JP3491850B2 - Polypropylene composite film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polypropylene composite film which is excellent in heat sealability such as low temperature heat sealability and heat seal strength, and excellent in slip property and blocking resistance.

[0002]

BACKGROUND OF THE INVENTION Crystalline polypropylene is known for its mechanical properties such as tensile strength, rigidity, surface hardness, impact strength and cold resistance, optical properties such as gloss and transparency, and non-toxicity.
It is excellent in food hygiene such as odorlessness, and is widely used especially in the field of food packaging. The crystalline polypropylene film shrinks when heated to the heat sealing temperature, and it is difficult to heat seal with a single layer of the film. For this reason, 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 and propylene / ethylene random copolymer.

[0003] Incidentally, polymers forming such a heat seal layer include (1) heat sealability at a considerably lower temperature than that of a base material (crystalline polypropylene film), and (2) excellent heat seal strength. (3) Excellent adhesion to the substrate, (4) Excellent transparency equal to or higher than the substrate, (5) Storage Sometimes, it is required to have performances such as not causing blocking, (6) not sticking to a bag making device and a filling and packaging jig, and (7) having excellent scratch resistance.

[0004] However, conventionally known heat sealing materials do not satisfy all of these properties. For example, the above low density polyethylene can be heat sealed at a low temperature, but the heat sealing strength and the adhesion to the substrate are low. In addition, there are problems such as poor transparency and easy adhesion to packaging jigs and 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 heat-sealing temperature range of the polypropylene composite film is narrow. Therefore, when this composite film is heat-sealed by 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 blend of a propylene / ethylene random copolymer and an ethylene / α-olefin copolymer as a heat seal material. However, this blend is compared with a propylene / ethylene random copolymer. The low-temperature heat sealability is improved, but the transparency is poor.

By the way, the applicant of the present invention has proposed a propylene / 1-butene random copolymer having a propylene content of 55 to 85% by weight and a heat of crystal fusion measured by a differential scanning calorimeter of 20 to 80 J / g. It has been found that the coalescence 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 the isotactic polypropylene and containing the propylene / 1-butene random copolymer in an amount of 50% by weight or more is used as a heat seal layer of a polypropylene film. (Japanese Patent Laid-Open No. 54-11487). The heat seal layer formed from this composition has excellent low-temperature heat sealability and blocking resistance, but has better blocking resistance and heat resistance than the heat seal layer formed from the propylene / ethylene random copolymer. Slightly poor scratching properties.

A composition comprising a propylene / 1-butene copolymer and a crystalline propylene / 1-butene random copolymer, wherein the propylene / 1-butene copolymer is contained in an amount of 10 to 40% by weight. Has also been proposed by the present applicant as a composite film having excellent heat sealability (JP-B-61-42626).

However, such a polypropylene film is desired to have properties that can be applied to high-speed packaging, and it is desired that the polypropylene film has improved low-temperature heat sealability and excellent slip properties and blocking resistance.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and has excellent transparency, low-temperature heat sealability, and excellent mechanical strength such as blocking resistance and scratch resistance. And 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 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;
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 to 95 mol% of a structural unit derived from propylene, and 5 to 50 mol of a structural unit derived from 1-butene. (2) Intrinsic viscosity measured in decalin at 135 ° C. is 1 to
3 dl / g, and (3) gel permeation chromatography (GP
(C) the molecular weight distribution (Mw / Mn) determined by (C) is 3 or less, (4) the parameter B value indicating the randomness of the copolymer monomer chain distribution is 1.0 to 1.5, and (5) differential scanning. The melting point Tm measured by a mold calorimeter is 6
0 to 92 ° 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.

The propylene / 1-butene random copolymer (B) has the above-mentioned (4) parameter B value of 1.0 to 1.3, and in addition to these characteristics (1) to (4), , (6) and the crystallinity C measured by X-ray diffraction method, the relationship between the 1-butene constituent unit content M (mol%) is preferably a C ≧ -1.5M + 75.

The above crystalline polypropylene layer [I]
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]

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[Wherein, M is a transition metal of Groups 4, 5, and 6 of the periodic table , and R ¹ and R ² are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, 20 halogenated hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, R ³
Is a C3-C20 secondary or tertiary alkyl group or an aromatic group, and R ⁴ is a hydrogen atom or a C1-C2
X ¹ and X ² are a hydrogen atom,
Halogen atom, hydrocarbon group having 1 to 20 carbon atoms, 1 carbon atom
Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms,
A divalent silicon-containing group, a divalent germanium-containing group, a divalent tin-containing group, -O-, -CO-, -S-, -SO-,
-SO _2- , -NR ^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 carbon number of 1 to 2
0 hydrocarbon groups and halogenated hydrocarbon groups having 1 to 20 carbon atoms. )], [B] Organoaluminum oxy compound
The presence of a catalyst for olefin polymerization comprising [B-1] and / or a compound [B-2] which forms an ion pair by reacting with the transition metal compound [A] and, if desired, [C] an organoaluminum compound. Below, it is obtained by copolymerizing propylene and 1-butene.

[0016]

DETAILED DESCRIPTION OF THE INVENTION The polypropylene composite film according to the present invention comprises: [I] a crystalline polypropylene layer; [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.

Hereinafter, each component will be described specifically. [I] Crystalline polypropylene The substrate layer of the polypropylene composite film according to the present invention comprises:
It is formed of crystalline polypropylene.

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

The density of the crystalline polypropylene is:
0.89 to 0.92 g / cm ³ , melt index (23
(0 ° C.) is preferably 0.1 to 10. As the crystalline polypropylene, homopolypropylene is usually used, but a propylene random copolymer containing a small amount of a unit derived from an olefin other than propylene, for example, 5 mol% or less within a range not to impair the object of the present invention. It can also be used. As such other olefins, specifically, ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadecene, 4-methyl Α-olefins other than propylene having 2 to 20 carbon atoms, such as 1-pentene.

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.

The crystalline polypropylene can be used by adding a heat stabilizer, an ultraviolet absorber, an anti-blocking agent, a slip agent, an antistatic agent and the like. (A) Crystalline Polypropylene The polypropylene composition used for the heat seal layer of the polypropylene composite film according to the present invention comprises crystalline polypropylene (A) and a specific propylene / 1-butene random copolymer (B ).

Specific examples of the crystalline polypropylene (A) forming the polypropylene composition include the same as the crystalline polypropylene [I] forming the base 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 weight
Combination The polypropylene composition used in 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 50 to 95 mol%, preferably 55 to 93 mol%, more preferably 60 to 90 mol% of units derived from propylene. And contains a unit derived from 1-butene 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 structural units derived from olefins other than propylene and 1-butene, for example, in an amount of 10 mol% or less.

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

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

(4) Randomness The propylene / 1-butene random copolymer used in the present invention has a parameter B value indicating the randomness of the copolymer monomer chain distribution of 1.0 to 1.5, preferably 1.0. 0-1.3
More preferably, it is 1.0 to 1.2.

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

When the B value is 1, the B-value is in accordance with Bernoulli's statistics, and when B <1, the copolymer is block-like.
When it is 1, it is alternate. Further, the propylene / 1-butene random copolymer used in the present invention has, in addition to the above-mentioned properties, (5) a melting point Tm of 6 as measured by a differential scanning calorimeter.
0 to 140 ° C., preferably 80 to 130 ° C., and the melting point Tm and the 1-butene structural unit content M
(Mol%) is -2.6M + 130≤Tm
≦ −2.3M + 155 is desirable.

(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 ≧ −1.5M + 75.

The propylene / 1-butene random copolymer has a crystallinity of 15 to 65%, preferably 20 to 60%. Further, the propylene / 1-butene random copolymer used in the present invention has 0.05 of a position irregular unit based on 2,1-insertion of a propylene monomer in all propylene structural units determined from a ¹³ C-NMR spectrum.
% Or more.

At the time of polymerization, the propylene monomer is 1,2-inserted (the methylene side is bonded to the catalyst), but rarely 2,1-inserted. The 2,1-inserted monomers form regiorandom units in the polymer.

The proportion of 2,1-insertion of the propylene monomer in all the propylene structural units was determined by using ¹³ C-NMR.
It can be determined from the following formula with reference to lymer, 30 (1989) 1350.

[0035]

(Equation 1)

The peaks were 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. If it is difficult to obtain the area such as Iαβ directly from the spectrum due to overlapping peaks,
A carbon peak with a corresponding area can be substituted.

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

The tri-chain amount based on the 1,3-insertion of propylene can be determined from the βγ peak (resonance around 27.4 ppm). The polypropylene composition forming the heat seal layer of the polypropylene composite film according to the present invention contains the propylene / 1-butene random copolymer (B) having the above-described properties, and has excellent heat seal properties. Express. The characteristics of the propylene / 1-butene random copolymer, for example, the above (2) intrinsic viscosity [η]
If it exceeds 5 dl / g, it is inferior in moldability and it is difficult to form a thin layer having a desirable thickness as a heat seal layer, specifically, 50 μm or less. On the other hand, if it is less than 0.1 dl / g, heat seal strength is inferior. There is.

When the melting point exceeds 140 ° C., the appropriate heat sealing temperature of the film becomes as high as 130 ° C. or higher. On the other hand, when the melting point is lower than 60 ° C., the low temperature heat sealing property is improved. Scratch properties may be reduced, and the film may be blocked during storage, making practical use difficult.

It is preferable that the propylene / 1-butene random copolymer has a crystallinity of 15 to 65% because a film having excellent low-temperature heat sealability and excellent blocking resistance can be obtained. This crystallinity is 15
%, The scratch resistance of the film is insufficient, blocking tends to occur, and stickiness occurs,
On the other hand, if 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 as described below, [B] an organoaluminum oxy compound [B-1], And / or a compound [B-2] reacting with the transition metal compound [A] to form an ion pair;
If desired, it can be obtained by copolymerizing propylene with 1-butene in the presence of an olefin polymerization catalyst comprising [C] an 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]

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In the formula, M is a transition metal belonging to Groups 4, 5, and 6 of the periodic table , and 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.

Substituents R ¹ and R ² R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
Halogenated hydrocarbon groups, silicon-containing groups, oxygen-containing groups,
It is a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group.
Specifically, 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. Alkoxy groups such as eicosyl, norbornyl, adamantyl, vinyl, propenyl, alkenyl groups such as cyclohexenyl, benzyl, phenylethyl, arylalkyl groups such as phenylpropyl, phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl,
Examples include aryl groups such as propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthracenyl, and phenanthryl. Examples of the halogenated hydrocarbon groups include groups in which these hydrocarbon groups are substituted with halogen atoms.

Further, monohydrocarbon-substituted silyls such as methylsilyl and phenylsilyl, dihydrocarbon-substituted silyls such as dimethylsilyl and diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, Trihydrocarbon-substituted silyls such as methyldiphenylsilyl, tolylsilyl and trinaphthylsilyl; silyl ethers of hydrocarbon-substituted silyls such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; silicon-substituted aryl groups such as trimethylphenyl; Silicon-containing substituents, hydroxy groups, alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, phenoxy, methylphenoxy, dimethylphenoxy, naphtho Oxygen-containing substituents such as aryloxy groups such as phenylmethoxy and phenylethoxy; arylalkoxy groups such as phenylethoxy; sulfur-containing groups in which the oxygen of the oxygen-containing compound has been replaced by sulfur; amino groups; methylamino; dimethylamino; diethylamino; Alkylamino groups such as propylamino, dibutylamino and dicyclohexylamino, phenylamino, diphenylamino,
Examples 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.

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

As R ² , a hydrogen atom and a hydrocarbon group are preferable, and a hydrogen atom is particularly preferable. The substituent R ³ R ³ is a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom thereof, or a group substituted with a silicon-containing group. Among them, a secondary or tertiary alkyl group having 3 to 20 carbon atoms or an aromatic group is preferred. It is desirable that

Specifically, examples of the secondary or tertiary alkyl group include i-propyl, i-butyl, sec-butyl, tert-butyl, 1,2-dimethylpropyl, 2,3-dimethylbutyl,
o-pentyl, tert-pentyl, neopentyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, is
o-Hexyl, norbornyl, adamantyl and the like, and the aromatic group includes phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, α- or β-naphthyl, methylnaphthyl, anthracenyl, phenanthryl, Benzylphenyl, pyrenyl, acenaphthyl, phenalenyl, aceanthrenyl, tetrahydronaphthyl, indanyl, aryl groups such as biphenylyl, benzyl, phenylethyl, phenylpropyl, arylalkyl groups such as tolylmethyl, and the like; these are double bonds, It may contain a triple bond.

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

As the alkyl group, specifically, methyl,
Ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, pentyl, hexyl,
Examples 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 represented by R ¹ . X ¹ and X ² X ¹ and X ^{2 each} represent a hydrogen atom, a halogen atom,
-20 hydrocarbon groups, halogenated hydrocarbon groups having 1-20 carbon atoms, oxygen-containing groups or sulfur-containing groups.

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 those described above for R ¹ . Examples of the sulfur-containing group, still with groups represented by R ^1, methylsulfonate, trifluoromethanesulfonate,
Phenylsulfonate, benzylsulfonate, p-
Sulfonate groups such as toluenesulfonate, trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, pentafluorobenzenesulfonate, 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,
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- (where 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,
Alkylene groups such as 1,2-cyclohexylene and 1,4-cyclohexylene, and arylalkylene groups such as diphenylmethylene and diphenyl-1,2-ethylene having 1 to 2 carbon atoms
0 divalent hydrocarbon group, halogenated hydrocarbon group obtained by halogenating the above divalent hydrocarbon group having 1 to 20 carbon atoms such as chloromethylene, methylsilylene, dimethylsilylene,
Diethylsilylene, di (n-propyl) silylene, di (i-
Propyl) silylene, di (cyclohexyl) silylene,
Methylphenylsilylene, diphenylsilylene, di (p-
Alkylsilylenes such as (tril) silylene and di (p-chlorophenyl) silylene, alkylarylsilylenes, arylsilylene groups, alkyldisilyls such as tetramethyl-1,2-disilyl and tetraphenyl-1,2-disilyl, and alkylaryldiyls A divalent silicon-containing group such as a silyl or arylsilyl group, a divalent germanium-containing group obtained by substituting silicon for the divalent silicon-containing group with germanium, or a divalent silicon-containing group obtained by substituting silicon for the divalent silicon-containing group with tin. and the like valent tin-containing group substituents, R ^5, said R ¹ and same halogen atom, hydrocarbon group having 1 to 20 carbon atoms, 1 to 4 carbon atoms
To 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 preferred.

Specific examples of the transition metal compound represented by the above general formula [I] will be given below. rac-dimethylsilylene-
Bis (2,7-dimethyl-4-ethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,7-dimethyl-4-n-propyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene- Bis (2,7-dimethyl-4-
i-propyl-1-indenyl) zirconium dichloride, 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) silylenebis (2,7-dimethyl
-4-i-propyl-1-indenyl) zirconium dichloride, rac-di (n-butyl) silylenebis (2,7-dimethyl-4
-i-propyl-1-indenyl) zirconium dichloride,
rac-di (cyclohexyl) silylenebis (2,7-dimethyl
-4-i-propyl-1-indenyl) zirconium dichloride, rac-methylphenylsilylenebis (2,7-dimethyl-4
-i-propyl-1-indenyl) zirconium dichloride,
rac-methylphenylsilylenebis (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) silylenebis (2,
7-dimethyl-4-i-propyl-1-indenyl) zirconium dichloride, rac-di (p-chlorophenyl) silylenebis (2,7-dimethyl-4-i-propyl-1-indenyl) zirconium dichloride, rac-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-dimethylsilylene-
Bis (2-phenyl-4-i-propyl-7-methyl-1-indenyl) zirconium dichloride and the like.

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

[0058]

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(Where M, X ¹ , X ² , R ¹ , R ³ , Y
Is the same as in the formula [I], but preferably R ¹ is a hydrogen atom, a methyl group or an aromatic group. Preferred examples of the transition metal compound 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-
Toluenesulfonate), rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium di (methylsulfonate), 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) and the like.

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 a hydrocarbon group having 6 to 6 carbon atoms.
A transition metal compound which is 16 aryl groups is also preferably used. Among the compounds represented by the formula [I], such preferred 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 Len-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-biferinyl) indenyl) デ zirconium dichloride, rac-methylene-bis ｛1- (2-ethyl-4-phenylindenyl)｝ zirconium dichloride, rac-methylene-bis ｛1- ( 2-ethyl-4- (α-naphthyl) indenyl) ニ ル 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) 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.

In the present invention, zirconium metal is replaced with titanium metal, hafnium metal,
Transition metal compounds replaced with vanadium metal, niobium metal, tantalum metal, chromium metal, molybdenum metal, and tungsten metal can also be used.

The above-mentioned transition metal compound is usually used as a catalyst component for olefin polymerization in the form of a racemate, but R-type or S-type can also be used. The transition metal compound used in the present invention as described above is the Journal of Organomet
allic Chem. 288 (1985), pp. 63-67, EP-A-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. And JP-A-2-78.
It may be a benzene-insoluble organic aluminum oxy compound as exemplified in JP-A-687.

A conventionally known aluminoxane can be produced, for example, by the following method. (1) Compounds containing water of adsorption or salts containing water of crystallization, such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerous chloride A method of adding an organoaluminum compound such as trialkylaluminum to a hydrocarbon medium suspension of the above to react. (2) A method in which water, ice or 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 in which an organoaluminum compound such as trialkylaluminum is reacted 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 a solvent or suspended in a poor solvent for aluminoxane.

Examples of the organoaluminum compound used in preparing the aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum, trisec-butyl. Aluminum, trialkyl aluminum such as tritert-butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, tridecyl aluminum, etc., tricycloalkyl aluminum such as tricyclohexyl aluminum, tricyclooctyl aluminum, dimethyl aluminum chloride, diethyl aluminum Chloride, diethylaluminum bromide, diisobutylaluminum 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 preferred, and trimethylaluminum is particularly preferred. Further, as an organoaluminum compound used for preparing aluminoxane, isoprenylaluminum represented by the following general formula can also be used.

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

Solvents used for the solution or suspension of aluminoxane include benzene, toluene, xylene,
Aromatic hydrocarbons such as 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 And petroleum fractions such as gasoline, kerosene and gas oil, and hydrocarbon solvents such as the above-mentioned aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbon halides, especially chlorinated products and brominated products. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons and aliphatic hydrocarbons are particularly preferred.

[B-2] which forms the olefin polymerization catalyst used in the present invention [B-2] A compound which forms an ion pair by reacting with the transition metal compound [A] (hereinafter referred to as "component [B-2]") Japanese Patent Application Laid-Open No. 1-501950).
Japanese Patent Application Laid-Open No. Hei.
JP 79005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704
No. 5,547,718, Lewis acids, ionic compounds and carborane compounds.

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

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 can be exemplified.

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 can be exemplified.

The compound [B-2] which forms an ion pair by reacting with the above-mentioned transition metal compound [A] can be used as a mixture of two or more kinds. The [C] organoaluminum compound (hereinafter sometimes referred to as “component [C]”) forming the olefin polymerization catalyst used in the present invention is, for example, an organoaluminum compound represented by the following general formula [III]. Compounds can be exemplified.

R ⁹ _n AlX _3-n ... [III] (wherein R ⁹ is a hydrocarbon group having 1 to 12 carbon atoms;
Is a halogen atom or a hydrogen atom, and n is 1-3. In the general formula [III], R ⁹ is a hydrocarbon group having 1 to 12 carbon atoms, for example, 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]
Specific examples include the following compounds. Trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri (2-ethylhexyl) aluminum, tridecylaluminum, alkenylaluminum such as isoprenylaluminum, dimethylaluminumchloride, diethylaluminumchloride Dialkylaluminum halides such as diisopropylaluminum chloride, diisobutylaluminum chloride and dimethylaluminum bromide, methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, alkylaluminum such as butylaluminum sesquichloride and ethylaluminum sesquibromide Alkyl aluminum dihalides such as um sesquihalide, 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.

Further, 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] (wherein R ⁹ is the same as above, L is —OR ¹⁰ group,
OSiR ¹¹ ₃ group, -OAlR ¹² ₂ group, -NR ¹³ ₂ group, -Si
A R ¹⁴ ₃ group or -N (R ¹⁵⁾ AlR ¹⁶ ₂ group, n represents 1
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, etc., and R ¹³ is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group. Group, phenyl group, trimethylsilylene group, etc., and R ¹⁴ and R ¹⁵ are methyl group, ethyl group, etc. ) Among such organoaluminum compounds, R ⁷ _n A
a compound represented by l (OAlR ¹⁰ ₂ ) _3-n , for example, 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 catalyst for olefin polymerization used in the present invention comprises the component [A], the component [B-1] (or the component [B-2]) and optionally the 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 catalyst for olefin polymerization include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene, cyclopentane, and the like. 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 components when preparing the catalyst for olefin polymerization 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] and then 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 / l, preferably 10 ^{-7 to} 5 × 10 ^-2 mol / l. It is desirable.

When component [B-1] is used as component [B], aluminum in component [B-1] is replaced by component [A]
The atomic ratio to 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]
Molar ratio between component and component [B-2] (component [A] / component [B-2])
However, it is usually used so as to be 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 can be used as needed in an amount of from 02 to 20, preferably from 0.2 to 10.

The above-mentioned components may be mixed in a polymerization vessel, or a pre-mixed one may be added to the polymerization vessel. The mixing temperature at the time of pre-mixing is usually -50 to 150C, preferably -20 to 120C, 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 catalyst for olefin polymerization used in the present invention is prepared by adding the above-mentioned component [A] and component [B] to an inorganic or organic, particulate carrier which is a granular or particulate solid.
And a solid olefin polymerization catalyst carrying at least one component of component [C].

As the inorganic carrier, a porous oxide is preferable, and examples thereof include SiO ₂ and Al ₂ O ₃ . Examples of the granular or particulate solid of the organic compound include α-olefins such as ethylene, propylene, and 1-butene, and polymers or copolymers containing styrene as a main component.

In the present invention, olefins may be prepolymerized and used for each component forming the olefin polymerization catalyst as described above. The olefin used for the prepolymerization is preferably propylene, ethylene, 1-butene, or the like, but may be a mixture of these with other olefins.

The olefin polymerization catalyst used in the present invention may contain, in addition to the above 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 that the above composition ratio is finally obtained. It can be manufactured by doing.

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 propylene can be used as the solvent.

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

The polymerization is usually carried out at normal pressure to 100 kg / cm ²
Preferably, it is carried out under a pressure of normal pressure to 50 kg / cm ² .
The polymerization reaction can be performed in any of a batch system, a semi-continuous system, and a continuous system, and the polymerization can be performed in two or more stages under different reaction conditions.

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

In the present invention, the propylene
The butene random copolymer may be partially or completely modified with an unsaturated carboxylic acid or its anhydride. This modified product of the propylene / 1-butene random copolymer has excellent overlap packaging properties and adhesion to metals and the like.

[II] Polypropylene Composition The polypropylene layer forming the heat seal layer of the polypropylene composite film according to the present invention comprises (A) crystalline polypropylene as described above and (B) propylene • 1-
A crystalline polypropylene (A) in an amount of 50% by weight or more and less than 90% by weight, and a propylene / 1-butene random copolymer (B) in an amount of 10% by weight or more and less than 50% by weight. It is contained in the amount.

From such a polypropylene composition,
A polypropylene composite film having a heat seal layer that is excellent in transparency and low-temperature heat sealability and has excellent mechanical strength such as blocking resistance and scratch resistance can be formed.

When the amount of the crystalline polypropylene (A) in the polypropylene composition exceeds 90% by weight, the softening temperature of the film rises remarkably, and the low-temperature heat sealability is extremely lowered. If so, the blocking resistance and scratch resistance of the film may be reduced.

The above-mentioned polypropylene composition includes:
Heat stabilizers, ultraviolet absorbers, anti-blocking agents, slip agents, antistatic agents and the like 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] a polypropylene composition layer.

The polypropylene composition layer [II] is a heat seal layer and is provided on one side or both sides of the crystalline polypropylene layer [I] as 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 may be uniaxially or biaxially stretched. One or both surfaces of the substrate layer [I] may be subjected to a corona treatment by a known method.

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

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

The laminated sheet may be uniaxially stretched in the vertical or horizontal direction, or may be biaxially stretched separately or simultaneously in the vertical or horizontal direction. (3) The crystalline polypropylene [I] is melt-extruded to form a base layer that is uniaxially stretched either vertically or horizontally, and then the polypropylene composition [II] is melted on the uniaxially stretched base layer. Extrusion or lamination of a previously formed film of the polypropylene composition [II] is performed, and the obtained laminated sheet is stretched in the unstretched direction of the base material layer.

(4) The crystalline polypropylene [I] is melt-extruded to form a base layer that is biaxially stretched separately or simultaneously on the vertical and horizontal axes, and a polypropylene composition is formed on the biaxially stretched base layer. The product [II] is melt-extruded or a previously formed film of the polypropylene composition [II] is laminated.

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

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.
m is desirable.

In the composite film according to the present invention, when the crystalline polypropylene [I] as the base material layer is stretched, it is preferably 3 to 7 times, preferably 4 to 6 times in the longitudinal direction, and 3 to 12 times in the horizontal direction. It is desirable that the film is stretched at a magnification 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, heat sealing can be performed even at a low temperature, heat sealing can be performed at a wide range of temperatures, and heat sealing strength is excellent. Further, even when the film is stored for a long period of time, the heat sealing temperature does not change with time, and a stable heat sealing operation is ensured.

The polypropylene composite film according to the present invention is excellent in transparency, scratch resistance, blocking resistance and the like, 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 Next, the present invention will be described specifically 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 Determined using ¹³ C-NMR.

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

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 0.025% by weight of T (Takeda Pharmaceutical), 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.

When the molecular weight is Mw <1000 and Mw> 4 ×
Using the Tosoh Co., Ltd. standard polystyrene for 10 ^6,
For 1000 <Mw <4 × 10 ⁶ , standard polystyrene manufactured by Pressure Chemical Company was used.

(4) B value The composition distribution B value is about 200 mg in a 10 mmφ sample tube.
Homogenized in 1 ml of hexachlorobutadiene
Of the dissolved sample¹³The C-NMR spectrum is usually
Measurement temperature 120 ° C, measurement frequency 25.05MHz, spectrum
1,500 Hz for filter width, 1500 Hz for filter width,
Loose repetition time 4.2sec, total number of times 2000-5
Measured under 000 measurement conditions, from this spectrum
P_E, P _o, P_OEWas calculated.

(5) Melting point (Tm) The melting point (Tm) was measured using a DSC-7 apparatus (differential scanning calorimeter (DSC)) manufactured by PerkinElmer.

Approximately 5 mg of a sample was packed in an aluminum pan, and 200
Temperature, and kept at 200 ° C for 5 minutes, then 10 ° C /
After cooling to −40 ° C. per minute and holding at −40 ° C. for 5 minutes, the temperature was determined from an endothermic curve when the temperature was increased at 10 ° C./min.

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

[Measurement of Physical Properties of Composite Film] (1) Cloudiness It was measured in accordance with 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) Gloss It was measured in accordance with 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 The composite film was kept at 50 ° C. for one week and allowed to cool, and then the blocking property was measured in the same manner as in (5) above.

(7) The polypropylene composition layer [II] of the heat seal adhesive strength composite film was overlaid on each other, and at each temperature shown in Table 1, 2 kg / cm ²
After heat sealing at a pressure of 5 mm for 1 second with a seal bar width of 5 mm, the mixture was allowed to cool.

Test pieces each having a width of 15 mm were cut out 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] 900 ml of hexane and 60 g of 1-butene were charged into a 2-liter autoclave sufficiently purged with nitrogen, and 1 mmol of triisobutylaluminum was added. After the temperature was raised to ℃, propylene was supplied to make the total pressure 7 kg / cm ² G, methylaluminoxane 0.30 mmol, rac-dimethylsilylene-bis {1- (2-methyl-4-phenyl-1-indenyl)) ｝ 0.001 mmol of zirconium dichloride in terms of Zr atom was added, and propylene was continuously supplied to carry out polymerization for 30 minutes while keeping the total pressure at 7 kg / cm ² G. After the polymerization, the polymer was degassed, and the polymer was recovered in a large amount of methanol and dried under reduced pressure at 110 ° C. for 12 hours.

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

[0129]

Production Examples 2-3 Propylene / 1-butene random copolymers as shown in Table 1 were prepared in the same manner as in Production Example 1 except that the amount of hexane, the amount of 1-butene and the amount of propylene were changed. Got.

[0130]

Comparative Production Example 4 In a 2-liter autoclave sufficiently purged with nitrogen, 830 ml of hexane and 10 parts of 1-butene were added.
After charging 0 g, adding 1 mmol of triisobutylaluminum and raising the temperature to 70 ° C., propylene was supplied to a total pressure of 7 kg / cm ² G, and 1 mmol of triethylaluminum was added.
Then, 0.005 mmol of a titanium catalyst supported on magnesium chloride in terms of Ti atoms was added, and propylene was continuously supplied to carry out polymerization for 30 minutes while keeping the total pressure at 7 kg / cm ² G. After the polymerization, the polymer was degassed, and the polymer was recovered in a large amount of methanol and dried under reduced pressure at 110 ° C. for 12 hours.

The amount of the obtained polymer was 33.7 g, and the polymerization activity was 14 kg · polymer / mmol Zr · hr. This polymer has two units derived from 1-butene.
The content was 3 mol%. The intrinsic viscosity [η] is 1.91 dl
/ G, melting point 110 ° C. Table 1 shows the physical properties measured for the obtained polymer.

[0132]

Example 1, Reference Example 1 A homopolypropylene [I] having an isotactic index (II) of 96% and a melt index of 1.5 was formed into a sheet at 240 ° C.
The film was stretched 5 times vertically at 0 ° C.

The obtained sheet was used as a base material layer, and a polypropylene composition [II] as described below was laminated on one surface of the sheet. 96% isotactic index (II),
Melt index (230 ° C) 6.5, melting point 140 ° C
75% by weight of random polypropylene pellets, 25% by weight of propylene / 1-butene random copolymer (B) (PBR) pellets produced as described above, and 100 parts by weight of these in total, an antiblocking agent 0.1 After mixing with 0.16 parts by weight of the slip agent and 0.16 parts by weight of the slip agent, the mixture was melted by an extruder and extruded at 200 ° C. onto the above-mentioned base material layer to be laminated.

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

[0135]

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

[0136]

Example 2, Reference Examples 2, 3 Homopolypropylene [I] having an isotactic index (II) of 96% and a melt index of 6.5 was melted and supplied to a composite film forming 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. were mixed with the propylene / 1-butene random copolymer (B) produced above. (PBR) 25 parts by weight of pellets, and 0.1 part by weight of an antiblocking agent and 0.16 part by weight of a slip agent with respect to 100 parts by weight of the total are blended and melted by an extruder. Polypropylene composition [II] at a resin temperature of 200 ° C.
And supplied to the die for forming a composite film.

The homopolypropylene [I] and the polypropylene composition [II] were simultaneously extruded from the die for forming a composite film and laminated to form a homopolypropylene [I] layer (base layer) having a thickness of 45 μm. A composite film comprising a 5 μm polypropylene composition [II] layer (heat seal layer) was obtained. The results are shown in Table 1 (continued).

[0139]

Comparative Example 2 The propylene / 1-butene random copolymer obtained in Comparative Production Example 4 was replaced with the propylene / 1-butene random copolymer (B) obtained in Production Example 1 in Example 2 . Except for using, a composite film was obtained in the same manner as in Example 2 . The results are shown in Table 1 (continued).

[0140]

[Table 1]

[0141]

[Table 2]

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-54-48845 (JP, A) JP-A-61-106245 (JP, A) JP-A-6-263935 (JP, A) JP-A 8- 59916 (JP, A) EP 629632 (EP, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) B32B 1/00-35/00 C08L 23/00-23/16 C08J 5/18

Claims (5)

(57) [Claims] 1. A crystalline polypropylene layer comprising: [I] a crystalline polypropylene layer; and [II] a polypropylene composition layer laminated on at least one surface of the crystalline polypropylene layer [I]. (A) crystalline polypropylene containing 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;
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 structural units derived from propylene; The structural unit derived from 1-butene in an amount of 5 to 50 mol%, and (2) an intrinsic viscosity measured in decalin at 135 ° C. of 1 to
3 dl / g, and (3) gel permeation chromatography (GP
(C) the molecular weight distribution (Mw / Mn) determined by (C) is 3 or less, (4) the parameter B value indicating the randomness of the copolymer monomer chain distribution is 1.0 to 1.5, and (5) differential scanning. The melting point Tm measured by a mold calorimeter is 6
0 to 92 ° 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. 2. The propylene / 1-butene random copolymer (B) has a parameter B value indicating randomness of the (4) copolymerized monomer chain distribution of 1.0 to 1.3, and (6) The relationship between the crystallinity C measured by X-ray diffraction and the 1-butene constituent unit content M (mol%) is C ≧ 1.5 M + 75. The polypropylene composite film according to item 1. 3. The polypropylene composite film according to claim 1, wherein [I] the crystalline polypropylene layer is unstretched. 4. The polypropylene composite film according to claim 1, wherein [I] the crystalline polypropylene layer 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 Groups 4, 5, and 6 of the periodic table , and R ¹ and R ² are a hydrogen atom, a halogen atom, and a carbon atom of 1;
20 hydrocarbon group, 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 having 1 to 20 carbon atoms, R ³ is a carbon number 3 to 20 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 carbon atom 1
Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, 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.
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, a halogenated hydrocarbon group having 1 to 20 carbon atoms.)], [B] organoaluminum oxy compound [B-1] ,and/
Alternatively, propylene and 1-butene are reacted in the presence of an olefin polymerization catalyst containing a compound [B-2] which forms an ion pair by reacting with the transition metal compound [A] and, if desired, an organoaluminum compound. The polypropylene composite film according to claim 1, which is obtained by copolymerizing