneader Brabender Plasticorder (manufactured by Brabender). Kneading was performed 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 120 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 thermoplastic elastomer composition using the olefin-based copolymer of Example 3 that satisfies the conditions of the present invention has excellent weather resistance.

[0071]

[Table 2]

(B): Copolymer obtained in Example 2 Components other than (b): Dynaron 1320P (hydrogenated SBR manufactured by JSR) (a): MFR of 14 at 230 ° C. and 2.16 kg load was 14.
(G / 10 min) homopolypropylene (c): Buron M3110 (manufactured by Mitsui Chemicals, Inc., polybutene-1 having a melting point of 112 ° C) Antioxidant: Irganox 1010 (manufactured by Ciba Specialty Chemicals)

[0073]

As described above, the present invention is excellent in weather resistance, strength, flexibility, transparency and heat resistance, has no risk of causing hygiene and other problems in use due to the dissolution of the plasticizer, and has styrene. The present invention provides a thermoplastic elastomer composition which is excellent in light stability, particularly ultraviolet stability because it does not contain an aromatic vinyl compound as described above, and is also excellent in recyclability since the constituent components are composed entirely of olefin components. Was completed.

Claims (17)

[Claims] 1. The following (A) 1 to 98% by weight, (B) 1 to
A thermoplastic elastomer composition containing 98% by weight and (c) 1 to 98% by weight. (A): polypropylene (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. (C): The melting point measured by a differential scanning calorimeter (DSC) is 3
Poly-1-butene at 0 to 130 ° C. 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 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 thermoplastic elastomer composition according to claim 2, wherein the cyclic olefin is a cyclic monoolefin. 4. The thermoplastic elastomer composition according to claim 2, wherein the cyclic olefin is a cyclic polyene. 5. The thermoplastic elastomer composition according to claim 1, which contains propylene as the olefin of (b). 6. The thermoplastic elastomer composition according to claim 1, which contains ethylene and propylene as the olefin (b). 7. The thermoplastic elastomer composition according to claim 1, wherein the content of ethylene as the olefin in (b) is 80 mol% or less. 8. The 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 thermoplastic elastomer composition according to claim 1, wherein the intrinsic viscosity [η] of the (b) with a tetralin solvent at a temperature of 135 ° C. is 0.3 to 10. 10. The 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 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 heat according to claim 1, which is the obtained olefin copolymer.
Plastic 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 thermoplastic elastomer composition according to claim 12, wherein A in the general formula [I] is an oxygen atom. 14. The 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 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 thermoplastic elastomer composition according to claim 12, wherein the compound (B) is triethylaluminum, triisobutylaluminum or methylaluminoxane. 17. The thermoplastic elastomer composition according to claim 12, wherein the compound (C) is dimethylanilinium tetrakis (pentafluorophenyl) borate or triphenylmethyltetrakis (pentafluorophenyl) borate.