JP2001072717A - Shrinkable film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a film which is shrinkable at a low temp., which has a high shrinking rate and which hardly shows spontaneous shrinking by using a copolymer obtd. by copolymerizing ethylene and/or an α-olefin with a cyclic olefin and an arom. alkenyl hydrocarbon. SOLUTION: This film is prepd. by using a copolymer having a glass transition temp. of 70-95 deg.C which is obtd. by copolymerizing ethylene and/or a 3-20C α-olefin with a cyclic olefin such as 2norbornene and an arom. alkenyl hydrocarbon such as styrene in the presence of an addn. polymerization catalyst. The catalyst is obtd. by blending a transition metal complex (A), a cyclic aluminoxane (B) and a boron compd. (C) such as tris(pentaphenyl) borane which are represented by the formulas, etc., at molar ratios of B/A=0.1-10,000 and C/A=0.01-100. In the formula, M1 is a group IV transition metal atom of the Periodic Table; A is a group XVI atom and J is a group XIV atom; Cp1 is a cyclopentadiene-type anion; and X1, X2 and R1-R6 are each hydrogen, alkyl or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a shrink film. More specifically, the present invention relates to a shrink film using a non-chlorine resin.

[0002]

2. Description of the Related Art Shrink films that are easy to remove from containers are often used for labels and the like on plastic and glass containers because of disposal and recycling after use. As a raw material resin for the shrink film, a polyvinyl chloride resin, a styrene-butadiene block copolymer resin, a polyethylene terephthalate resin, a polyolefin resin, or the like is used. In particular, shrink films used for food packaging containers, etc., from the viewpoint of content protection,
Low-temperature shrink characteristics that can be shrink-wrapped at a temperature of about 100 ° C. are required. Also, if the shrink film at room temperature has a large shrink (called natural shrinkage), the natural shrinkage during storage of the film may cause the shrink wrapping machine not to be attached to the shrink wrapping machine, or the printed design may be deformed, thereby deteriorating the commercial value. Therefore, a film having a low natural shrinkage is required.

[0003] Until now, this shrink film has been used for
Polyvinyl chloride resin has been widely used because of its low temperature shrinkability and small natural shrinkage. However, with the recent rise in environmental awareness, there has been a demand for conversion to non-chlorine resin materials for one-way containers. As the non-chlorine resin, styrene-butadiene block copolymer resin and polyethylene terephthalate resin are known. However, since styrene-butadiene block copolymer resin has Tg at 0 ° C. or less, natural shrinkage is large. In addition, refrigerated storage is required in summer, which is not industrially desirable.
On the other hand, in the case of polyethylene terephthalate resin, when the container is the same polyethylene terephthalate resin (for example, a PET bottle), it is necessary to separate the container (plain) and the label (print) in the recycling process, but since the specific gravity is the same, Also, there are industrial problems such as difficulty in separation and the necessity of a special separation device.

As described above, various resins have been used and developed for use in shrink films, but no satisfactory resin has been obtained yet.

[0005]

In such a situation,
The problem to be solved by the present invention is to provide a shrink film made of a non-chlorine-based resin, which has a low-temperature shrink property, a high shrinkage, and a small natural shrinkage.

[0006]

Means for Solving the Problems The present inventors have made intensive studies on a shrink film using a non-chlorine-based resin in order to achieve the above object, and have reached the present invention. That is, the present invention relates to a shrink film using a copolymer obtained by copolymerizing ethylene and / or an α-olefin, a cyclic olefin, and an alkenyl aromatic hydrocarbon.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The shrink film of the present invention comprises ethylene and / or
Alternatively, a copolymer obtained by copolymerizing an α-olefin, a cyclic olefin, and an alkenyl aromatic hydrocarbon is used.

The ethylene used in the present invention and / or
Alternatively, the α-olefin is any one of ethylene alone, α-olefin only, and a mixture of ethylene and α-olefin, and is particularly preferably ethylene.

As the α-olefin mentioned here, olefins having 3 to 20 carbon atoms are preferable. Specific examples of such α-olefins include propylene, butene-1, pentene-1, hexene-1, heptene-1,
Linear olefins such as octene-1, nonene-1 and decene-1, and branched olefins such as 3-methylbutene-1, 3-methylpentene-1, 4-methylpentene-1, 5-methyl-hexene-1 , Vinylcyclohexane and the like. More preferred α-olefins are propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, 4-methylpentene-1, or vinylcyclohexane, particularly preferably propylene. In the present invention, such α-olefin is used alone or in combination.

The cyclic olefin used in the present invention may have various substituents, four or more carbon atoms form a ring, and one carbon-carbon double bond is formed in the ring. It is a compound containing. Examples of such cyclic olefins include monocyclic olefins such as cyclobutene, cyclopentene, cyclohexene, and cyclooctene; substituted monocyclic olefins such as 3-methylcyclopentene, 4-methylcyclopentene, and 3-methylcyclohexene; norbornene, 1,2-dihydro Polycyclic olefins such as dicyclopentadiene and tetracyclododecene; 5-methyl-2
And substituted polycyclic olefins such as norbornene.

Among these, preferred cyclic olefins are
It is a compound represented by the following general formula [IV]. (Wherein, R ^{7 to} R ¹⁸ are each independently a hydrogen atom, a hydroxyl group, an amino group, a phosphino group, or a group having 1 to 2 carbon atoms.
0 is an organic group, and R ¹⁶ and R ¹⁷ may form a ring.
m represents an integer of 0 or more. )

Here, the number of carbon atoms which contribute to the substituent is 1 to 1.
Specific examples of the organic group of 20 include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group and a dodecyl group; an aryl group such as a phenyl group, a tolyl group and a naphthyl group; An aralkyl group such as a phenethyl group; an alkoxy group such as a methoxy group and an ethoxy group;
Aryloxy groups such as phenoxy groups; acyl groups such as acetyl groups; alkoxycarbonyl groups such as methoxycarbonyl groups and ethoxycarbonyl groups; aryloxycarbonyl groups or aralkyloxycarbonyl groups; acyloxy groups such as acetyloxy groups; methoxysulfonyl groups;
An alkoxysulfonyl group such as an ethoxysulfonyl group, an aryloxysulfonyl group or an aralkyloxysulfonyl group; a substituted silyl group such as a trimethylsilyl group; a dialkylamino group such as a dimethylamino group or a diethylamino group; a carboxyl group; a cyano group; Groups in which part of the hydrogen atoms of an aryl group and an aralkyl group are substituted with a hydroxyl group, an amino group, an acyl group, a carboxyl group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, a substituted silyl group, an alkylamino group, or a cyano group be able to.

R ^{7 to} R ¹⁸ are preferably each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a carbon atom. An acyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms,
An acyloxy group of 20 or a disubstituted silyl group having 1 to 20 carbon atoms.

M is an integer of 0 or more, preferably 0 ≦
It is an integer in the range of m ≦ 3.

Specific examples of the preferred cyclic olefin represented by the general formula [IV] include 2-norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, -Phenyl-2
-Norbornene, 5-benzyl-2-norbornene, tetracyclododecene, tricyclodecene, tricycloundecene, pentacyclopentadecene, pentacyclohexadecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 5-acetyl-2-norbornene, 5-acetyloxy-2-norbornene, 5-
Methoxycarbonyl-2-norbornene, 5-ethoxycarbonyl-2-norbornene, 5-methyl-5-methoxycarbonyl-2-norbornene, 5-cyano-2-
Norbornene, 8-methoxycarbonyltetracyclododecene, 8-methyl-8-tetracyclododecene, 8-
Cyanotetracyclododecene and the like can be listed.

In the polymerization, these cyclic olefins are used alone or in combination.

The alkenyl aromatic hydrocarbon used in the present invention is preferably a compound represented by the following formula [V]. (In the formula, R ¹⁹ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and Ar represents an aromatic hydrocarbon group having 6 to 25 carbon atoms.)

R ¹⁹ is a hydrogen atom or a group having 1 to 20 carbon atoms.
Specific examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, and a dodecyl group. Preferably, it is a hydrogen atom or a methyl group.

Ar is an aromatic hydrocarbon group having 6 to 25 carbon atoms, and specific examples thereof include phenyl, tolyl, xylyl, tertiary butylphenyl, vinylphenyl, naphthyl, and phenanthryl. , Anthracenyl group, benzyl group and the like. Preferably, it is a phenyl group, a tolyl group, a xylyl group, a tertiary butylphenyl group, a vinylphenyl group or a naphthyl group.

Specific examples of such alkenyl aromatic hydrocarbons include p-methylstyrene, m-methylstyrene,
o-methylstyrene, p-ethylstyrene, m-ethylstyrene, o-ethylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, 3- Methyl-5
Ethyl styrene, p-tertiary butyl styrene, p-second
Alkyl styrene such as butyl styrene; styrene;
Alkenylbenzenes such as 2-phenylpropylene, 2-phenylbutene and 3-phenylpropylene; bisalkenylbenzenes such as divinylbenzene; and alkenylnaphthalenes such as 1-vinylnaphthalene can be listed. The alkenyl aromatic hydrocarbon used in the present invention is preferably styrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, p-tertiary butylstyrene, 2-phenylpropylene, or 1-vinylnaphthalene. And particularly preferred is styrene.

In the polymerization, other monomers besides those described above can be copolymerized. Examples of such other monomers include various dienes and various vinyl compounds. Specific examples of dienes include 1,5-hexadiene,
1,7-octadiene, norbornadiene, dicyclopentadiene, 5-vinyl-2-norbornene, vinylcyclohexene, 5-ethylidene-2-norbornene and the like can be mentioned. Specific examples of the vinyl compound include methyl vinyl ether, ethyl vinyl ether, acrylic acid, methyl acrylate, ethyl acrylate,
Methyl methacrylate, acrylonitrile, vinyl acetate and the like can be mentioned.

In the copolymer used in the present invention, it is preferable that the copolymer composition of the alkenyl aromatic hydrocarbon is more than half of the copolymer composition of the cyclic olefin because the balance between heat resistance and elastic recovery is excellent. When the copolymerization composition of the alkenyl aromatic hydrocarbon is less than half of the copolymerization composition of the cyclic olefin, the elastic recovery may be particularly reduced. More preferably, the copolymer composition of the alkenyl aromatic hydrocarbon of the copolymer of the present invention is equal to or greater than the copolymer composition of the cyclic olefin.

In the copolymer of the present invention, when the copolymer composition of the cyclic olefin is 0.01 to 66 mol%,
It is particularly excellent in oil resistance and heat resistance, and is preferable. A more preferred copolymer composition of the cyclic olefin is 0.1 to 40 mol%, and a particularly preferred copolymer composition of the cyclic olefin is 1 to 3 mol%.
0 mol%. The copolymer composition of such a cyclic olefin can be easily determined from a ¹ H-NMR spectrum or a ¹³ C-NMR spectrum.

In the copolymer of the present invention, when the copolymer composition of the alkenyl aromatic hydrocarbon is from 3 to 99 mol%, the heat resistance and flexibility are particularly excellent, and the refractive index is high. A more preferred alkenyl aromatic hydrocarbon copolymer composition is 3 to 55 mol%, and a particularly preferred alkenyl aromatic hydrocarbon copolymer composition is 5 to 50 mol%. The copolymer composition of such an alkenyl aromatic hydrocarbon is
^{It is} easily determined from a ¹ H-NMR spectrum and a ¹³ C-NMR spectrum.

The copolymer used in the present invention is preferably an amorphous copolymer having no crystallinity from the viewpoint of transparency. The absence of crystallinity can be confirmed by not showing a melting point in a melting curve measured by a differential scanning calorimeter (DSC).

As such a copolymer, a copolymer having a high Tg can be obtained, and a shrink film which is less likely to contract naturally can be obtained. In order to obtain a copolymer having a high Tg, for example, the copolymer composition of a cyclic olefin and / or an alkenyl aromatic hydrocarbon is increased. From the viewpoint of natural shrinkage, the copolymer of the present invention has a Tg of less than 30 ° C.
Are preferred, and those having no Tg below 35 ° C are preferred. When the temperature at the time of shrinking the shrink film of the present invention is about 100 ° C, the copolymer preferably has a Tg of 30 to 95 ° C.
And more preferably has a Tg of 35 to 85.
° C copolymer. When the temperature at the time of shrinking is about 80 ° C, the copolymer is preferably a copolymer having a Tg of 30 to 75 ° C, more preferably 35 to 75 ° C.
~ 65 ° C copolymer. Here, Tg is measured by a differential scanning calorimeter (DSC).

The specific gravity of the copolymer used in the present invention is usually in the range of 0.9 to 1.1 g / cm ³ , and that of the polyethylene terephthalate resin (1.33 to 1.52 g / c 3).
m ³ ).

The copolymer is preferably as follows:
Bringing (A) into contact with (B) and / or (C)
Ethylene in the presence of the addition polymerization catalyst
And / or an α-olefin, a cyclic olefin,
Obtained by copolymerizing alkenyl aromatic hydrocarbons.
Copolymer. (A): represented by the following general formula [I], [II] or [III]
Transition metal 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 of the Elements, and J is the period of the element
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 independent of each other,
Hydrogen atom, halogen atom, alkyl group, aralkyl group,
Aryl group, substituted silyl group, alkoxy group, aralkyl
Represents an oxy group, an aryloxy group or a disubstituted amino group
You. X^ThreeRepresents an atom belonging to Group 16 of the periodic table of the elements.
R¹, R^Two, R^Three, R^Four, R^FiveAnd R⁶Is optionally bonded to a ring
May be formed. In general formula [II] or [III]
Two M¹, A, J, Cp¹, X¹, X^Two, X^Three, R¹, R
^Two, R ^Three, R^Four, R^FiveAnd R⁶Are the same even if
It may be 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
Yes, all E¹, All E^TwoAnd all E^ThreeIs the same
May be different. Z is a hydrogen atom or halo
Gen atom, all Z are the same or different
May be. a is a number satisfying 0 <a ≦ 3, b is 2 or more
And c represents an integer of 1 or more. (C): one or more selected from the following (C1) to (C3)
Boron compound of (C1) General formula BQ¹Q^TwoQ^ThreeBoron compound represented by
Object, (C2) general formula G⁺(BQ¹Q^TwoQ^ThreeQ^Four)^-Represented by
Boron compound, (C3) general formula (LH)⁺(BQ¹
Q^TwoQ^ThreeQ^Four)^-(Where B is a trivalent boron atom and Q is
¹~ Q^FourIs a halogen atom, hydrocarbon group, halogenated hydrocarbon
Group, substituted silyl group, alkoxy group or disubstituted amino
Groups, which may be the same or different
No. G⁺Is an inorganic or organic cation, and L is neutral
A Lewis base, (LH)⁺Is Bronsted acid
is there. Hereinafter, the production method will be described in more detail.

(A) Transition metal complex In the general formula [I], [II] or [III], the transition metal atom represented by M ¹ is a periodic table of elements (IUPAC).
Inorganic chemical nomenclature, revised edition 1989), it indicates a transition metal element of Group 4 and includes, for example, a titanium atom, a zirconium atom, and a hafnium atom. Preferably it is a titanium atom or a zirconium atom.

The atom of Group 16 of the periodic table of the element represented by A in the general formulas [I], [II] or [III] includes, for example, an oxygen atom, a sulfur atom, a selenium atom and the like. Is an oxygen atom.

In the general formulas [I], [II] and [III], examples of atoms belonging to Group 14 of the periodic table of the element represented by J include a carbon atom, a silicon atom, and a germanium atom. Is a carbon atom or a silicon atom, particularly preferably a carbon 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 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
-Propylfluorenyl group,? ⁵ -di-n-propylfluorenyl group,? ⁵ -isopropylfluorenyl group,? 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 alkenyl group, eta ^{5-n-hexyl-fluorenyl} group, eta ^{5-n-octyl-fluorenyl} group, eta ^{5-n-decyl-fluorenyl} group, eta ^{5-n-dodecyl-fluorenyl} group, eta 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 - tetramethylcyclopentadienyl group, eta ⁵ - fluorenyl group - indenyl group or eta ^5,.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
Examples of the halogen atom for ⁵ or R ⁶ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Preferably it is a chlorine atom or a bromine atom, 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 carbon atom
To 20 alkyl groups, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a neopentyl group, an isopentyl group and a -Hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, n-eicosyl group and the like, more preferably methyl group, ethyl group, isopropyl group, tert-butyl group or Isopentyl group.

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 by 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 group, iodomethyl group, diiodomethyl group,
Triiodomethyl, fluoroethyl, difluoroethyl, trifluoroethyl, tetrafluoroethyl, pentafluoroethyl, chloroethyl, dichloroethyl, trichloroethyl, tetrachloroethyl, pentachloroethyl, bromoethyl , Dibromoethyl group, tribromoethyl group, tetrabromoethyl group, pentabromoethyl group, perfluoropropyl group,
Perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluorooctyl, perfluorododecyl, perfluoropentadecyl, perfluoroeicosyl, perchloropropyl, perchlorobutyl, perchloropentyl Group, perchlorohexyl group, perchlorooctyl group, perchlorododecyl group,
Perchloropentadecyl group, perchloroeicosyl group,
Perbromopropyl, 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 is preferably an aralkyl group having 7 to 20 carbon atoms, for example, benzyl, (2-methylphenyl) methyl, (3-methylphenyl) methyl, (4-methylphenyl) Methyl group,
(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
The aryl group for ⁵ or R ⁶ has 6 carbon atoms.
~ 20 aryl groups are preferable, for example, a phenyl group,
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, te
rt-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-
Examples include an octylphenyl group, an n-decylphenyl group, an n-dodecylphenyl group, an n-tetradecylphenyl group, a naphthyl group, an anthracenyl group and the like, and more preferably a phenyl group. Each of these aryl groups is
Partially substituted with 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 aralkyloxy group such as a benzyloxy group. You may.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
The substituted silyl group in ⁵ or R ⁶ is a silyl group substituted with a hydrocarbon group, wherein the hydrocarbon group includes
For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert
-Alkyl groups having 1 to 10 carbon atoms such as -butyl group, isobutyl group, n-pentyl group, n-hexyl group and cyclohexyl group, and aryl groups such as 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. All of these substituted silyl groups have a hydrocarbon group such as a fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as an iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or a benzyloxy group. May be partially substituted with an aralkyloxy group such as a group.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
^{As the} alkoxy group for ⁵ or R ^6, an alkoxy group having 1 to 20 carbon atoms is preferable. For example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a 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 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
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. A (methylphenyl) methoxy group, a (2,3-dimethylphenyl) methoxy group, a (2,4-dimethylphenyl) methoxy group, a (2,5-dimethylphenyl) methoxy group,
(2,6-dimethylphenyl) methoxy group, (3,4-
(Dimethylphenyl) methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl)
A 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 (octylphenyl) methoxy, (n-decylphenyl) methoxy, (n-tetradecylphenyl) methoxy, naphthylmethoxy, and anthracenylmethoxy, and more preferably benzyloxy. 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, a phenoxy group, a 2-methylphenoxy group, a 3-methylphenoxy group, a 4-methylphenoxy group, a 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
-A trimethylphenoxy group, a 2,4,5-trimethylphenoxy group, a 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, etc. Is raised. All of these aryloxy groups are 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 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 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, an isopropyl group, -Alkyl group having 1 to 10 carbon atoms such as -butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group and cyclohexyl group, and 6 to 6 carbon atoms such as 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-ter
t-butylamino group, di-isobutylamino group, ter
t-butylisopropylamino group, di-n-hexylamino group, di-n-octylamino group, di-n-decylamino group, diphenylamino group, bistrimethylsilylamino group, 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 bonded to form a ring.

Preferably, R ¹ is an alkyl, aralkyl, aryl or substituted silyl group. Preferably, X ¹ and X ² are each independently a halogen atom, an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a disubstituted amino group, and more preferably a halogen atom or an alkoxy group.

The atom of Group 16 of the periodic table of the element represented by X ³ in the general formula [II] or [III] includes, for example, an oxygen atom, a sulfur atom, a selenium atom and the like, preferably an oxygen atom It is.

Examples of the transition metal complex represented by the general formula [I] include methylene (cyclopentadienyl) (3,
5-dimethyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert
-Butyl-2-phenoxy) titanium dichloride,
Methylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) ) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl)
(3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2)
-Phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Methylene (methylcyclopentadienyl)
(3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl)
(3-tert-butyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3 -Phenyl-2-phenoxy)
Titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyldimethylsilyl-
5-methyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyl- 5-methoxy-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyl-5-
Chloro-2-phenoxy) titanium dichloride,

Methylene (tert-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride , Methylene (tert
-Butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (tert) -Butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-
Methyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3
-Trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadiene) Enil) (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-ter
t-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-trimethylsilyl-5-
Methyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-t
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 (trimethylsilyl) Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) ) (3-tert-butyldimethylsilyl-5-)
Methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3
-Trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3
-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-tert-butyl- 5-methyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-ter
t-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl-5- Methoxy-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Isopropylidene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene ( Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) ) (3-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 Riden (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 (te
rt-butylcyclopentadienyl) (3-tert-
Butyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (t
tert-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-t
tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3- tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-trimethylsilyl-5-
Methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl)
(3-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-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene ( Cyclopentadienyl) (3-tert-butyl-5-methyl-2
-Phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-phenyl-2-
Phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-trimethylsilyl-5-methyl- 2-
Phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl)
(3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (methylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenyl Methylene (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-te
rt-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-butyldimethylsilyl-
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 (ter
t-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride , Diphenylmethylene (tetramethylcyclopentadienyl)
(3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-phenyl-2
-Phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-t
tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopenta Dienyl) (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-te
rt-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-t
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-tert-butyl- 5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-te
rt-butyl-5-chloro-2-phenoxy) titanium dichloride and the like, compounds obtained by changing titanium to zirconium or hafnium, dibromide to dichloride, diiodide, bis (dimethylamide), bis (diethylamide), -A compound changed to n-butoxide or diisopropoxide,
(Cyclopentadienyl) is replaced by (dimethylcyclopentadienyl), (trimethylcyclopentadienyl), (n
-Butylcyclopentadienyl), (tert-butyldimethylsilylcyclopentadienyl) or a compound modified to (indenyl), (3,5-dimethyl-2-
Phenoxy) to (2-phenoxy), (3-methyl-2)
-Phenoxy), (3,5-di-tert-butyl-2)
-Phenoxy), (3-phenyl-5-methyl-2-phenoxy), (3-tert-butyldimethylsilyl-
2-phenoxy) or (3-trimethylsilyl-2)
A transition metal complex wherein J in the general formula [I] is a carbon atom, such as a compound changed to -phenoxy);

Dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-methyl-
2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-dimethyl-
2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-
Butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl)
(3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl)
(5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert
-Butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-diisopentyl-2-phenoxy) titanium dichloride,

Dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium dichloride,
Dimethylsilylene (methylcyclopentadienyl) (3
-Methyl-2-phenoxy) titanium dichloride,
Dimethylsilylene (methylcyclopentadienyl)
(3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert -Butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy)
Titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (5-methyl-3-trimethylsilyl- 2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl- 5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3,5-diisopentyl-2-phenoxy) titanium dichloride,

Dimethylsilylene (n-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (n- Butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (n- Butylcyclopentadienyl) (3-tert-
Butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopenta Dienyl) (5-methyl-3
-Phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadiene) Enyl) (5-
Methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopenta Dienyl)
(3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (n-
Butylcyclopentadienyl) (3,5-diisopentyl-2-phenoxy) titanium dichloride,

Dimethylsilylene (tert-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butyl Butylcyclopentadienyl) (3,5-dimethyl-2-
Phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-t
tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2)
-Phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3
5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (5-methyl-3-phenyl-
2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3
-Tert-butyldimethylsilyl-5-methyl-2-
Phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyl- 5
-Methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-
Phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3,5
-Diisopentyl-2-phenoxy) titanium dichloride,

Dimethylsilylene (tetramethylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopenta Dienyl) (3,5-dimethyl-2-phenoxy)
Titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-
2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-t
tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopenta Dienyl) (5-
Methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopenta Dienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert
-Butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadiene) Enil) (3,
5-diisopentyl-2-phenoxy) titanium dichloride,

Dimethylsilylene (trimethylsilylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-
Phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-t
tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methyl-2)
-Phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3,
5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (5-methyl-3-phenyl-
2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3
-Tert-butyldimethylsilyl-5-methyl-2-
Phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5)
-Methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-chloro-2-
Phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3,5
-Diisopentyl-2-phenoxy) titanium dichloride,

Dimethylsilylene (indenyl) (2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl)
(3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-te
rt-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-
Butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3,5-
Di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-te
rt-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (5-methyl-3-trimethylsilyl-2-
Phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl-5
-Chloro-2-phenoxy) titanium dichloride,
Dimethylsilylene (indenyl) (3,5-diisopentyl-2-phenoxy) titanium dichloride,

Dimethylsilylene (fluorenyl) (2-
Phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3
-Tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-t
tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl)
(3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl Dimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert
-Butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3
-Tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3,5-diisopentyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl)) (1-naphthoxy) -2-yl) titanium dichloride and the like, and (cyclopentadienyl) of these compounds is replaced with (dimethylcyclopentadienyl), (trimethylcyclopentadienyl), (ethylcyclopentadienyl), (n-propylcyclo). Pentadienyl), (isopropylcyclopentadienyl),
(Sec-butylcyclopentadienyl), (isobutylcyclopentadienyl), (tert-butyldimethylsilylcyclopentadienyl), (phenylcyclopentadienyl), (methylindenyl), or (phenylindenyl) (2-phenoxy) is replaced with (3-phenyl-2-phenoxy), (3-trimethylsilyl-2-phenoxy), or (3-tert)
-Butyldimethylsilyl-2-phenoxy), a compound in which dimethylsilylene is changed to diethylsilylene, diphenylsilylene, or dimethoxysilylene, a compound in which titanium is changed to zirconium or hafnium, dichloride is dibromide, diiodide, bis ( J in the general formula [I] such as a compound changed to dimethylamide), bis (diethylamide), di-n-butoxide or diisopropoxide is an atom belonging to Group 14 of the periodic table of an element other than a carbon atom. Transition metal complexes.

The transition metal complex represented by the general formula [I] can be produced, for example, by the method described in WO 97/03992. In addition, the above general formula [II] or [II
The transition metal complex represented by the formula [I] is produced by reacting the transition metal complex represented by the general formula [I] with 0.5 times or 1 times the amount of water, respectively. At that time, a method of directly reacting the required amount of water with the transition metal complex represented by the general formula [I], the method represented by the general formula [I] in a solvent such as a hydrocarbon containing the required amount of water. The transition metal complex represented by the above general formula [I] is introduced into a solvent such as a dried hydrocarbon, and an inert gas or the like containing a necessary amount of water is allowed to flow. A method or the like can be adopted.

(B) Aluminum Compound The aluminum compound (B) used in the present invention is at least one aluminum compound selected from the following (B1) to (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 and dihexylaluminum chloride; alkylaluminum dichlorides such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride and 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.

[0075] 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 to 40 and c is 1 to 40.

The above aluminoxane is 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) in a suitable organic solvent (benzene, 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.

(C) Boron Compound In the present invention, the boron compound (C) includes (C1)
A boron compound represented by the general formula BQ ¹ Q ² Q ³ , (C
2) a boron compound represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^— , (C3) a general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q)
^{4) -} one or more boron compounds selected from boron compound represented by is used.

In the boron compound (C1) represented by the general formula BQ ¹ Q ² Q ³ , B is a trivalent boron atom, and Q ^{1 to} Q ³ are a halogen atom, a hydrocarbon group or a halogen atom. A substituted hydrocarbon group, a substituted silyl group, an alkoxy group or a disubstituted amino group, which may be the same or different. Q ^{1 to} Q ³ are preferably a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms, 1 to 20
A halogenated hydrocarbon group containing 1 to 20 carbon atoms, a substituted silyl group containing 1 to 20 carbon atoms, an alkoxy group containing 1 to 20 carbon atoms or an amino group containing 2 to 20 carbon atoms. Q ^{1 to} Q ³ are more preferably a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms, or 1
Halogenated hydrocarbon groups containing up to 20 carbon atoms. More preferably, Q ^{1 to} Q ⁴ are each a fluorinated hydrocarbon group having 1 to 20 carbon atoms containing at least one fluorine atom, and particularly preferably, Q ^{1 to} Q ⁴ each have at least one fluorine atom. 6 to 2 carbon atoms including atoms
0 is a fluorinated aryl 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 Q ^{1 to} Q ³ in the above (C1).
Is the same as

[0081] 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, and 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,
Triphenylmethyltetrakis (3,5-bistrifluoromethylphenyl) borate and the like can be mentioned, and most preferred is triphenylmethyltetrakis (pentafluorophenyl) borate.

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

The compound represented by the general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^— is a Bronsted acid (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,
Tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, tri (dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate and the like can be mentioned, and most preferably, tri (n-butyl) ammonium tetrakis (pentafluoro) Phenyl) borate or N, N-
Dimethylanilinium tetrakis (pentafluorophenyl) borate.

[Polymerization] The above-mentioned addition polymerization catalyst comprises the transition metal complex (A), the above (B) and / or the above (C)
And a catalyst for addition polymerization obtained by contacting When using the addition polymerization catalyst obtained by bringing (A) and (B) into contact, (B) is preferably the cyclic aluminoxane (B2) and / or the linear aluminoxane (B3) described above. . Other preferred embodiments of the addition polymerization catalyst include an addition polymerization catalyst obtained by bringing the above (A), (B) and (C) into contact with each other. (B
1) Easy to use.

The amount of each component used is usually such that the molar ratio of (B) / (A) is from 0.1 to 10,000, preferably from 5 to 200.
It is desirable to use each component so that the molar ratio of 0, (C) / (A) is 0.01 to 100, preferably 0.5 to 10. 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 μm
ol / g, (C) is usually 0.01 to 500 μmol /
g, more preferably 0.05 to 200 μmol /
g, more preferably 0.05 to 100 μmol / g
It is desirable to use each component so as to fall within the range.

As such an addition polymerization catalyst, S
A particulate carrier including an inorganic carrier such as iO ₂ and Al ₂ O _{3 and} an organic polymer carrier such as a polymer such as ethylene and styrene may be used in combination.

The polymerization method is not particularly limited. For example, any method such as a batch-type or continuous-type gas phase polymerization method, a bulk polymerization method, a solution polymerization method using an appropriate solvent, or a slurry polymerization method may be used. Can be used. When a solvent is used, various solvents can be used provided that they do not deactivate the catalyst. Examples of such a solvent include hydrocarbons such as benzene, toluene, pentane, hexane, heptane, and cyclohexane; And halogenated hydrocarbon groups such as styrene chloride.

The polymerization temperature is not particularly limited, and is generally -100 to 250 ° C, preferably -50 to 200 ° C. The pressure is not limited, but is generally 100 kg / cm ² or less, preferably 2 kg / cm ² to 50 kg / cm ² . In addition, a chain transfer agent such as hydrogen can be added to adjust the molecular weight of the polymer.

The copolymer used in the present invention may be used as a resin composition with another thermoplastic resin. As such a resin composition, a resin composition using 5 to 99 wt% of the copolymer and 95 to 1 wt% of another thermoplastic resin is preferable.

The other thermoplastic resin is not particularly limited, and examples thereof include a polystyrene resin, a polybutadiene resin, a polyethylene resin, a polypropylene resin, a methacryl resin, an ABS resin, a polyphenylene ether resin, and a polycarbonate resin. Can be Preferably, it is a polystyrene resin, a polyethylene resin, a polyphenylene ether resin, or a polycarbonate resin, and particularly preferably, a polystyrene resin.

The copolymer or resin composition of the present invention may contain, if necessary, a lubricant, an antistatic agent, an antioxidant, a heat stabilizer, an ultraviolet absorber, a flame retardant, an antibacterial agent, a pigment, a dye, an antiblocking agent. And inorganic fillers such as talc, mica, barium sulfate, calcium carbonate, and alumina silicate; and plasticizers such as mineral oil.

The shrink film of the present invention is used for labels such as glass containers and plastic bottles or for overlap packaging such as trays, and is obtained by stretching a sheet or film obtained by a conventional method in at least one direction. . As a specific production method, it can be obtained by subjecting a sheet or film obtained by a T-die extruder or the like to uniaxial or biaxial stretching using a tenter machine or a tubular stretching machine. Generally, it is usually 60
The bottle provided with the label is passed through a heating furnace having an atmosphere temperature of about 120 ° C. to be shrink-wrapped.

The shrink film of the present invention can be used in the form of a multilayer film of two or more layers with another material. At that time, the film can be manufactured by various known laminating methods such as a co-extrusion method, a dry lamination method, a sandwich lamination method, and an extrusion lamination method. Other materials include cellophane, nylon, polyethylene terephthalate (PET), polypropylene, ethylene-vinyl alcohol copolymer (EVO)
H), known materials such as various adhesive resins can be used.

The shrink film of the present invention can be subjected to known post-treatments such as corona discharge treatment, plasma treatment, ozone treatment, ultraviolet irradiation, and electron beam irradiation.

[0097]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the scope of the present invention is not limited by these Examples. In addition, the property of the polymer in an Example was measured by the following method.

The glass transition point was measured using a DSC (SSC-5200 manufactured by Seiko Instruments Inc.) under the following conditions, and determined from the inflection point. Heating 20 ° C to 200 ° C (20 ° C / min) 10 minutes hold Cooling 200 ° C to -50 ° C (20 ° C / min) Hold 10 minutes Measurement -50 ° C to 300 ° C (20 ° C / min)

Copolymer composition (moles of norbornene, styrene, etc. in the monomers constituting the copolymer)
%) And the like are represented by ¹³ C-NMR (JNM-
EX270) was determined by analysis. Measurement solvent orthodichlorobenzene Measurement temperature 135 ° C

The solid viscoelasticity of the polymer was measured using a spectrometer (measurement / analysis device, Reostation SDM5600H manufactured by Seiko Denshi Kogyo Co., Ltd., tension module DMS200).
Was obtained under the following conditions. Specimen 20mm × 3.0mm × 0.3mm press sheet Frequency 5Hz Heating rate 2 ° C / min Displacement amplitude 10μm

The heat shrinkage was measured by heating a circular stretched film having a diameter of 65 mm in a silicone oil bath for 5 seconds, and measuring the diameter of the film before and after heating (the average value of the minor axis and the major axis).
Was measured, and the shrinkage was calculated from the following equation. Shrinkage (%) = [(diameter before shrinkage) − (diameter after shrinkage)] ÷ (diameter before shrinkage) × 100

Example 1 400 m purged with argon
In a 1 l autoclave, 114 ml of styrene and 2-
40ml of toluene solution of norbornene (5mol / l)
After charging, ethylene was charged at 0.8 MPa. The isopropylidene (cyclopentadienyl) (3-
15.5 mg of tert-butyl-5-methyl-2-phenoxy) titanium dichloride was added to 15 m of dehydrated toluene.
1 and a toluene solution of triisobutylaluminum [Tosoh Akzo Co., Ltd., 1 mol / l]
After mixing 2.0 ml in advance and charging, a solution prepared by dissolving 96.1 mg of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate in 38 ml of dehydrated toluene was added, and the reaction solution was stirred at 60 ° C. for 100 minutes. . Thereafter, the reaction solution was poured into a mixture of 5 ml of hydrochloric acid (12N) and 1000 ml of acetone, and the precipitated white solid was collected by filtration. The solid was washed with acetone and dried under reduced pressure to obtain 33.5 g of a polymer. The glass transition point of this polymer is 81 ° C., and the copolymer composition of norbornene is 20 mol.
%, And the copolymer composition of styrene was 39 mol%. FIG. 1 shows a DSC chart of the polymer. FIG. 2 shows the solid viscoelasticity data. According to FIG. 2, the storage elastic modulus (E ') has no inflection point at room temperature or less and is unlikely to be naturally contracted, and E' has a sharp decrease near Tg and has less unevenness during shrinking. Can be heard.

A press sheet of about 0.6 mm thickness of the polymer was prepared by hot press molding at 200 ° C. The prepared press sheet was very transparent. Cut out the press sheet into 80 mm x 80 mm square,
After the fixed sample was sufficiently preheated at 115 ° C. by a desktop biaxial stretching machine manufactured by Toyo Seiki Co., Ltd., the stretching temperature was increased to 23 ° C.
C., a stretching speed of 1.8 m / min, and simultaneous biaxial stretching of 3 times long and 3 times wide were performed to obtain a stretched film having a thickness of about 65 μm. The stretchability was good. As a result of measuring the heat shrinkage, 120
Shrinkage rate at 52 ° C, 49% at 110 ° C, 100 ° C
At 32 ° C., 22% at 90 ° C., and less than 2% at 80 ° C. In this method of measuring the heat shrinkage, the shrinkage when returning to the press sheet before stretching completely due to shrinkage is 67%.
Thus, the polymer was found to exhibit a high shrinkage.

[0104]

As described above in detail, according to the present invention, there is provided a shrink film made of a non-chlorine resin having a low-temperature shrink property, a high shrinkage rate and a small natural shrinkage. A transparent film can be obtained as the shrink film of the present invention, and its industrial utility value is extremely large.

[Brief description of the drawings]

FIG. 1 is a DSC measurement result (DSC chart) of the polymer obtained in Example 1.

FIG. 2 shows the measurement results of the solid viscoelasticity of the polymer obtained in Example 1.

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Claims (4)

[Claims] 1. A shrink film comprising a copolymer obtained by copolymerizing ethylene and / or an α-olefin, a cyclic olefin, and an alkenyl aromatic hydrocarbon. 2. The shrink film according to claim 1, wherein the copolymer is a copolymer having a copolymer composition of an alkenyl aromatic hydrocarbon which is more than half of a copolymer composition of a cyclic olefin. 3. The copolymer has a glass transition point (Tg) of 30.
The shrink film according to claim 1, wherein the shrink film is a copolymer having a temperature of up to 95 ° C. 4. 4. A copolymer comprising the following (A), (B) and
And / or addition obtained by contacting with (C)
In the presence of a polymerization catalyst, ethylene and / or α-ole
Fins, cyclic olefins, and alkenyl aromatic hydrocarbons
Is a copolymer obtained by copolymerizing
The shrink according to any one of claims 1 to 3, wherein
Ink film. (A): represented by the following general formula [I], [II] or [III]
Transition metal 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 of the Elements, and J is the period of the element
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 independent of each other,
Hydrogen atom, halogen atom, alkyl group, aralkyl group,
Aryl group, substituted silyl group, alkoxy group, aralkyl
Represents an oxy group, an aryloxy group or a disubstituted amino group
You. X^ThreeRepresents an atom belonging to Group 16 of the periodic table of the elements.
R¹, R^Two, R^Three, R^Four, R^FiveAnd R⁶Is optionally bonded to a ring
May be formed. In general formula [II] or [III]
Two M¹, A, J, Cp¹, X¹, X^Two, X^Three, R¹, R
^Two, R ^Three, R^Four, R^FiveAnd R⁶Are the same even if
It may be different. (B): at least one selected from the following (B1) to (B3)
Aluminum compound (B1) of the general formula E¹ _aAlZ_3-a
(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
Yes, all E¹, All E^TwoAnd all E^ThreeIs the same
May be different. Z is a hydrogen atom or halo
Gen atom, all Z are the same or different
May be. a is a number satisfying 0 <a ≦ 3, b is 2 or more
And c represents an integer of 1 or more. (C): one or more selected from the following (C1) to (C3)
Boron compound of (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
Groups, which may be the same or different
No. G⁺Is an inorganic or organic cation, and L is neutral
A Lewis base, (LH)⁺Is Bronsted acid
is there. )