JP2001151818A - Polypropylene and polypropylene film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polypropylene which is excellent in rigidity, has good metal vapor deposition property and is suitable for film forming, and a polypropylene film formed by forming the polypropylene. SOLUTION: Isotactic pentad fraction,
Melt flow rate, 0 ° C or less by cross fractionation,
Polypropylene whose properties such as the weight average molecular weight, the boiling pentane extraction ratio, and the boiling heptane extraction ratio of each soluble component at 50 ° C. or lower and 90 ° C. or lower are in specific ranges, and a film is formed from the polypropylene to form a film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polypropylene and a polypropylene film formed from the polypropylene. More specifically, the present invention relates to a polypropylene which is excellent in rigidity, has good metal vapor deposition property, and is suitable for film forming, and a polypropylene film formed from the polypropylene.

[0002]

2. Description of the Related Art Polypropylene film has excellent rigidity,
Since it has transparency and gloss, it is widely used as a packaging material. Generally, since a polypropylene film has gas permeability, a material obtained by vapor-depositing a metal on the surface of a polypropylene film is used for applications requiring gas barrier properties such as food packaging materials. However, since the adhesive strength between the polypropylene film surface and the deposited metal is low, there is a problem that the deposited metal layer is easily peeled off. In order to improve the peel strength of the deposited metal, a technique of subjecting a polypropylene film surface to a corona treatment, a flame treatment, or the like, and then depositing metals is known. However, these techniques are still insufficient to improve the peel strength, and further improvement of the peel strength is desired from practical demands.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polypropylene film which is excellent in rigidity and has good metal vapor deposition property, and a polypropylene suitable for producing the polypropylene film. In particular, it is an object of the present invention to provide a polypropylene which is excellent in film processability, has good aluminum vapor deposition properties, and is excellent in rigidity, and a polypropylene film comprising the polypropylene.

[0004]

Means for Solving the Problems The present inventors have intensively studied to solve the above problems. As a result, the isotactic pentad fraction, the melt flow rate, the weight average molecular weight of each soluble component at 0 ° C. or less, 50 ° C. or less, and 90 ° C. or less, the boiling pentane extraction rate, and the boiling heptane extraction rate by the cross fractionation method It has been found that a polypropylene having each of the above-mentioned properties in a specific range has an expected performance, and based on this finding, the present invention has been completed.

That is, according to the present invention, the isotactic pentad fraction [mmmm] is 0.
89 ≦ [mmmm] ≦ 0.95, and the abundance of meso- and racemic dyads in the pentad is based on a two-active center model based on Bernoulli statistics, where the statistical parameter α is 0.989 ≦
α ≦ 0.995, the melt flow rate (230 ° C., 21.18N)
0.5 to 20 dg / min, the weight-average molecular weight of the soluble component at 0 ° C or lower by the cross fractionation method is 7 × 10 ⁴ or more, and the weight-average molecular weight of the soluble component at 50 ° C or lower is 6 × The weight-average molecular weight of the soluble component of 10 ⁴ or more and 90 ° C. or less is 6 × 10 ⁴ or more, and the boiling pentane extraction rate (C5-Ext) is 0.5% by weight.
The boiling heptane extraction rate (C7-Ext) is 5
% Or less, and (C5-Ext) and (C7-
(Ext) is (C7-Ext)> 3.5 · (C5-E)
xt) and a polypropylene film formed from the polypropylene.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. The polypropylene of the present invention has an isotactic pentad fraction [mmmm], which is an index of stereoregularity,
0.89 ≦ [mmmm] ≦ 0.95. More preferably, it is in the range of 0.90 ≦ [mmmm] ≦ 0.94. [Mmmm] is A. A. Zambelli e
t al., Macromolecules Volume 8
Volume 8), measured according to the method described in pp. 687-689 (1975). When [mmmm] is less than 0.89, the metal vapor deposition property is improved, but the rigidity of the film is reduced.
If the [mmmm] exceeds 0.95, the film has high rigidity, but the metal vapor deposition property is impaired. Here, the metal vapor deposition property means that, in a metal vapor deposition film obtained by heating and evaporating a desired metal at a degree of vacuum of 10 ⁻⁴ Torr or less and vapor-depositing the metal on the polypropylene film surface, polypropylene and vapor deposition metal It refers to the adhesive strength with the film.

In the polypropylene of the present invention, the abundance of meso- and racemic dyads in a pentad, which is an index of the stereoregularity of polypropylene, is determined according to a two-active center model based on Bernoulli statistics, and the statistical parameter α at that time is determined. , 0.989 ≦ α ≦ 0.994, preferably 0.989 ≦ α ≦ 0.994, more preferably 0.990 ≦ α ≦ 0.994, high rigidity and metal A film with good vapor deposition properties is obtained. The bi-active center model based on Bernoulli statistics is described in Y.
Inoue, Itabashi, R. Chujo, Y. Doi, Polymer, Volum
e 25, pp 1640-1644 (1984). If the statistical parameter α exceeds 0.995, a highly rigid film is obtained, but the metal vapor deposition property is reduced. If the statistical parameter α is less than 0.989, the metal deposition property of the film is good, but the rigidity decreases.

The polypropylene of the present invention has a melt flow rate (230 ° C., 21.18 N) of 0.5 to 20 dg.
/ Min, preferably in the range of 1 to 15 dg / min, more preferably in the range of 1 to 10 dg / min, a film having high rigidity and good metal deposition properties can be obtained.

The polypropylene of the present invention has a weight-average molecular weight of 7 × 10 ^{4 of the} soluble component at 0 ° C. or lower by the cross fractionation method.
Polypropylene having a composition in which the weight average molecular weight of the soluble component at 50 ° C. or less is 6 × 10 ⁴ or more and the weight average molecular weight of the soluble component at 90 ° C. or less is 6 × 10 ⁴ or more It is. The weight-average molecular weight of the soluble component at 0 ° C. or less by the cross fractionation method is less than 7 × 10 ⁴ , the weight-average molecular weight of the soluble component at 50 ° C. or less is less than 6 × 10 ⁴ , and the soluble component at 90 ° C. or less In the case of a polypropylene having a composition having a weight average molecular weight of less than 6 × 10 ⁴ , metal vapor deposition property is reduced.

Here, the cross fractionation method includes a temperature-rise elution fractionation method (TREF) and a gel filtration chromatography (G
(PC) method, and the crystallinity distribution and molecular weight distribution of the polymer can be simultaneously known. That is, a high-temperature sample solution in which polypropylene is completely dissolved in ortho-dichlorobenzene is injected into a column filled with an inert carrier such as glass beads, and the temperature of the column is lowered to attach the sample to the surface of the filler. Then, while flowing ortho-dichlorobenzene through the column, gradually raise the column temperature to detect the concentration of the polypropylene eluted at each temperature, and at the same time, elute the components eluted at each temperature together with the fraction. Is sent to GPC online, and the molecular weight and molecular weight distribution of each component are calculated from the obtained chromatogram. Since the elution temperature increases as the crystallinity of the eluted component increases, the distribution of the crystallinity of the polymer can be known by determining the relationship between the elution temperature and the amount of elution of the polymer (% by weight).

In the above method, the rate of decrease in the column temperature is the rate required for crystallization of the crystalline component contained in the sample polypropylene at each temperature, and the rate of increase in the temperature of the column is the elution rate at each temperature. It is necessary to adjust the rate at which the dissolution of the components can be completed, and the rate at which the column temperature decreases and the rate at which the column temperature rises are determined by preliminary experiments.

The polypropylene of the present invention has a boiling pentane extraction rate (C5-Ext) of 0.5% by weight or more, a boiling heptane extraction rate (C7-Ext) of 5% by weight or less, and both of them have a boiling point extraction rate (C7-Ext) of 5% by weight or less. , (C7-Ext)> 3.5 ×
(C5-Ext). If (C5-Ext) is less than 0.5% by weight, metal vapor deposition properties become insufficient, and (C5-Ext)
If 7-Ext) exceeds 5% by weight, the rigidity decreases. When (C7−Ext) ≦ 3.5 × (C5−Ext), there are many low molecular weight components, and the rigidity is reduced.

(1) Method for Producing the Polypropylene of the Present Invention The method for producing the polypropylene of the present invention is not particularly limited as long as the obtained polypropylene satisfies the above-mentioned properties, but the following method is exemplified. You can do it. That is, propylene is produced using a catalyst comprising a solid catalyst component (A) containing magnesium, titanium, halogen and an electron donating organic compound as essential components, an organoaluminum compound (B), and an electron donating organic silicon compound (C). Polymerization method.

The solid catalyst component (A) is a catalyst component for olefin polymerization in which a titanium halide is supported on a carrier whose main component is a Mg compound precipitated from a solution, and is produced by the following method. Can be. General formula Mg
(OR ¹ ) n (OR ² ) _2-n or MgR ³ _m (OR ⁴ )
_2-m (wherein, R ¹ , R ² , R ³ , and R ⁴ are each independently an alkyl group having 3 to 20 carbon atoms, an aryl group, or an aromatic group having 5 to 20 carbon atoms; m and n are each independently an integer of 0 to 2) or a mixture thereof in the presence of carbon dioxide in the presence of carbon dioxide of the general formula R ⁵ OH (where R ⁵ is 2
0 is a saturated or unsaturated alkyl group)
The component (a) is obtained by reacting a monohydric alcohol or a polyhydric alcohol with an inert hydrocarbon solvent.

The obtained component (a) is represented by the general formula TiX _p
(OR ⁶ ) _4-p (where X is chlorine (Cl), bromine (Br), or iodine (I), and R ⁶ has 1 carbon atom.
To 20 alkyl groups, aryl groups, or 3 to 2 carbon atoms
0 is a cycloalkyl group, and P is an integer of 1 to 4);
_q (OR ⁷ ) _4-q (where X is Cl, Br or I, and R ⁷ is an alkyl group having 1 to 20 carbon atoms, an aryl group,
Or a cycloalkyl group having 3 to 20 carbon atoms, and q is an integer of 1 to 4).
i-O-Si siloxane compound having a bond, or with the siloxane compound of the general formula ^{_{R 8 s Si (OR 9)}} 4-s ( wherein, R ⁸ and R ^9, carbon atoms each independently from 1 to 20
And a mixture with a silane compound represented by the formula: wherein R is a cycloalkyl group having 3 to 20 carbon atoms, and s is an integer of 1 to 4). Obtain product (I).

The solid product (I) is represented by the general formula R ¹⁰ OH
(Where R ¹⁰ is a saturated or unsaturated alkyl group having 1 to 20 carbon atoms) and a cyclic ether.
The solid product (II) is obtained by reprecipitation, and the solid product (II) is reacted with a component (b) comprising a titanium halide represented by the general formula TiX _p (OR ⁶ ) _4-p. A solid component (III) is obtained. The solid product (IV) is obtained by reacting the solid component (III) with a mixture of the component (b) and the electron donating compound (IED). The solid product (IV) thus obtained can be exemplified as the solid catalyst component (A).

The electron donating compound (IED) includes alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides. And organic silicon compounds such as dialkoxysilane and trialkoxysilane.

More specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, phenol, cresol, naphthol, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, acetaldehyde, propionaldehyde, octyl aldehyde, Benzaldehyde, naphthaldehyde, methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, cellosolve acetate, ethyl propionate, methyl butyrate, ethyl valerate,
Ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, butyl benzoate, propyl benzoate, octyl benzoate, cyclohexyl benzoate, benzoate Phenyl acid, benzyl benzoate, ethyl toluate, methyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, γ-butyrolactone, α-valerolactone, coumarin, phthalide, diethyl phthalate, dibutyl phthalate, phthalate 2-Methylpropyl acid di-phthalate
Ethylhexyl, dioctyl phthalate, diheptyl phthalate, di-iso-propyl phthalate, dipropyl phthalate,
Dimethyl phthalate, succinic anhydride, benzoic anhydride, ethyl silicate,

Dimethyldimethoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, diisopropyldimethoxysilane, dibutyldimethoxysilane,
Diisobutyldimethoxysilane, di-t-butyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclohexyldimethoxysilane, methylethyldimethoxysilane, methylpropyldimethoxysilane, methylisopropyldimethoxysilane, methylisobutyldimethoxysilane, methylcyclopentyldimethoxysilane, methylcyclohexyldimethoxysilane , Dialkoxysilanes such as isopropylisobutyldimethoxysilane,
Methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, etc. And the like trialkoxysilane. Two or more of these electron donors (IEDs) can be used in combination.

As the organoaluminum compound (B),
Examples thereof include trialkylaluminums such as triethylaluminum, triisobutylaluminum, and trihexylaluminum, and dialkylaluminum halides such as a diethylaluminum halide, and further, a mixture of a trialkylaluminum and a dialkylaluminum halide. Preferred examples of the organoaluminum compound (B) include triethylaluminum and triisobutylaluminum.

Examples of the electron donating organic silicon compound (C) include tetraalkoxysilanes such as tetraethoxysilane and tetrapropoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, dibutyldimethoxysilane, diisobutyldimethoxysilane, Dicyclopentyldimethoxysilane,
Methyl ethyl dimethoxy silane, methyl propyl dimethoxy silane, methyl isopropyl dimethoxy silane, methyl isobutyl dimethoxy silane, methyl cyclopentyl dimethoxy silane, methyl cyclohexyl dimethoxy silane, dimethyl diethoxy silane, diethyl diethoxy silane, dipropyl diethoxy silane, dibutyl ethoxy silane, Diisobutyldiethoxysilane, t-butylmethyldiethoxysilane, dicyclopentyldiethoxysilane, methylethyldiethoxysilane, methylpropyldiethoxysilane, methylisopropyldiethoxysilane, methylisobutyldiethoxysilane, methylcyclopentyldiethoxysilane, methyl Dials such as cyclohexyldiethoxysilane and isopropylisobutyldimethoxysilane Kishishiran such,

Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, butyltrimethoxysilane, butyltrimethoxysilane Ethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, octyltrimethoxysilane, octyltri Trialkoxy such as ethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane Silanes can be exemplified.

Among these, diisobutyldimethoxysilane, isopropylisobutyldimethoxysilane, diisobutyldiethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, isopropyltrimethoxysilane, isopropyltrimethoxysilane, isopropyltrimethoxysilane Examples include ethoxysilane, isobutylmethyldimethoxysilane, isobutylmethyldiethoxysilane, ethyltriethoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltriethoxysilane, and pentyltrimethoxysilane. These electron donating organic silicon compounds (C)
Two or more types can be used in combination.

In the polymerization method for producing polypropylene according to the present invention, the solid catalyst component (A) is preferably used in a state in which a small amount of ethylene or α-olefin has been reacted in advance and subjected to a preliminary polymerization treatment. The preliminary polymerization treatment can be performed using the solid catalyst component (A) and the organoaluminum compound (E).

As the organoaluminum compound (E),
The above-mentioned organoaluminum compound (B) can be used, and the organoaluminum compound (B) and the organoaluminum compound (E) may be the same or different. Preferred examples of the organoaluminum compound (E) include triethylaluminum and triisobutylaluminum.

In the prepolymerization treatment, an electron-donating organic silicon compound (D) can be used if necessary. The electron donating organic silicon compound (D) and the electron donating organic silicon compound (C) may be the same or different. Preferred electron-donating organic silicon compounds (D) include diisobutyldimethoxysilane, diisobutyldiethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, isopropyltrimethoxysilane, and isopropyltriethoxysilane. , Isobutylmethyldimethoxysilane, isobutylmethyldiethoxysilane, ethyltriethoxysilane,
Examples include ethyltrimethoxysilane, butyltriethoxysilane, and pentyltriethoxysilane.

These organosilicon compounds can be used as a mixture of two or more kinds.

In the prepolymerization treatment, a hydrocarbon solvent which is inert to the polymerization reaction is used.
Examples include propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, benzene, and toluene. The proportion of each catalyst component used in the pre-polymerization treatment is determined based on the titanium atom (T
i), the ratio of the aluminum atom (Al) in the organoaluminum compound (E) and the silicon atom (Si) in the electron-donating organosilicon compound (D) was set to 1000> Al / Ti>
0.05>100> Al / Si> 0.05, preferably 300> Al / Ti>0.1; 6
0> Al / Si> 0.1, more preferably 5
0> Al / Ti>0.5;40> Al / Si> 0.
8 can be selected.

The concentration of the solid catalyst component (A) in the hydrocarbon solvent is 0.05 to 30% by weight, preferably 0.1 to 15%.
%, More preferably in the range of 0.5 to 8% by weight.

In the prepolymerization treatment, the reaction temperature is -10 to 90.
° C, preferably 0 to 60 ° C, more preferably 5 to 60 ° C.
It can be performed in the range of 40 ° C. The pre-polymerization treatment is
Propylene as ethylene or α-olefin,
1-butene, 1-hexene and the like can be used. Preferred are ethylene and propylene, and more preferred is propylene. The amount of ethylene or α-olefin polymerized by the prepolymerization treatment is 0.05 to 100 g, preferably 0.05 to 30 g, more preferably 0.1 to 10 g, based on 1 g of the solid catalyst (A).
It is. Regarding the method of supplying each catalyst component into the hydrocarbon solvent during the prepolymerization treatment, (A), (E), and (D) may be supplied simultaneously or separately. Further, the solvent used in the prepolymerization may be replaced with the same solvent or a solvent different from the solvent used in the prepolymerization as a decant.

The main polymerization is carried out using propylene as a monomer raw material. The polymerization method includes a slurry polymerization method in which propylene is polymerized using a hydrocarbon solvent, a solution polymerization method, and propylene itself to be subjected to polymerization as liquefied propylene. Any of a bulk polymerization method using a dispersion medium and a gas phase polymerization method using no dispersion medium in propylene gas can be used, but the gas phase polymerization method is preferably used. When the slurry polymerization method is used, the main polymerization may be performed using a solvent of the same kind as the solvent used for the pre-polymerization treatment or a solvent different from the solvent used for the pre-polymerization treatment.

The ratio of each catalyst component used in the main polymerization is within the following range. Titanium atom in solid catalyst component (A)
(Ti) with respect to the aluminum atom (A) in the organoaluminum compound (B) and the organoaluminum compound (E)
The ratio of the total amount of l) is selected from the range of 700> Al / Ti> 5, preferably the range of 500> Al / Ti> 10, more preferably the range of 300> Al / Ti> 10.

Titanium atom (Ti) in the solid catalyst component (A)
For the silicon atom in the electron-donating organosilicon compound (C)
The ratio of (Si) is in the range of 300> Al / Si> 0.1, preferably in the range of 100> Al / Si> 0.51, and more preferably in the range of 60> Al / Si> 1. select. (Silicon atoms (Si) in the electron-donating organic silicon compound (D) used in the prepolymerization treatment are excluded from the calculation.)
When two or more kinds of electron donating organic silicon compounds (C) are used, they can be added so as to have the same molar ratio to each electron donating organic silicon compound.

In the main polymerization, the solid catalyst component (A), the organoaluminum compound (B), and the electron-donating organosilicon compound (C) are supplied to the propylene polymerization system as follows:
(A), (B) and (C) can be supplied simultaneously or separately.

The main polymerization can be carried out at an industrially suitable polymerization temperature and pressure, although polymerization conditions vary depending on the production method selected. For example, the polymerization temperature is 0
To 100 ° C, preferably 20 to 90 ° C, more preferably 30 to 85 ° C.
In the slurry polymerization method, the polymerization pressure is set so that the partial pressure of propylene in the gas phase is in the range of 0.01 to 105 MPa, preferably 0.1 MPa.
The range is from 1 to 1.3 MPa, and more preferably from 0.3 to 1.3 MPa.
It can be in the range of 2 MPa. In the bulk polymerization method,
The partial pressure of propylene in the gas phase is basically determined by the polymerization temperature. In the gas phase polymerization method, the propylene partial pressure is 0.1
~ 3.5MPa, preferably 0.5 ~ 3.0MPa
a, more preferably in the range of 1 to 2.8 MPa.

In the present polymerization, a molecular weight regulator can be appropriately used for the purpose of adjusting the molecular weight of the obtained polypropylene. Hydrogen can be suitably used as a molecular weight regulator, that is, a chain transfer agent. Further, the polymerization can be performed by arranging several polymerization vessels in series. At this time, the polymerization conditions for each polymerization vessel may be the same or different.

In the main polymerization, ethylene, 1-butene and propylene are added to propylene within a range not to impair the effects of the present invention.
An unsaturated hydrocarbon selected from 1-pentene, 1-hexene, 1-octene and the like can be copolymerized. When using the slurry polymerization method and the bulk polymerization method, the components (soluble polymers) dissolved in the hydrocarbon solvent or liquefied propylene can be removed from the polypropylene, but can be added to the product if necessary. It is. Thus, the polypropylene of the present invention that satisfies the above requirements is obtained.

(2) Polypropylene Film The polypropylene of the present invention is suitably used as a raw material of a biaxially oriented polypropylene film by a conventionally known film forming method, for example, a tenter method for performing sequential stretching or a tubular method for performing simultaneous biaxial stretching. Can be used. Hereinafter, a method for producing a polypropylene film using the polypropylene of the present invention will be specifically described using a tenter method as an example.

If necessary, additives such as an antioxidant and an anti-blocking agent are added to the polypropylene to the extent that the object of the present invention is not impaired to prepare a polypropylene composition. Usually, the composition is pelletized by an extruder or the like. The polypropylene composition melted by an extruder is extruded into a plate shape from a T-die, cooled and solidified on a cooling roll, and then the plate-like molded product is heated by a heated roll in a longitudinal direction (axial direction of the extruder: hereinafter). This direction is sometimes referred to as a “longitudinal direction”) to obtain a uniaxially stretched film. Next, the obtained uniaxially stretched film is guided into a tenter, stretched in a lateral direction (a direction perpendicular to an extruder axis: hereinafter, this direction may be referred to as “lateral direction”) through a preheating unit, and wound up. The polypropylene film of the present invention is obtained.

In the above tenter method, the melting temperature of the polypropylene composition in the extruder is in the range of 200 to 300 ° C., preferably in the range of 220 to 280 ° C. It is preferable that the preheating temperature in the longitudinal stretching is 110 to 160 ° C, the longitudinal stretching temperature is 110 to 160 ° C, and the longitudinal stretching ratio is 3.0 to 9.0 times. The preheating temperature in the transverse stretching is 160 to 200 ° C, and the transverse stretching temperature is 14
The range is 0 to 170 ° C., and the transverse stretching ratio is 3.0 to 1.
It is preferably set to 1.0 times.

By using the polypropylene composition of the present invention, a biaxially stretched film can be formed at high speed and high efficiency by the above tenter method. The obtained film may be subjected to a heat treatment for stress relaxation, or a corona treatment or a flame treatment for improving printability and vapor deposition properties, if necessary. The film of the present invention can be used as a single layer by itself or laminated with another film.

Further, the biaxially stretched film according to the present invention can be used after metal deposition. As a method of depositing a metal on the biaxially oriented polypropylene film according to the present invention, a commonly used method can be applied. For example, in a vacuum deposition apparatus in which the inside of the apparatus has a degree of vacuum of 10 ⁻⁴ Torr or less, a desired metal is heated to dissolve and evaporate, and biaxial stretching in which wettability is improved by corona discharge, flame treatment, or the like. The gaseous metal is vapor-deposited on the film surface, and a method can be used. Further, in addition to the vacuum evaporation method, a sputtering evaporation method or an ion plating method can be used. Examples of the metal to be deposited include generally used gold, silver, platinum, copper, nickel, chromium, tin, titanium, zinc, germanium, aluminum, and selenium, and aluminum is particularly preferably used as a packaging material.

[0043]

Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples. The measuring methods of each physical property value used in Examples and Comparative Examples are shown below.

(I) Isotactic pentad fraction ¹³ C-NMR measuring apparatus (GSX-27 manufactured by JEOL Ltd.)
0 type). A. Zambelli et a
l., Macromolecules Vol. 8
ume 8), 687-689 (1975).

(Ii) Bi-active center model and statistical parameters based on Bernoulli statistics Y. Inoue, Y. Itabashi, R. Chujo, Y. Doi, Poly
mer, Volume 25, pp. Statistical parameters were obtained according to the model described in 1640-1644 (1984). When the abundance ratio of meso dyad and racemic dyad in the pentad actually measured by nuclear magnetic resonance (NMR) of the obtained polypropylene obeys the relational expression of the two-active center model described in the literature, the statistical parameter α is determined. Can be done. In the present specification, the polypropylene according to the two-active center model based on the Bernoulli statistics means that when the correlation coefficient between the actually measured value and the calculated value of the model calculation is 0.999 or more,
The polypropylene was a polypropylene according to a two-active center model based on Bernoulli statistics.

(Iii) Melt flow rate (dg / min) The method described in JIS K7210 (condition 14: 230)
C., 21.18 N).

(Iv) Young's modulus (MPa) MD (vertical direction) from biaxially stretched polypropylene film
And TD (horizontal direction) in each direction, width 10 mm,
A test piece having a length of 150 mm was cut out and subjected to ASTM D-88.
According to the method described in 2, the Young's modulus was measured at a chuck-to-chuck distance of 50 mm and a tensile speed of 5 mm / min.

(V) Heat shrinkage (%) From the biaxially stretched polypropylene film, a length (L ₀ ) of 20 cm × a width of 1 cm in (vertical direction) and (lateral direction), respectively.
Was cut out, and each test piece was heated in an oven at 140 ° C. for 15 minutes, each length (L ₁ ) cm was measured, and the shrinkage rate (S%) in each measurement direction was determined by the following formula. Was. S = 100 × (L ₀ −L ₁ ) / L ₀

(Vi) Cross-fractionation method A CFC device manufactured by Mitsubishi Chemical Corporation (T150A, detector: infrared detector, measurement wavelength: 3.41 μm, column: 4.
The measurement was carried out under the following conditions using 6φm × 150 mm, filler: glass beads (Shodex GPC AD-806MS manufactured by Showa Denko). The sample solution (solvent: ortho-dichlorobenzene, sample concentration: 4) was added to the column heated to 40 ° C.
(0 mg / 10 mL), and then cooled to 0 ° C. at a rate of 60 ° C./hour to adsorb (precipitate) the sample polymer on the filler surface. At this time, the components which did not adsorb to the filler surface and were dissolved in the solvent were sent as soluble components at 0 ° C. or lower to a GPC column online, and after molecular weight fractionation, the elution amount was detected by an infrared detector. Then, the column was gradually heated to 90 ° C. while flowing ortho-dichlorobenzene at a flow rate of (60 ml / h),
The polymer eluted from the surface of the filler at each temperature was sequentially sent online to a GPC column to separate the molecular weight, and the elution amount was detected by an infrared detector. The soluble matter at 50 ° C or lower is
It means the total amount of the soluble components at 50 ° C. or lower including the soluble components at 0 ° C. or lower, and was determined by integrating the results obtained at each step temperature increase up to the temperature. Similarly, the soluble matter at 90 ° C. or lower
It means the total amount of soluble components up to 90 ° C. including soluble components at 0 ° C. or lower, and was determined by integrating the results obtained at each step temperature increase up to the temperature.

(Vii) Boiling pentane extraction ratio and boiling heptane extraction ratio A sheet obtained by pressing polypropylene at 230 ° C. and 10 MPa was cut into small pieces of about 3 cm × 3 cm by a cutter. About 50 g of the obtained strip was ground for about 20 minutes using a Willet grinder (Ikeda: W140). 2 g of this pulverized product was subjected to Soxhlet extraction (150 mL of solvent;
Pentane or heptane, extraction time: 3h). The extraction residue was vacuum dried at 80 ° C. for 2 hours when pentane was used, and 3 hours when heptane was used, allowed to cool in a desiccator for 1 hour, weighed, and the extraction rate was calculated.

(Viii) Vapor deposition strength (N / 15 mm) Aluminum was vapor-deposited on one side of a biaxially stretched polypropylene film, and the aluminum vapor-deposited surface of the obtained vapor-deposited film and a non-stretched polypropylene film (thickness: 20 mm) were used for dry lamination. Laminated with adhesive, 40
After aging for 2 days at ℃, the adhesive is completely dried,
The 90 degree peel strength at the interface was measured with a tensile tester.

Example 1 (1) Synthesis of Solid Catalyst Component (A) A 30 liter (hereinafter, liter is referred to as L) autoclave equipped with a stirrer, a pressure gauge, and a thermometer and replaced with high-purity nitrogen was placed in an autoclave. 2.3 kg of magnesium ethoxide,
4.15 L of 2-ethyl-1-hexanol and 16.5 L of toluene were added. 0.2 MPa
Under a carbon dioxide gas atmosphere (hereinafter referred to as a gauge pressure), the mixture was heated to 90 ° C. and stirred at 150 rpm for 3 hours.
The obtained solution was cooled, and carbon dioxide gas was degassed to obtain a solution (a). This solution (a) contained 0.1 g / L of magnesium ethoxide. The above operation was handled at 1 atmosphere.

Stirrer, thermometer, condenser, nitrogen sea
15L autoclave equipped with line and baffle
Into a tube (baffle ratio 0.15), toluene 3L, Ti
Cl _Four190 mL, hexamethyldisiloxane 250 m
L, and mixed at room temperature for 5 minutes at 250 rpm.
Thereafter, 1.5 L of the solution (a) was charged for 10 minutes. After input
Immediately, solid particles (I) were precipitated. The solid particles (I)
Add 30 mL of ethanol and tetrahydrofura to the solution
(THF) 0.5L and stirring at 150 rpm.
When the temperature was raised to 60 ° C within 15 minutes while maintaining
Once the solid particles (I) have dissolved, then within 15 minutes
Solid particles began to precipitate again. The formation of these solid particles is 1
Finished within 0 minutes. Stir at 60 ° C for 45 minutes
After the continuation, the stirring was stopped and the resulting solid (II) was settled.
I let it.

The supernatant was removed by decantation, and the remaining solid product (II) was washed twice with 2 L of toluene. 2 L of toluene and 1 L of TiCl ₄ were added to the resulting solid (II), and the temperature was raised to 135 ° C. within 20 minutes while stirring at 250 rpm, and this temperature was maintained for 1 hour. Stop stirring,
The resulting solid (III) was allowed to settle, and the supernatant was decanted.

1 L of TiCl ₄ , 2.5 L of toluene and 21 mL of diisobutyl phthalate were added to the resulting solid (III).
Was added and heated to 135 ° C. and stirred at 250 rpm for 1.5 hours. The supernatant was removed by decantation, ₂ L of TiCl ₄ was added to the residue, and the mixture was refluxed for 10 minutes with stirring. The supernatant was removed by decantation, and the residue was washed three times with 2 L of toluene and further with 4 L of hexane.
After washing twice, 116 g of a solid catalyst component (A) was obtained. This solid catalyst component (A) contained 17.3% by weight of magnesium, 2.3% by weight of titanium, 55.6% by weight of chlorine and 8.6% by weight of diisobutyl phthalate.

(2) Preliminary Polymerization Treatment A stirrer was equipped, and the internal volume was replaced with high-purity nitrogen.
20 L of hexane, 100 g of the solid catalyst component (A), 0.1 mol of triethylaluminum, and 0.015 mol of diisobutyldimethoxysilane were added to a L stainless steel reactor. While stirring at 30 ° C. and a stirring rotation speed of 200 rpm, propylene gas was introduced and pressurized until the propylene partial pressure became 0.1 MPa, and a prepolymerization treatment was performed for 6 hours. Thereafter, propylene gas was purged. The amount of polymerized propylene was 3 g per 1 g of the solid catalyst component (A).

(3) Main Polymerization A stirrer was installed, and the internal volume was replaced with high-purity nitrogen.
In a 0 L stainless steel reactor, 0.5 g / h of the pre-polymerized solid catalyst component (A) was used as the solid catalyst component, 0.018 mol / h of triethylaluminum, and 0.003 mol / h of diisobutyldimethoxysilane.
, And each was continuously supplied. At the same time, polymerization temperature 70
Propylene was continuously supplied so that the polymerization pressure was maintained at 2.3 MPa under the condition of
Hydrogen is continuously supplied so that the propylene molar ratio becomes 0.003, and continuous gas phase polymerization of propylene is performed.
Powdered polypropylene was obtained at a production rate of 15 kg / h.

(4) Granulation (Production of Polypropylene Composition) With respect to 100 parts by weight of the obtained powdery polypropylene,
The antioxidant tetrakis- [methylene-3- (3 ′,
5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane 0.10 parts by weight, tris (2,4
0.10 parts by weight of (-di-t-butylphenyl) phosphite and 0.03 parts by weight of hydrotalcite were added and uniformly mixed with a Henschel mixer (trade name). The obtained mixture was subjected to 65 mm diameter, L / D = 30.
Using an extruder, melt kneading at an extrusion temperature of 230 ° C.
A pellet-shaped polypropylene composition was obtained.

(5) Film Formation The pellet-shaped polypropylene composition was extruded at 250 ° C. with an extruder equipped with a T-die and taken up by a cooling roll at 30 ° C. to obtain a polypropylene plate-like molded product. Next, the plate-like molded product was stretched at a stretching temperature of 145 ° C. by a tenter-type sequential stretching apparatus.
The film is stretched 5 times in the machine direction in the longitudinal direction, and then stretched 10 times in the transverse direction in a tenter at a temperature of 160 ° C. in the bath of the stretching zone, and further subjected to an 8% stress relaxation treatment at 170 ° C.
A biaxially stretched polypropylene film having a thickness of 20 μm was obtained.

(6) Evaluation Regarding the polypropylene and the biaxially stretched polypropylene film thus obtained, the above (i) to (vi)
The physical property measurement of i) was performed. Tables 1, 2 and 3 show the results.
It was shown to. Table 1 shows isotactic pentad fraction [mmmm] of polypropylene, boiling pentane extraction rate, boiling heptane extraction rate, ethylene content, and melt flow rate. Table 2 shows analysis results by the cross fractionation method.
Table 3 shows the results of measuring various physical properties of the biaxially stretched polypropylene film.

Comparative Example 1 A solid catalyst component (A) was obtained according to the method described in Example 1, (1). The pre-polymerization treatment is performed in the same manner as in Example 1 (2).
Was carried out in accordance with Example 1, except that diisopropyldimethoxysilane was used in place of diisobutyldimethoxysilane used in Example 1. In the main polymerization, the hydrogen / propylene molar ratio of 0.003 in Example 1 (3) was changed to 0.005.
, And the procedure was performed in the same manner as in Example 1 except that diisopropyldimethoxysilane was used instead of diisobutyldimethoxysilane, to obtain a powdery polypropylene at a production rate of 14 kg / h. Granulation and film formation were performed according to Example 1. Tables 1 and 2 show the physical properties of the polypropylene and biaxially stretched polypropylene films thus obtained.
And Table 3.

Example 2 A solid catalyst was prepared according to the method described in Example 1, except that a mixture of 16 mL of diisobutyl phthalate and 6 mL of dinormal octyl phthalate was used instead of 21 mL of diisobutyl phthalate used in (1) of Example 1. The component (A) was obtained. The pre-polymerization treatment was performed by the method described in Example 1 (2). The main polymerization was carried out by the method described in (3) of Example 1 except that the hydrogen / propylene ratio was set to 0.0025, to obtain a powdery polypropylene at a production amount of 15 kg / h. Granulation and film formation were performed according to Example 1. Tables 1 and 2 show the physical properties of the polypropylene and biaxially stretched polypropylene films thus obtained.
And Table 3.

Example 3 According to the method described in Example 1, the production of the solid catalyst component (A) and the preliminary polymerization treatment were carried out. In this polymerization, the hydrogen / propylene molar ratio is set to 0.003, and ethylene / propylene having a molar ratio of ethylene / propylene of 0.0015 is used instead of propylene.
Except that a propylene mixed gas was used, the procedure was performed in the same manner as in Example 2 to obtain a powdery polypropylene at a production rate of 15.5 kg / h. Granulation and film formation were performed according to Example 1. Tables 1 and 2 show the physical properties of the polypropylene and biaxially stretched polypropylene films thus obtained.
And Table 3.

Example 4 Production of a solid catalyst component (A) and prepolymerization were carried out in the same manner as described in Example 2. In the main polymerization, the hydrogen / propylene molar ratio is set to 0.0025, and ethylene / propylene having a molar ratio of ethylene / propylene of 0.001 is used instead of propylene.
Except that a propylene mixed gas was used, the procedure was performed in the same manner as in Example 2 to obtain a powdery polypropylene at a production amount of 16 kg / h. Granulation and film formation were also performed according to Example 1. The physical properties of the thus obtained polypropylene and biaxially oriented polypropylene films are shown in Tables 1, 2 and 3.

Comparative Example 2 In the main polymerization of Comparative Example 1, an ethylene / propylene mixed gas having a hydrogen / propylene molar ratio of 0.004 instead of 0.005 and an ethylene / propylene molar ratio of 0.0017 instead of propylene was used. A powdered polypropylene was obtained at a production rate of 16.1 kg / h based on Comparative Example 1, except that Granulation and film formation were performed according to Example 1. The physical properties of the thus obtained polypropylene and biaxially oriented polypropylene films are shown in Tables 1, 2 and 3.

Example 5 In the main polymerization of Example 4, the hydrogen / propylene molar ratio was 0.0025, and the ethylene / propylene molar ratio was 0.1.
15.9 kg / h according to the method described in Example 4, except that 1 ethylene / propylene mixed gas of 001 was used.
The powdery polypropylene was obtained with the production amount. Granulation and film formation were performed according to the method described in Example 1. The physical properties of the thus obtained polypropylene and biaxially oriented polypropylene films are shown in Tables 1, 2 and 3.

[0067]

[Table 1]

[0068]

[Table 2]

[0069]

[Table 3]

[0070]

The polypropylene obtained by the present invention has a high Young's modulus (excellent in rigidity), a small heat shrinkage ratio (excellent in heat resistance), and is suitable for forming a film having good metal vapor deposition property. Are suitable. In other words, the conventional metal-deposited biaxially stretched polypropylene film has the drawback that the vapor-deposited film is lifted up or detached due to weak adhesion to metal and friction, or the vapor-deposited film is peeled off by blocking under high temperature and high humidity. However, the polypropylene film of the present invention is characterized in that the adhesive strength to the vapor-deposited film is increased and the heat-resistance is excellent, so that the vapor-deposited film is unlikely to float. When the composition containing the polypropylene of the present invention is used as a forming raw material, a biaxially stretched film can be formed with high efficiency by a tenter method.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] June 26, 2000 (2006.2.
6)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0004

[Correction method] Change

[Correction contents]

[0004]

Means for Solving the Problems The present inventors have intensively studied to solve the above problems. As a result, the isotactic pentad fraction, the melt flow rate, the weight average molecular weight of each soluble component at 0 ° C. or less, 50 ° C. or less, and 90 ° C. or less, the boiling pentane extraction rate, and the boiling heptane extraction rate by the cross fractionation method The present inventors have found that a polypropylene having each of the above properties in a specific range has the expected performance, and based on this finding, completed the present invention.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction contents]

In the polypropylene of the present invention, the abundance of meso- and racemic dyads in a pentad, which is an index of the stereoregularity of polypropylene, is determined according to a two-active center model based on Bernoulli statistics, and the statistical parameter α at that time is determined. , a range of 0.989 ≦ α ≦ 0.995, preferably in the range of 0.989 ≦ α ≦ 0.994, more preferably when in the range of 0.990 ≦ α ≦ 0.994, and a high rigidity A film having good metal vapor deposition properties can be obtained. The bi-active center model based on Bernoulli statistics is
Y. Inoue, Itabashi, R. Chujo, Y. Doi, Polymer, Vol
ume 25, pp 1640-1644 (1984). When the statistical parameter α exceeds 0.995,
Although a highly rigid film is obtained, the metal vapor deposition property is reduced. If the statistical parameter α is less than 0.989, the metal deposition property of the film is good, but the rigidity decreases.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0049

[Correction method] Change

[Correction contents]

(Vi) Cross-fractionation method A CFC device manufactured by Mitsubishi Chemical Corporation (T150A, detector: infrared detector, measurement wavelength: 3.41 μm, column: 4.
The measurement was carried out under the following conditions using 6φm × 150 mm, filler: glass beads (Shodex GPC AD-806MS manufactured by Showa Denko). The sample solution (solvent: ortho-dichlorobenzene, sample concentration: 4) was added to the column heated to 40 ° C.
After injection of 4 mL (0 mg / 10 mL), the sample polymer was cooled to 0 ° C. at a rate of 60 ° C./hour, and the sample polymer was adsorbed (precipitated) on the surface of the filler. At this time, the components which did not adsorb to the filler surface and were dissolved in the solvent were sent as soluble components at 0 ° C. or lower to a GPC column online, and after molecular weight fractionation, the elution amount was detected by an infrared detector. Then, the column was gradually heated to 90 ° C. while flowing ortho-dichlorobenzene at a flow rate of (60 ml / h),
The polymer eluted from the surface of the filler at each temperature was sequentially sent online to a GPC column to separate the molecular weight, and the elution amount was detected by an infrared detector. The 50 ° C. or less solubles, by integrating means the total amount of 50 ° C. below solubles containing solubles of 0 ℃ below, the results obtained in each step raising the temperature to the temperature I asked for it. Similarly, the 90 ° C. or less solubles, means the total amount of extractables to 90 ° C. containing soluble matter of 0 ℃ or less, until the temperature results obtained for each step heating It was determined by integrating.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0064

[Correction method] Change

[Correction contents]

Example 4 According to the method described in Example 2, the production of the solid catalyst component (A) and the preliminary polymerization treatment were carried out. In the main polymerization, the hydrogen / propylene molar ratio is set to 0.0025, and ethylene / propylene having a molar ratio of ethylene / propylene of 0.001 is used instead of propylene.
Except that a propylene mixed gas was used, the procedure was performed in the same manner as in Example 2 to obtain a powdery polypropylene at a production amount of 16 kg / h. Granulation and film formation were also performed according to Example 1. The physical properties of the thus obtained polypropylene and biaxially oriented polypropylene films are shown in Tables 1, 2 and 3.

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0066

[Correction method] Change

[Correction contents]

Example 5 In the main polymerization of Example 4, the hydrogen / propylene molar ratio was 0.0025, and the ethylene / propylene molar ratio was 0.1.
15.9 kg / h according to the method described in Example 4, except that an ethylene / propylene mixed gas of 001 was used.
The powdery polypropylene was obtained with the production amount. Granulation and film formation were performed according to the method described in Example 1. The physical properties of the thus obtained polypropylene and biaxially oriented polypropylene films are shown in Tables 1, 2 and 3. that's all

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Naonobu Minamizawa 4-100 Shinjo, Nonoichi-machi, Ishikawa-gun, Ishikawa Prefecture Famille Uit 202 (72) Inventor Ichiro Sakabe 1963-4, Yawata Kaigandori, Ichihara-shi, Chiba Pref. Inventor Katsuhiko Ohno 2-17, Tatsumidaihigashi, Ichihara-shi, Chiba F-term (reference) 4F071 AA20 AA81 AA88 AA89 AB30 AC05 AC11 AE05 AE22 AF05Y AH04 BA01 BB06 BB08 BC01 4J100 AA03P CA01 DA01 DA39 DA41 DA42 JA58

Claims (2)

[Claims] 1. A polypropylene having the following characteristics: When the isotactic pentad fraction [mmmm] is 0.
It is in the range of 89 ≦ [mmmm] ≦ 0.95. The abundance of meso- and racemic dyads in the pentad was determined according to a two-active center model based on Bernoulli statistics, and the statistical parameter α at that time was 0.989 ≦
α ≦ 0.995. Melt flow rate (230 ° C, 21.18N)
It is in the range of 0.5 to 20 dg / min. The weight-average molecular weight of the soluble component at 0 ° C. or less by the cross fractionation method is 7 × 10 ⁴ or more, and the weight-average molecular weight of the soluble component at 50 ° C. or less is 6 × 10 ⁴ or more and 90 ° C. or less The weight-average molecular weight of the soluble component is 6 × 10 ⁴ or more. Boiling pentane extraction rate (C5-Ext) is 0.5% by weight
The boiling heptane extraction rate (C7-Ext) is 5
% Or less, and (C5-Ext) and (C7-
(Ext) is (C7-Ext)> 3.5 · (C5-E)
xt). 2. A polypropylene film obtained by forming the polypropylene according to claim 1 into a film.