JP2000052510A - Laminate, film or sheet and stretch film for packaging - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate extremely excellent in transparency, flexibility, deformation restoring properties, impact resistance and heat resistance and film, a sheet and a stretch film for packaging comprising the laminate. SOLUTION: A laminate is constituted of a layer comprising an olefinic resin compsn. (c), which contains 97-5 wt.% of a crystalline olefinic resin (a) and 3-95 wt.% of an amorphous olefinic copolymer (b) obtained by polymerizing at least two kinds of monomer components selected from 3-20C α-olefin and ethylene in the presence of a polymerizing catalyst using a complex of a group IV-VI transition metal having at least one group having a cyclopentadiene type anion skeleton, and an ethylenic resin (d) and a film, a sheet and a stretch film for packaging are composed of this laminate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a laminate, a film or sheet comprising the laminate, and a stretch film for packaging comprising the laminate. More specifically, in a stretch film for packaging, in which the food is placed directly or on a plastic tray or the like and stretch-wrapped, the stretch film for packaging has good transparency, flexibility, deformation recovery property, impact strength and heat resistance. It relates to a suitable laminate.

[0002]

2. Description of the Related Art Conventionally, polyvinyl chloride resin is mainly used as a stretch film for packaging in which foods such as fruits and vegetables, fresh fish, fresh meat, and prepared foods are placed directly or on a plastic tray or the like and stretch-wrapped with a film. ing. In recent years, from the viewpoint of safety and health, development of an ethylene-based resin such as low-density polyethylene or ethylene-vinyl acetate copolymer instead of the conventional vinyl chloride resin has been actively conducted.

However, when low-density polyethylene or the like is used alone, the desired uniformity of film elongation, film rigidity and the like cannot be satisfied at the same time.
In addition, the ethylene-vinyl acetate copolymer film can solve the above-described problems of the low-density polyethylene film by appropriately selecting the content and the molecular weight of the repeating unit derived from vinyl acetate. There has been a problem that when the food is packaged with sharp corners or foods having sharp portions, the food is torn and torn.

For this reason, for example, Japanese Patent Publication No. 2-12187
Patent Document 1: Japanese Patent Publication No. 2-18983 and Japanese Patent Publication No. 2-18983, stretch packaging for the purpose of simultaneously satisfying the required performance by laminating an ethylene-vinyl acetate copolymer on an ethylene-α-olefin copolymer Films have been proposed. However, although the film is excellent in mechanical strength, there is a problem that holes are formed in the film when the film at the bottom of the tray is heat-sealed due to lack of heat resistance.

Japanese Patent Application Laid-Open No. 5-147174 discloses propylene, ethylene and α-C 4-8.
A layer mainly composed of an ethylene-vinyl acetate copolymer is laminated on both sides of a layer mainly composed of a propylene-α-olefin random copolymer resin obtained by polymerizing at least one type of α-olefin selected from olefins. Stretch packaging films have been proposed. However,
Although this film is excellent in heat resistance, there is a problem that flexibility, deformation recovery and impact resistance are inferior.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a laminate, a film or a sheet, and a stretch film for packaging, which are extremely excellent in transparency, flexibility, deformation recovery, impact strength and heat resistance. It is in.

[0007]

Means for Solving the Problems The present inventors have developed a film or sheet having excellent transparency, flexibility, deformation recovery, impact strength and heat resistance, as well as conventional performance, and a stretch film for packaging. As a result of intensive research, a layer made of an olefin resin composition containing an amorphous olefin copolymer and a crystalline olefin resin obtained using a specific metallocene catalyst, and a layer made of an ethylene resin , A film or sheet comprising the laminate, and a packaging stretch film comprising the laminate achieve the object of the present invention, thereby completing the present invention.

That is, the present invention relates to a transition metal complex of Group 4 to Group 6 of the Periodic Table having 97 to 5% by weight of a crystalline olefin resin (a) and at least one group having a cyclopentadiene type anion skeleton. A non-crystalline olefin copolymer (b) obtained by polymerizing at least two kinds of monomer components selected from an α-olefin having 3 to 20 carbon atoms and ethylene in the presence of a polymerization catalyst using A) a laminate comprising a layer composed of an olefin-based resin composition (c) containing 3 to 95% by weight and a layer composed of an ethylene-based resin (d).
The present invention also provides a film or a sheet comprising the above-mentioned laminate. Further, the present invention is a stretch film for packaging, comprising the above laminate. Hereinafter, the present invention will be described in detail.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The amorphous olefin copolymer (b) used in the present invention is a transition metal complex of Groups 4 to 6 of the periodic table having at least one group having a cyclopentadiene-type anion skeleton. In the presence of a polymerization catalyst using
It is an amorphous olefin-based copolymer obtained by polymerizing at least two kinds of monomer components selected from an α-olefin having 3 to 20 carbon atoms and ethylene.
In the amorphous olefin-based copolymer (b) used in the present invention, the propylene unit and / or the α-olefin unit side chain preferably has an atactic structure. When the orientation of the side chain of the propylene unit and / or the α-olefin unit having 4 to 20 carbon atoms has an atactic structure is defined as the case where the orientation of the side chain of the propylene chain in the copolymer is an atactic structure. When the orientation of the side chain of the α-olefin chain having 4 to 20 carbon atoms is an atactic structure,
The case where the orientation of the side chain of the propylene / α-olefin composite chain having 4 to 20 carbon atoms in the copolymer has an atactic structure is shown.

Amorphous olefin copolymer used in the present invention
The fact that the body (b) has an atactic structure means that, for example,
Metal complexes used for the polymerization of crystalline olefin copolymers
When homopolypropylene is polymerized using
Homopolypropylene ¹³From CNMR spectrum
Mm, mr and r of propylene methyl carbon which can be determined
r [mm], [mr], and
Using [rr], the F (1) value defined by the following equation is 40 or less.
Upper 60 or less, preferably 43 or more and 57 or less, more preferably
The structure is between 45 and 55
Wear. F (1) = 100 × [mr] / ([mm] + [mr] + [r
r])

[0011] From the above background, the amorphous olefin copolymer (b) used in the present invention also has propylene methyl carbon, α-olefin branched methylene carbon, α-olefin branched terminal methyl carbon. Mm, m, etc.
When the value corresponding to F (1) obtained using the intensities of the signals assigned to r and rr is within the above range, it can be confirmed that the structure is an atactic structure. When the olefin-based copolymer does not have an atactic structure, the resulting laminate may have poor flexibility and deformation recovery.
The laminate of the present invention is excellent in flexibility, deformation recovery, and transparency because the amorphous olefin copolymer used in the present invention has an arrangement of propylene and / or α-olefin side chains in the copolymer. It is presumed to be due to the atactic structure. The assignment of mm, mr, and rr signals of propylene methyl carbon, branched methylene carbon of α-olefin, branched terminal methyl carbon of α-olefin, etc.
For example, T. Asakura, Macromolecu
les, Vol. 24, p. 2334 (1991), and Kinokuniya Publishing Co., Ltd., New Handbook of Polymer Analysis (1995) can be referred to.

For the above reasons, the amorphous olefin-based copolymer (b) is a non-stereospecific member of Groups 4 to 6 of the periodic table having at least one group having a cyclopentadiene-type anion skeleton. Amorphous olefin obtained by polymerizing at least two kinds of monomer components selected from an α-olefin having 3 to 20 carbon atoms and ethylene in the presence of a polymerization catalyst using a transition metal complex having a structure It is preferably a system copolymer. The transition metal complex having a non-stereospecific structure includes a Cs chirality and a Cn chirality (n
Does not have an integer of 1 or more). Further, the amorphous olefin-based copolymer (b) has a carbon number of 3 to 20 in the presence of an olefin polymerization catalyst comprising the following (A) and the following (B) and / or (C): Can be optimally produced by copolymerizing at least two kinds of monomer components selected from the group consisting of α-olefins and ethylene.

Compound (A): represented by the following general formula [I]
Transition metal complex(Where M¹Is the transition metal atom of Group 4 of the Periodic Table of the Elements
A represents an atom of Group 16 of the Periodic Table of the Elements,
J represents an atom belonging to Group 14 of the periodic table of the elements. Cp¹Is
A group having a cyclopentadiene-type anion skeleton is shown.
X¹, X^Two, R¹, R ^Two, R^Three, R^Four, R^FiveAnd R⁶Are each
Independently, hydrogen atom, halogen atom, alkyl group, arral
A kill group, an aryl group, a substituted silyl group, an alkoxy group,
Aralkyloxy group, aryloxy group or disubstituted amino
Represents a group. R¹, R^Two, R^Three, R^Four, R ^FiveAnd R⁶Is optional
They may combine to form a ring. )

(B): selected from the following (B1) to (B3)
One or more aluminum compounds (B1)¹ _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. )

[0015] (C): the following (C1) ~ one of boron compound (C3) (C1) a boron compound represented by the general formula ^{BQ 1 Q 2 Q 3, (} C2) the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- , a boron compound represented by the formula (C3): (LH) ⁺ (BQ ¹
Q ² Q ³ Q ^{4) -} In the boron compound represented by (wherein, B is a boron atom in the trivalent valence state, Q ¹ to Q ⁴ are a halogen atom, a hydrocarbon group, halogenated hydrocarbon group, A substituted silyl group, an alkoxy group or a disubstituted amino group, which may be the same or different, G ⁺ is an inorganic or organic cation, L is a neutral Lewis base, (L
-H) ⁺ is a Bronsted acid. )

Hereinafter, the production methods (A) to (C) will be described in more detail. (A) Transition metal complex In the general formula [I], the transition metal atom represented by M ¹ represents a transition metal element belonging to Group 4 of the Periodic Table of the Elements (IUPAC revised edition of inorganic chemical nomenclature 1989), For example, a titanium atom, a zirconium atom, a hafnium atom and the like can be mentioned. 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 the general formula [I] include an oxygen atom, a sulfur atom and a selenium atom, and are preferably an oxygen atom.

In the general formula [I], 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.
Preferably it is a carbon atom or a silicon atom.

The substituent Cp¹Cyclopenta shown as
Examples of the group having a diene-type anion skeleton include η
^Five-(Substituted) cyclopentadienyl group, η^Five-(Replacement) a
Ndenyl group, η^Five-(Substituted) fluorenyl group, etc.
You. Specifically, η^Five-Cyclopentadienyl group, η^Five−
Methylcyclopentadienyl group, η^Five-Dimethylcyclo
Pentadienyl group, η^Five-Trimethylcyclopentadie
Nil group, η^FiveA tetramethylcyclopentadienyl group,
η^Five-Ethylcyclopentadienyl group, η^Five-N-propi
Rucyclopentadienyl group, η^Five-Isopropylcyclo
Pentadienyl group, η^Five-N-butylcyclopentadie
Nil group, η^Five-Sec-butylcyclopentadienyl
Group, η^Five-Tert-butylcyclopentadienyl group,
η^Five-N-pentylcyclopentadienyl group, η^Five-Neo
Pentylcyclopentadienyl group, η^Five-N-hexyl
Cyclopentadienyl group, η^Five-N-octylcyclo}
Antadienyl group, η^Five-Phenylcyclopentadienyl
Group, η^Five-Naphthylcyclopentadienyl group, η^Five-Bird
Methylsilylcyclopentadienyl group, η^Five− Triet
Lucylylcyclopentadienyl group, η^Five-Tert-b
Tyldimethylsilylcyclopentadienyl group, η^Five-B
Ndenyl group, η^Five-Methylindenyl group, η^Five-Dimethyl
Indenyl group, η^Five-Ethylindenyl group, η^Five-N-pu
Ropylindenyl group, η^Five-Isopropylindenyl
Group, η^Five-N-butylindenyl group, η^Five-Sec-buchi
Ruindenyl group, η^Five-Tert-butylindenyl
Group, η^Five-N-pentylindenyl group, η^Five-Neo pliers
Ruindenyl group, η^Five-N-hexylindenyl group, η^Five
-N-octylindenyl group, η^Five-N-decylindene
Nil group, η^Five-Phenylindenyl group, η^Five-Methylfe
Nylindenyl group, η^Five-Naphthylindenyl group, η^Five−
Trimethylsilylindenyl group, η^Five-Triethylsili
Ruindenyl group, η^Five-Tert-butyldimethylsilyl
Ruindenyl group, η^FiveA tetrahydroindenyl group, η^Five
A fluorenyl group, η^Five-Methylfluorenyl group, η^Five−
Dimethylfluorenyl group, η^Five-Ethylfluorenyl
Group, η^Five-Diethylfluorenyl group, η^Five-N-propyl
Fluorenyl group, η^Five-Di-n-propylfluorenyl
Group, η ^Five-Isopropylfluorenyl group, η^Five-Diisop
Ropylfluorenyl group, η^Five-N-butylfluorenyl
Group, η^Five-Sec-butylfluorenyl group, η^Five−ter
t-butylfluorenyl group, η^Five-Di-n-butyl full
Olenyl group, η^Five-Di-sec-butylfluorenyl
Group, η^Five-Di-tert-butylfluorenyl group, η^Five−
n-pentylfluorenyl group, η^Five-Neopentyl full
Olenyl group, η^Five-N-hexylfluorenyl group, η^Five−
n-octylfluorenyl group, η^Five-N-decylfluoro
Renyl group, η^Five-N-dodecylfluorenyl group, η^Five−
Phenylfluorenyl group, η^Five-Di-phenylfluorenyl
Group, η^Five-Methylphenylfluorenyl group, η^Five-Nuff
Tylfluorenyl group, η^Five-Trimethylsilyl fluore
Nil group, η^Five-Bis-trimethylsilylfluorenyl
Group, η^FiveA triethylsilylfluorenyl group, η^Five−te
rt-butyldimethylsilylfluorenyl group and the like.
And preferably η^Five-Cyclopentadienyl group, η^Five−
Methylcyclopentadienyl group, η^Five-Tert-buty
Rucyclopentadienyl group, η^Five-Tetramethylcyclo
Pentadienyl group, η^Five-An indenyl group, or η^Five−full
It is an olenyl group.

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, an iodine atom and the like, 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.
20 alkyl groups are preferred, 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 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 group, perbromobutyl group, perbromopentyl group, perbromohexyl group, Bromooctyl, perbromododecyl, perbromopentadecyl, perbromoeicosyl and the like can be mentioned.

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, (3,5
-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-
Examples thereof include a (dodecylphenyl) methyl group, a (n-tetradecylphenyl) methyl group, a naphthylmethyl group, and an anthracenylmethyl group, and a benzyl group is more preferable.

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; It may be partially substituted with an aralkyloxy group or the like.

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 include halogen atoms such as fluorine, chlorine, bromine and iodine, alkoxy such as methoxy and ethoxy, aryloxy such as phenoxy and benzyloxy. It may be partially substituted with an aralkyloxy group or the like.

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.

In these substituted silyl groups, the hydrocarbon group 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, or an aryloxy group such as a phenoxy group. Alternatively, it may be partially substituted with an aralkyloxy group such as a benzyloxy group.

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.
To 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 include halogen atoms such as fluorine, chlorine, bromine and iodine, alkoxy such as methoxy and ethoxy, aryloxy such as phenoxy and benzyloxy. It may be partially substituted with an aralkyloxy group or the like.

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.

Each of these aralkyloxy 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 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 Groups, n-tetradecylphenoxy group, naphthoxy group, anthracenoxy group and the like.

Each of these aryloxy groups is 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 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 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.

The substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R
⁶ may be optionally bonded to form a ring.

Preferably, R ¹ is an alkyl group, an aralkyl group, an aryl group or a 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.

Examples of the transition metal complex (A) include methylene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride and 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 obtained by changing n-butoxide or diisopropoxide, (dimethylcyclopentadienyl), (trimethylcyclopentadienyl), (n-butylcyclopentadienyl), (tert) -Butyldimethylsilylcyclopentadienyl) or a compound changed to (indenyl), (3,5-dimethyl-2-phenoxy) is converted to (2-phenoxy), (3-methyl-2-phenoxy), (3, 5-di-tert-butyl-2-phenoxy), (3- Eniru-5-methyl-2-phenoxy), (3-tert- butyldimethylsilyl-2-
A transition metal complex wherein J in the general formula [I] is a carbon atom, such as a compound changed to (phenoxy) or (3-trimethylsilyl-2-phenoxy);

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, dimethyi Silyl (cyclopentadienyl) (3-tert-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-tert-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-t
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 (te
rt-butylcyclopentadienyl) (3-tert-
Butyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (te
rt-butylcyclopentadienyl) (3,5-di-t
tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (ter
t-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2- Phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-
Phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-te
rt-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 (tetramethylcyclopenta Dienyl) (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 Chloride, dimethylsilyl (tetramethylcyclopentadienyl) (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 (trimethylsilylcyclopentadienyl) (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-t
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-tert-butyl-5-methoxy-2-
Phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-te
rt-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-tert-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-te
rt-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-te
rt-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) ), (Ter
t-butyldimethylsilylcyclopentadienyl),
(Phenylcyclopentadienyl), (methylindenyl), or a compound changed to (phenylindenyl),
A compound in which (2-phenoxy) is changed to (3-phenyl 2-phenoxy), (3-trimethylsilyl-2-phenoxy), or (3-tert-butyldimethylsilyl-2-phenoxy), dimethylsilyl is diethylsilyl, Compound in which diphenylsilyl or dimethoxysilyl is changed, compound in which titanium is changed to zirconium or hafnium, dichloride is dibromide, diiodide, bis (dimethylamide), bis (diethylamide), di-n-butoxide, or diisopropoxide And a transition metal complex in which J in the general formula [I] is an atom belonging to Group 14 of the periodic table of an element other than a carbon atom.

The transition metal complex represented by the general formula [I] can be synthesized, for example, by the method described in JP-A-9-87313.

(B) Aluminum Compound As the aluminum compound (B), the following (B1) to (B1)
One or more aluminum compounds selected from (B3). (B1) Organoaluminum compound represented by the general formula E ¹ _a AlZ _3-a (B2) Cyclic aluminoxane having a structure represented by the general formula ｛-Al (E ² ) -O-｝ _b (B3) General 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 trialkylaluminum, more preferably, triethylaluminum or triisobutylaluminum.

[0071] 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 containing crystallization water (for example, copper sulfate hydrate or the like) can be exemplified.

(C) Boron Compound The boron compound (C) includes (C1) a compound of the general formula BQ ¹
A boron compound represented by Q ² Q ³ , (C2) a general formula G ⁺
A boron compound represented by (BQ ¹ Q ² Q ³ Q ⁴ ) ^— , (C
3) General formula ^{(L-H) + (BQ} 1 Q 2 Q 3 Q 4) - one of boron compound represented by can be used.

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

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

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

[0077] 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 examples of these combinations 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.
^{(BQ 1 Q 2 Q 3 Q} 4) - as are mentioned those similar to the aforementioned.

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.

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

The method for producing the amorphous olefin-based copolymer (b) includes, for example, aliphatic hydrocarbons such as butane, pentane, hexane, heptane and octane; aromatic hydrocarbons such as benzene and toluene; Solvent polymerization using a halogenated hydrocarbon such as dichloride as a solvent, 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 used and the reaction apparatus, 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.

As the amorphous olefin copolymer (b), amorphous, for example, ethylene-propylene copolymer,
Ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-1-octene Binary copolymers such as copolymers, ethylene-propylene-1-butene copolymer, ethylene-propylene-1-hexene copolymer, ethylene-propylene-1-octene copolymer, ethylene-1-butene- 1-hexene copolymer, ethylene-1-
Butene-1-octene copolymer, propylene-1-butene-1-hexene copolymer, propylene-1-butene-
Terpolymers such as terpolymers such as 1-octene copolymers, ethylene-propylene-1-butene-1-hexene copolymers and ethylene-propylene-1-butene-1-octene copolymers Is mentioned.

The amorphous olefin copolymer (b) used in the present invention, when measured by a differential scanning calorimeter (DSC), has a peak of 1 J / g or more based on the melting of the crystal and 1 J / g based on the crystallization. Amorphous olefin-based copolymers having no peaks / g or more are preferred. When such a peak is present, the resulting laminate may have poor flexibility and deformation recovery. 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 raising and constant temperature processes.

The amorphous olefin copolymer (b) used in the present invention has a molar content% of a repeating unit derived from propylene (hereinafter referred to as “propylene unit”).
P defined by the following formula using (x) and the molar content% (y) of a repeating unit derived from an α-olefin having 4 to 20 carbon atoms (hereinafter referred to as “α-olefin unit”).
An ethylene-propylene-α-olefin copolymer having a value of 0.3 or more, preferably 0.4 or more, more preferably 0.5 or more is preferable. P = y / (100-x) When the ratio is out of the range, the flexibility, deformation recovery property, and transparency of the obtained laminate may be poor.

The amorphous olefin copolymer (b) used in the present invention has an intrinsic viscosity [η] at 135 ° C. with a tetralin solvent of preferably 0.3 to 10 dl / g, more preferably 0.5 to 7 dl. / G, more preferably 0.7 to 5
dl / g. If the intrinsic viscosity is too low, the resulting laminate may have poor deformation recovery properties. On the other hand, if the intrinsic viscosity is too high, the resulting laminate may have poor flexibility. The intrinsic viscosity [η] is measured at 135 ° C. in tetralin using an Ubbelohde viscometer. 300mg sample
Was dissolved in 100 ml of xylene to prepare a 3 mg / ml solution. Further, the solution is diluted to １ ／, 、, and １ ／, and each is measured in a constant temperature water bath at 70 ° C. (± 0.1 ° C.). The measurement is repeated three times at each concentration, and the obtained values are averaged and used.

The amorphous olefin copolymer (b) used in the present invention has a molecular weight distribution (Mw / Mn) measured by gel permeation chromatography (GPC).
Is preferably 5 or less, more preferably 4 or less, and most preferably 3 or less. If the molecular weight distribution is too broad,
The resulting laminate may have poor impact resistance. Molecular weight distribution is determined by gel permeation chromatography (GPC)
(For example, 150C / GPC apparatus manufactured by Waters). The elution temperature is 140 ° C, and the column used is
For example, Sodex Packed Co manufactured by Showa Denko KK
lumnA-80M, the molecular weight standard substance is polystyrene (for example, manufactured by Tosoh Corporation, molecular weight 68-8,400,0).
00) is used. The obtained polystyrene-equivalent weight average molecular weight (Mw), number average molecular weight (Mn), and the ratio (M
w / Mn) is defined as the molecular weight distribution. Measurement sample is about 5m
g of polymer is dissolved in 5 ml of o-dichlorobenzene to a concentration of about 1 mg / ml. 4 of the obtained sample solution
00 μl was injected, and the elution solvent flow rate was 1.0
ml / min and detect with a refractive index detector.

The α-olefin of the amorphous olefin copolymer (b) used in the present invention has 3 to 20 carbon atoms, and preferably, the α-olefin is propylene or 1-carbon.
Butene, 1-hexene, 1-octene or 1-decene. The amorphous olefin copolymer (b) used in the present invention, when the laminate is particularly required to have cold resistance,
The glass transition temperature (Tg) measured by a differential scanning calorimeter (DSC) is preferably −10 ° C. or lower, more preferably −20 ° C. or lower, further preferably −25 ° C. or lower, and most preferably −30 ° C. or lower. . The differential scanning calorimeter uses, for example, DSC220C manufactured by Seiko Denshi Kogyo Co., Ltd., and measures both the temperature raising and constant temperature processes at a rate of 10 ° C./min.

Crystalline olefin resin used in the present invention
(a) is not particularly limited as long as it is a crystalline olefin resin. For example, high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene, propylene resin, poly-4-methylpentene -1 and the like. Crystalline olefin resin (a)
Has a melting point of preferably 60 ° C. or higher, more preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and particularly preferably 120 ° C. or higher, in order to maintain the heat resistance of the laminate. Further, the crystalline olefin-based resin (a) is preferably a crystalline olefin-based resin containing, as a main component, a repeating unit derived from an olefin having 3 or more carbon atoms in order to maintain the heat resistance of the laminate. For example, a propylene-based resin, poly-4-methylpentene-1, and the like, and more preferably a crystalline propylene-based resin are exemplified.

The olefin resin composition (c) used in the present invention contains 97 to 5% by weight, preferably 90 to 20% by weight, more preferably 7 to 5% by weight of the crystalline olefin resin (a).
0 to 30% by weight and amorphous olefin copolymer (b)
The resin composition contains 3 to 95% by weight, preferably 10 to 80% by weight, and more preferably 30 to 70% by weight. If the amount of the crystalline olefin-based resin (a) exceeds 97% by weight, it is difficult to obtain the effects of exhibiting flexibility and deformation recovery properties.

The olefin resin composition (c) preferably has a melt flow rate (MFR) of 1 to 80 g / min.
More preferably, it is 10 to 30 g / min. The MFR value is
It is measured by the method specified in JIS-K-7203.

Further, the olefin resin composition (c) includes:
Various additives as required, fillers, such as antioxidants,
An antifogging agent, an antistatic agent, a nucleating agent, an ultraviolet absorber and the like can be included. Further, within the range not hindering the present invention, for example, a recycled resin generated from a trimming loss or the like, or another resin may be blended and used for the purpose of improving cutability in automatic packaging. Specific examples of other resins include rosin resins, polyterpene resins, synthetic petroleum resins, chroman resins, phenolic resins, xylene resins, styrene resins, isoprene resins, and cyclic olefin resins. At least one that can be used.

Examples of the rosin-based resin include natural rosin, polymerized rosin, partially and completely hydrogenated rosin, esterified products of these rosins such as glycerin ester, pentaerythritol ester, ethylene glycol ester, methyl ester, and the like. Rosin derivatives obtained by converting, fumaric, or lime, or a combination thereof as appropriate. Examples of the polyterpene resin include α
-Pinene, β-pinene, homopolymers or copolymers of cyclic terpenes such as dipentene, and α-pinene-phenol resin which is a copolymer of the above various terpenes with phenol and a phenolic compound such as bisphenol; Examples include terpene-phenol resins such as dipentene-phenol resins and terpene-bisphenol resins, and aromatic modified terpene resins which are copolymers of the above various terpenes and aromatic monomers.

[0097] The synthetic petroleum resins, for example, C ₅ fraction naphtha cracked oil, C ₆ -C ₁₁ fraction, and homopolymers or copolymers of other olefinic fraction and by hydrogenated products of these polymers Certain aliphatic petroleum resins, aromatic petroleum resins, alicyclic petroleum resins, aliphatic-alicyclic copolymer resins, and the like. Further, copolymers of the above-mentioned various naphtha-decomposed oils with the above-mentioned various terpenes and copolymerized petroleum resins which are hydrogenated products thereof can also be mentioned. The C ₅ fraction here naphtha cracked oil, isoprene, cyclopentadiene, 1,3
Pentadiene, 2-methyl-1-butene, 2-methyl-
Methylbutenes such as 2-butene, 1-pentene, 2-
Pentenes such as pentene, dicyclopentadiene and the like are preferable, and methyl styrenes such as indene, styrene, o-, m-, p-vinyltoluene, α-, β-methylstyrene as the C ₆ -C ₁₁ fraction; Methylindene,
Ethylindene, vinylxylene, propenylbenzene and the like are preferable, and other olefin-based fractions are preferably butene, hexene, heptene, octene, butadiene, octadiene and the like.

Examples of the chroman resin include a copolymer resin of chroman and indene. Examples of the phenolic resin include an alkylphenol resin, an alkylphenol-acetylene resin obtained by condensation of an alkylphenol and acetylene, and modified products thereof. Here, as these phenolic resins,
Either a novolak resin obtained by converting phenol to methylol with an acid catalyst or a resol type resin obtained by converting phenol to methylol with an alkali catalyst may be used. As the xylene-based resin, for example, xylene-containing m-xylene and formaldehyde
A formaldehyde resin, a modified resin obtained by adding and reacting a third component to the formaldehyde resin, and the like are mentioned. Examples of the styrene resin include a low molecular weight product of polystyrene, a copolymer resin of α-methylstyrene and vinyltoluene, and a copolymer resin of styrene, acrylonitrile and indene. The isoprene-based resin, for example, C ₁₀ alicyclic compound and C ₁₀ chain compound copolymerized with a copolymer resin obtained a dimer product of isoprene.

As the cyclic olefin resin, for example, a cyclic olefin polymer, a cyclic olefin and a compound having 2 to 2 carbon atoms can be used.
20 copolymers with an α-olefin. Specific examples of the cyclic olefin include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, 1-
Methyl norbornene, 7-methyl norbornene, 5,
5,6-trimethylnorbornene, 5-phenylnorbornene, 5-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, 5,8,8
a-octahydronaphthalene, 2-cyclohexyl-
1,4,5,8-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene, 2,3-dichloro-1,4,5,8-dimethano-1,2,3,4,4
a, 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, cyclopentene, 3-methylcyclopentene, 4-methylcyclopentene, 3,4-dimethylcyclopentene, 3,5-dimethylcyclopentene, 3- Chlorocyclopentene, cyclohexene, 3-methylcyclohexene, 4-methylcyclohexene, 3,4-dimethylcyclohexene, 3-
Chlorocyclohexene, cycloheptene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 3-vinylcyclohexene, 4-vinylcyclohexene, 5-
Vinyl norbornene, 5-allyl norbornene, 5,6
-Diethylidene-2-norbornene, dicyclopentadiene, dimethylcyclopentadiene, 2,5-norbornadiene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 5-ethyl-1, Examples include 3-cyclohexadiene, 1,3-cycloheptadiene, 1,3-cyclooctadiene, and the like. Examples of the α-olefin having 2 to 20 carbon atoms include linear and branched α-olefins. Specifically, the linear α-olefin includes ethylene,
Propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene , 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nanodecene, 1-eicosene and the like, and branched α-
Examples of olefins include 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene,
Ethyl-1-hexene, 2,2,4-trimethyl-1-
Penten and the like are exemplified.

Further, a bleed inhibitor having a low molecular weight component may be blended and used, for example, for the purpose of preventing blocking of the laminate, within a range not to hinder the present invention. As a bleeding inhibitor for low molecular weight components, it forms a molecular aggregate by hydrogen bonding formed by itself, forms a three-dimensional structure, and incorporates low molecular weight substances such as oil and liquid paraffin inside. , Which can maintain a certain shape. Specific examples include 12-hydroxystearic acid, N-acylamino acid amine salts, N-acylamino acid amides, and N-acylamino acid esters. Among these, N-acylamino acid amine salt, N-
For acylamino acid amides and N-acylamino acid esters, α, β, ω-amine acids are used, and in particular, glycine, α or β alanine, valine, serine, phenylalanine, 3,4-dioxyphenylalanine, cysteine, methionine, β-Aminocaproic acid, lysine ornithine, arginine, glutamic acid, aspartic acid and the like are preferred. The N-acyl group may be a linear or branched saturated or unsaturated aliphatic acyl group or aromatic acyl group having 1 to 30 carbon atoms, and particularly, a caproyl group, a lauroyl group, a myristoyl group, a stearoyl group, Are preferred. As the alcohol used for the esterification, a linear or branched saturated or unsaturated aliphatic alcohol having 1 to 30 carbon atoms is used, and particularly, octyl alcohol, lauryl alcohol, cetyl alcohol, isostearyl alcohol, stearyl alcohol and the like are preferable. .
Further, alicyclic alcohols such as cyclohexanol,
Benzyl alcohol is used as well. In addition, ammonium used for amidation and amine salt and carbon number 1 to 1
60 linear and branched saturated and unsaturated primary and secondary amines, mono- and dialcoholamines are used. As the amine salt, a tertiary amine and a trialcoholamine are also used, and butylamine, octylamine, laurylamine, stearylamine and the like are particularly preferable. In addition to the aliphatic amine, an alicyclic amine or an aromatic amine may be used. Further, the olefin resin composition (c) may be crosslinked, if necessary, by a conventionally known method such as sulfur crosslinking, peroxide crosslinking, metal ion crosslinking or silane crosslinking.

Examples of the ethylene resin (d) used in the present invention include low-density polyethylene, medium-density polyethylene, high-density polyethylene, ethylene-propylene copolymer, ethylene-butene-1 copolymer, and ethylene-4-methyl. Pentene-1 copolymer, ethylene-hexene-1 copolymer, ethylene-octene-1 copolymer, ethylene-
Ethylene-α-olefin copolymers such as decene-1 copolymers, and further, from ethylene and unsaturated compounds such as conjugated dienes or non-conjugated dienes or copolymer components such as acrylic acid, methacrylic acid and vinyl acetate. Ethylene copolymers. Further, these polymers may be those modified with an acid, for example, polymers modified by grafting with an α, β-unsaturated carboxylic acid, an alicyclic carboxylic acid, or a derivative thereof. As the α-olefin, an α-olefin having 3 to 10 carbon atoms is preferable.

The ethylene resin (d) used in the present invention is:
Low-density polyethylene, ethylene-α-olefin copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer and ethylene-methacrylate copolymer at least one ethylene resin selected from preferable. Examples of the ethylene-α-olefin copolymer include ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene-4-methylpentene-1 copolymer, ethylene-hexene-1 copolymer, and ethylene-propylene copolymer. A copolymer of ethylene and an α-olefin having 3 to 10 carbon atoms, such as an octene-1 copolymer and an ethylene-decene-1 copolymer, is preferred.

The ethylene resin (d) used in the present invention has a content of a repeating unit derived from ethylene (hereinafter referred to as "ethylene unit") of 70 to 95.
% By weight, the content of a repeating unit derived from vinyl acetate (hereinafter referred to as "vinyl acetate unit") is 30 to 5
% By weight of ethylene-vinyl acetate copolymer is particularly preferred.

The method for producing the ethylene-vinyl acetate copolymer is not particularly limited, and includes a known method, for example, a method of copolymerizing ethylene, vinyl acetate and a radical initiator.

The ethylene resin (d) used in the present invention contains various additives and fillers, if necessary, such as an antioxidant, an antifogging agent, an antistatic agent, a nucleating agent, and an ultraviolet absorber. Can be made. Furthermore, other resins may be blended and used within a range not to hinder the present invention. For example, a recycled resin generated from a trimming loss or the like, or a petroleum resin or a hydrogenated product thereof for the purpose of improving self-adhesion can be blended.

The laminate, film or sheet of the present invention,
The thickness of each layer constituting the stretch film for packaging is not particularly limited and can be arbitrarily selected. Usually, each layer of the laminate and sheet is about 2 to 10
It is formed in a range of 00 μm. Usually, each layer of the film and the stretch film for packaging is about 2 to 100 μm.
Formed in the range. Furthermore, the thickness ratio of both surface layers to the total thickness is not particularly limited, and can be arbitrarily selected. Usually, the thickness of both surface layers is set to 20% of the total thickness.
９０90%.

The method for producing the laminate of the present invention is not particularly limited, and may be a known method, for example, a method of forming a film by a usual method such as an inflation method or a T-die method, followed by heat bonding. For example, it is possible to form a film using a two-type two-layer or two-type three-layer co-extrusion type blown film forming machine or a T-die film forming machine.

When the laminate of the present invention requires shrinkage, it is preferable to stretch at least uniaxially after film formation. Stretching can be uniaxial or biaxial. In the case of uniaxial stretching, for example, a commonly used roll stretching method is preferable. In the case of biaxial stretching, for example, a sequential stretching method in which biaxial stretching is performed after uniaxial stretching may be used, or a simultaneous biaxial stretching method such as tubular stretching may be used.

The film or sheet of the present invention comprises the above-mentioned laminate. Moreover, the stretch film for packaging of the present invention is composed of the laminate.

[0110]

As described in detail above, according to the present invention,
A laminate excellent in transparency, flexibility, deformation recovery, impact strength and heat resistance can be provided. Further, the laminate of the present invention has excellent physical properties as described above, and thus is suitable for a stretch film for packaging. Further, the film or sheet of the present invention is soft and can be applied to various uses instead of the soft vinyl chloride film or sheet.

[0111]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but these examples do not limit the present invention in any way.

First, methods for measuring physical properties in the following Examples and Comparative Examples will be described. (1) Maximum melting peak temperature (Tm) Using a differential scanning calorimeter (DSC manufactured by PerkinElmer), 10 mg of a sample was previously melted at 220 ° C. for 5 minutes in a nitrogen atmosphere, and then the temperature was lowered at a rate of 5 ° C./min. The temperature was lowered to 40 ° C. Thereafter, the temperature was raised at 5 ° C./min, and the peak temperature of the maximum peak of the obtained melting endothermic curve was defined as the maximum melting peak temperature (Tm). The melting point of indium (In) measured at a heating rate of 5 ° C./min using this measuring instrument was 15
6.6 ° C. In addition, the ethylene-α-olefin copolymer had a thickness of about 0.1 produced by hot pressing.
Approximately 10 mg of specimen cut out from a 5 mm sheet is DS
Place in a sample pan for C measurement, preheat at 150 ° C for 5 minutes, cool down to 40 ° C at 1 ° C / min, hold for 5 minutes, then heat up to 150 ° C at a rate of 10 ° C / min to obtain a thermogram Was. The ratio of the amount of heat of fusion at the melting peak to the total amount of heat is a value obtained by dividing the area of the endothermic curve having the above-mentioned melting peak by the total endothermic area. (2) Melt flow rate (MFR) In accordance with JIS K7210, measurement was performed for ethylene-based polymer under Condition 4 of Table 1 and for propylene-based polymer under Condition 14 of Table 1. (3) Content of vinyl acetate unit The measurement was performed according to JIS K6730. (4) Transparency (haze) Measurement was performed according to ASTM D1003.

(5) Flexibility (1% SM) A 120 mm × 20 mm strip test piece having a length in the take-up direction (MD) and the direction perpendicular to the take-up direction (TD) of the laminate was placed between the grips. The film was pulled at a tension of 60 mm and a pulling speed of 5 mm / min, and the stress at 1% elongation was measured. (6) Deformation recovery (deformation recovery) A circular laminate sample 1 having a diameter of 44.45 mm is fixed to a laminate fixing jig 2, and the tip of the laminate has a radius of 6.35 mm at the center.
The pin 3 having a hemispherical shape of
It was pushed into a predetermined depth 5 at a speed of mm / min, immediately pulled up at the same speed, and it was measured whether or not the push completely disappeared within 30 seconds. The maximum indentation depth 5 at which the pressure disappears completely after the pressing was defined as the degree of deformation recovery. FIG. 1 is a plan view of an apparatus for measuring the degree of deformation recovery. (7) Impact strength Using a film impact tester manufactured by Toyo Seiki Seisaku-sho, and making the penetrating tip of the pendulum into a semicircular shape of 15 mmφ,
The area of the effective test piece was made into a circle of 50 mmφ, and the impact piercing strength of the laminate at 0 ° C. was measured. (8) Heat resistance (heat resistance temperature) The laminate is placed in contact with a hot plate for heat sealing of a commercially available hand-type tray packaging machine (polywrapper manufactured by ARC Co., Ltd.) for 2 seconds, and the laminate does not have holes. The hot plate temperature was measured and set as the heat resistant temperature.

Reference Example 1 [I] Preparation of catalyst for polymerization (1) Preparation of transition metal complex (dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride) Synthesis

(A) Synthesis of 1-bromo-3-tert-butyl-5-methyl-2-phenol In a 500 ml four-necked flask equipped with a stirrer under a nitrogen atmosphere, 2-tert-butyl-4-methyl was added. 20.1 g (123 mmol) of phenol was dissolved 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
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 In a 100 ml four-necked flask equipped with a stirrer under a nitrogen atmosphere, 1 -Bromo-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. 84% yield
Met.

(D) Synthesis of (3-tert-butyl-2-methoxy-5-methylphenyl) dimethyl (tetramethylcyclopentadienyl) silane (3-tert-butyl-2-silane synthesized in the above (c)) (Methoxy-5-methylphenyl) chlorodimethylsilane (5.24 g) and tetrahydrofuran (50 ml) were added to a solution of tetramethylcyclopentadienyl lithium (2.73 g) at -35 ° C. for 2 hours. The mixture was heated to room temperature, and 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. 97% yield
Met.

(E) Synthesis of dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (3-tert-butyl-2) synthesized in (d) above. -Methoxy-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 to give orange columnar crystals of dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-butyl-5 3.46 g of methyl-2-phenoxy) titanium dichloride 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

[II] Amorphous olefin copolymer (b)
Polymerization of ethylene, propylene, and 1-butene were continuously performed using a 100 L SUS polymerization vessel equipped with stirring blades. That is, hexane was continuously supplied as a polymerization solvent at a rate of 83 L / hour from the lower part of the polymerization vessel. On the other hand, the polymerization liquid was continuously withdrawn from the upper part of the polymerization vessel such that the polymerization liquid in the polymerization vessel became 100 L. Dimethylsilyl (tetramethylcyclopentadienyl) (3-ter
t-butyl-5-methyl-2-phenoxy) titanium dichloride, triphenylmethyltetrakis (pentafluorophenyl) borate and triisobutylaluminum at a rate of 0.018 g / hr, 0.276 g / hr and 1.584 g / hr, respectively. To continuously feed into the polymerization vessel from the lower part of the polymerization vessel. The molecular weight was adjusted with hydrogen. The copolymerization reaction was carried out at 50 ° C. by circulating cooling water through a jacket attached to the outside of 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,
Ethylene-propylene-1-butene copolymer (hereinafter, referred to as
"EPBR") was obtained at a rate of 6.12 kg / hr. Table 1 shows the conditions and results.

Reference Example 2 An experiment was carried out under the same conditions as in Reference Example 1, except that the amounts of the catalyst and hydrogen used were changed. Table 1 shows the conditions and results. In addition, the measuring method of the content of the propylene unit and the 1-butene unit in the EPBR obtained in Reference Example 1 and Reference Example 2 is as follows.

(A) Preparation of Calibration Curve A mixture of propylene homopolymer and ethylene-1-butene copolymer at various mixing ratios was hot-pressed to form a film having a thickness of 0.05 mm. Using an infrared spectrometer, a peak derived from propylene units (wave number 1150 cm
^-1 ) and a peak derived from 1-butene unit (wave number 770 cm ^-1 )
The propylene and 1-butene unit content in the mixture were plotted against the absorbance. A regression line was determined from these plots and used as a calibration curve. In addition, the mixture of the propylene homopolymer and the ethylene-1-butene copolymer was dissolved in toluene, methanol was added, and the obtained precipitate was dried and used.

(B) Measurement of Propylene Unit and 1-Butene Unit Content The olefin copolymer was hot-pressed to form a 0.05 mm-thick film, and then the propylene copolymer was obtained using an infrared spectrometer. The absorbance between the peak and the peak derived from the 1-butene unit was determined, and the content of the propylene unit and the 1-butene unit in the olefin copolymer was calculated from the calibration curve obtained by the above method.

Reference Example 3 Using a 100 L SUS polymerization vessel equipped with stirring blades, propylene and 1-butene were continuously copolymerized. That is, 83 L of hexane was used as a polymerization solvent from the lower part of the polymerization vessel.
/ Hour continuously. 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. 0.068 g of dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, triphenylmethyltetrakis (pentafluorophenyl) borate and triisobutylaluminum were each used as a catalyst. H, 2.067 g / h, 3.9
It was continuously fed from the lower part of the polymerization vessel into the polymerization vessel at a rate of 64 g / hour. The molecular weight was adjusted with hydrogen. The copolymerization reaction was carried out at 50 ° C. by circulating cooling water through a jacket attached to the outside of 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 take out the copolymer.
It dried under reduced pressure at ℃ day and night. Through the above operations, a propylene-1-butene copolymer (hereinafter, referred to as “PBR”) was obtained at a rate of 5.60 kg / hour. Table 1 shows the conditions and results. The method for measuring the 1-butene content in the obtained PBR is as follows. (A) Preparation of calibration curve Mixtures of propylene and 1-butene homopolymer at various mixing ratios were each hot-pressed and formed into a film having a thickness of 0.05 mm. Using an infrared spectrometer, the absorbance ratio between the peak derived from propylene units (wave number 1150 cm ^-1 ) and the peak derived from 1-butene units (wave number 770 cm ^-1 ) was determined, and this absorbance ratio was compared with the 1-butene unit in the mixture. Was plotted. A regression line was determined from these plots and used as a calibration curve. In addition, propylene and 1
-A mixture of butene homopolymers was obtained by dissolving both in toluene, adding methanol, and drying the obtained precipitate.

(B) Measurement of the content of 1-butene unit The propylene-1-butene copolymer was hot-pressed to form a 0.05 mm-thick film, and then the propylene unit was measured using an infrared spectrometer. The absorbance ratio between the derived peak and the 1-butene unit-derived peak was determined, and the content of the 1-butene unit in the propylene-1-butene copolymer was calculated from the calibration curve obtained by the above method. Differential scanning calorimeter (DS
C) The measurement was carried out using a differential scanning calorimeter (DS manufactured by Seiko Instruments Inc.)
C220C) for both the temperature raising and the constant temperature process.
The measurement was performed at a rate of 0 ° C./min.

The intrinsic viscosity [η] was measured in tetralin at 135 ° C. using an Ubbelohde viscometer. The sample was prepared by dissolving 300 mg in 100 ml xylene and adding 3 mg / m
1 solution was prepared. Further, the solution was １ ／, ３,
After diluting to 1/5, each was measured in a thermostat at 135 ° C. (± 0.1 ° C.). The measurement was repeated three times at each concentration, and the obtained values were averaged and used.

The molecular weight distribution was measured by gel permeation chromatography (GPC) (Waters, 150C /
GPC device). The elution temperature was 140 ° C, and the column used was Sodex Packed C manufactured by Showa Denko KK
As the molecular weight standard substance, polystyrene (manufactured by Tosoh Corporation, molecular weight: 68-8, 400,000) was used. The obtained polystyrene equivalent weight average molecular weight (M
w), number average molecular weight (Mn), and this ratio (Mw / M
n) was taken as the molecular weight distribution. As a measurement sample, about 5 mg of a polymer was dissolved in 5 ml of o-dichlorobenzene, and about 1 mg was dissolved.
/ Ml. 400μ of the obtained sample solution
1 was injected. Elution solvent flow rate is 1.0ml
/ Min and detected with a refractive index detector.

[0128]

[Table 1]

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

Example 1 Preparation of Surface Layer Resin Composition Ethylene-vinyl acetate copolymer (Evatate H2081, M manufactured by Sumitomo Chemical Co., Ltd.)
FR (190 ° C.) = 2 g / 10 min, content of vinyl acetate unit = 15.8% by weight) 98% by weight, antifogging agent (STO-405 manufactured by Marubishi Yuka Kogyo KK) 2% by weight The resin composition prepared by melt-kneading with a mixer was used as the resin composition constituting the surface layer. [Preparation of Intermediate Layer Resin Composition] Propylene-ethylene random copolymer (Noblen S131 manufactured by Sumitomo Chemical Co., Ltd., Tm = 135 ° C.,
MFR (230 ° C.) = 1.0 g / 10 min, propylene unit content = 95% by weight, ethylene unit content = 5% by weight) 49% by weight, and Reference Example 1 as an amorphous olefin-based copolymer Resin obtained by melt-kneading 49% by weight of the EPBR obtained in the above and 2% by weight of an anti-fogging agent (STO-405 manufactured by Marubishi Yuka Kogyo Co., Ltd.) using a Banbury mixer and then melt-kneading with a single screw extruder. The composition was used as a resin composition constituting an intermediate layer. [Production of Laminate] The obtained ethylene-vinyl acetate copolymer composition was used as a surface layer, and the resin composition containing a propylene-ethylene random copolymer and the EPBR obtained in Reference Example 1 was used as an intermediate layer. The two-layer three-layer laminate is supplied to a three-layer inflation film processing machine manufactured by Placo Co., Ltd., and processed at a die temperature of 200 ° C. and a blow ratio of 4.5, so that the thickness composition ratio is surface layer / intermediate layer / 38% / 24 in order of surface layer
% / 38%, a laminate having a total thickness of 13 μm was produced. Table 2 shows various characteristic values of the obtained laminate.

Example 2 EP obtained as a non-crystalline olefin resin in Reference Example 2
Except for using BR, in the same manner as in Example 1, the thickness composition ratio was 38% / 24% / 38 in the order of surface layer / intermediate layer / surface layer.
%, A laminate having a total thickness of 13 μm was produced. Table 2 shows various characteristic values of the obtained laminate.

Example 3 PB obtained in Reference Example 3 as an amorphous olefin resin
Except for using R, the thickness composition ratio was 38% / 24% / 38 in the order of surface layer / intermediate layer / surface layer in the same manner as in Example 1.
%, A laminate having a total thickness of 13 μm was produced. Table 2 shows various characteristic values of the obtained laminate.

Comparative Example 1 [Production of Laminate] The same procedure as in Example 1 was carried out except that the intermediate layer resin composition was changed to the propylene-ethylene random copolymer used in Example 1, and the thickness composition ratio was changed to the surface layer / A laminate having an intermediate layer / surface layer order of 38% / 24% / 38% and a total thickness of 13 μm was produced. Table 2 shows various characteristic values of the obtained laminate.

[0134]

[Table 2]

[Brief description of the drawings]

FIG. 1 is a plan view of an apparatus for measuring a degree of deformation recovery.

[Explanation of Symbols] 1 ... laminate sample 2 ... laminate fixture jig, 3 ...
・ Pin, 4 ・ ・ ・ Load cell, 5 ・ ・ ・ Pushing depth

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hidetake Hozumi 5-1, Anesaki Beach, Ichihara City, Chiba Prefecture Sumitomo Chemical Co., Ltd. F term (reference) 3E086 AD05 AD17 BA04 BA15 BB22 BB85 BB90 CA17 CA18 CA22 CA25 4F100 AK03A AK04 AK04B AK04C AK04J AK07 AK07A AK07B AK62B AK66B AK66J AK68C AK80B AL01B AL03 BA03 BA07 BA10A BA10C CA10 EH23 EJ37 GB15 JA06B JA07B JA11A JA12B JJ03 JK10 JK13 JN01 YY00B

Claims (17)

[Claims] 1. A method comprising using 97 to 5% by weight of a crystalline olefin resin (a) and a transition metal complex of Groups 4 to 6 of the periodic table having at least one group having a cyclopentadiene-type anion skeleton. In the presence of a polymerization catalyst, carbon number 3 to
An olefin-based resin composition containing 3 to 95% by weight of an amorphous olefin-based copolymer (b) obtained by polymerizing at least two kinds of monomer components selected from α-olefins and ethylene (b). A laminate comprising a layer composed of c) and a layer composed of an ethylene-based resin (d). 2. The amorphous olefin-based copolymer (b), as measured by a differential scanning calorimeter (DSC), has a peak of 1 J / g or more based on melting of a crystal and 1 J based on crystallization.
The laminate according to claim 1, which is an amorphous olefin-based copolymer having no peaks of at least / g. 3. The laminate according to claim 1, wherein the amorphous olefin copolymer (b) is a propylene-α-olefin copolymer comprising propylene and an α-olefin having 4 to 20 carbon atoms. 4. The method according to claim 1, wherein the amorphous olefin-based copolymer (b) is an ethylene-propylene-α-olefin copolymer comprising ethylene, propylene and an α-olefin having 4 to 20 carbon atoms. Laminate. 5. The molar content% of a repeating unit derived from propylene, wherein the amorphous olefin-based copolymer (b) is
(X) and an ethylene-propylene having a P value of 0.3 or more defined by the following formula using the molar content% (y) of a repeating unit derived from an α-olefin having 4 to 20 carbon atoms.
The laminate according to claim 1, which is an α-olefin copolymer. P = y / (100−x) 6. The amorphous olefin-based copolymer (b) has a molar content% of repeating units derived from propylene.
(X) and ethylene-propylene having a P value defined by the following formula of 0.5 or more using the molar content% (y) of a repeating unit derived from an α-olefin having 4 to 20 carbon atoms.
The laminate according to claim 1, which is an α-olefin copolymer. P = y / (100−x) 7. The amorphous olefin copolymer has a molecular weight distribution (Mw / Mn) of 5 or less as measured by gel permeation chromatography (GPC).
The laminate according to the above. 8. An amorphous olefin-based copolymer (b) 13
The intrinsic viscosity [η] of the tetralin solvent at 5 ° C. is 0.
The laminate according to claim 1, wherein the thickness is 3 to 10 dl / g. 9. A transition metal wherein the amorphous olefin-based copolymer (b) has a non-stereospecific structure of Groups 4 to 6 of the Periodic Table having at least one group having a cyclopentadiene-type anion skeleton. In the presence of a polymerization catalyst using a complex,
The laminate according to claim 1, which is an amorphous olefin-based copolymer obtained by polymerizing at least two kinds of monomer components selected from an α-olefin having 3 to 20 carbon atoms and ethylene. 10. An amorphous olefin copolymer (b) comprising:
Use the following (A) and the following (B) and / or (C)
C3 to C2 in the presence of the resulting olefin polymerization catalyst.
0 selected from among α-olefins and ethylene
Obtained by polymerizing at least two types of monomer components.
The amorphous olefin copolymer according to claim 1,
Laminate. Compound (A): transition metal complex represented by the following general formula [I](Where M¹Is the transition metal atom of Group 4 of the Periodic Table of the Elements
A represents an atom of Group 16 of the Periodic Table of the Elements,
J represents an atom belonging to Group 14 of the periodic table of the elements. Cp¹Is
A group having a cyclopentadiene-type anion skeleton is shown.
X¹, X^Two, R¹, R ^Two, R^Three, R^Four, R^FiveAnd R⁶Are each
Independently, hydrogen atom, halogen atom, alkyl group, arral
A kill group, an aryl group, a substituted silyl group, an alkoxy group,
Aralkyloxy group, aryloxy group or disubstituted amino
Represents a group. R¹, R^Two, R^Three, R^Four, R ^FiveAnd R⁶Is optional
They may combine to form a ring. (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
Boron compound (where B is trivalent valence state)
Q is a urine atom¹~ Q^FourIs a halogen atom, hydrocarbon
Group, halogenated hydrocarbon group, substituted silyl group, alkoxy
Groups or disubstituted amino groups, even if they are the same
It may be different. G⁺Is an inorganic or organic cation
Where L is a neutral Lewis base and (LH)⁺Is blurred
Is a Stonsted acid. ) 11. The olefin resin composition (c) has a melt flow rate of 1 to 80 g / 10 minutes.
The laminate according to the above. 12. The laminate according to claim 1, wherein the crystalline olefin-based resin (a) is a crystalline olefin-based resin whose main component is a repeating unit derived from an olefin having 3 or more carbon atoms. 13. The laminate according to claim 1, wherein the crystalline olefin resin (a) is a crystalline propylene resin. 14. The ethylene-based resin (d) is a low-density polyethylene, ethylene-α-olefin copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer and ethylene-methacrylate copolymer. The laminate according to claim 1, wherein the laminate is at least one kind of ethylene resin selected from the coalescing. 15. An ethylene resin (d) having a content of a repeating unit derived from ethylene of 70 to 95% by weight,
When the content of the repeating unit derived from vinyl acetate is 30
The laminate according to claim 1, which is an ethylene-vinyl acetate copolymer in an amount of 5 to 5% by weight. 16. A film or sheet comprising the laminate according to any one of claims 1 to 15. 17. A stretch film for packaging comprising the laminate according to any one of claims 1 to 15.