JPH08238733A - Polypropylene composite film - Google Patents

Abstract

PURPOSE: To provide a polypropylene composite film which has an excellent heat sealability such as low-temperature heat sealability and heat sealing strength and excellent slipping properties and blocking resistance. CONSTITUTION: A polypropylene composite film comprises [I] a crystalline polypropylene layer, and [II] a polypropylene composition layer, wherein the composition [II] contains (A) crystalline polypropylene and (B) propylene-1- butene random copolymer of 10 to less than 50wt.%. The (B) copolymer contains (1) 1-butene constituent unit content of 5 to 50mol%, (2) critical viscosity of 0.1 to 5dl/g, (3) 3 or less of Mw/Mn, (4) B value of 1.0 to 1.5. Further, more preferably (1) 1-butene content and a melting point (60 to 140 deg.C) and (1) and the crystallizability satisfy the specific relation formula. The copolymer (B) is manufactured by using a specific metallocene catalyst.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polypropylene composite film having excellent heat sealability such as low temperature heat sealability and heat seal strength, and also excellent slip property and blocking resistance.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Crystalline polypropylene has mechanical properties such as tensile strength, rigidity, surface hardness, impact strength, and cold resistance, optical properties such as gloss and transparency, or nontoxicity.
It is excellent in food hygiene such as odorlessness and is widely used especially in the field of food packaging. This crystalline polypropylene film shrinks when heated to the heat-sealing temperature, and it is difficult to heat-seal with this film single layer. Therefore, a crystalline polypropylene film is usually provided with a heat seal layer, and this heat seal layer is generally formed of a polymer such as low density polyethylene or propylene / ethylene random copolymer.

By the way, the polymer forming such a heat-sealing layer is (1) capable of being heat-sealed at a considerably lower temperature than a base material (crystalline polypropylene film), and (2) excellent in heat-sealing strength. That the heat seal strength does not change over time, (3) it has excellent adhesion to the substrate, (4) it has transparency equal to or higher than that of the substrate, (5) storage Performances such as no blocking at times, (6) no sticking to bag making equipment and filling and packaging jigs, and (7) excellent scratch resistance are required.

However, conventionally known heat-sealing materials cannot be said to satisfy all of these performances. For example, the above-mentioned low-density polyethylene can be heat-sealed at a low temperature, but the heat-sealing strength and the adhesiveness to the base material. In addition, there is a problem in that it is poor in transparency and easily sticks to a packaging jig or the like.

The propylene / ethylene random copolymer satisfies the above performances (2) to (7), but does not satisfy (1), and the propylene / ethylene random copolymer is used as a heat seal layer. The polypropylene composite film used has a narrow heat seal temperature range. Therefore, when heat-sealing this composite film with an automatic packaging machine, an automatic bag-making machine or the like, there is a problem that the heat-sealing temperature must be strictly controlled. Further, it has been proposed to use a blended product of a propylene / ethylene random copolymer and an ethylene / α-olefin copolymer as a heat seal material, but this blended product is better than the propylene / ethylene random copolymer. Improved low temperature heat sealability, but poor transparency.

[0006] By the way, the present applicant previously noted that the propylene / 1-butene random copolymer has a propylene content of 55 to 85% by weight and a crystal fusion heat of 20 to 80 J / g as measured by a differential scanning calorimeter. It was found that the coalesced material has excellent transparency and good low temperature heat sealability, and is useful as a heat seal material. A composition comprising the propylene / 1-butene random copolymer and isotactic polypropylene and containing the propylene / 1-butene random copolymer in an amount of 50% by weight or more is used as the heat-sealing layer of the polypropylene film. It has been proposed (Japanese Patent Application Laid-Open No. 54-114887). The heat-sealing layer formed from this composition is excellent in low-temperature heat-sealing property and blocking resistance, but compared with the heat-sealing layer formed from the above-mentioned propylene / ethylene random copolymer, blocking resistance, resistance Scratch property is slightly inferior.

A composition comprising a propylene / 1-butene copolymer and a crystalline propylene / α-olefin random copolymer, containing the propylene / 1-butene copolymer in an amount of 10 to 40% by weight. A composite film having a heat-sealing layer of isotactic polypropylene has also been proposed by the applicant as a composite film having excellent heat-sealing properties (Japanese Patent Publication No. 61-42626).

However, such a polypropylene film is desired to have properties that can be applied to higher-speed packaging, and is desired to have excellent slip properties and blocking resistance as well as improved low-temperature heat-sealing properties.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and is excellent in transparency, low temperature heat sealability, and mechanical strength such as blocking resistance and scratch resistance. The present invention aims to provide a polypropylene composite film.

[0010]

The polypropylene composite film according to the present invention comprises [I] a crystalline polypropylene layer and [II] a polypropylene composition layer laminated on at least one side of the crystalline polypropylene layer [I], The polypropylene composition [II] is a crystalline polypropylene containing (A) a unit derived from propylene in an amount of 90 mol% or more; 50 wt% or more 9
Less than 0% by weight, (B) the following propylene / 1-butene random copolymer;
It is characterized by comprising 10% by weight or more and less than 50% by weight.

The propylene / 1-butene random copolymer (B) comprises (1) 50 units of a structural unit derived from propylene.
In an amount of ˜95 mol%, containing a constitutional unit derived from 1-butene in an amount of 5 to 50 mol%, (2) an intrinsic viscosity measured in decalin at 135 ° C. of 0.1 to 5 dl / g. And (3)
Gel permeation chromatography (GPC)
Has a molecular weight distribution (Mw / Mn) of 3 or less, and (4) the parameter B value showing the randomness of the copolymerized monomer chain distribution is 1.0 to 1.5.

This propylene / 1-butene random copolymer (B) has a parameter B value of (4) of 1.0 to 1.3.
In addition to these characteristics (1) to (4), (5)
The melting point Tm measured by a differential scanning calorimeter is 60 to
140 ° C., and the relationship between the melting point Tm and the 1-butene constitutional unit content M (mol%) is −2.6 M + 130 ≦
Tm ≤ -2.3M + 155, and (6) the relationship between the crystallinity C measured by the X-ray diffraction method and the 1-butene constitutional unit content M (mol%) is C ≥ -1.5M + 75.
It is preferred that

The above crystalline polypropylene layer [I] is
It may be unstretched or biaxially stretched. The propylene / 1-butene random copolymer (B) as described above is
[A] a transition metal compound represented by the following general formula [I],

[0014]

Embedded image

[Wherein M is IVa, Va, VIa of the periodic table]
Group ¹ transition metals, R ¹ and R ² are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a carbon atom having 1 to 1 carbon atoms.
20 is a halogenated hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, and 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 halogenated carbon group having 1 to 20 carbon atoms Hydrogen group, divalent silicon-containing group, divalent germanium-containing group, divalent tin-containing group, -O-, -CO-, -S-,-.
_{SO -, - SO 2 -,} - NR 3 -, - P (R 3) -, -
^{P (O) (R 3)} -, - BR 3 - or -AlR ³ - a. (However, R ³ 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.)], [B] 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 can be obtained by copolymerizing propylene and 1-butene in the presence of an olefin polymerization catalyst containing a [C] organoaluminum compound, if desired.

[0016]

DETAILED DESCRIPTION OF THE INVENTION A polypropylene composite film according to the present invention comprises [I] a crystalline polypropylene layer and [II] a polypropylene composition layer laminated on at least one surface of the crystalline polypropylene layer [I]. The polypropylene composition [II] comprises (A) a crystalline polypropylene containing a unit derived from propylene in an amount of 90 mol% or more, and (B) a propylene / 1-butene random copolymer described below. Become.

Each component will be specifically described below. [I] Crystalline Polypropylene The base material layer of the polypropylene composite film according to the present invention is
It is made of crystalline polypropylene.

In the present invention, as the crystalline polypropylene, those known as polypropylene for films can be used, but the isotactic index II (boiling n-heptane insoluble component) is 75% or more, preferably 75. It is preferred to use ˜99% polypropylene.

The density of this crystalline polypropylene is
0.89-0.92 g / cm ³ , melt index (23
0 ° C.) is preferably 0.1-10. Homopolypropylene is usually used as the crystalline polypropylene, but a propylene random copolymer containing a small amount of units derived from olefins other than propylene, for example, 5 mol% or less, is used as long as the object of the present invention is not impaired. It can also be used. Specific examples of such other olefin include ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, and 4-methyl. -1-Pentene and other α-olefins other than propylene having 2 to 20 carbon atoms.

The crystalline polypropylene used in the present invention can be produced by a known method using a conventionally known solid titanium catalyst component or metallocene compound catalyst component.

A heat-resistant stabilizer, an ultraviolet absorber, an anti-blocking agent, a slip agent, an antistatic agent, etc. can be added to the crystalline polypropylene for use. (A) Crystalline Polypropylene The polypropylene composition used for the heat-sealing layer of the polypropylene composite film according to the present invention comprises a crystalline polypropylene (A) and a specific propylene / 1-butene random copolymer (B) described below. ) And formed.

Specific examples of the crystalline polypropylene (A) forming the polypropylene composition include the same crystalline polypropylene [I] forming the base material layer as described above. Among them, polypropylene containing a unit derived from propylene in an amount of 90 mol% or more is used.

(B) Propylene / 1-butene random co-weight
Coalescence The polypropylene composition used for the heat seal layer of the polypropylene composite film according to the present invention contains a specific propylene / 1-butene random copolymer (B).

(1) The propylene / 1-butene random copolymer used in the present invention contains propylene-derived units in an amount of 50 to 95 mol%, preferably 55 to 93 mol%, and more preferably 60 to 90 mol%. The unit derived from 1-butene is contained in an amount of 5 to 50 mol%, preferably 7 to 45 mol%, more preferably 10 to 40 mol%.

The propylene / 1-butene random copolymer may contain a small amount of a structural unit derived from an olefin other than propylene and 1-butene, for example, 10 mol% or less.

(2) Intrinsic Viscosity [η] The propylene / 1-butene random copolymer used in the present invention has an intrinsic viscosity [η] measured in decalin at 135 ° C. of preferably 0.1 to 5 dl / g. Is from 0.5 to 4 dl / g, more preferably from 1 to 3 dl / g.

(3) Molecular Weight Distribution The propylene / 1-butene random copolymer used in the present invention is gel permeation chromatography GP.
The molecular weight distribution (Mw / Mn) determined by C is 3 or less, preferably 2.5 or less.

(4) Randomness In the propylene / 1-butene random copolymer used in the present invention, the parameter B value showing the randomness of the copolymerized monomer chain distribution is 1.0 to 1.5, preferably 1. 0-1.3
More preferably, it is 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 ), where P ₁ and P ₂ are the first monomer and second monomer content fractions, respectively, and P ₁₂ is the (first
The ratio of (monomer)-(second monomer) chain.

When this B value is 1, Bernoulli statistics are followed, and when B <1, the copolymer is block-like, and B>
When 1 is alternating. Further, the propylene / 1-butene random copolymer used in the present invention has (5) a melting point Tm of 6 as measured by a differential scanning calorimeter, in addition to the above characteristics.
0 to 140 ° C., preferably 80 to 130 ° C., and the melting point Tm and 1-butene constitutional unit content M
The relationship with (mol%) is -2.6 M + 130 ≤ Tm
It is desirable that ≦ −2.3M + 155.

(6) The relationship between the crystallinity C measured by the X-ray diffraction method and the 1-butene structural unit content M (mol%) is C
It is desirable that ≧ −1.5 M + 75.

The crystallinity of the propylene / 1-butene random copolymer is 15 to 65%, preferably 20 to 60%. Further, the propylene / 1-butene random copolymer used in the present invention has a position disorder unit of 0.05 based on the 2,1-insertion of propylene monomer in all propylene constitutional units determined from ¹³ C-NMR spectrum.
It may be contained in a proportion of not less than%.

During the polymerization, the propylene monomer makes 1,2-insertion (the methylene side bonds with the catalyst), but rarely makes 2,1-insertion. The 2,1-inserted monomers form regiorandom units in the polymer.

The ratio of 2,1-insertion of the propylene monomer in all propylene constitutional units was determined by using ¹³ C-NMR to determine the Po
lymer, 30 (1989) 1350, and can be calculated from the following formula.

[0035]

[Equation 1]

The peaks were named according to the method of Carman et al. (Rubber Chem. Technol., 44 (1971), 781). In addition, Iαβ and the like indicate peak areas such as αβ peaks. If it is difficult to directly obtain the area such as Iαβ from the spectrum due to overlapping peaks,
Carbon peaks with corresponding areas can be substituted.

The propylene / 1-butene random copolymer used in the present invention may have a position irregular unit of 0.05% or less based on 1,3-insertion of propylene monomer.

The amount of three chains based on the 1,3-insertion of propylene can be determined from the βγ peak (resonance near 27.4 ppm). The polypropylene composition forming the heat-sealing layer of the polypropylene composite film according to the present invention contains the propylene / 1-butene random copolymer (B) having the above-mentioned properties, and has excellent heat-sealing properties. Express. The characteristics of this propylene / 1-butene random copolymer, such as (2) intrinsic viscosity [η] above
Is less than 5 dl / g, the moldability is poor, and it is difficult to form a thin layer having a desirable thickness as a heat-sealing layer, specifically 50 μm or less, while if it is less than 0.1 dl / g, the heat-sealing strength is poor. There is.

Further, in the above characteristic (5), when the melting point exceeds 140 ° C., the suitable heat sealing temperature of the film becomes as high as 130 ° C. or higher, while when it is less than 60 ° C., the low temperature heat sealing property is improved, The scratch resistance may be deteriorated, and the film may be blocked during storage, which may make practical use difficult.

Further, when the crystallinity of the propylene / 1-butene random copolymer is 15 to 65%, a film excellent in low-temperature heat sealability and blocking resistance can be obtained, which is preferable. This crystallinity is 15
If it is less than%, the scratch resistance of the film is insufficient, blocking is likely to occur, and stickiness occurs,
On the other hand, when it exceeds 65%, the low temperature heat sealability is not sufficiently improved.

The propylene / 1-butene random copolymer used in the present invention as described above includes [A] a specific transition metal compound described below 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,
If desired, it can be obtained by copolymerizing propylene and 1-butene in the presence of an olefin polymerization catalyst composed of an [C] organoaluminum compound.

The olefin polymerization catalyst used in the present invention will be described below. The transition metal compound [A] (hereinafter sometimes referred to as “component [A]”) that forms the olefin polymerization catalyst used in the present invention is represented by the following general formula [I].

[0043]

Embedded image

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 1 to 20 carbon atoms.
A halogenated hydrocarbon group, a silicon-containing group, an oxygen-containing group,
It is 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, and examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, nonyl and dodecyl. Alkyl groups such as eicosyl, norbornyl and adamantyl, alkenyl groups such as vinyl, propenyl and cyclohexenyl, arylalkyl groups such as benzyl, phenylethyl and phenylpropyl, phenyl, tolyl, dimethylphenyl, trimethylphenyl and ethylphenyl,
Examples thereof include aryl groups such as propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthracenyl, and phenanthryl. Examples of the halogenated hydrocarbon group include groups in which these hydrocarbon groups are substituted with a halogen atom.

Further, monohydrocarbon-substituted silyl such as methylsilyl and phenylsilyl, dihydrocarbon-substituted silyl such as dimethylsilyl and diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, Such as trihydrocarbon-substituted silyl such as methyldiphenylsilyl, tritolylsilyl, trinaphthylsilyl, silyl ether of hydrocarbon-substituted silyl such as trimethylsilyl ether, silicon-substituted alkyl group such as trimethylsilylmethyl, silicon-substituted aryl group such as trimethylphenyl, etc. Silicon-containing substituents, hydroxy groups, methoxy, ethoxy, propoxy, butoxy and other alkoxy groups, phenoxy, methylphenoxy, dimethylphenoxy, naphtho An aryloxy group such as Si, an oxygen-containing substituent such as an arylalkoxy group such as phenylmethoxy and phenylethoxy, a sulfur-containing group in which oxygen of the oxygen-containing compound is replaced by sulfur, an amino group, methylamino, dimethylamino, diethylamino, di Alkylamino groups such as propylamino, dibutylamino, dicyclohexylamino, phenylamino, diphenylamino,
Examples thereof include nitrogen-containing groups such as arylamino groups or alkylarylamino groups such as ditolylamino, dinaphthylamino and methylphenylamino, 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 or an aromatic group, and particularly preferably a methyl group or a hydrocarbon group having 2 to 6 carbon atoms. .

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, and among them, a secondary or tertiary alkyl group having 3 to 20 carbon atoms or an aromatic group. Is desirable.

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 include aryl groups such as benzylphenyl, pyrenyl, acenaphthyl, phenalenyl, aceanthrylenyl, tetrahydronaphthyl, indanyl, biphenylyl, and arylalkyl groups such as benzyl, phenylethyl, phenylpropyl, tolylmethyl, etc. It may contain a triple 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,
Examples thereof include chain alkyl groups and cyclic alkyl groups such as cyclohexyl, heptyl, octyl, nonyl, dodecyl, eicosyl, norbornyl and adamantyl.

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

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-
Sulfonate groups such as toluene sulphonate, trimethylbenzene sulphonate, triisobutylbenzene sulphonate, p-chlorobenzene sulphonate, pentafluorobenzene sulphonate, methylsulfinate, phenylsulfinate, benzenesulfinate And sulfinate groups such as p-toluenesulfinate, trimethylbenzenesulfinate, pentafluorobenzenesulfinate and trifluoromethanesulfinate.

Y Y is a divalent hydrocarbon group having 1 to 20 carbon atoms and 1 to 1 carbon atoms.
20 divalent halogenated hydrocarbon groups, divalent silicon-containing groups, divalent germanium-containing groups, divalent tin-containing groups,
O -, - CO -, - S -, - SO -, - SO 2 -, - N
^{R 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, 1 to 2 carbon atoms
0 halogenated hydrocarbon group), specifically, methylene, dimethylmethylene, 1,2-ethylene, dimethyl-1,2
-Ethylene, 1,3-trimethylene, 1,4-tetramethylene,
1 to 2 carbon atoms such as alkylene groups such as 1,2-cyclohexylene and 1,4-cyclohexylene, aryl alkylene groups such as diphenylmethylene and diphenyl-1,2-ethylene
A divalent hydrocarbon group of 0, a halogenated hydrocarbon group obtained by halogenating the above divalent hydrocarbon group having 1 to 20 carbon atoms such as chloromethylene, methylsilylene, dimethylsilylene,
Diethyl silylene, di (n-propyl) silylene, di (i-
Propyl) silylene, di (cyclohexyl) silylene,
Methylphenylsilylene, diphenylsilylene, di (p-
Tolyl) silylene, di (p-chlorophenyl) silylene and other alkyl silylenes, alkyl aryl silylenes, aryl silylene groups, tetramethyl-1,2-disilyl, tetraphenyl-1,2-disilyl and other alkyl disilyls, alkyl aryl di A divalent silicon-containing group such as a silyl or arylsilyl group, a divalent germanium-containing group obtained by substituting germanium for silicon in the above-mentioned divalent silicon-containing group, and a substituting tin for silicon in the above-mentioned divalent silicon-containing group. A valent tin-containing group substituent, etc., and R ⁵ is the same halogen atom as R ¹ above, a hydrocarbon group having 1 to 20 carbon atoms, or 1 carbon atom.
20 halogenated hydrocarbon groups.

Of these, a divalent silicon-containing group, a divalent germanium-containing group and a divalent tin-containing group are preferable, and a divalent silicon-containing group is more preferable,
Of these, alkylsilylene, alkylarylsilylene, and arylsilylene are particularly preferable.

Specific examples of the transition metal compound represented by the above general formula [I] will be given below. rac-dimethyl silylene-
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, r
ac-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, r
ac-dimethylsilylene-bis (2,7-dimethyl-4-methylcyclohexyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,7-dimethyl-4-phenylethyl-1-indenyl) zirconium dichloride, r
ac-Dimethylsilylene-bis (2,7-dimethyl-4-phenyldichloromethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,7-dimethyl-4-chloromethyl-1-indenyl) zirconium Dichloride, rac
-Dimethylsilylene-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) silylene bis (2,7-dimethyl
-4-i-Propyl-1-indenyl) zirconium dichloride, rac-methylphenylsilylene bis (2,7-dimethyl-4)
-i-propyl-1-indenyl) zirconium dichloride,
rac-Methylphenylsilylene bis (2,7-dimethyl-4-t-
Butyl-1-indenyl) zirconium dichloride, rac-
Diphenylsilylene bis (2,7-dimethyl-4-t-butyl-1-
Indenyl) zirconium dichloride, rac-diphenylsilylenebis (2,7-dimethyl-4-i-propyl-1-indenyl) zirconium dichloride, rac-diphenylsilylenebis (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) silylene bis (2,7-dimethyl-4-i-propyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene Bis (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-dimethylsilylene- Bis (2,7-dimethyl-4-i-propyl-1-indenyl) zirconium methyl chloride, ra
c-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-dimethyl silylene-
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.

[0058]

[Chemical 4]

(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-dimethylsilylene-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, r
ac-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-tolyl) -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-dimethylsilylene-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-bis (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-
Toluene sulfonate), rac-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.

Of the above, compounds in which R ¹ is a methyl group are particularly preferred. In the above formula [Ia], R ¹
Is a hydrocarbon group having 2 to 6 carbon atoms, and R ³ is 6 to 6 carbon atoms.
A transition metal compound having 16 aryl groups 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, r
ac-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, ra
c-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-dimethylsilyl Ren-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, ra
c-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- Screw {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-dimethylstannylene-bis {1 -(2-Ethyl-4-phenylindenyl)} 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.

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 organoaluminum oxy compound as exemplified in Japanese Patent No. 687.

The conventionally known aluminoxane can be produced, for example, by the following method. (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. A method in which an organoaluminum compound such as trialkylaluminum is added to the hydrocarbon medium suspension and reacted. (2) A method in which water, ice or water vapor 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. Further, the solvent or the unreacted organoaluminum compound may be removed by distillation from the recovered solution of the aluminoxane, and then redissolved in the solvent or suspended in the poor solvent of the aluminoxane.

Specific examples of the organoaluminum compound used when preparing the aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum and trisec-butyl. Aluminum, trialkyl aluminum such as 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, diethyl aluminum bromide, diisobutyl aluminum chloride, etc. Alkylaluminum halides, diethylaluminum hydride, dialkylaluminum hydride such as diisobutylaluminum hydride, dimethyl aluminum methoxide, dialkylaluminum alkoxides such as diethylaluminum ethoxide and dialkylaluminum Ally Loki Sid such as diethyl aluminum phenoxide 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.

[0070] _{(i-C 4 H 9)} x Al y (C 5 H 10) z ... [II] ( wherein, x, y, z are each a positive number, and z ≧ 2x.) Above Such organoaluminum compounds may be 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 Application Laid-Open No. 1-501950
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 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
Examples include O _{3 and the} like.

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.

The carborane compounds include dodecaborane, 1-carbaundecaborane, bis-n-butylammonium (1-carbedodeca) borate, tri-n-butylammonium (7,8-dicarbaundeca) borate, tri-n-butylammonium. (Trideca hydride-7-carbaundeca) borate etc. can be illustrated.

Two or more compounds [B-2] which react with the above transition metal compound [A] to form an ion pair can be used as a mixture. Examples of the [C] organoaluminum compound (hereinafter sometimes referred to as “component [C]”) forming the olefin polymerization catalyst used in the present invention include, for example, organoaluminum represented by the following general formula [III]. A compound can be illustrated.

R ⁹ _n AlX _3-n [III] (wherein R ⁹ is a hydrocarbon group having 1 to 12 carbon atoms, and X is
Is a halogen atom or a hydrogen atom, and n is 1 to 3. ) In the above general formula [III], R ⁹ is a hydrocarbon group having 1 to 12 carbon atoms such as an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, an 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]
Specifically, the following compounds may be mentioned. Trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum, tri (2-ethylhexyl) aluminum, trialkyl aluminum such as tridecyl aluminum, alkenyl aluminum such as isoprenyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride. , Diisopropyl aluminum chloride, diisobutyl aluminum chloride, dimethyl aluminum bromide, etc., dialkyl aluminum halides, methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide, etc. Alkyl aluminum dihalides such as umsesquihalide, methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride and ethyl aluminum dibromide, and alkyl aluminum hydrides such as diethyl 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 above, L is an —OR ¹⁰ group,
OSiR ¹¹ ₃ group, -OAlR ¹² ₂ group, -NR ¹³ ₂ group, -Si
R ¹⁴ ₃ group or —N (R ¹⁵ ) AlR ¹⁶ ₂ group, and 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, a methyl group, an ethyl group, isopropyl group. Group, phenyl group, trimethylsilylene group and the like, and R ¹⁴ and R ¹⁵ are methyl group, ethyl group and the like. ) Among such organoaluminum compounds, R ⁷ _n A
a compound represented by l (OAlR ¹⁰ ₂ ) _3-n , such as Et ₂
AlOAlEt ₂ , (iso-Bu) ₂ AlOAl (iso-Bu) ₂
Are preferred.

[0080] Among the above general formula [III] and an organoaluminum compound represented by the [IV], formula R ⁷ compound represented by ₃ Al are preferred, especially compounds wherein R is an isoalkyl group.

The olefin polymerization catalyst used in the present invention comprises a component [A], a component [B-1] (or a component [B-2]) and, if desired, a component [C] in an inert hydrocarbon solvent or an olefin. It can be prepared by mixing in a solvent.

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

The order of mixing the respective components when preparing the olefin polymerization catalyst is arbitrary, but the component [B-1] or the component [B
-2]) and component [A], or component [B-1] and component [C], and then component [A], or component [A] and component [B- 1] (or component [B-2]) and then component [C], or alternatively component [A] and component [C], then component component [B-1]
(Or component [B-2]) is preferably mixed.

When the above components are mixed 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 component [B-1] is used as component [B], aluminum in component [B-1] is replaced by 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.

[0086] 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.
It may be used in an amount of 02 to 20, preferably 0.2 to 10, if 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 1000.
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 comprises an inorganic or organic particulate carrier, which is a granular or particulate solid, and the above-mentioned components [A] and [B].
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 mainly from α-olefin such as ethylene, propylene, 1-butene, or styrene.

In the present invention, it is also possible to preliminarily polymerize an olefin with each of the components forming the above olefin polymerization catalyst. The olefin used in the prepolymerization is preferably propylene, ethylene, 1-butene, etc., but may be a mixture of these and other olefins.

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

The propylene / 1-butene random copolymer used in the present invention is obtained by copolymerizing propylene and 1-butene in the presence of the above-mentioned olefin polymerization catalyst so as to finally obtain the above composition ratio. Can be manufactured.

Polymerization can be carried out by either liquid phase polymerization such as suspension polymerization or solution polymerization, or gas phase polymerization. In the liquid phase polymerization method, it is possible to use the same inert hydrocarbon solvent used in the above-mentioned catalyst preparation, and propylene can also be used as a solvent.

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

The polymerization is usually carried out at atmospheric pressure to 100 kg / cm ^2.
It is preferably carried out under atmospheric pressure to a pressure of 50 kg / cm ² .
The polymerization reaction can be carried out by any of a batch system, a semi-continuous system and a continuous system, and the polymerization can also be carried out in two or more stages under different reaction conditions.

The molecular weight of the obtained propylene / 1-butene random copolymer can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature and the polymerization pressure.

In the present invention, propylene.
The butene random copolymer may be partially or completely modified with an unsaturated carboxylic acid or its anhydride. The modified product of this propylene / 1-butene random copolymer is excellent in overlap wrapping property and adhesiveness to metal and the like.

[II] Polypropylene Composition The polypropylene layer forming the heat-sealing layer of the polypropylene composite film according to the present invention includes the above-mentioned (A) crystalline polypropylene and (B) propylene.
A butene random copolymer, the crystalline polypropylene (A) in an amount of 50% by weight or more and less than 90% by weight, and the propylene / 1-butene random copolymer (B) in an amount of 10% by weight or more and less than 50% by weight. Contains in quantity.

From such a polypropylene composition,
It is possible to form a polypropylene composite film having a heat-sealing layer that is excellent in transparency and low-temperature heat-sealing property and is also excellent in mechanical strength such as blocking resistance and scratch resistance.

When the amount of the crystalline polypropylene (A) in the polypropylene composition exceeds 90% by weight, the softening temperature of the film remarkably rises and the low temperature heat-sealing property is extremely lowered, while when it is less than 50% by weight. If so, the blocking resistance and scratch resistance of the film may be deteriorated.

The polypropylene composition as described above includes
A heat resistance stabilizer, an ultraviolet absorber, an anti-blocking agent, a slip agent, an antistatic agent, etc. can be added and used. Polypropylene Composite Film The polypropylene composite film according to the present invention is formed from the above-mentioned [I] crystalline polypropylene layer and [II] polypropylene composition layer.

The polypropylene composition layer [II] is a heat-sealing layer and is provided on one side or both sides of the crystalline polypropylene layer [I] which is the base material layer. In the polypropylene composite film according to the present invention, the base material layer made of crystalline polypropylene [I] may be unstretched or uniaxially or biaxially stretched. Further, one or both surfaces of the base material layer [I] may be subjected to corona treatment by a known method.

Such a composite film comprises a crystalline polyolefin [I] and a polypropylene composition [II],
For example, it can be obtained as follows. (1) A crystalline polypropylene [I] and a polypropylene composition [II] are coextruded to form a laminated sheet.

This laminated sheet may be uniaxially stretched in the vertical axis or the horizontal axis direction, or biaxially stretched by separately or simultaneously stretching in the vertical axis or the horizontal axis direction. (2) The polypropylene composition [II] is melt-extruded and laminated on the film (base material layer) obtained by melt-extruding the crystalline polypropylene [I].

This laminated sheet may be uniaxially stretched in the vertical axis or the horizontal axis direction, or may be biaxially stretched in the vertical axis or the horizontal axis direction separately or simultaneously. (3) Crystalline polypropylene [I] is melt-extruded to form a base layer uniaxially stretched longitudinally or horizontally, and then the polypropylene composition [II] is melted on the uniaxially stretched base layer. An extruded or preformed film of the polypropylene composition [II] is laminated, and the obtained laminated sheet is stretched in the unstretched direction of the substrate layer.

(4) Crystalline polypropylene [I] is melt-extruded to form a base layer which is biaxially stretched separately on the ordinate and the abscissa or simultaneously, and the polypropylene composition is formed on the biaxially stretched base layer. The object [II] is melt extruded or a film of the polypropylene composition [II] which has been formed in advance is laminated.

(5) The crystalline polypropylene [I] film and the polypropylene composition [II] film are bonded together with an adhesive. This laminated sheet may be uniaxially stretched in the vertical axis or the horizontal axis direction, or may be biaxially stretched by separately or simultaneously stretching in the vertical axis or the horizontal axis direction.

In the composite film according to the present invention, the thickness of the crystalline polypropylene [I] layer is 5 to 200 μm, preferably 10 to 60 μm, and the polypropylene composition [II].
The thickness of the layer is 0.1 to 50 μm, preferably 0.5 to 20 μm.
It is desirable that it is m.

In the composite film according to the present invention, when the crystalline polypropylene [I] as the base material layer is stretched, it is 3 to 7 times, preferably 4 to 6 times in the longitudinal direction and 3 to 12 times in the transverse direction. It is desirable that the film is stretched at a draw ratio of preferably 6 to 10 times.

[0110]

The polypropylene composite film according to the present invention as described above is excellent in heat sealability. In particular, it can be heat-sealed even at a low temperature, can be heat-sealed over a wide range of temperatures, and has excellent heat-sealing strength. Further, even when the film is stored for a long period of time, the heat sealing temperature does not change with time, and stable heat sealing work can be secured.

The polypropylene composite film according to the present invention is also excellent in transparency, scratch resistance, blocking resistance, etc., and can be packaged at high speed. Such a polypropylene composite film according to the present invention is suitably used for applications such as food packaging, filling packaging, and fiber packaging.

[0112]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited to these examples.

[Measurement of Physical Properties of Propylene / 1-Butene Random Copolymer (B)] (1) Propylene Content, 1-Butene Content It was determined by using ¹³ C-NMR.

(2) Intrinsic viscosity [η] Measured in decalin at 135 ° C. and shown in dl / g. (3) Molecular weight distribution (Mw / Mn) The molecular weight distribution (Mw / Mn) is GPC-1 manufactured by Millipore.
It measured using 50C as follows.

The separation column was TSK GNH HT, the column size was 27 mm in diameter and 600 mm in length, the column temperature was 140 ° C., and the mobile phase was o-dichlorobenzene (Wako Pure Chemical Industries) and an antioxidant. As BH
Using T (Takeda Yakuhin) 0.025% by weight, the sample was moved at 1.0 ml / min, the sample concentration was 0.1% by weight, the sample injection amount was 500 μl, and a differential refractometer was used as a detector.

Molecular weight Mw <1000 and Mw> 4 ×
For 10 ⁶ , standard polystyrene manufactured by Tosoh Corporation was used,
For 1000 <Mw <4 × 10 ⁶ , standard polystyrene manufactured by Pressure Chemical Co. was used.

(4) B value The composition distribution B value is about 200 mg in a 10 mmφ sample tube.
1 ml of hexachlorobutadiene in a uniform manner
Of dissolved sample¹³The C-NMR spectrum is
Measurement temperature 120 ° C, measurement frequency 25.05MHz, space
Cutler width 1500 Hz, filter width 1500 Hz, power
Loose repetition time 4.2 sec, number of integration 2000-5
Measured under the condition of 000 measurements, and from this spectrum
P_E, P _o, P_OEIt was calculated by determining

(5) Melting point (Tm) The melting point (Tm) was measured using a Perkin-Elmer DSC-7 type device (differential scanning calorimeter (DSC)).

About 5 mg of a sample was packed in an aluminum pan and the amount of 200
After heating up to 200 ° C and holding at 200 ° C for 5 minutes,
It was determined from the endothermic curve when the temperature was decreased to −40 ° C. in minutes, the temperature was maintained at −40 ° C. for 5 minutes, and the temperature was raised at 10 ° C./minute.

(6) Crystallinity The crystallinity was determined by X-ray diffraction measurement of a 1.0 mm-thick press sheet which had been at least 24 hours after molding.

[Measurement of Physical Properties of Composite Film] (1) Haze Measured according to ASTM D1003.

(2) Time-dependent change in haze The composite film was kept at 80 ° C. for 3 days and allowed to cool, and then the haze was measured in the same manner as in (1) above.

(3) Glossiness The glossiness was measured according to ASTM D523. (4) Slip property It was measured according to ASTM D1894.

(5) Blocking property The blocking property was measured according to ASTM D1893. (6) Time-dependent change in blocking property After the composite film was kept at 50 ° C for 1 week and allowed to cool, the blocking property was measured in the same manner as in (5) above.

(7) Heat-seal adhesion strength The polypropylene composition layer [II] layers of the composite film were laminated on each other, and at each temperature shown in Table 1, 2 kg / cm ²
After heat-sealing for 1 second with the width of the seal bar of 5 mm, it was left to cool.

Test pieces each having a width of 15 mm were cut from the film heat-sealed at each temperature, and the peel strength of each test piece when the heat-sealed portion was peeled off at a crosshead speed of 300 mm / min was measured.

[0127]

Production Example 1 Production of Propylene / 1-Butene Random Copolymer [I] To a 2 liter autoclave, which had been sufficiently replaced with nitrogen, 900 ml of hexane and 60 g of 1-butene were charged, and 1 mmol of triisobutylaluminum was added. After the temperature was raised to ℃, propylene was supplied to adjust the total pressure to 7 kg / cm ² G, methylaluminoxane 0.30 mmol, rac-dimethylsilylene-bis {1- (2-methyl-4-phenyl-1-indenyl). } Zirconium dichloride was converted to Zr atom to add 0.001 mmol, 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.

39.7 g of a polymer (propylene / 1-butene random copolymer) was obtained. Polymerization activity is 79 kg
Polymer / mmol Zr.hr. This polymer contained 24 mol% of units derived from 1-butene. Intrinsic viscosity [η] is 1.63dl / g, melting point is 92 ° C.
Met. Table 1 shows the measured physical properties of the obtained polymer.

[0129]

[Production Examples 2 to 3] A propylene / 1-butene random copolymer as shown in Table 1 in the same manner as in Production Example 1 except that the amounts of hexane, 1-butene and propylene were changed. Got

[0130]

[Comparative Production Example 4] 830 ml of hexane and 10 parts of 1-butene were placed in a 2 liter autoclave which had been sufficiently replaced with nitrogen.
After charging 0 g, 1 mmol of triisobutylaluminum was added and the temperature was raised to 70 ° C., propylene was supplied to adjust the total pressure to 7 kg / cm ² G, and 1 mmol of triethylaluminum,
And 0.005 mmol of titanium catalyst supported on magnesium chloride in terms of Ti atoms were 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 obtained polymer was 33.7 g, and the polymerization activity was 14 kg.polymer / mmol Zr.hr. This polymer contains 2 units derived from 1-butene.
The content was 3 mol%. Intrinsic viscosity [η] is 1.91dl
/ G, the melting point was 110 ° C. Table 1 shows the measured physical properties of the obtained polymer.

[0132]

Examples 1-2: Isotactic index (I.
I.) 96% homopolypropylene [I] having a melt index of 1.5 was formed into a sheet at 240 ° C. and stretched at 140 ° C. to a length of 5 times.

The polypropylene sheet [II] described below was laminated on one side of the obtained sheet as a substrate layer. Isotactic index (II) 96%,
Melt index (230 ℃) 6.5, melting point 140 ℃
75% by weight of the random polypropylene pellets, and 25% by weight of the propylene / 1-butene random copolymer (B) (PBR) pellets produced as described above, and the antiblocking agent 0.1 Parts by weight and 0.16 parts by weight of a slip agent were blended, melted in an extruder, and then extruded and laminated on the above base material layer at 200 ° C.

Next, the laminated sheet was stretched laterally 10 times at 170 ° C. and cooled while substantially maintaining this stretched state. As described above, a biaxially stretched composite film composed of a homopolypropylene [I] layer (base material layer) having a thickness of 22 μm and a polypropylene composition [II] layer (heat seal layer) having a thickness of 3 μm was obtained. . The results are shown in Table 1.

[0135]

[Comparative Example 1] In Example 1, when the polypropylene composition was formed, the propylene / 1-butene random copolymer (B) obtained in Production Example 1 was replaced with the propylene obtained in Comparative Production Example 4. A composite film was obtained in the same manner as in Example 1 except that the 1-butene random copolymer was used. The results are shown in Table 1.

[0136]

[Examples 3 to 5] Isotactic index (I.
I.) 96% homopolypropylene [I] having a melt index of 6.5 was melted and supplied to a composite film molding die at a resin temperature of 240 ° C.

On the other hand, in another extruder, 75% by weight of random polypropylene pellets having a melt index (230 ° C.) of 6.5 and a melting point of 140 ° C. and the propylene / 1-butene random copolymer (B) produced above (PBR) pellets (25% by weight), 0.1 parts by weight of an anti-blocking agent and 0.16 parts by weight of a slip agent were added to 100 parts by weight of the pellets, and the mixture was obtained by melting in an extruder. Polypropylene composition [II] with a resin temperature of 200 ° C
Was supplied to the composite film forming die.

A homopolypropylene [I] layer (base material layer) having a thickness of 45 μm and a thickness of 45 μm were obtained by simultaneously extruding and laminating homopolypropylene [I] and a polypropylene composition [II] from a composite film molding die. A composite film having a polypropylene composition [II] layer (heat seal layer) of 5 μm was obtained. The results are shown in Table 1 (continued).

[0139]

Comparative Example 2 In Example 3, the propylene / 1-butene random copolymer obtained in Comparative Example 4 was replaced by the propylene / 1-butene random copolymer obtained in Production Example 1. A composite film was obtained in the same manner as in Example 3 except that it was used. The results are shown in Table 1 (continued).

[0140]

[Table 1]

[0141]

[Table 2]

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Claims (5)

[Claims] 1. A crystalline polypropylene layer [I], and [II] a polypropylene composition layer laminated on at least one side of the crystalline polypropylene layer [I]. The polypropylene composition [II] comprises: (A) Crystalline polypropylene containing units derived from propylene in an amount of 90 mol% or more; 50 wt% or more 9
Less than 0% by weight, (B) the following propylene / 1-butene random copolymer;
A polypropylene composite film comprising 10% by weight or more and less than 50% by weight; the propylene / 1-butene random copolymer (B) comprises (1) 50 to 95 mol% of a structural unit derived from propylene. In an amount of 5 to 50 mol% of a structural unit derived from 1-butene,
(2) Intrinsic viscosity measured in decalin at 135 ° C is 0.
1 to 5 dl / g, (3) the molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) is 3 or less, and (4) a parameter indicating the randomness of the copolymerized monomer chain distribution. B value is 1.0-1.
It is 5. 2. The propylene / 1-butene random copolymer (B) has a parameter B value of 1.0 to 1.3 indicating the randomness of the (4) copolymerized monomer chain distribution, and Further, (5) the melting point Tm measured by a differential scanning calorimeter is 60 to 140 ° C., and the relationship between the melting point Tm and the 1-butene structural unit content M (mol%) is -2.6M.
+130 ≤ Tm ≤ -2.3M + 155,
(6) The relationship between the crystallinity C measured by X-ray diffractometry and the 1-butene constitutional unit content M (mol%) is C ≧ −
The polypropylene composite film according to claim 1, wherein the polypropylene composite film is 1.5M + 75. 3. The polypropylene composite film according to claim 1, wherein the crystalline polypropylene layer [I] is unstretched. 4. The polypropylene composite film according to claim 1, wherein the crystalline polypropylene layer [I] is biaxially stretched. 5. The propylene / 1-butene random copolymer (B) comprises [A] a transition metal compound represented by the following general formula [I]: [In the formula, M is a transition metal of Group IVa, Va, or VIa of the Periodic Table, and R ¹ and R ² are a hydrogen atom, a halogen atom, or a carbon number 1
To a hydrocarbon group having 20 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, and R ³ has 3 to 20 carbon atoms. Is a secondary or tertiary alkyl group or aromatic group, R ⁴ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and X ¹ and X ² are a hydrogen atom, a halogen atom, or a carbon number 1
To a hydrocarbon group having 20 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, and 1 to carbon atoms.
20 divalent halogenated hydrocarbon groups, divalent silicon-containing groups, divalent germanium-containing groups, divalent tin-containing groups,
O -, - CO -, - S -, - SO -, - SO 2 -, - N
^{R 3 -, - P (R} 3) -, - P (O) (R 3) -, - B
R ³ — or —AlR ³ —. (However, R ³ 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.)],
[B] Organoaluminum oxy compound [B-1], and /
Alternatively, propylene and 1-butene may be added in the presence of an olefin polymerization catalyst containing a compound [B-2] that reacts with the transition metal compound [A] to form an ion pair, and optionally [C] an organoaluminum compound. The polypropylene composite film according to claim 1, which is obtained by copolymerizing and.