JPH09137013A - Releasable protective film and composition therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the above composition excellent in flexibility, scratch resistance, heat resistance, transparency, etc., having proper adhesive force and releasability, leaving no bleeded matter on adherends, thus useful for automtoive surface coating, etc., comprising specific different kinds of olefin-based copolymers and a tackifier. SOLUTION: This composition comprises a total 100 pts.wt. of (A) 30-85pts. by wt. of a propylene-1-butene random copolymer with a propylene content of 50-90mol%, melt flow rate(MFR) at 230 deg.C under a load of 2.16kg of 0.1-100g/10min, molecular weight distribution determined by gel permeation chromatography of 1.5-3.0 in terms of the ratio of weight-average molecular weight (Mw ) to number-average molecular weight (Mn ):Mw /Mn and copolymerized monomer chain distribution randomness of 1.0-1.5 in terms of B-number, (B) 15-70 pts.wt. of an ethylene-3-10Cα-olefin copolymer with an ethylene content of 75-95wt.% and MFR of 0.1-100g/10min at 190 deg.C under a load of 2.16kg, and (C) 0-20 pts.wt. of a tackifier.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a composition for a peelable protective film and a film thereof, and more specifically, to scratches and stains generated during processing, transportation or storage of metal products, plastic products, rubber products and the like. To prevent corrosion, etc., temporarily coat the surface of the above products,
The present invention relates to a composition capable of providing a polyolefin-based peelable protective film that can be easily and integrally peeled after achieving the above object, and the film.

[0002]

BACKGROUND OF THE INVENTION A peelable protective film is used for the purpose of preventing scratches, pollution, corrosion, etc., which occur during processing, transportation or storage of metal products, plastic products, rubber products, etc. It is required to have a property that the surface of the product or the like is temporarily covered, and after the purpose is achieved, the product can be easily and integrally peeled off.

As a conventional peelable protective film, for example, a resin composition containing an ethylene / vinyl acetate copolymer (hereinafter abbreviated as EVA) or a low crystalline ethylene / α-olefin copolymer as a main component. Is used. Although these have good initial adhesiveness, they have the drawback that the adhesive strength increases due to lack of heat resistance during storage for a long period of time, especially when placed at high temperature, and the peeling property deteriorates significantly. ing.

Japanese Patent Publication No. 58-45974 discloses an EV.
A polyolefin-based peelable protective film having improved heat resistance of the A-based film has been proposed. However, in this film, although the heat resistance is improved, the adhesive strength of the film increases with time when stored for a long period of time, or bleeding is caused on the surface of the adherend when peeled from the adherend. There were problems such as remaining.

The applicant of the present application has filed Japanese Patent Application Laid-Open Nos. 3-66737, 3-62838 and 3-6283.
In Japanese Patent Laid-Open No. 9, a method was proposed in which a propylene / 1-butene random copolymer was used to reduce aging and bleeding on the surface of an adherend during long-term storage. For example, in JP-A-3-66737, a specific propylene
A composition comprising a butene random copolymer and a specific ethylene / α-olefin copolymer, and a specific propylene / 1-butene random copolymer and a specific ethylene / α-olefin copolymer.
A composition comprising an α-olefin copolymer and a tackifier, and a peelable protective film formed from these compositions have been proposed. The above composition has flexibility,
In addition to being excellent in scratch resistance and heat resistance, it also has a suitable initial adhesive force and peeling property to an adherend, excellent cold workability at the time of adhesion, and less change over time when stored for a long time. It is possible to provide a peelable protective film in which a bleeding material does not remain on the surface of an adherend even after peeling.

However, since this propylene / 1-butene random copolymer is produced by a conventional Ziegler catalyst system, the propylene / 1-butene random copolymer has a wide molecular weight distribution and composition distribution. The peelable protective film is not always sufficiently satisfactory even if the change in adhesive strength with time is small, and there is a case where bleeding on the surface of the adherend may occur, but the quality of the peelable protective film is further improved. Improvement is desired.

[0007] Therefore, the inventors of the present application have conducted diligent studies to solve the above problems, and in the presence of an olefin polymerization catalyst containing a specific transition metal compound (metallocene compound) as a catalyst component, propylene and 1 -A specific propylene / 1-butene random copolymer (A) copolymerized with -butene, and a specific ethylene / α-olefin copolymer consisting of ethylene and an α-olefin having 3 to 10 carbon atoms ( The composition containing B) in a specific ratio shows less change over time when stored for a longer period of time than the peelable protective film proposed in JP-A-3-66737, and the surface of an adherend even after peeling It was found that a peelable protective film in which no bleeding material remains can be obtained, and the present invention has been completed.

[0008]

SUMMARY OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, and is excellent in flexibility, scratch resistance and heat resistance, and has a proper initial adhesive force to an adherend. Also, it has peeling property and is excellent in cold workability during adhesion. Moreover, it does not change with time when stored for a long time, and bleeding does not remain on the adherend surface even after peeling. It is an object of the present invention to provide a peelable protective film composition capable of supplying a film and the film.

[0009]

SUMMARY OF THE INVENTION The composition for a peelable protective film according to the present invention comprises [I] propylene / 1-butene random copolymer (A) 3.
0-85 parts by weight, [II] ethylene / α-olefin copolymer (B) 1 comprising ethylene and an α-olefin having 3 to 10 carbon atoms
5 to 70 parts by weight, and [III] tackifier (C) 0 to 20 parts by weight [total amount of components (A), (B) and (C) is 100 parts by weight], and propylene. -The butene random copolymer (A) has (i) a propylene content of 50 to 9
0 mol% and (ii) melt flow rate (ASTM D 1
(238, 230 ° C, 2.16 kg) is 0.1 to 100 g / 10 minutes, and (iii) molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC).
Is 1.5 to 3.0 (Mw is a weight average molecular weight and Mn is a number average molecular weight), and (iv) the parameter B value showing the randomness of the copolymerized monomer chain distribution is 1.0 to 1.
5, which is an ethylene / α-olefin copolymer (B)
(I) Melt flow rate (ASTM D 1238, 190 ° C,
2.16 kg) is 0.1 to 100 g / 10 minutes, and (ii) the ethylene content is 75 to 95 mol%.

The above-mentioned propylene / 1-butene random copolymer (A) has a parameter B value (i) showing the randomness of the copolymerized monomer chain distribution of 1.0 to 1.3,
(Ii) melting point (T measured by a differential scanning calorimeter
m) is 60 to 140 ° C., and (iii) this melting point (T
The relationship between m) and the 1-butene content (M [mol%]) is −
2.6M + 130 ≤ Tm ≤ -2.3M + 155, and (iv) crystallinity (α) measured by X-ray diffraction method.
The relationship between [%]) and the 1-butene content (M [mol%]) is preferably α ≧ −1.5 M + 75.

The propylene / 1-butene random copolymer (A) as described above comprises [A] a transition metal compound represented by the following general formula [〓] and [B] an organoaluminum oxy compound [B-1]. ] And / or a compound [B-2] which reacts with the transition metal compound [A] to form an ion pair,
It is obtained by copolymerizing propylene and 1-butene in the presence of an olefin polymerization catalyst containing a [C] organoaluminum compound, if desired.

[0012]

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[Wherein M is the periodic table IVa, Va, VI
is a group a transition metal, R ¹ and R ² are hydrogen atoms,
A halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, R ³ is a secondary or tertiary alkyl group having 3 to 20 carbon atoms or an aromatic group, R ⁴ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, X
¹ and X ² are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group,
Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, a divalent tin-containing group, -O -, - CO -, - S -, - SO -, - SO 2
-, -NR ^5- , -P (R ⁵ )-, -P (O) (R ⁵ )
-, - BR ⁵ - or -AlR ⁵ - is. (However,
R ⁵ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms. )] In the general formula [〓] showing the above transition metal compound [A], it is preferable that R ¹ is a methyl group.

Further, the peelable protective film according to the present invention is a film composed of a single layer or a multilayer, and at least one layer of the film located on the outermost surface is composed of the composition as described above. It has a feature.

[0015]

DETAILED DESCRIPTION OF THE INVENTION The peelable protective film and the composition thereof according to the present invention will be specifically described below.

The composition for a peelable protective film according to the present invention comprises a propylene / 1-butene random copolymer (A) and an ethylene / α-olefin copolymer (B), and A tackifier (C) may be contained in addition to the components (A) and (B).

Each component will be specifically described below. Propylene / 1-butene Random Copolymer (A) (1) Composition The propylene / 1-butene random copolymer (A) used in the present invention has a constitutional unit content (propylene content) derived from propylene of 50. ~ 90 mol%, preferably 55-90 mol%, more preferably 60-85 mol%
And the content of the structural unit derived from 1-butene (1-butene content) is 10 to 50 mol%, preferably 10 to 45.
Mol%, more preferably 15 to 40 mol%.

The propylene / 1-butene random copolymer (A) may contain a small amount of structural units derived from olefins other than propylene and 1-butene, for example, 10 mol% or less, preferably 5 mol% or less. Good.

(2) Melt Flow Rate The propylene / 1-butene random copolymer (A) used in the present invention has a melt flow rate (MFR; ASTM D).
1238, 230 ℃, 2.16kg load) is 0.1-100g / 10
Min, preferably 0.5 to 50 g / 10 min, more preferably 1 to 20 g / 10 min.

(3) Molecular weight distribution (Mw / Mn) The propylene / 1-butene random copolymer (A) used in the present invention has a molecular weight distribution (Mw / M) determined by gel permeation chromatography (GPC).
n) is 3 or less, preferably 1.5 to 3.0, more preferably 1.5 to 2.5.

(4) Randomness The propylene / 1-butene random copolymer (A) used in the present invention has a parameter B value of 1.0 to 1.5 indicating the randomness of the copolymerized monomer chain distribution. It is preferably 1.0 to 1.3, more preferably 1.0 to 1.2.

This parameter B value is calculated by Coleman et al. (BD
Cole-man and TGFox, J. Polym.Sci., Al , 3183 (1963)
) And is defined as follows. B = P ₁₂ / (2P ₁ · P ₂ ) Here, P ₁ and P ₂ are the first monomer and the second monomer content fraction, respectively, and P ₁₂ is (1st
Monomer)-(second monomer) chain ratio.

The B value is 1 according to Bernoulli statistics, and when B <1, the copolymer is blocky.
It is alternate when B> 1. Further, the propylene / 1-butene random copolymer (A) used in the present invention has, in addition to the above characteristics, (5) a melting point (Tm) measured by a differential scanning calorimeter.
Is 60 to 140 ° C., preferably 80 to 130 ° C., and the relationship between the melting point (Tm) and the 1-butene content [M (mol%)] is −2.6 M + 130 ≦ Tm ≦ − It is preferably 2.3M + 155.

(6) The relationship between the crystallinity (α [%]) measured by the X-ray diffraction method and the 1-butene content (M [mol%]) is α ≥ -1.5 M + 75. Is desirable.

The propylene / 1-butene random copolymer (A) has a crystallinity of 15 to 65%, preferably 30 to 65%.
Desirably, it is 60%. The propylene / 1-butene random copolymer (A) as described above comprises [A] a specific transition metal compound as described below, [B] an organoaluminum oxy compound [B-1], and / or the above transition. A compound that reacts with a metal compound [A] to form an ion pair [B-
2] and optionally [C] an organoaluminum compound in the presence of a catalyst for olefin polymerization, and propylene
Obtained by copolymerizing with 1-butene.

Propylene 1-obtained as described above
The butene random copolymer has high stereoregularity and is excellent in scratch resistance, heat resistance, transparency and blocking resistance.

The olefin polymerization catalyst used in the present invention will be described below. The transition metal compound [A] that forms the olefin polymerization catalyst used in the present invention (hereinafter,
It may be described as "component [A]". ) Is represented by the following general formula [I].

[0028]

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In the formula, M is a transition metal of Group IVa, Va or VIa of the Periodic Table, specifically titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum or tungsten, preferably Is titanium, zirconium or hafnium, and particularly preferably zirconium.

Substituents R ¹ and R ² R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms. , A silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group.

Specific examples of the halogen atom include fluorine, chlorine, bromine and iodine, which have 1 to 2 carbon atoms.
As the hydrocarbon group of 0, methyl, ethyl, propyl,
Butyl, hexyl, cyclohexyl, octyl, nonyl, dodecyl, eicosyl, norbornyl, adamantyl and other alkyl groups, vinyl, propenyl, cyclohexenyl and other alkenyl groups, benzyl, phenylethyl, phenylpropyl and other arylalkyl groups, phenyl, tolyl, Dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl,
Examples thereof include aryl groups such as methylnaphthyl, anthracenyl, phenanthryl and the like. Examples of the halogenated hydrocarbon group include groups in which these hydrocarbon groups are substituted with a halogen atom.

Further, monohydrocarbon-substituted silyl groups such as methylsilyl and phenylsilyl, dihydrocarbon-substituted silyl groups such as dimethylsilyl and diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl and dimethyl. Trihydrocarbon-substituted silyl groups such as phenylsilyl, methyldiphenylsilyl, tritolylsilyl, and trinaphthylsilyl; hydrocarbon-substituted silyl silyl ether groups such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; and silicon such as trimethylphenyl. A silicon-containing substituent such as a substituted aryl group, a hydroxy group,
Alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, phenoxy, methylphenoxy, dimethylphenoxy, allyxy groups such as naphthoxy, oxygen-containing substituents such as arylalkoxy groups such as phenylmethoxy and phenylethoxy, and oxygen of the oxygen-containing compound are Sulfur-containing groups substituted with sulfur, amino groups, alkylamino groups such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino, phenylamino, diphenylamino, ditolylamino, dinaphthylamino, methylphenylamino, etc. Nitrogen-containing groups such as arylamino groups or alkylarylamino groups, and phosphorus-containing groups such as phosphino groups such as dimethylphosphino and diphenylphosphino.

Of these, R ¹ is preferably a hydrogen atom, a methyl group, a hydrocarbon group having 2 to 6 carbon atoms, an aromatic group or the like, and particularly a methyl group or a hydrocarbon group having 2 to 6 carbon atoms. Groups are preferred.

Of these, R ² is preferably a hydrogen atom or a hydrocarbon group, and particularly preferably a hydrogen atom. The substituent R ³ R ³ is a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom thereof, or a group substituted with a silicon-containing group, among which a secondary or tertiary alkyl group having 3 to 20 carbon atoms or It is preferably an aromatic group.

Specifically, as the secondary or tertiary alkyl group, i-propyl, i-butyl, sec-butyl, tert-butyl, 1,2-dimethylpropyl, 2,3-dimethylbutyl, is
o-pentyl, tert-pentyl, neopentyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, is
o-hexyl, norbornyl, adamantyl and the like, aromatic groups include phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, α- or β-naphthyl, methylnaphthyl, anthracenyl, phenanthryl, Examples thereof include aryl groups such as benzylphenyl, pyrenyl, acenaphthyl, phenalenyl, aceanthrylenyl, tetrahydronaphthyl, indanyl, biphenylyl, etc., arylalkyl groups such as benzyl, phenylethyl, phenylpropyl, tolylmethyl, etc. Three
It may contain a heavy bond.

These groups may be substituted with a halogen atom as shown for R ^{1 or} a silicon-containing group. The substituent R ⁴ R ⁴ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

Specific examples of the alkyl group include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclohexyl, heptyl and octyl. Chain alkyl groups and cyclic alkyl groups such as, nonyl, dodecyl, eicosyl, norbornyl and adamantyl.

These groups may be substituted with a halogen atom as shown for R ^{1 or} a silicon-containing group. X ¹ and X ² X ¹ and X ² are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group. is there.

Specifically, the halogen atom, the oxygen-containing group, the hydrocarbon group having 1 to 20 carbon atoms, and the halogenated hydrocarbon group having 1 to 20 carbon atoms are the same as R ¹ . As the sulfur-containing group, in addition to the group represented by R ¹ , methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, trimethylbenzene sulfonate and tri Sulfonate groups such as isobutylbenzene sulfonate, p-chlorobenzene sulfonate and pentafluorobenzene sulfonate, methylsulfinate, phenylsulfinate, benzenesulfinate, p-toluenesulfinate, trimethylbenzenes Examples thereof include sulfinate groups such as ruffinate, pentafluorobenzenesulfinate, and trifluoromethanesulfinate.

Y Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group , divalent tin-containing group, -O -, - CO -, - S -, - SO -, - SO 2
^{-, - NR 5 -, -} P (R 5) -, - P (O) (R 5)
-, - BR ⁵ - or -AlR ⁵ - (provided that, R ⁵ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms) shows a Specifically, methylene, dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene, 1,3-trimethylene,
1,4-tetramethylene, 1,2-cyclohexylene, 1,4-cyclohexylene and other alkylene groups, diphenylmethylene,
A halogenated divalent hydrocarbon group having 1 to 20 carbon atoms such as an arylalkylene group such as diphenyl-1,2-ethylene, or a divalent hydrocarbon group having 1 to 20 carbon atoms such as chloromethylene. Halogenated hydrocarbon group, methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenylsilylene, diphenylsilylene, di (p-tolyl) Alkylsilylene groups such as silylene and di (p-chlorophenyl) silylene, alkylarylsilylene groups, arylsilylene groups, alkyldisilyl groups such as tetramethyl-1,2-disilyl, tetraphenyl-1,2-disilyl, alkylaryl Disilyl group,
A divalent silicon-containing group such as an arylsilyl group, a divalent germanium-containing group obtained by substituting germanium for silicon in the divalent silicon-containing group, and a divalent silicon-containing group obtained by substituting tin for silicon in the divalent silicon-containing group. R ⁵ is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms, which is the same as R ¹ described above.

Of these, Y is a divalent silicon-containing group, 2
It is preferably a divalent germanium-containing group, a divalent tin-containing group, more preferably a divalent silicon-containing group, and among these, an alkylsilylene group, an alkylarylsilylene group, and an arylsilylene group are particularly preferable. preferable.

The transition metal compound represented by the above general formula [I] will be specifically exemplified below. rac-dimethylsilylene
-Bis (2,7-dimethyl-4-ethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,
7-Dimethyl-4-n-propyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,7-dimethyl-4-i-propyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis ( 2,7-dimethyl-4
-n-butyl-1-indenyl) zirconium dichloride,
rac-Dimethylsilylene-bis (2,7-dimethyl-4-sec-butyl-1-indenyl) zirconium dichloride, rac-Dimethylsilylene-bis (2,7-dimethyl-4-t-butyl-1-
Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,7-dimethyl-4-n-pentyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene
-Bis (2,7-dimethyl-4-n-hexyl-1-indenyl)
Zirconium dichloride, rac-Dimethylsilylene-bis (2,7-dimethyl-4-cyclohexyl-1-indenyl) zirconium dichloride, rac-Dimethylsilylene-bis (2,7-dimethyl-4-methylcyclohexyl-1-indenyl) zirconium Dichloride, rac-Dimethylsilylene-
Bis (2,7-dimethyl-4-phenylethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2,7-dimethyl-4-phenyldichloromethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,7-dimethyl-4-chloromethyl-1-indenyl) zirconium dichloride, rac-dimethyl Silylene
-Bis (2,7-dimethyl-4-trimethylsilylenemethyl-1
-Indenyl) zirconium dichloride, rac- dimethylsilylene-bis (2,7-dimethyl-4-trimethylsiloxymethyl-1-indenyl) zirconium dichloride, rac-
Diethylsilylene-bis (2,7-dimethyl-4-i-propyl
-1-Indenyl) zirconium dichloride, rac-di (i-
Propyl) silylene bis (2,7-dimethyl-4-i-propyl
-1-Indenyl) zirconium dichloride, rac-di (n-
Butyl) silylene bis (2,7-dimethyl-4-i-propyl-1
-Indenyl) zirconium dichloride, rac-di (cyclohexyl) silylenebis (2,7-dimethyl-4-i-propyl-1-indenyl) zirconium dichloride, rac-methylphenylsilylenebis (2,7-dimethyl-4-i- Propyl
-1-Indenyl) zirconium dichloride, rac-methylphenylsilylene bis (2,7-dimethyl-4-t-butyl-1-
Indenyl) zirconium dichloride, rac-diphenylsilylenebis (2,7-dimethyl-4-t-butyl-1-indenyl) zirconium dichloride, rac-diphenylsilylenebis (2,7-dimethyl-4-i-propyl-1- Indenyl) zirconium dichloride, rac-diphenylsilylene bis (2,7-dimethyl-4-ethyl-1-indenyl) zirconium dichloride, rac-di (p-tolyl) silylene bis (2,7-
Dimethyl-4-i-propyl-1-indenyl) zirconium dichloride, rac-di (p-chlorophenyl) silylenebis (2,7-dimethyl-4-i-propyl-1-indenyl) zirconium dichloride, rac-dimethylsilylenebis ( 2-Methyl-4-i-propyl-7-ethyl-1-indenyl) zirconium dibromide, rac-dimethylsilylene-bis (2,7-dimethyl-4-i-propyl-1-indenyl) zirconium dimethyl, rac- Dimethyl silylene-bis (2,7-dimethyl-4
-i-Propyl-1-indenyl) zirconium methyl chloride, rac-dimethylsilylene-bis (2,7-dimethyl-4-i
-Propyl-1-indenyl) zirconium-bis (trifluoromethanesulfonato), rac-dimethylsilylene-
Bis (2,7-dimethyl-4-i-propyl-1-indenyl) zirconium-bis (p-phenylsulfinato), rac-dimethylsilylene-bis (2-phenyl-4-i-propyl-7-
Methyl-1-indenyl) zirconium dichloride and the like.

In the present invention, among the transition metal compounds represented by the above formula [I], the transition metal compounds represented by the following formula [Ia] are particularly preferably used.

[0044]

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(In the formula, M, X ¹ , X ² , R ¹ , R ³ , Y
Is the same as in formula [I], but preferably R ¹ is a hydrogen atom, a methyl group or an aromatic group. ) Examples of preferable transition metal compounds represented by the formula [Ia] are shown below.

Rac-Dimethylsilylene-bis (4-phenyl)
-1-Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2-methyl-4- (α-naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (β-naphthyl) -1-indenyl) zirconium dichloride, rac-dimethyl Silylene-bis (2-methyl-4- (1-anthracenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (2-anthracenyl) -1-indenyl) zirconium dichloride, rac -Dimethylsilylene-bis (2-methyl-4- (9-anthracenyl) -1-indenyl) zirconium dichloride, rac-Dimethylsilylene-bis (2-methyl-4- (9-phenanthryl) -1-indenyl) zirconium dichloride , Rac-Dimethylsilylene-bis (2-methyl-4- (p-fluorophenyl) -1-indenyl) zirconium dichloride, rac-Dimethylsilylene-bis (2-
Methyl-4- (pentafluorophenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2-methyl-4- (p-chlorophenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2-methyl-4- (m-chlorophenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2-methyl-4- (o-chlorophenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2-methyl-4- (o, p-dichlorophenyl) phenyl
-1-Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (p-bromophenyl)
-1-Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (p-tolyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (m- Trily) -1-indenyl)
Zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (o-tolyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (o, o'-dimethylphenyl) ) -1-Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-
Methyl-4- (p-ethylphenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-
Methyl-4- (pi-propylphenyl) -1-indenyl)
Zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (p-benzylphenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2-methyl-4- (p-biphenyl) -1-indenyl zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (m-biphenyl) -1-indenyl) zirconium dichloride, rac-dimethyl Silylene-bis (2-
Methyl-4- (p-trimethylsilylphenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene
-Bis (2-methyl-4- (m-trimethylsilylphenyl))
-1-Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-phenyl-4-phenyl-1-indenyl) zirconium dichloride, rac-diethylsilylene
-Bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-di- (i-propyl) silylene-
Bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-di- (n-butyl) silylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-dicyclohexylsilylene- Screw (2-
Methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-methylphenylsilylene-bis (2-methyl)
-4-Phenyl-1-indenyl) zirconium dichloride, rac-diphenylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-di (p-tolyl) silylene-bis (2-methyl- 4-phenyl-1
-Indenyl) zirconium dichloride, rac-di (p-chlorophenyl) silylene-bis (2-methyl-4-phenyl)
-1-Indenyl) zirconium dichloride, rac-methylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-ethylene-bis (2-methyl-4)
-Phenyl-1-indenyl) zirconium dichloride,
rac-Dimethylgermylene-bis (2-methyl-4-phenyl
-1-Indenyl) zirconium dichloride, rac-dimethylstannylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene
-Bis (2-methyl-4-phenyl-1-indenyl) zirconium dibromide, rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dimethyl, rac-dimethylsilylene-bis (2- Methyl-4-phenyl-1-indenyl) zirconium methyl chloride, rac-
Dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium chloride SO ₂ Me, rac-Dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium chloride OSO ₂ Me, rac- Dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium monochloride mono (trifluoromethanesulfonate), rac-dimethylsilylene-bis (2-
Methyl-4-phenyl-1-indenyl) zirconium di (trifluoromethanesulfonate), rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium di (p-toluenesulfonate), ra
c-Dimethylsilylene-bis (2-methyl-4-phenyl-1-
Indenyl) zirconium di (methyl sulfonate), rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium di (trifluoromethanesulfinate), rac-dimethylsilylene-bis (2-methyl) -4-Phenyl-1-indenyl) zirconium di (trifluoroacetate), rac-dimethylsilylene
-Bis (2-methyl-4-phenyl-1-indenyl) zirconium monochloride (n-butoxide), rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl)
Zirconium di (n-butoxide), rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium monochloride (phenoxide), etc.

Among the above, compounds in which R ¹ is a methyl group are particularly preferable. Also, in the above formula [Ia],
R ¹ is a hydrocarbon group having 2 to 6 carbon atoms, R ^1
A transition metal compound in which ³ is an aryl group having 6 to 16 carbon atoms is also preferably used. Among the compounds represented by the above formula [I], such preferable compounds are exemplified below.

Rac-Dimethylsilylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4-)
(Α-Naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4-
(Β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (2
-Methyl-1-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl
-4- (5-acenaphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl
-4- (9-anthracenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-Ethyl-4- (o-methylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-
Ethyl-4- (m-methylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1-
(2-Ethyl-4- (p-methylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,3-dimethylphenyl) indenyl)} zirconium dichloride, rac -Dimethylsilylene
-Bis {1- (2-ethyl-4- (2,4-dimethylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,5-dimethylphenyl)) Indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,4,6-trimethylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2- Ethyl-4- (o
-Chlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4-
(M-chlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl
-4- (p-Chlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,3-dichlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis { 1-
(2-Ethyl-4- (2,6-dichlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-ethyl-4- (3,5-dichlorophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (2-bromophenyl)
Indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (3-bromophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (4-Bromophenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-ethyl-4- (4-biphenylyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2 -Ethyl-4- (4-trimethylsilylphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-propyl)
-4-phenylindenyl)} zirconium dichloride,
rac-Dimethylsilylene-bis {1- (2-n-propyl-4-
(Α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-propyl-4)
-(Β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-propyl-4)
-(2-Methyl-1-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-
Propyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1-
(2-n-Propyl-4- (9-anthracenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-n-propyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-propyl-4-phenylindenyl)} zirconium dichloride , Rac-dimethylsilylene
-Bis {1- (2-i-propyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-i-propyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-i-propyl-4- (2-methyl-1-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-propyl-4- (5- Acenaphthyl) indenyl)} zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2-i-propyl-4- (9-anthracenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-propyl-4
-(9-phenanthryl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-s-butyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2- s-Butyl-4-
(Α-Naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-s-butyl-4-
(Β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-s-butyl-4-
(8-Methyl-9-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-s-
Butyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-
s-Butyl-4- (9-anthracenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1-
(2-s-butyl-4- (9-phenanthryl) indenyl)}
Zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-pentyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1-
(2-n-pentyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1-
(2-n-Butyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-butyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene -Bis {1- (2-n-butyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-butyl
-4- (2-Methyl-1-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-
n-Butyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1-
(2-n-butyl-4- (9-anthracenyl) indenyl)}
Zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-butyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-i-butyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-butyl-4- (α-naphthyl) indenyl)} zirconium dichloride , Rac-Dimethylsilylene-bis {1- (2-i-butyl-4- (β-naphthyl) indenyl)} zirconium dichloride, rac-Dimethylsilylene-bis {1- (2-i-butyl-4- (2 -Methyl-1-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-butyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1 -(2-i-Butyl-4- (9-anthracenyl)
Indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-i-butyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-neopentyl-4 -Phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-neopentyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n- Hexyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-n-hexyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1 -(2-Ethyl-4-phenylindenyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl] )} Zirconium dichloride, rac-methylphenylsilylene-bis {1- (2-ethyl-4- (9-anthracenyl) indenyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1- (2-ethyl-4-) (9-phenanthryl) indenyl)} zirconium dichloride,
rac-diphenylsilylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride , Rac-diphenylsilylene-bis {1- (2-ethyl-4- (9-anthracenyl) indenyl)} zirconium dichloride, rac-
Diphenylsilylene-bis {1- (2-ethyl-4- (9-phenanthryl) indenyl)} zirconium dichloride,
rac-diphenylsilylene-bis {1- (2-ethyl-4- (4-
Biferrinyl) indenyl)} zirconium dichloride, rac-methylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, rac-methylene-
Bis {1- (2-ethyl-4- (α-naphthyl) indenyl)}
Zirconium dichloride, rac-ethylene-bis {1- (2-
Ethyl-4-phenylindenyl)} zirconium dichloride, rac-ethylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-ethylene-bis {1- (2-n -Propyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylgermylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylgermylene-bis {1 -(2-Ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride, rac-dimethylgermylene-bis {1- (2-n-propyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylstanni Ren-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylstannylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride Lido, rac-dimethylstannylene-bis {1- (2-n-ethyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-dimethylstannylene-bis {1- (2-n-propyl-4) -Phenylindenyl)} zirconium dichloride and the like.

In the present invention, in the above compound, zirconium metal is replaced with titanium metal, hafnium metal,
It is also possible to use a transition metal compound in which vanadium metal, niobium metal, tantalum metal, chromium metal, molybdenum metal, or tungsten metal is substituted.

The above-mentioned transition metal compound is usually used as a racemate as a catalyst component for olefin polymerization, but R type or S type can also be used. The transition metal compounds used in the present invention as described above are the Journal of Organomet
Allic Chem. 288 (1985), pp. 63-67, European Patent Application Publication No. 0,320,762, and Examples.

The [B-1] organoaluminum oxy compound (hereinafter sometimes referred to as "component [B-1]") forming the olefin polymerization catalyst used in the present invention is a conventionally known aluminoxane. May also be used, and JP-A-2-78
It may be a benzene-insoluble organic aluminum oxy compound as exemplified in JP-A-687.

The conventionally known aluminoxane can be produced, for example, by the following method. (1) Compounds containing water of adsorption or salts containing water of crystallization, such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerous chloride A method of adding an organoaluminum compound such as trialkylaluminum to a hydrocarbon medium suspension of the above to react. (2) A method in which water, ice or steam is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of organometallic component. Alternatively, the solvent or unreacted organoaluminum compound may be removed from the recovered solution of aluminoxane by distillation, and then redissolved in a solvent or suspended in a poor solvent of aluminoxane.

Specific examples of the organoaluminum compound used when preparing the aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum and trisec-butyl. Trialkyl aluminum such as aluminum, tri-tert-butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, tridecyl aluminum, tricycloalkyl aluminum such as tricyclohexyl aluminum, tricyclooctyl aluminum, dimethyl aluminum chloride, diethyl aluminum Chloride,
Dialkyl aluminum halides such as diethyl aluminum bromide and diisobutyl aluminum chloride, dialkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride, dialkyl aluminum alkoxides such as dimethyl aluminum methoxide and diethyl aluminum ethoxide, and dialkyl aluminum aryloxy such as diethyl aluminum phenoxide. Do and the like.

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable. Further, as the organoaluminum compound used when preparing the aluminoxane, isoprenylaluminum represented by the following general formula can also be used.

(I-C ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z ... [II] (In the formula, x, y, and z are positive numbers, and z ≧ 2x.) The above organoaluminum compounds are used alone or in combination.

Solvents used for the aluminoxane solution or suspension include benzene, toluene, xylene,
Aromatic hydrocarbons such as cumene and cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane, alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane , Petroleum fractions such as gasoline, kerosene, and light oil, or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons, and particularly hydrocarbon solvents such as chlorinated compounds and brominated compounds. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferable.

[B-2] Forming Catalyst for Olefin Polymerization Used in the Present Invention [B-2] A compound that reacts with the transition metal compound [A] to form an ion pair (hereinafter referred to as "component [B-2]"). In some cases, Japanese Patent Laid-Open No. 501501950
Japanese Patent Laid-Open No. 1-502036, Japanese Patent Laid-Open No. 3-1
79005, JP-A-3-179006, JP-A-3-207703, and JP-A-3-207704.
Examples thereof include Lewis acids, ionic compounds and carborane compounds described in JP-A No. 547718 and the like.

As the Lewis acid, triphenylboron,
Tris (4-fluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-
Dimethylphenyl) boron, tris (pentafluorophenyl) _{boron, MgCl 2, Al 2 O 3} , SiO 2 -Al 2
O ₃ can be exemplified.

As the ionic compound, triphenylcarbenium tetrakis (pentafluorophenyl) borate, tri-n-butylammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferroferrite Examples include cerium tetra (pentafluorophenyl) borate.

Examples of the carborane compound are dodecaborane, 1-carbaundecaborane, bis-n-butylammonium (1-carbedodeca) borate, tri-n-butylammonium (7,8-dicarbaundeca) borate, tri-n-butylammonium. (Trideca hydride-7-carbaundeca) borate can be exemplified.

Two or more kinds of the compound [B-2] which forms an ion pair by reacting with the above transition metal compound [A] can be mixed and used. Examples of the organoaluminum compound [C] (hereinafter sometimes referred to as “component [C]”) that can be used when forming the olefin polymerization catalyst used in the present invention include the following general formula [III]. The organoaluminum compound represented by can be exemplified.

R ⁹ _n AlX _3-n ... [III] (wherein R ⁹ is a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, and n is 1 to 1).
3. ) In the above general formula [III], R ⁹ has 1 to 10 carbon atoms.
12 hydrocarbon groups such as an alkyl group, a cycloalkyl group or an aryl group, specifically, a methyl group,
Examples include ethyl group, n-propyl group, isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, and tolyl group.

Such an organoaluminum compound [C]
Specific examples include the following compounds. Trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum, tri (2-ethylhexyl) aluminum, tridecyl aluminum, alkenyl aluminum such as isoprenyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride. , Diisopropyl aluminum chloride, diisobutyl aluminum chloride, dialkyl aluminum halides such as dimethyl aluminum bromide, methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, alkyl aluminum such as ethyl aluminum sesquibromide Sukiharaido, methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, alkyl aluminum dihalides such as ethyl aluminum dibromide, diethyl aluminum hydride, alkyl aluminum hydride and diisobutyl aluminum hydride.

As the organoaluminum compound [C], a compound represented by the following general formula [IV] can also be used. R ⁹ _n AlL _3-n ... [IV] (In the formula, R ⁹ is the same as the above R ⁹ , and L is —OR ¹⁰
Group, -OSiR ¹¹ ₃ group, -OAlR ¹² ₂ group, -NR ¹³ ₂ group
A group, —SiR ¹⁴ ₃ group or —N (R ¹⁵ ) AlR ¹⁶ ₂ group,
n is 1 to 2, R ¹⁰ , R ¹¹ , R ¹² and R ¹⁶ are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group and the like, and R ¹³ is a hydrogen atom, methyl Group, ethyl group, isopropyl group, phenyl group, trimethylsilyl group and the like, and R ¹⁴ and R ¹⁵ are methyl group, ethyl group and the like. ) Among such organoaluminum compounds, R ⁷ _nA
l (OAlR ¹⁰ ₂ ) _3-n , for example, Et ₂
AlOAlEt ₂ and (iso-Bu) ₂ AlOAl (iso-Bu) ₂ are preferred.

Among the organoaluminum compounds represented by the above general formulas [III] and [IV], the general formula R ⁷ ₃ Al
The compound represented by is preferable, and the compound in which R is an isoalkyl group is particularly preferable.

The olefin polymerization catalyst used in the present invention comprises the above-mentioned component [A], component [B-1] and / or component [B-2] (hereinafter component [B]) and, if desired, component [B]. C]. The olefin polymerization catalyst comprises these component [A], component [B] and optionally component [C].
Can be prepared by mixing in an inert hydrocarbon solvent or in an olefin solvent.

Specific examples of the inert hydrocarbon solvent used for preparing the olefin polymerization catalyst include propane and
Butane, pentane, hexane, heptane, octane, decane, dodecane, aliphatic hydrocarbons such as kerosene, cyclopentane, cyclohexane, alicyclic hydrocarbons such as methylcyclopentane, benzene, toluene, aromatic hydrocarbons such as xylene, Examples thereof include halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane, or a mixture thereof.

The order of mixing the respective components in preparing the olefin polymerization catalyst is arbitrary, but the components [B] and [A] are mixed.
Or by mixing component [B] and component [C],
Then, the component [A] is mixed, the component [A] and the component [B] are mixed, and then the component [C] is mixed, or the component [A] and the component [C] are mixed, Next, it is preferable to mix the component [B].

When the above components are mixed 3 times in a solvent, the concentration of the component [A] is about 10 ^-8 to 10 ^-1 mol / liter, preferably 10 ^{-7 to} 5 × 10 ^-2 mol / liter. Is desirable.

When the component [B-1] is used as the component [B], the aluminum in the component [B-1] is replaced by the component [A].
The atomic ratio with the transition metal (Al / transition metal) is usually 1
0 to 10000, preferably 20 to 5000, and when the component [B-2] is used, the component [A]
To component [B-2] (Component [A] / Component [B-2])
Is usually used in an amount of 0.01 to 10, preferably 0.1 to 5.

[0072] Component [C], the atomic ratio of component [C] aluminum atom (Al _C) and the aluminum atom in the component [B-1] in _{(Al B-1) (Al} C / Al B-1 ) Is usually 0.02 to 20, preferably 0.2 to 10, and can be used as necessary.

The above components may be mixed in the polymerization vessel, or may be mixed in advance and added to the polymerization vessel. The mixing temperature at the time of premixing is usually −50 to 150 ° C., preferably −20 to 120 ° C., and the contact time is 1 to 100.
It is 0 minutes, preferably 5 to 600 minutes. Further, the mixing temperature may be changed during the mixing contact.

The olefin polymerization catalyst used in the present invention is prepared by adding the above-mentioned components [A] and [B] to an inorganic or organic particulate carrier which is a granular or particulate solid.
And a solid olefin polymerization catalyst carrying at least one component of the component [C].

The inorganic carrier is preferably a porous oxide, and examples thereof include SiO ₂ and Al ₂ O ₃ . Examples of the granular or fine particle solid of the organic compound include polymers or copolymers produced by using α-olefins such as ethylene, propylene and 1-butene, or styrene as a main component.

Further, in the present invention, olefin may be prepolymerized and used as each component forming the above olefin polymerization catalyst. As the olefin used for the prepolymerization, propylene, ethylene, 1-butene and the like are preferable, but a mixture of these with another olefin may be used.

The olefin polymerization catalyst used in the present invention may contain, in addition to the above components, other components useful for olefin polymerization, such as water as a catalyst component.

The propylene / 1-butene random copolymer (A) used in the present invention contains propylene and 1-butene in the above composition ratio in the presence of the above-mentioned olefin polymerization catalyst. Can be produced by copolymerization.

The copolymerization can be carried out by either liquid phase polymerization method such as suspension polymerization or solution polymerization or gas phase polymerization method. In the liquid phase polymerization method, the same solvent as the inert hydrocarbon solvent used in the above-mentioned catalyst preparation can be used, and propylene can also be used as the solvent.

The polymerization temperature is usually -50 to 100 ° C., preferably 0 to 90 ° C. when carrying out the suspension polymerization method, and usually 0 to 0 when carrying out the solution polymerization method. It is desirable that the temperature is 250 ° C, preferably 20 to 200 ° C. Further, when carrying out the gas phase polymerization method, the polymerization temperature is usually 0 to 120 ° C., preferably 20 to 100 ° C.

The polymerization pressure is usually from atmospheric pressure to 100 kg / c.
m ² , preferably under conditions of atmospheric pressure to 50 kg / cm ² ,
The polymerization reaction can be performed in any of a batch system, a semi-continuous system, and a continuous system.

It is also possible to carry out the polymerization in two or more stages under different reaction conditions. Propylene obtained
The molecular weight of the 1-butene random copolymer can be adjusted by allowing hydrogen to exist in the polymerization system or by changing the polymerization temperature and the polymerization pressure.

To the propylene / 1-butene random copolymer (A) as described above, a heat resistance stabilizer, an ultraviolet absorber, an antiblocking agent, a slip agent, an antistatic agent, etc. can be added and used.

Ethylene / α-olefin Copolymer (B) The ethylene / α-olefin copolymer (B) used in the present invention comprises ethylene and an α-olefin having 3 to 10 carbon atoms.

The ethylene / α-olefin copolymer (B) has a structural unit content (ethylene content) derived from ethylene of 75 to 95 mol%, preferably 80 to 9
1 mol%.

Examples of the α-olefin having 3 to 10 carbon atoms include propylene, 1-butene, 1-butene.
Examples include pentene, 1-hexene, 4-methylpentene-1, 3-methylpentene-1, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-octadecene. To be

The ethylene / α-olefin copolymer (B) used in the present invention has a melt flow rate (MFR;
ASTM D 1238, 190 ℃, 2.16kg load) 0.1-100g
/ 10 minutes, preferably 0.2 to 50 g / 10 minutes, and more preferably 0.4 to 20 g / 10 minutes.

By using the ethylene / α-olefin copolymer (B) having such properties, the composition with the propylene / 1-butene random copolymer (A) can be provided with tackiness. .

The ethylene / α-olefin copolymer as described above can be produced using a known vanadium catalyst or metallocene catalyst. Tackifier (C) In the present invention, propylene / 1-butene random copolymer (A) and ethylene / α-olefin copolymer (B)
The tackifier (C) may be used in order to make the initial adhesive force of the base resin consisting of (1) to the adherend have an appropriate strength.

The tackifier (C) is a solid amorphous polymer, which is generally used as a tackifying resin in the fields of adhesive tapes, paints, hot melt adhesives, etc. The following resins can be listed according to the difference in the monomer source.

For example, C ₄ fraction, C ₅ fraction obtained by cracking petroleum, naphtha, etc., a mixture thereof or any fraction thereof, for example, isoprene and 1,3-pentadiene in the C ₅ fraction. Aliphatic hydrocarbon resin containing as main raw material; C obtained by decomposing petroleum, naphtha, etc.
Aromatic hydrocarbon resin mainly composed of styrene derivative and indene in ₉ fraction; aliphatic / aromatic copolymer obtained by copolymerizing arbitrary fraction of C ₄ and C ₅ fractions and C ₉ fraction Polymerized hydrocarbon resin; Alicyclic hydrocarbon resin obtained by hydrogenating aromatic hydrocarbon resin; Synthetic terpene hydrocarbon resin having a structure containing aliphatic, alicyclic and aromatic; α, β in turpentine oil -A terpene-based hydrocarbon resin made from pinene as a raw material;
Examples include coumarone indene hydrocarbon resin, which uses indene and styrenes in coal tar naphtha as raw materials; low molecular weight styrene resin; and rosin hydrocarbon resin.

Among these tackifiers (C), an alicyclic hydrocarbon resin obtained by hydrogenating an aliphatic hydrocarbon resin and an aromatic hydrocarbon resin has good compatibility with the component (A). Therefore, the softening point (ring and ball method) is 70 to
An alicyclic hydrocarbon resin having a temperature of 150 ° C., preferably 80 to 140 ° C. and a hydrogenation rate of 80% or more, preferably 85% or more, to the aromatic nucleus is preferable.

Composition In the composition for peelable protective film according to the present invention,
The above propylene / 1-butene random copolymer (A),
The propylene / 1-butene random copolymer (A) is 30 to 85 parts by weight, preferably 100 parts by weight of the total amount of the ethylene / α-olefin copolymer (B) and the tackifier (C). 35 to 80 parts by weight, more preferably 3
It is used in a proportion of 5 to 75 parts by weight, and the ethylene / α-olefin copolymer (B) is used in a proportion of 15 to 70 parts by weight, preferably 20 to 65 parts by weight, more preferably 25 to 65 parts by weight. To be Further, the tackifier (C) is 0
˜20 parts by weight, preferably 2 to 15 parts by weight, more preferably 3 to 10 parts by weight.

By using a composition in which the above components (A), (B) and (C) are blended in the above proportions,
The film obtained from the composition has a suitable initial adhesive strength, has little change with time, has good peelability after adhesion, and can prevent blocking and bleeding after peeling.

The resin composition for a peelable protective film according to the present invention may contain other resin components within a range not impairing the object of the present invention, and further, an antioxidant, an ultraviolet absorber, a lubricant, a core. Various additives such as agents, antistatic agents, flame retardants, pigments, dyes, and inorganic or organic fillers can be added.

Any known method can be adopted for preparing the composition for a peelable protective film according to the present invention. For example, a method of mixing with a mixer such as a V-type blender, a ribbon blender, a tumbler blender or a Henschel mixer. And / or a kneading machine such as an extruder, a mixing roll, a Banbury mixer, or a kneader can be used.

Peelable Protective Film The peelable protective film according to the present invention is a film made of the above composition. As the peelable protective film according to the present invention, a single layer film composed of the above composition can be used as it is, or can be used as a film laminated with another resin film. When used as a laminated film with another resin film, the film comprising the composition of the present invention is laminated as an adhesive layer with an adherend so as to be positioned on at least one outermost surface.

In this case, as the other resin film serving as the base layer, a polyolefin film such as polyethylene, polypropylene or poly 1-butene having good adhesiveness to the composition of the present invention is preferable, but another adhesive layer is used. A film of polyamide, polyester, or the like may be laminated via this.

The peelable protective film according to the present invention is formed into a single layer from the above composition by using a film forming machine such as a T die forming machine or an inflation molding machine, or the above composition and another resin are combined. It can be prepared by lamination molding by coextrusion.

The peelable protective film prepared as described above has a layer comprising the composition of the present invention as an adhesive layer.
The surface of articles such as metal products, plastic products, and rubber products is coated to prevent scratches, pollution, corrosion, etc. during processing, transportation, and storage of the articles.

In this case, in the peelable protective film according to the present invention, the pressure-sensitive adhesive layer made of the composition of the present invention has appropriate adhesiveness, and therefore, the coating and peeling by adhesion are easy and the heat resistance is obtained. It is possible to maintain adhesiveness and peelability for a long period of time with little change in adhesive strength over time. Further, this film has excellent scratch resistance and transparency, and since it does not cause a blocking phenomenon, it can be easily processed in a coated state and has an excellent product appearance.

[0102]

The composition for a peelable protective film according to the present invention is excellent in flexibility, scratch resistance, heat resistance and transparency, and has a suitable initial adhesive force and peelability to an adherend. However, it also has excellent cold workability at the time of application, has little change over time when stored for a long period of time, and has a peelable protective film that does not leave bleeding on the surface of the adherend even after peeling.

The peelable protective film according to the present invention having such an effect can be used in a wide variety of applications, and is used for home appliances, automobiles, glass products, building materials, general miscellaneous metals, and various plastics. It can be suitably used for coating the surface of rubber or the like.

The present invention will be described below with reference to examples.
The present invention is not limited to these examples.

[0105]

Examples 1 and 2 [Production of Propylene / 1-Butene Random Copolymer] An autoclave having a capacity of 2 liters, which had been sufficiently purged with nitrogen, was charged with 900 ml of hexane and 50 g of 1-butene, and 1 mmol of triisobutylaluminum was added to the autoclave at 70 ° C. After the temperature was raised to 0, the total pressure was adjusted to 7 kg / cm ² G, methylaluminoxane 0.30 mmol, rac-dimethylsilylene-bis {1- (2-methyl-4-phenyl-1-indenyl)} zirconium dichloride. 0.001 mmol of Zr atoms was added, and propylene was continuously supplied to carry out polymerization for 30 minutes while keeping the total pressure at 7 kg / cm ² G. After the polymerization, the mixture was degassed, the polymer was recovered in a large amount of methanol, and dried under reduced pressure at 110 ° C. for 12 hours.

The propylene / 1-butene random copolymer thus obtained had a 1-butene content of 15 mol%, that is, a propylene content of 85 mol%, and a melt flow rate (230 ° C., 2. 16 kg) is 8.0
g / 10 minutes, melting point (Tm) is 110 ° C., molecular weight distribution (Mw / Mn) is 2.18, and B value is 1.
And the crystallinity was 53%. [Production of Ethylene / 1-Butene Random Copolymer] Using vanadium oxytrichloride and ethylene aluminum sesquichloride as a catalyst, a mixture of ethylene and 1-butene was polymerized in a hexane solvent at 50 ° C. in the presence of hydrogen. The ethylene / 1-butene random copolymer obtained had an ethylene content of 89 mol%, a density of 0.885 g / cm ³ , and a melt flow rate (190 ° C., 2.16 kg) of 3.5 g / 10. It was a minute.

[Preparation of Composition and Film] A propylene / 1-butene random copolymer (hereinafter abbreviated as PBC-1) obtained as described above and ethylene / 1-.
Butene random copolymer (hereinafter abbreviated as EBC)
And 2 with the tumbler blender at the compounding ratio shown in Table 1.
Mix for 1 minute, extruder with a diameter of 40 mm (set temperature = 230
The composition was prepared by melt mixing at ° C.

Next, this composition was formed into a single-layer film having a thickness of 50 μm by using a T-die molding machine (set temperature = 230 ° C.). The physical properties of the prepared composition and film were measured by the following methods. (1) Adhesive force to adherend The film formed by the above method is applied on an acrylic resin base material preheated to 55 ° C. with a pinch roll having a linear pressure of 3.6 kg / cm. Then, after leaving it in an air oven at 50 ° C. for a predetermined time, its adhesive force was measured by a 180 ° peeling method (pulling speed: 300 mm / min). (2) Surface hardness A 2 mm thick press sheet of the above composition was prepared (200
℃ -quenching method) and measured by the method of ASTM-D-2240. (3) Surface state of adherend The surface of the adherend after peeling the film for measuring the adhesive strength was visually observed and evaluated according to the following criteria. ◯: No stain Δ: Slight stain X: Scratch results are shown in Table 1.

[0109]

Example 3 PBC-1 and EBC shown in Example 1
In addition, alicyclic hydrocarbon resin "Alcon P125"
Example 1 was carried out in the same manner as in Example 1, except that the composition prepared by Arakawa Chemical Co., Ltd. under the compounding ratio shown in Table 1 was used. The results are shown in Table 1.

[0110]

Example 4 Instead of the ethylene / 1-butene random copolymer shown in Example 1, a mixture of ethylene and 1-octene was polymerized using a metallocene catalyst to obtain an ethylene / 1-octene copolymer. Polymer (hereinafter abbreviated as EOC)
The same procedure as in Example 1 was carried out except that was used in the mixing ratio shown in Table 1.

The EOC used here had an ethylene content of 90 mol%, a density of 0.885 g / cm ³ and a melt flow rate (190 ° C., 2.16 kg) of 4.7 g / 10 minutes. there were. The results are shown in Table 1.

[0112]

Comparative Example 1 The procedure of Example 1 was repeated except that PBC-1 shown in Example 1 was used alone instead of the composition used in Example 1. The results are shown in Table 1.

[0113]

Comparative Example 2 A composition was prepared in the same manner as in Example 1 except that the mixing ratio of PBC-1 and EBC was changed to the ratio shown in Table 1. Hereinafter, Example 1
Was performed in the same manner as described above. The results are shown in Table 1.

[0114]

Comparative Example 3 In the same manner as in Example 3, except that propylene / 1-butene random copolymer (PBC-2) prepared as described below was used in place of PBC-1. , A composition was prepared. Thereafter, the same procedure as in Example 3 was performed. The results are shown in Table 1.

[Preparation of Propylene / 1-Butene Random Copolymer (PBC-2)] In a 20 liter capacity stainless steel polymerization vessel equipped with a stirring blade, 20
0 g anhydrous magnesium chloride, 46 ml ethyl benzoate and 30 ml methylpolysiloxane were ball milled in a nitrogen atmosphere.

Next, the ball-milled catalyst component was suspended in titanium tetrachloride and filtered so that the titanium concentration was 0.01 mmol / liter, and the triethylaluminum concentration in the polymerization vessel was 1. The concentration of p-methyl toluate as an electron donor was 0.33 mmol / l so that the concentration was 0 mmol / l.
While supplying so as to be a liter, while using n-heptane as a polymerization solvent, while supplying a mixed gas of propylene and 1-butene (68 mol% of propylene, 32 mol% of 1-butene) at a rate of 4 kl / hour, The copolymerization reaction was carried out at 70 ° C.

The propylene / 1-butene random copolymer thus obtained had a propylene content of 71.0 mol% as measured by nuclear magnetic resonance spectroscopy and a melt flow rate (ASTM D 1238, 230 ° C.). , 2.16 kg) is 7.0 g / 10 min, melting point (Tm) is 110 ° C., molecular weight distribution (Mw / Mn) is 4.52, B value is 0.92, and crystallinity is Was 48%.

[0118]

[Table 1]

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Claims (5)

[Claims] 1. An [I] propylene / 1-butene random copolymer (A) 30 to 85 parts by weight, [II] an ethylene / α-olefin copolymer comprising ethylene and an α-olefin having 3 to 10 carbon atoms. Polymer (B) 1
5 to 70 parts by weight, and [III] tackifier (C) 0 to 20 parts by weight [the total amount of components (A), (B) and (C) is 100 parts by weight], and propylene. -The butene random copolymer (A) is
(I) the propylene content is 50 to 90 mol%,
(Ii) Melt flow rate (ASTM D 1238, 230 ℃, 2.16)
kg) is 0.1 to 100 g / 10 minutes, and (iii) the molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) is 1.5 to 3.0.
(Mw is a weight average molecular weight and Mn is a number average molecular weight.), And (iv) the parameter B value showing the randomness of the copolymerized monomer chain distribution is 1.0 to 1.5, and ethylene.α- The olefin copolymer (B) has a (i) melt flow rate (ASTM D 1238, 190 ° C., 2.16 kg) of 0.
1-100 g / 10 minutes, (ii) ethylene content is 75-95 mol%, The composition for peelable protective films characterized by the above-mentioned. 2. The propylene / 1-butene random copolymer (A) has a parameter B value of 1.0 to 1.3 indicating the randomness of the (i) copolymerized monomer chain distribution,
(Ii) melting point (T measured by a differential scanning calorimeter
m) is 60 to 140 ° C., and (iii) this melting point (T
m) and the 1-butene content (M [mol%]) have a relationship of -2.6M + 130 ≤ Tm ≤ -2.3M + 155.
And (iv) the relationship between the crystallinity (α [%]) measured by X-ray diffraction and the 1-butene content (M [mol%]) is α ≧ −1.5 M + 75. The composition for a peelable protective film according to claim 1, wherein: 3. The propylene / 1-butene random copolymer (A) comprises [A] a transition metal compound represented by the following general formula [〓] and [B] an organoaluminum oxy compound [B].
-1] and / or a compound [B-2] that reacts with the transition metal compound [A] to form an ion pair, and optionally [C] an organoaluminum compound in the presence of an olefin polymerization catalyst. A composition for a peelable protective film according to claim 1, which is obtained by copolymerizing propylene with 1-butene; [In the formula, M is a transition metal of Group IVa, Va, or VIa of the Periodic Table, R ¹ and R ² are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or the number of carbon atoms. 1 to 20 halogenated hydrocarbon group, silicon-containing group, oxygen-containing group, sulfur-containing group, nitrogen-containing group or phosphorus-containing group, R ³ is a secondary or tertiary alkyl group having 3 to 20 carbon atoms. Or an aromatic group, R ⁴ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, X ¹ and X ² are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, A halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group, Y represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent hydrocarbon group having 1 to 20 carbon atoms Halogenated hydrocarbon group, divalent silicon-containing group, divalent germanium-containing group Group, a divalent tin-containing group, -O -, - CO -, - S -, - SO -, - SO 2
-, -NR ^5- , -P (R ⁵ )-, -P (O) (R ⁵ )
-, - BR ⁵ - or -AlR ⁵ - is. (However,
R ⁵ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms. )]. 4. The composition for a peelable protective film according to claim 3, wherein in the general formula [〓] showing the transition metal compound [A], R ¹ is a methyl group. 5. A film comprising a single layer or multiple layers, wherein at least one outermost layer of the film comprises the composition according to any one of claims 1 to 4. Peelable protective film.