JPH11245355A - Polypropylene composite film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polypropylene composite film excellent in transparency, low temperature heat sealability, slipability, heat seal strength, blocking resistance, and hot tackiness. SOLUTION: In a composite film in which a sealant layer is laminated on a crystalline polypropylene layer, the sealant layer consists of a composition of 95-40 wt.% of a propylene-butene-1 random copolymer of 50-95 mole % of propylene, 5-50 mole % of butene-1 and of 0.1-5 dl/g limiting viscosity and 5-60 wt.% of a butene α-olefin random copolymer in which the content of butene-1 is 50-99 mole %, the content of 2-20C α-olefin is 1-50 mole %, and a melt flow rate measured at 190 deg.C and under 2.16 kg load is 0.1-20 g/10 min.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polypropylene composite film in which a sealant layer containing a propylene / 1-butene random copolymer and a butene / α-olefin random copolymer is laminated on a polypropylene layer.

[0002]

2. Description of the Related Art A crystalline polypropylene film is excellent in mechanical properties such as tensile strength, rigidity, surface hardness, impact strength and cold resistance, and optical properties such as gloss and transparency, and is non-toxic and odorless. Because of its excellent food hygiene properties, it is widely used in the field of packaging, especially in the field of food packaging. In this case, since the crystalline polypropylene film shrinks when heated to the heat sealing temperature, a composite film in which a sealant layer (heat sealing layer) is laminated is usually used.

[0003] Such a composite film is disclosed in
JP-A-238729 and JP-A-8-238730 describe a polypropylene composite film in which a sealant layer comprising a propylene / 1-butene random copolymer is laminated. However, this composite film has insufficient hot tack property for application to high-speed packaging, and its improvement is desired.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polypropylene composite film which is excellent in transparency, low-temperature heat sealability, heat seal strength, slip property, blocking resistance and the like, and is excellent in hot tack property. That is.

[0005]

The present invention is the following polypropylene composite film. (1) A polypropylene composite film in which a sealant layer made of a sealant composition is laminated on at least one surface of a polypropylene layer made of crystalline polypropylene (A), wherein the sealant composition is derived from (B) propylene. Unit content 50-95 mol%, 1-
A content of structural units derived from butene of 5 to 50 mol%,
95 to 40% by weight of a propylene / 1-butene random copolymer having an intrinsic viscosity [η] of 0.1 to 5 dl / g measured at 135 ° C. in decahydronaphthalene; and (C)
50 mol% of the content of the structural unit derived from 1-butene
More than 99 mol%, the content of structural units derived from α-olefins having 2 to 20 carbon atoms (excluding 1-butene) is 1 mol% or more and less than 50 mol%, 190 ° C.
2. Butene having a melt flow rate (MFR) of 0.1 to 20 g / 10 min measured under a load of 16 kg.
A polypropylene composite film, which is a sealant composition containing 5 to 60% by weight of an α-olefin random copolymer. (2) Propylene / 1-butene random copolymer (B)
Is a gel permeation chromatography (GP
The polypropylene composite film according to the above (1), wherein the molecular weight distribution (Mw / Mn) determined by C) is 3 or less, and the parameter B value indicating the randomness of the copolymer monomer chain distribution is 1.0 to 1.5. (3) Propylene / 1-butene random copolymer (B)
Means that the melting point (Tm) measured by a differential scanning calorimeter is 60 to
140 ° C., and the melting point and the content (Bm) of the structural unit derived from 1-butene are represented by the formula [I]

[Formula 2] -2.6Bm + 130≤Tm≤-2.3Bm + 155 ... [I] [wherein Tm is a melting point and the unit is ° C. Bm is 1
The content of structural units derived from butenes, the units being mol%. ] The polypropylene composite film according to the above (1) or (2), which satisfies the above relational expression. (4) Propylene / 1-butene random copolymer (B)
Is the crystallinity (Cd) measured by the X-ray diffraction method and 1
-The content of structural units derived from butene (Bm) is
Formula [II] Cd ≧ −1.5 Bm + 75 [II] [wherein Cd is the degree of crystallinity, and the unit is%. Bm
Is the content of the structural unit derived from 1-butene, and the unit is mol%. ] The polypropylene composite film according to any one of the above (1) to (3), which satisfies the following relationship: (5) Propylene / 1-butene random copolymer (B)
Is obtained by adding propylene and 1 in the presence of a metallocene-based catalyst.
-The polypropylene composite film according to any one of the above (1) to (4), which is a random copolymer obtained by randomly copolymerizing butene. (6) The metallocene-based catalyst has the formula (1)

Embedded image [Wherein, M is a transition metal atom of Groups IV to VIB of the periodic table, and R ¹ , R ² , R ³ , and R ⁴ are the same or different and are a hydrogen atom, a halogen atom, a carbon atom of 1 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. May be bonded to form a ring together with the carbon atom to which those groups are bonded. X ¹ and X ² are the same or different and 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 has 1 to 20 carbon atoms
A divalent hydrocarbon group, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, -O-, -CO-, -S-,- SO-, -S
O _2- , -NR ^5- , -P (R ⁵ )-, -P (= O) (R ⁵ )-,
—BR ⁵ — or —AlR ⁵ —. Where 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. And a compound capable of activating the bridge-type transition metal compound (a) represented by the above formula (1) and the organoaluminum compound (b) ), An organic aluminum oxy compound (c), and an ionized ionic compound (d) which forms an ion pair by reacting with the transition metal compound represented by the formula (1). The polypropylene composite film according to the above (5), which is a metallocene-based catalyst containing at least one selected compound. (7) The polypropylene composite film according to any one of the above (1) to (6), wherein the butene / α-olefin random copolymer (C) is 1-butene / ethylene random copolymer.

<< Crystalline Polypropylene (A) >> In the present invention, as the crystalline polypropylene (hereinafter sometimes simply referred to as polypropylene) (A) which forms the polypropylene layer (base layer), conventionally known crystalline polypropylene is used. It can be appropriately selected and used. Examples of such a polypropylene (A) include a propylene homopolymer, a propylene / α-olefin random copolymer of propylene and another α-olefin other than propylene, and a propylene / α-olefin block copolymer. Can be. The content of structural units derived from α-olefins other than propylene is preferably at most 10 mol%, more preferably at most 5 mol%. Further, the polypropylene (A) may be a modified product modified with a polar group-containing monomer such as maleic anhydride.

The other α-olefin forming the propylene / α-olefin random copolymer or propylene block copolymer is preferably an α-olefin having 2 to 20 carbon atoms other than propylene. Examples thereof include ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, and 4-methyl-1-pentene. These α-olefins are 1
The species can be used alone or in combination of two or more.

The polypropylene (A) has an isotactic index (II) (boiling n-heptane insoluble component) of 75% by weight or more, preferably 75 to 99% by weight.
Is preferred. The density is 0.89 ~ 0.92
g / cm ³ , melt flow rate (MFR: 230 ° C., 2.16K) measured according to ASTM D1238.
(under g load) is preferably 0.1 to 10 g / 10 min.

The polypropylene (A) can be used alone or in combination of two or more. An additive can also be compounded in the polypropylene (A). For example, weather stabilizers, heat stabilizers, antifogging agents, antiblocking agents, slip agents, lubricants, antistatic agents, flame retardants, pigments, dyes, antioxidants, antioxidants, chlorine absorbers, fillers, etc. It can also be blended.

The polypropylene (A) can be produced by a method known per se using a solid titanium catalyst or a metallocene catalyst known per se.

<< Propylene / 1-butene random copolymer (B) >> The propylene / 1-butene random copolymer (B) used in the present invention has a content of structural units derived from propylene of 50 to 95 mol%. , Preferably 55 to 93
Mol%, more preferably 60 to 90 mol%, the content of the structural unit derived from 1-butene is 5 to 50 mol%, preferably 7 to 45 mol%, more preferably 10 to 40 mol%, 135 ° C, The intrinsic viscosity [η] measured in decahydronaphthalene is 0.1 to 5 dl / g, preferably 0.5
It is a propylene / 1-butene random copolymer having a viscosity of 4 to 4 dl / g, more preferably 1 to 3 dl / g.

When the propylene / 1-butene random copolymer (B) has the above-mentioned physical properties, it is excellent in transparency, low-temperature heat sealability, heat seal strength, slip property, blocking resistance and the like, and has a hot tack. A polypropylene composite film having excellent properties can be obtained.

When the intrinsic viscosity [η] of the propylene / 1-butene random copolymer (B) exceeds 5 dl / g, the moldability decreases, and a thin layer having a desirable thickness as a sealant layer, for example, 10 μm or less is formed. 0.1
If it is less than dl / g, the moldability is reduced and the heat sealing strength is also reduced.

The propylene / 1-butene random copolymer (B) has a molecular weight distribution (Mw / Mw) determined by gel permeation chromatography (GPC).
n) is 3 or less, preferably 1.5 to 2.5, and the parameter B value indicating the randomness of the copolymer monomer chain distribution is 1.
It is desirably 0 to 1.5, preferably 1.0 to 1.3, more preferably 1.0 to 1.2.

The B value is a parameter indicating the randomness of the copolymer monomer chain distribution, that is, an index indicating the composition distribution state of the structural units in the copolymer chain, and is indicated by Coleman et al. (J. Polym. Sci., A1, 3183 (1963)) and can be calculated by the following equation.

B = P ₁₂ / (2P ₁ · P ₂ ) (where P ₁ and P ₂ are the first monomer (propylene monomer) and the second monomer (1-butene monomer) in the copolymer, respectively. a content fraction, P ₁₂ is the proportion of total 2 molecules in the chain (the first monomer) - (second monomer) chains.)

The values of P ₁ , P ₂ and P ₁₂ are ¹³ C—N
From the MR spectrum, GJ Ray (Macromolecules, 1
0, 773 (1977)), JC Randall (Macro-molecules, 1
5, 353 (1982)) and K. Kimura (Polymer, 25,4418 (198
4)) It can be obtained based on the reports of them.

The B value is 1 according to Bernoulli statistics, and if B <1, the copolymer is blocky and B>
One case is alternating. The value is 2 when both monomers are alternately distributed, and becomes 0 when a complete block copolymer is obtained in which both monomers are completely separated and polymerized.

The propylene / 1-butene random copolymer (B) has a melting point (Tm) measured by a differential scanning calorimeter of 60 to 140 ° C., preferably 80 to 130 ° C.
And the melting point and the content (Bm) of the structural unit derived from 1-butene are represented by the formula [I]

[Formula 3] -2.6Bm + 130≤Tm≤-2.3Bm + 155 ... [I] [wherein Tm is a melting point and the unit is ° C. Bm is 1
The content of structural units derived from butenes, the units being mol%. Are preferably satisfied.

When the melting point (Tm) exceeds 140 ° C., the suitable heat sealing temperature of the film increases, while when it is lower than 60 ° C., the low-temperature heat sealing property is improved, but the scratch resistance is reduced. In some cases, the film is blocked during storage, which makes practical use difficult.

The propylene / 1-butene random copolymer (B) has a crystallinity (Cd) measured by an X-ray diffraction method and a content of structural units derived from 1-butene (Bm): Formula [II] Cd ≧ −1.5 Bm + 75 [II] [wherein Cd is the degree of crystallinity, and the unit is%. Bm
Is the content of the structural unit derived from 1-butene, and the unit is mol%. Are preferably satisfied.

The propylene / 1-butene random copolymer (B) desirably has a crystallinity (Cd) of 15 to 65%, preferably 20 to 60%, as measured by an X-ray diffraction method. When the crystallinity (Cd) is in the range of 15 to 65%, a film having excellent low-temperature heat sealability and blocking resistance can be obtained.

The propylene / 1-butene random copolymer (B) is composed of 2,1 of propylene monomers in all propylene structural units determined from ¹³ C-NMR spectrum.
-It is desirable that the proportion of the position irregular units based on insertion be 0.05% or more, preferably 0.05 to 0.4%, more preferably 0.05 to 0.3%.

Further, in the propylene / 1-butene random copolymer (B), the proportion of the position irregular units based on the 1,3-insertion of the propylene monomer is preferably 0.05% or less. The propylene monomer undergoes 1,2-insertion (the methylene side binds to the catalyst) during polymerization, but rarely
-Insertion or 1,3-insertion. 2,1-
Inserted or 1,3-inserted monomers form regio-irregular units in the polymer.

The ratio of 2,1-insertion of the propylene monomer in all the propylene units can be determined by using ¹³ C-NMR.
It can be determined from the following formula [III] with reference to Lymer, 30 (1989) 1350.

## EQU4 ## Ratio of regio-irregular units based on 2,1-insertion = ([0.25Iαβ [structure (i)] + 0.5Iαβ [structure (ii)]] × 100) / (Iαα + Iαβ [structure (ii )] + 0.5 [Iαγ + Iαβ [Structure (i)] + Iαδ]) ... [III]

Here, the peaks are named according to the method of Carman et al. (Rubber Chem. Technol., 44 (1971), 781). Iαβ and the like indicate peak areas such as αβ peaks.
When it is difficult to determine the area such as Iαβ directly from the spectrum due to overlapping peaks, a carbon peak having a corresponding area can be used instead.

Further, 3 based on 1,3-insertion of propylene
The chain amount is expressed in% by dividing 1/2 of the area of the βγ peak (resonating at around 27.4 ppm) by the sum of 1/2 of the total methyl group peak and 1/2 of the βγ peak and multiplying by 100. You can ask.

The propylene / 1-butene random copolymer (B) is a titanium catalyst containing a Ziegler-Natta catalyst; a solid titanium catalyst component and an organometallic compound catalyst component, and if necessary, an electron donor component. It can be produced by polymerizing a monomer by a known polymerization method such as a gas phase method, a bulk method and a slurry method in the presence of a known catalyst such as a metallocene catalyst. As the propylene / 1-butene random copolymer (B), those obtained by polymerizing monomers in the presence of a metallocene catalyst, particularly a bridge-type metallocene catalyst, are preferable.

<< Butene / α-olefin random copolymer (C) >> The butene / α-olefin random copolymer (C) used in the present invention is composed of 1-butene and 2-2 carbon atoms.
0, preferably 2 to 8 α-olefins (provided that 1-
(Butenes are excluded) and a 1-butene content of 50 to 99 mol%, preferably 70 to 99 mol%.
MFR measured under the conditions of mol%, 190 ° C., and a load of 2.16 kg is 0.1 to 20 g / 10 min, preferably 0.1 to 20 g / 10 min.
It is a butene-α-olefin random copolymer of 5 to 10 g / 10 min.

When the butene / α-olefin random copolymer (C) has the above properties, it is excellent in transparency, low-temperature heat sealability, heat seal strength, slip properties, blocking resistance, etc. A polypropylene composite film having excellent properties can be obtained.

As the α-olefin to be copolymerized with 1-butene, there can be mentioned propylene and the same ones as exemplified for the polypropylene resin (A). Specific examples of the butene / α-olefin random copolymer (C) include 1-butene / ethylene random copolymer,
Examples thereof include 1-butene / propylene random copolymer, 1-butene / 1-hexene random copolymer, and 1-butene / 1-octene random copolymer. Among them, a 1-butene / ethylene random copolymer is preferred. The butene / α-olefin random copolymer (C) can be used alone or in combination of two or more.

The butene / α-olefin random copolymer (C) is a titanium catalyst containing a Ziegler-Natta catalyst; a solid titanium catalyst component and an organometallic compound catalyst component; and, if necessary, an electron donor component. It can be produced by polymerizing a monomer by a known polymerization method such as a gas phase method, a bulk method and a slurry method in the presence of a known catalyst such as a metallocene catalyst.

As the metallocene-based catalyst, a bridge-type transition metal compound (a) represented by the above formula (1) (hereinafter sometimes simply referred to as a transition metal compound)
And a compound capable of activating the transition metal compound (a), and reacting with the organoaluminum compound (b), the organoaluminum oxy compound (c), and the transition metal compound (a) to form an ion pair. A metallocene catalyst containing at least one compound selected from the group of compounds (b) to (d) consisting of the ionized ionic compound (d) to be formed is preferred.

In the above formula (1), M is the periodic table IV to VIB
Group transition metals, specifically, titanium, zirconium, hafnium, vanadium, niobium, tantalum,
Chromium, molybdenum, and tungsten are preferable, and titanium, zirconium, and hafnium are preferable, and zirconium is particularly preferable.

In the above formula (1), R ¹ , R ² , R ³ and R ⁴
Are the same or different, and each has 1 carbon atom which may be substituted with a hydrogen atom, a halogen atom, or halogen.
To 20 hydrocarbon groups, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups or phosphorus-containing groups, and some of the groups adjacent to each other are bonded to form a carbon atom to which those groups are bonded. It may form a ring. Incidentally, R ¹ to R ⁴ present two each in the formula indicates that it is preferable to bind a combination between the same symbols in forming these bonded to ring, for example, a R ¹ R ¹
Indicate that it is preferable to combine with and to form a ring.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, cyclohexyl, Alkyl groups such as octyl, nonyl, dodecyl, iconosyl, norbornyl, and adamantyl; alkenyl groups such as vinyl, propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, Ethylphenyl, propylphenyl, biphenyl,
α- or β-naphthyl, methylnaphthyl, anthracenyl, phenanthryl, benzylphenyl, pyrenyl,
Aryl groups such as acenaphthyl, phenalenyl, aceanthrenyl, tetrahydronaphthyl, indanyl, biphenylyl and the like can be mentioned.

The ring formed by combining these hydrocarbon groups includes a condensed ring such as a benzene ring, a naphthalene ring, an acenaphthene ring and an indene ring; Examples include a group in which a hydrogen atom on a group is substituted with an alkyl group such as methyl, ethyl, propyl, and butyl. Further, these hydrocarbon groups may be substituted with halogen.

Examples of the silicon-containing group include monohydrocarbon-substituted silyls such as methylsilyl and phenylsilyl; dihydrocarbon-substituted silyls such as dimethylsilyl and diphenylsilyl; trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenyl Trihydrocarbon-substituted silyls such as silyl, dimethylphenylsilyl, methyldiphenylsilyl, tolylsilyl, and trinaphthylsilyl; silyl ethers of hydrocarbon-substituted silyls such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; And a silicon-substituted aryl group.

As the oxygen-containing group, a hydroxy group,
Alkoxy groups such as methoxy, ethoxy, propoxy and butoxy; allyloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy; and arylalkoxy groups such as phenylmethoxy and phenylethoxy.

Examples of the sulfur-containing group include a substituent in which oxygen of the oxygen-containing compound is substituted by sulfur, methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, and p-toluene sulfonate. , Trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, pentafluorobenzenesulfonate and other sulfonate groups; methylsulfinate, phenylsulfinate, benzenesulfinate, p- Sulfinate groups such as toluenesulfinate, trimethylbenzenesulfinate, pentafluorobenzenesulfinate and the like can be mentioned.

Examples of the nitrogen-containing group include an amino group, an amino group such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino and dicyclohexylamino; phenylamino, diphenylamino, ditolylamino, dinaphthylamino and methylphenyl. An arylamino group such as amino or an alkylarylamino group can be mentioned.

Examples of the phosphorus-containing group include dimethylphosphino and diphenylphosphino.

In the above formula (1), X ¹ and X ² may be the same or different from each other and represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may be substituted by halogen, It is an oxygen-containing group or a sulfur-containing group. Specific examples of these atoms or groups include those similar to the atoms or groups represented by R ^{1 to} R ⁴ .

In the above formula (1), Y is substituted by halogen.
A divalent hydrocarbon group having 1 to 20 carbon atoms which may be
Divalent silicon-containing group, divalent germanium-containing group, -O
-, -CO-, -S-, -SO-, -SO_Two-, -NR^Five
-, -P (R^Five)-, -P (O) (R ^Five)-, -BR^Five-Or
-AlR^Five-. Where R^FiveIs a hydrogen atom, as above
Halogen atoms and charcoals optionally substituted with halogen
It is a hydrocarbon group having a prime number of 1 to 20.

The divalent hydrocarbon group having 1 to 20 carbon atoms which may be substituted by halogen includes methylene,
Alkylene groups such as dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene and 1,4-cyclohexylene; diphenylmethylene And arylalkylene groups such as diphenyl-1,2-ethylene and the like. Further, a halogenated hydrocarbon group obtained by halogenating the above-mentioned divalent hydrocarbon group having 1 to 20 carbon atoms such as chloromethylene can be mentioned.

The divalent silicon-containing group includes methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene,
Alkyl silylene such as di (cyclohexyl) silylene, methylphenylsilylene, diphenylsilylene, di (p-tolyl) silylene, di (p-chlorophenyl) silylene; alkylarylsilylene, arylsilylene group,
Examples thereof include alkyldisilyl such as tetramethyl-1,2-disilyl and tetraphenyl-1,2-disilyl, alkylaryldisilyl and aryldisilyl groups.

Examples of the divalent germanium-containing group include compounds in which silicon of the above-mentioned divalent silicon-containing group is substituted with germanium.

Specific examples of the bridge type transition metal compound (a) represented by the above formula (1) are described below. Bis (cyclopentadienyl) zirconium dichloride, bis (indenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, bis (n-propylcyclopentadienyl) zirconium dichloride, bis (t-butylcyclopentadienyl) zirconium dichloride, Bis (trimethylsilylcyclopentadienyl) zirconium dichloride, bis (neopentylcyclopentadienyl) zirconium dichloride, rac-
Dimethylsilylene-bis (1-cyclopentadienyl) zirconium dichloride, rac-dimethylsilylene-bis ｛1
-(3-methylcyclopentadienyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2,4-dimethylcyclopentadienyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2, 3,5-trimethylcyclopentadienyl) zirconium dichloride.

In the present invention, among the transition metal compounds (a) represented by the above formula (1), bridge type transition metal compounds represented by the following formula (2) are preferably used.

[0050]

Embedded image (In the formula (2), M, R ¹ , R ³ , X ¹ , X ² and Y are the same as defined in the above formula (1), and R ^{21 to} R ²⁴ and R ⁴¹
To R ⁴⁴ is a hydrogen atom, a halogen atom, an alkyl group or an aryl group, the alkyl group or aryl group may be substituted by halogen or an organic silyl group).

Specific examples of the bridge type transition metal compound represented by the above formula (2) are described below. rac-dimethylsilylene-bis {1- (2-n-propyl-4-)
(9-phenanthryl) indenyl) zirconium dichloride, rac-ethylene-bis (1-indenyl) zirconium dichloride, rac-ethylene-bis (1-indenyl)
Zirconium dibromide, rac-ethylene-bis (1-indenyl) dimethyl zirconium, rac-ethylene-bis (1
-Indenyl) diphenylzirconium, rac-ethylene-
Bis (1-indenyl) methyl zirconium monochloride, rac-ethylene-bis (1-indenyl) zirconium bis (methanesulfonate), rac-ethylene-bis (1-indenyl) zirconium bis (p-toluenesulfonate), rac -Ethylene-bis (1-indenyl) zirconium bis (trifluoromethanesulfonato), rac-ethylene-bis {1- (4,5,6,7-tetrahydroindenyl)} zirconium dichloride, rac-isopropylidene-bis ( 1
-Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- ( 2-methyl-4-i-propylindenyl) zirconium dichloride,

Rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-ethylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-)
n-propylindenyl) zirconium dichloride, ra
c-Dimethylsilylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-n-butylindene) Nil)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2,7-dimethyl-4-sec-butylindenyl)｝ zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,7-dimethyl-4-t-butylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis
-(2,7-dimethyl-4-n-pentylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2,7
-Dimethyl-4-n-hexylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2,7-dimethyl-4-cyclohexylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2,7-dimethyl-4-methylcyclohexylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2,7
-Dimethyl-4-phenylethylindenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2,7-
Dimethyl-4-phenyldichloromethylindenyl) {zirconium dichloride, rac-dimethylsilylene-bis} 1
-(2,7-dimethyl-4-chloromethylindenyl) zirconium dichloride, rac-dimethylsilylene-bis
(2,7-dimethyl-4-trimethylsilylenemethylindenyl) zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2,7-dimethyl-4-trimethylsiloxymethylindenyl)} zirconium dichloride, rac-diethylsilylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium Dichloride,

Rac-di (i-propyl) silylenebis ｛1-
(2,7-dimethyl-4-i-propylindenyl) zirconium dichloride, rac-di (n-butyl) silylenebis
(2,7-dimethyl-4-i-propylindenyl)｝ zirconium dichloride, rac-di (cyclohexyl) silylenebis ｛1- (2,7-dimethyl-4-i-propylindenyl)｝ zirconium dichloride, rac- Methylphenylsilylenebis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride, rac-methylphenylsilylenebis {1- (2,7-dimethyl-4-t-butylindenyl) ｝ Zirconium dichloride, rac-diphenylsilylene bis ｛1-
(2,7-dimethyl-4-t-butylindenyl)｝ zirconium dichloride, rac-diphenylsilylenebis ｛1- (2,7-
Dimethyl-4-i-propylindenyl)｝ zirconium dichloride, rac-diphenylsilylenebis ｛1- (2,7-dimethyl-4-ethylindenyl)｝ zirconium dichloride, rac-di (p-tolyl) silylenebis ｛1 -(2,7-dimethyl-4-i-propylindenyl)｝ zirconium dichloride, rac-di (p-chlorophenyl) silylenebis ｛1- (2,
7-dimethyl-4-i-propylindenyl) zirconium dichloride, rac-dimethylsilylene bis 1- (2-methyl
-4-i-propyl-7-ethylindenyl) zirconium dibromide, rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-i-propyl-1-indenyl) zirconium dimethyl, rac-dimethyl Silylene-bis ｛1- (2,7-dimethyl-4-
i-propyl-1-indenyl) zirconium methyl chloride,

Rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-i-propyl-1-indenyl) zirconium-bis {1- (trifluoromethanesulfonato), rac-dimethylsilylene-bis} 1 -(2,7-dimethyl-4-i-propyl-1-indenyl) zirconium-bis {1- (p-phenylsulfinato), rac-dimethylsilylene-bis {1- (2-phenyl-
4-i-propyl-7-methyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (1,2-dihydroacenaphtho [4,5-b] cyclopentadienyl) zirconium dichloride, rac-dimethyl Silylene-bis (benzo [e] indenyl) zirconium dichloride, rac-
Dimethylsilylene-bis {1- (4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene
-Bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2
-Methyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (β-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛ 1- (2-methyl-4-
(1-anthracenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4-
(2-anthracenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (9
-Anthracenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (9
-Phenanthryl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (p
-Fluorophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4-
(Pentafluorophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (p-chlorophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2- Methyl-4- (m-chlorophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (o-chlorophenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1 -(2-methyl-4- (o, p-dichlorophenyl) phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (p-bromophenyl) indenyl)} zirconium Dichloride,

Rac-dimethylsilylene-bis {1- (2-methyl-4- (p-tolyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (m-
Tolyl) indenyl) zirconium dichloride, rac-
Dimethylsilylene-bis ｛1- (2-methyl-4- (o-tolyl)
Indenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (o, o'-dimethylphenyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2 -Methyl-4- (p-ethylphenyl) indenyl) zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (pi-propylphenyl) indenyl)} zirconium dichloride, rac-
Dimethylsilylene-bis {1- (2-methyl-4- (p-benzylphenyl) indenyl)} zirconium dichloride, ra
c-dimethylsilylene-bis {1- (2-methyl-4- (p-biphenyl) indenyl)} zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4- (m-biphenyl) indenyl) ｝ Zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- (p-trimethylsilylenephenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4- ( m-
Trimethylsilylenephenyl) indenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis (2-phenyl-4-phenylindenyl)｝ zirconium dichloride, rac-dimethylsilylene-bis ｛1- (2-methyl-4-phenylindenyl) )｝ Zirconium dibromide, rac-dimethylsilylene-bis ｛1- (2-methyl-4-phenylindenyl)｝ zirconium dimethyl, rac-dimethylsilylene-
Bis {1- (2-methyl-4-phenylindenyl)} zirconium methyl chloride, rac-dimethylsilylene-bis
-(2-methyl-4-phenylindenyl) zirconium chloride SO ₂ Me, rac-dimethylsilylene-bis {1- (2-
Methyl-4-phenylindenyl)｝ zirconium chloride OSO ₂ Me, rac-dimethylsilylene-bis ｛1- (2-methyl-4-phenylindenyl)｝ zirconium monochloride mono (trifluoromethanesulfonate),

Rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium di (trifluoromethanesulfonate), rac-dimethylsilylene
-Bis {1- (2-methyl-4-phenylindenyl)} zirconium di (p-toluenesulfonate), rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium Di (methylsulfonate), rac-
Dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium di (trifluoromethanesulfinate), rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} Zirconium di (trifluoroacetate), rac-dimethylsilylene-bis ｛1-
(2-methyl-4-phenylindenyl) zirconium monochloride (n-butoxide), rac-dimethylsilylene-
Bis {1- (2-methyl-4-phenylindenyl)} zirconium di (n-butoxide), rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium monochloride (phenoxide) ), Rac-methylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-ethylene-bis {1- (2-methyl-4-)
Phenylindenyl) zirconium dichloride, rac-
Di- (i-propyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-di-
(N-butyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-dicyclohexylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-methylphenylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-diphenylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac -Di (p-tolyl) silylene-
Bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-di (p-chlorophenyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,

Rac-dimethylgermylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-dimethylstannylene-bis {1- (2-methyl-4-phenylindenyl)} Zirconium dichloride, 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-dimethylsilyl -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
-(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-trimethylsilylenephenyl) indenyl) zirconium dichloride, ra
c-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
(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) デ 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-biferinyl) indenyl)｝ zirconium dichloride, rac-methylene-bis ｛1- (2-ethyl-4-phenylindenyl)｝ zirconium dichloride, rac-methylene-bis ｛1- ( 2-ethyl-4- (α-naphthyl) indenyl) デ zirconium dichloride, rac-ethylene-bis ｛1- (2-ethyl-4-phenylindenyl)｝ zirconium dichloride, rac-ethylene-bis ｛1- (2 -Ethyl-4- (α-naphthyl) indenyl) コ 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-dimethylstannylene-bis ｛1 -(2-ethyl-4-phenylindenyl) デ zirconium dichloride, rac-dimethylstannylene-bis ｛1- (2-ethyl-4- (α-naphthyl) indenyl)｝ zirconium dichloride, rac-dimethylstannylene- Bis {1- (2-n-ethyl-4- (9-phenanthryl) indenyl)} zirconium dichloride, rac-dimethylstannylene-bis {1- (2-n-propyl-4-phenylindenyl)} zil Such as Niumujikurorido.

Further, a transition metal compound in which zirconium of the above transition metal compound is replaced with titanium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, or tungsten can be used.

The transition metal compound (a) is generally used as a catalyst component for olefin polymerization in the form of a racemate, but R-type or S-type can also be used. In the present invention, the above transition metal compounds (a) can be used in combination.

The activating compound capable of activating the transition metal compound (a) is at least one selected from the group consisting of an organic aluminum compound (b), an organic aluminum oxy compound (c), and (c) an ionic compound. One compound is used.

The organoaluminum compound (b) is represented, for example, by the following formula (3). R ¹ _n AlX _3-n (3) (in the formula (3), R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, and n is 1 to 3)
3. )

In the above formula (3), R ¹ has 1 to ¹ carbon atoms.
12 hydrocarbon groups, for example, an alkyl group, a cycloalkyl group or an aryl group, specifically, methyl, ethyl, n-propyl, isopropyl, isobutyl, pentyl, hexyl, octyl Group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group and the like.

Such an organoaluminum compound (b)
As, specifically, trimethylaluminum, triethylaluminum, triisopropylaluminum,
Trialkylaluminums such as triisobutylaluminum, trioctylaluminum and tri-2-ethylhexylaluminum; alkenylaluminums such as isoprenylaluminum; dialkylaluminums such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride and dimethylaluminum bromide Halides; alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, and ethyl aluminum sesquibromide; methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum Examples thereof include alkylaluminum dihalides such as mudichloride and ethylaluminum dibromide; and alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride.

As the organoaluminum compound (b), a compound represented by the following formula (4) can also be used. R ¹ _n AlY _3-n (4) (In the formula (4), R ¹ is the same as above, and Y is -OR
² group, -OSiR ³ ₃ group, -OAlR ⁴ ₂ group, -NR ⁵ ₂ group, -
SiR ⁶ ₃ group or -N (R ⁷⁾ is AlR ⁸ ₂ group, n represents 1
R ² , R ³ , R ⁴ and R ⁸ are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, etc., and R ⁵ is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group. Group, phenyl group, trimethylsilyl group and the like, and R ⁶ and R ⁷ are a methyl group, an ethyl group and the like. )

Specifically, the following compounds may be mentioned.
it can. (1) R¹ _nAl (OR^Two)_3-nA compound represented by, for example,
Dimethyl aluminum methoxide, diethyl aluminum
Muethoxide, diisobutylaluminum methoxide
Th, (2) R¹ _nAl (OSiR^Three _Three)_3-nA compound represented by
For example, Et_TwoAl (OSiMe_Three), (Iso-Bu)_TwoAl (OSi
Me_Three), (Iso-Bu)_TwoAl (OSiEt_Three), Etc. (3) R¹ _n
Al (OALR^Four _Two)_3-nA compound represented by, for example, Et_TwoA
lOAlEt_Two, (Iso-Bu)_TwoAlOAl (iso-Bu)_TwoSuch,
(4) R¹ _nAl (NR^Five _Two)_3-nA compound represented by, for example,
Me_TwoAlNEt_Two, Et_TwoAlNHMe, Me_TwoAlNHEt, Et
_TwoAlN (SiMe_Three)_Two, (Iso-Bu)_TwoAlN (SiMe_Three) _TwoSuch,
(5) R¹ _nAl (SiR⁶ _Three)_3-nA compound represented by
Ba (iso-Bu)_TwoAlSiMe_Three(6) R¹ _nAl (N (R⁷)
AlR⁸ _Two)_3-nA compound represented by, for example, Et_TwoAlN (M
e) AlEt_Two, (Iso-Bu)_TwoAlN (Et) Al (iso-Bu)_TwoWhat
And so on.

[0071] Of these, the formula ^{_{R 1 3 Al, R 1 n}} Al
(OR ²⁾ _3-n, preferably compounds represented by ^{_{R 1 n Al (OAlR 4 2}} ) 3-n, in particular R is an isoalkyl radical, n is 2
Are preferred. These can be used in combination.

The above-mentioned organoaluminum oxy compound (c)
May be a conventionally known benzene-soluble aluminoxane, or may be a benzene-insoluble organic aluminum oxy compound as disclosed in JP-A-2-276807.

The aluminoxane as described above 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 an organic metal component. Alternatively, the solvent or unreacted organoaluminum compound may be removed from the recovered aluminoxane solution by distillation, and then redissolved in the solvent.

As the organoaluminum compound used for producing the aluminoxane, the same compounds as those described above as the organoaluminum compound (b) can be specifically mentioned. Of these, trialkyl aluminum and tricycloalkyl aluminum are particularly preferred. Organoaluminum compounds can be used in combination.

Solvents used in the production of aluminoxane include benzene, toluene, xylene, cumene,
Aromatic hydrocarbons such as cymene; pentane, hexane, heptane, octane, decane, dodecane, hexadecane,
Aliphatic hydrocarbons such as octadecane; cyclopentane,
Alicyclic hydrocarbons such as cyclohexane, cyclooctane and methylcyclopentane; petroleum fractions such as gasoline, kerosene and light oil; halides of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons, especially chlorinated products And hydrocarbon solvents such as bromides. Others
Ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons are particularly preferred.

The benzene-insoluble organoaluminum oxy compound used in the present invention has an Al component soluble in benzene at 60 ° C. of not more than 10%, preferably not more than 5%, particularly preferably not more than 2% in terms of Al atom. And insoluble or slightly soluble in benzene.

The solubility of such an organoaluminum oxy compound in benzene is determined by comparing the solubility of the organoaluminum oxy compound with 100 mg atom of Al to 10 mg.
After suspending in 0 ml of benzene, the mixture was mixed at 60 ° C. for 6 hours with stirring, and then subjected to hot filtration at 60 ° C. using a jacketed G-5 glass filter. It is determined by measuring the abundance (X mmol) of Al atoms present in the total filtrate after washing four times with 50 ml of benzene at 50 ° C. (X%).

The ionized ionic compound (d) is a compound which reacts with the transition metal compound (a) represented by the formula (1) to form an ion pair. Examples of such an ionized ionic compound (d) include JP-A-1-50195.
No. 0, Japanese Patent Application Laid-Open No. Hei.
JP 179005, JP-A-3-179006,
JP-A-3-207703, JP-A-3-20770
No. 4, US Pat. No. 5,321,106, Lewis acids, ionic compounds, carborane compounds and the like can be used.

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 and the} like can be given.

Examples of the ionic compound include triphenylcarbenium tetrakis (pentafluorophenyl) borate, tri-n-butylammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and ferrocarbon. Cenium tetra (pentafluorophenyl) borate and the like can be mentioned.

Examples of the carborane compound include dodecaborane, 1-carboundecaborane, bis-n-butylammonium (1-carbedodeca) borate, tri-n-butylammonium (7,8-dicarboundeca) borate, and tri-n-butylammonium (Trideca hydride-7-carboundeca) borate and the like.

The ionized ionic compound (d) can be used in combination of two or more kinds. Further, as the activating compound capable of activating the transition metal compound (a), the above components (b), (c) and (d) can be used in combination.

The metallocene-based catalyst is obtained by mixing the transition metal compound (a) and at least one activating compound selected from the group consisting of (b) to (d) in an inert hydrocarbon solvent or an olefin solvent. Can be prepared.

As the inert hydrocarbon solvent used for preparing the metallocene catalyst, for example, propane, butane,
Aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane and hexadecane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene Halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane; petroleum fractions such as gasoline, kerosene, and light oil; mixtures thereof;

In preparing a metallocene catalyst from each of these components, the transition metal compound (a) is usually used in an amount of about 10 ^-8.
10 ^-1 mol / liter (polymerization volume), preferably 10
It is desirable to use a concentration of ^{-7 to} 5 × 10 ^-2 mol / liter.

As the activating compound, component (b) and / or
Alternatively, when the component (c) is used, the atomic ratio of aluminum to the transition metal of the transition metal compound (a) (A
1 / transition metal), usually in an amount of from 10 to 10,000, preferably from 20 to 5,000, as component (b) and / or (c).
It is preferred to use components. When the organoaluminum compound (b) and the organoaluminum oxy compound (c) are used in combination, the aluminum atom (A
The atomic ratio (Al-1 / Al-2) of the aluminum atom (Al-2) in the component (l-1) to the component (c) is 0.02 to 3, preferably 0.02.
It is desirable to use it in an amount of 5 to 1.5.

When the ionized ionic compound (d) is used, the molar ratio of the transition metal compound (a) to the component (d) ((a) / (d)) is usually 0.01 to 10%. ,
Preferably it is used in an amount of 0.1 to 5.

The above catalyst components may be mixed in a polymerization vessel, or may be mixed in advance and added to the polymerization vessel.
When mixing these components in advance, usually -50 to +15
0 ° C., preferably at a temperature of −20 to + 120 ° C., for 1 minute to
The contact can be carried out for 50 hours, preferably 5 minutes to 25 hours. Further, the mixing temperature may be changed during the mixing contact.

The metallocene catalysts described in the above (a) to (d)
A solid catalyst in which all or any of the components are supported on a granular or particulate solid (carrier) may be used.

The carrier may be an inorganic carrier or an organic carrier. As the inorganic carrier, for example, Si
Porous oxides such as O ₂ and Al ₂ O ₃ are preferably used. Examples of the organic carrier include those having 2 carbon atoms such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene.
(Co) polymers formed mainly with α-olefins of Nos. To 14 or polymers or copolymers formed mainly with vinylcyclohexane or styrene can be used.

The metallocene catalyst may be used after preliminarily polymerizing an olefin with each of the above catalyst components to form a prepolymerized catalyst. As the olefin used for the prepolymerization, olefins such as propylene, ethylene and 1-butene are used, and these can be used in combination with other olefins.

In forming the metallocene catalyst, other components useful for olefin polymerization, such as water as a catalyst component, can be used in addition to the above components.

When a polymer is produced using the above-mentioned metallocene catalyst, it can be produced by polymerizing a monomer in the presence of the metallocene catalyst. For example, the propylene / 1-butene random copolymer (B) used in the present invention can be produced by copolymerizing propylene with 1-butene in the presence of the metallocene catalyst.

The polymerization can be carried out by any of liquid phase polymerization such as suspension polymerization and solution polymerization or gas phase polymerization. In the liquid phase polymerization method, the same inert hydrocarbon solvent as used in the above catalyst preparation can be used, and an α-olefin such as propylene can be used as the solvent.

When the polymerization is carried out by the suspension polymerization method, -5
It is desirable to carry out the reaction at a temperature of 0 to + 100 ° C, preferably 0 to 90 ° C, and when performing the solution polymerization method, at a temperature of 0 to 250 ° C, preferably 20 to 200 ° C. When the polymerization is carried out by a gas phase polymerization method, at a temperature of 0 to 120 ° C., preferably 20 to 100 ° C., at normal pressure to 100 kg / cm ² ,
It is preferable to perform the treatment under a pressure of normal pressure to 50 kg / cm ² .

The polymerization can be carried out in any of a batch system, a semi-continuous system and a continuous system. Further, the polymerization can be performed in two or more stages having different reaction conditions. The molecular weight of the obtained copolymer can be adjusted by allowing hydrogen to exist in the polymerization system or by changing the polymerization temperature and the polymerization pressure.

The content of each component of the sealant composition used in the present invention is 95 to 40% by weight, preferably 90 to 45% by weight of the propylene / 1-butene random copolymer (B), The content of the olefin random copolymer (C) is 5 to 60% by weight, preferably 10 to 55% by weight.

The sealant composition used in the present invention comprises, in addition to the propylene / 1-butene random copolymer (B) and the butene / α-olefin random copolymer (C),
Other components such as other polymers and additives may be contained as long as the object of the present invention is not impaired. As the other polymer blended in the sealant composition, the above-mentioned crystalline polypropylene (A) and the like can be mentioned. Among the crystalline polypropylene (A), a random polypropylene having a content of a structural unit derived from an α-olefin other than propylene of 10 mol% or less is preferable. Additives to be added to the sealant composition include tackifiers, weather stabilizers, heat stabilizers, anti-fogging agents, anti-blocking agents, slip agents, lubricants, antistatic agents, flame retardants, pigments, dyes, anti-aging agents , An antioxidant, a chlorine absorbent, a filler and the like.

The sealant composition used in the present invention is prepared by a general method known as a method for preparing a resin composition. For example, a propylene / 1-butene random copolymer (B) and a butene · α-olefin It can be prepared by melt-kneading the random copolymer (C) and other components to be blended if desired. For example, the above components are charged simultaneously or sequentially into a Henschel mixer, a V-type blender, a tumbler mixer, a ribbon blender, and the like, and then mixed and melted with a single-screw extruder, a multi-screw extruder, a kneader, a Banbury mixer, or the like. It can be obtained by kneading.

<< Composite Film >> The polyolefin composite film of the present invention is a film in which a sealant layer made of the sealant composition is laminated on a polyolefin layer made of the crystalline polypropylene (A). The sealant layer is laminated on one side or both sides of the polyolefin layer serving as the base material layer.

The thickness of the polyolefin layer varies depending on the application, but is usually 5 to 200 μm, preferably 10 to 60 μm.
μm, the thickness of the sealant layer is usually 0.1 to 50 μm, preferably 0.5 to 20 μm. When there are a plurality of sealant layers, each sealant layer preferably has the above thickness. The thickness of the entire polyolefin composite film of the present invention is 5 to 250 μm, preferably 10 to 250 μm.
Desirably, it is 100 μm.

The polyolefin composite film of the present invention may be an unstretched film or a uniaxially or biaxially stretched film. One or both surfaces of the polyolefin may be subjected to corona treatment by a known method.

The polyolefin composite film of the present invention comprises:
For example, it can be molded by a known method such as inflation molding, air-cooled two-stage inflation molding, T-die film molding, and extrusion lamination molding. As a specific method, the following method is exemplified.

1) The polypropylene (A) and the sealant composition are laminated by co-extrusion. The obtained laminated film can be used as the composite film of the present invention without stretching, or can be uniaxially stretched in the longitudinal or transverse direction to form a uniaxially stretched film, or the longitudinal or transverse axis. The film may be stretched separately or simultaneously in the directions to form a biaxially stretched film. 2) The sealant composition is melt-extruded and laminated on a film (base layer) obtained by melt-extruding the polypropylene (A). The obtained laminated film can be used as the composite film of the present invention without stretching, or can be uniaxially stretched in the longitudinal or transverse direction to form a uniaxially stretched film, or the longitudinal or transverse axis. The film may be stretched separately or simultaneously in the directions to form a biaxially stretched film.

3) The polypropylene (A) is melt-extruded and uniaxially stretched in either the vertical or horizontal axis to form a uniaxially stretched film (base layer). Then, the sealant composition is melt-extruded to laminate a sealant layer, or a previously formed sealant layer is laminated, and the obtained laminated film is stretched in the unstretched direction of the base material layer. 4) Polypropylene (A) is melt-extruded and biaxially stretched separately or simultaneously on the vertical and horizontal axes to form a biaxially stretched film (substrate layer). The sealant composition is melt extruded to laminate the sealant layer or a preformed sealant layer. 5) A polypropylene (A) film and a sealant film are bonded to each other with an adhesive to produce. The obtained composite film can be monoaxially or biaxially stretched in the same manner as in 1) above.

When the composite film of the present invention is a stretched film, it is stretched at a ratio of 3 to 7 times, preferably 4 to 6 times in the vertical axis direction and 3 to 12 times, preferably 6 to 10 times in the horizontal axis direction. It is desirable.

The composite film of the present invention has a transparency, a low-temperature heat-sealing property, and a polyolefin layer on which a sealant layer made of the specific sealant composition is laminated.
Excellent heat seal strength, slip property, blocking resistance, etc., and also excellent hot tack property. For this reason, high-speed packaging becomes possible.

The composite film of the present invention can be suitably used as various packaging films such as food packaging, filling packaging, and fiber packaging, and can be particularly suitably used as a packaging film for high-speed packaging. .

[0110]

According to the polypropylene composite film of the present invention, a specific propylene / 1
-Since a sealant layer composed of a sealant composition containing a specific amount of a butene random copolymer and a specific butene / α-olefin random copolymer is laminated, transparency, low-temperature heat sealability, heat seal strength, slip property It has excellent blocking resistance and the like, and also has excellent hot tack properties.

[0111]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited by the examples. The evaluation method in each case is
It is as follows.

<< Haze >> Haze (cloudiness) as an index of transparency was measured in accordance with ASTM D1003. << Gloss (gloss) >> In accordance with ASTM D523,
Gloss was measured. << Static friction coefficient >> Measured in accordance with ASTM D1894. << Dynamic friction coefficient >> It was measured in accordance with ASTM D1894. << Blocking Force >> The blocking force was measured according to ASTM D1893. << Heat seal strength >> A composite film is laminated with sealant layers, and 80 ° C, 90 ° C, 100 ° C, 110 ° C,
After heat sealing at a pressure of ² kg / cm ² for 1 second at a seal bar width of 5 mm at each temperature of 20 ° C., the mixture was allowed to cool. Next, from the heat-sealed film at each temperature, 1
A test piece having a width of 5 mm was cut out, and the separation strength of each test piece when the heat seal portion was peeled off at a crosshead speed of 300 mm / min was measured. << Hot tackiness >> A composite film is laminated with sealant layers, and the resulting mixture is 70 ° C, 80 ° C, 90 ° C, 100 ° C, 110
After heat sealing at a pressure of ² kg / cm ² for 0.8 seconds at a temperature of 120 ° C. and a temperature of 120 ° C., a load of 45 g was applied to measure the distance at which the seal portion was peeled off.

Production Example 1 (Production of propylene / 1-butene random copolymer (B)) A propylene / 1-butene random copolymer was produced using a metallocene catalyst. That is, 900 m of hexane was added to a 2-liter autoclave sufficiently purged with nitrogen.
60 g of 1,1-butene, 1 mmol of triisobutylaluminum was added, and the temperature was raised to 70 ° C., and propylene was supplied to a total pressure of 7 kg / cm ² G, 0.30 mmol of methylaluminoxane, rac-dimethylsilylene −
Bis {1- (2-methyl-4-phenyl-1-indenyl)} zirconium dichloride was added in an amount of 0.001 mmol in terms of Zr atom, and propylene was continuously supplied to give a total pressure of 7%.
Polymerization was carried out for 30 minutes while maintaining Kg / cm ² G.

After the polymerization, the polymer was degassed, the polymer was recovered in a large amount of methanol, and dried at 110 ° C. for 12 hours under reduced pressure. The obtained polymer (propylene / 1-butene random copolymer) B-1 was 39.7 g, and the polymerization activity was 79 kg.
Polymer / mmol Zr · hr Table 1 shows the composition, physical properties, and the like of this polymer.

[0115]

[Table 1]

Note B value in Table 1 was determined by the following method. That is, a sample was prepared by uniformly dissolving about 200 mg of the propylene / 1-butene random copolymer (B) in 1 ml of hexachlorobutadiene in a 10 mmφ test tube, and the ¹³ C-NMR spectrum of this sample was measured under the following conditions. Measured below. It was determined from the obtained spectrum based on the literature. Measurement temperature: 120 ° C. Measurement frequency: 20.05 MHz Spectral width: 1500 Hz Filter width: 1500 Hz Pulse repetition time: 4.2 sec Pulse width: 7 μsec Number of times of integration: 2000 to 5000 times

Example 1 75 parts by weight of the polymer B-1 obtained in Production Example 1
After mixing 25 parts by weight of polymer C-1 shown below, 0.08 parts by weight of a lubricant (erucamide) and 0.16 parts by weight of an antiblocking agent (silica) with a mixer,
The sealant composition melt-kneaded at a temperature of 200 ° C. with an extruder and extruded into a strand was cut in water.
Was prepared.

The pellets were melted by an extruder and supplied to a composite film forming die at a resin temperature of 200 ° C. on the other hand,
In another extruder, isotactic index 96%,
Homopolypropylene (A) having a melt flow rate of 6.5 g / 10 min was supplied to the above-mentioned die for forming a composite film at a resin temperature of 220 ° C. These are co-extruded to a thickness of 40μ.
m homopolypropylene layer (substrate layer), thickness 10 μm
A composite film comprising a sealant layer was obtained. Table 4 shows the evaluation results of this film.

Examples 2 to 5 The procedure of Example 1 was repeated, except that the sealant composition shown in Table 3 was used. The results are shown in Tables 4 and 5.

Comparative Example 1 The procedure of Example 1 was repeated except that the sealant composition shown in Table 3 was used. Table 5 shows the results.

[0121]

[Table 2]

[0122]

[Table 3]

[0123]

[Table 4]

[0124]

[Table 5]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 23/20 C08L 23/20

Claims (7)

[Claims] 1. A polypropylene composite film in which a sealant layer made of a sealant composition is laminated on at least one surface of a polypropylene layer made of crystalline polypropylene (A), wherein the sealant composition is derived from (B) propylene. 50 to 95 mol% of the structural unit to be obtained, and 5 to 50 mol% of the structural unit derived from 1-butene.
Mol%, 135-40 ° C., 95-40% by weight of a propylene / 1-butene random copolymer having an intrinsic viscosity [η] of 0.1-5 dl / g measured in decahydronaphthalene, and (C) 1-butene Content of structural units derived from
More than 0 mol% and 99 mol% or less, α-
The content of structural units derived from olefins (excluding 1-butene) is 1 mol% or more and less than 50 mol%;
5 to 60% by weight of a butene / α-olefin random copolymer having a melt flow rate (MFR) of 0.1 to 20 g / 10 min measured at 0 ° C. under a load of 2.16 kg
A polypropylene composite film, which is a sealant composition containing: 2. The propylene / 1-butene random copolymer (B) has a molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC).
The polypropylene composite film according to claim 1, wherein the value of B is 3 or less, and the parameter B value indicating the randomness of the copolymer monomer chain distribution is 1.0 to 1.5. 3. The propylene / 1-butene random copolymer (B) has a melting point (Tm) measured by a differential scanning calorimeter.
Is 60 to 140 ° C., and the melting point and the content (Bm) of the structural unit derived from 1-butene are represented by the following formula [I]: −2.6Bm + 130 ≦ Tm ≦ −2.3Bm + 155 [I] wherein Tm is a melting point and the unit is ° C. Bm is 1
The content of structural units derived from butenes, the units being mol%. The polypropylene composite film according to claim 1 or 2, which satisfies the following relationship: 4. The propylene / 1-butene random copolymer (B) has a crystallinity (C) determined by an X-ray diffraction method.
d) and the content of structural units derived from 1-butene (B
m) is the formula [II] Cd ≧ −1.5 Bm + 75... [II] [wherein, Cd is the crystallinity and the unit is%. Bm
Is the content of the structural unit derived from 1-butene, and the unit is mol%. The polypropylene composite film according to any one of claims 1 to 3, which satisfies the following relationship: 5. The propylene / 1-butene random copolymer (B) is a random copolymer obtained by randomly copolymerizing propylene and 1-butene in the presence of a metallocene catalyst. 5. The polypropylene composite film according to any one of items 4 to 4. 6. The metallocene-based catalyst represented by the formula (1): [Wherein, M is a transition metal atom of Groups IV to VIB of the periodic table, and R ¹ , R ² , R ³ , and R ⁴ are the same or different and are a hydrogen atom, a halogen atom, a carbon atom of 1 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. May be bonded to form a ring together with the carbon atom to which those groups are bonded. X ¹ and X ² are the same or different and 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 has 1 to 20 carbon atoms
A divalent hydrocarbon group, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, -O-, -CO-, -S-,- SO-, -S
O _2- , -NR ^5- , -P (R ⁵ )-, -P (= O) (R ⁵ )-,
—BR ⁵ — or —AlR ⁵ —. Where 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. And a compound capable of activating the bridge-type transition metal compound (a) represented by the above formula (1),
And (b) to (b) to (b) to (b) an organoaluminum compound (b), an organoaluminum oxy compound (c), and an ionized ionic compound (d) which forms an ion pair by reacting with the transition metal compound represented by the formula (1) The polypropylene composite film according to claim 5, which is a metallocene-based catalyst containing at least one compound selected from the group of compounds d). 7. The polypropylene composite film according to claim 1, wherein the butene / α-olefin random copolymer (C) is 1-butene / ethylene random copolymer.