JP2000143731A - Propylene-based random copolymer and film made therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject copolymer capable of giving films with excellent heat sealability, slipperiness and anti-blocking tendency and enabling high-speed film formation process. SOLUTION: This copolymer is an ethylene-propylene random copolymer satisfying the requirements described below: (1) ethylene unit content (α) determined by 13C-NMR is 0.2-10 wt.%, (2) the elution amount (Wp) between (Tp-5) deg.C and (Tp+5) deg.C is >=20 wt.% (Tp( deg.C) is the principal elution peak temperature in the ascending temperature partition chromatograph), and (3) the elution amount at <=0 deg.C (W0, wt.%) in the ascending temperature chromatograph and α satisfy the relationship: W0<=[(3+2α)/4].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a propylene random copolymer and a film comprising the same. More specifically, the present invention relates to a propylene-based binary random copolymer of propylene and ethylene, and a film formed from the same. This film is suitably used as a component of at least one layer of a laminated or coextruded laminated film.

[0002]

2. Description of the Related Art Crystalline propylene-based polymer films are widely used as packaging films, taking advantage of their excellent rigidity, transparency and moisture-proof properties. Packaging films are often used in the form of a bag, but the process of closing the bag mouth after processing the film into a bag and filling the contents is usually performed by pressing the film with a heated rod. It is performed by an operation called heat sealing for melting and bonding together. In recent years, in a series of bag making and packaging processes, high-speed film forming has been attempted by a large film forming machine in order to improve productivity, and development of a material having excellent heat sealability has been strongly demanded. In addition, in order to perform these secondary processing steps smoothly, it is required that the packaging film has excellent slipping properties and antiblocking properties as essential properties.

[0003] However, the propylene homopolymer film has a disadvantage that heat sealing requires high-temperature and long-time pressing. Therefore, copolymerization of ethylene, 1-butene, and other α-olefins with propylene has been widely performed for the purpose of remedying this drawback. However, in the prior art for producing a propylene-based polymer using a Ziegler-Natta catalyst,
In order to obtain a sufficient heat sealing property improving effect, it was necessary to copolymerize a large amount of comonomers such as ethylene, 1-butene, and other α-olefins. Also, these comonomers are often concentrated in low molecular weight components, and have become tacky components with poor crystallinity (hereinafter referred to as tacky components). Therefore, the rigidity, which is the original characteristic of the polypropylene film, is greatly reduced, the films are blocked from each other, hindering the secondary processing, or the appearance is poor due to whitening of the bleeding, and it has not become practically usable. .

In order to remedy this drawback, in the prior art, attempts have been made to dissolve and remove sticky components in an inert solvent. However, it is very difficult to efficiently wash away the sticky components and to prevent the low-temperature melting components that contribute to the heat sealing property from being reduced by washing, and this has not been industrially satisfactory. On the other hand, in recent years, the application of a propylene polymer using a so-called metallocene catalyst has been actively studied. Polymers based on metallocene catalysts are characterized by a very narrow molecular weight distribution and composition distribution. However, maintaining the molding stability,
It has been pointed out that it is better to broaden the molecular weight distribution and composition distribution in order to impart several contradictory physical properties to the molded body, and various compositions of propylene-based polymers with metallocene catalysts have been pointed out. Proposed. However, it has not yet been possible to obtain a polymer having resin characteristics suitable for the application and the molding method by an industrially satisfactory method.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above point of view, and exhibits excellent heat sealing properties without impairing desirable properties such as rigidity, transparency and moisture resistance inherent in a polypropylene film. And a propylene-based random copolymer having a very small decrease in film quality even when the film-forming speed is increased, and a film having both the slip property and the anti-blocking property required for high-speed bag-making, and It is intended to provide a film.

[0006]

The applicant of the present invention relates to a Ziegler-Natta catalyst, which is a catalyst component for producing an olefin polymer which exhibits a small decrease in polymerization activity with time, exhibits high activity and high stereoregularity, and an olefin polymer. A catalyst for production and a method for producing an olefin polymer have been found (Japanese Patent Application No. 10-71).
No. 752).

The inventors of the present invention have conducted intensive studies on the film properties of a propylene-based polymer produced using the above-mentioned catalyst component. As a result, the propylene-based random copolymer which satisfies the above-mentioned object of the invention at a very high level has been obtained. The inventors have found that a polymer can be obtained, and have completed the present invention. That is, the present invention provides the following propylene-based random copolymer and a film comprising the same. 1. A random copolymer of propylene and ethylene, which satisfies the following criteria: The ethylene unit content (α (% by weight)) in the copolymer measured by ¹³ C-NMR is 0.2 to 10% by weight. Tp is the main elution peak temperature of the fractionated chromatograph
(C), the amount (Wp (% by weight)) eluted in the temperature range of (Tp-5) C to (Tp + 5) C is 20.
% By weight or more. The amount (W0 (% by weight)) eluted in the temperature range of 0 ° C. or lower in the temperature rising fractionation chromatograph and α satisfy the relationship of the following formula (1). W0 ≦ (3 + 2α) / 4 (1) 2. The propylene-based random copolymer according to 1 above, wherein the melting point (Tm (° C.)) of the copolymer measured by a differential scanning calorimeter (DSC) and α satisfy the relationship of the following formula (2). Tm ≦ 160−5α (2) The main elution peak temperature of the fractionated chromatograph
Assuming that p (° C.), the amount (WH (% by weight)) eluted in a temperature range of (Tp + 5) ° C. or more and α satisfy the relationship of the following formula (3). Polymer. 0.1 ≦ WH ≦ 3α (3) The amount of the boiling diethyl ether extractable component (E (% by weight)) in the copolymer is 2.5% by weight or less, and E and α satisfy any one of the above-mentioned formulas (1) to (3). The propylene-based random copolymer according to the above. E ≦ (2α + 15) / 10 (4) Melt index (MI (g / 10min))
The propylene-based random copolymer according to any one of the above items 1 to 4, wherein is 0.1 to 200 g / 10 min. 6. The propylene random copolymer according to any one of the above 1 to 5, wherein the stereoregularity index (P (mol%)) in the copolymer measured by ¹³ C-NMR is 98 mol% or more. 7. 7. The propylene random copolymer according to any one of the above 1 to 6, wherein α is 3 to 7% by weight. 8. A film comprising the propylene random copolymer according to any one of the above 1 to 7.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. 1. Propylene random copolymer The propylene random copolymer of the present invention is a random copolymer of propylene and ethylene,
Meet.

The content of ethylene units (α (% by weight)) in the copolymer measured by ¹³ C-NMR is from 0.2 to 1
0% by weight. Preferably it is 0.5 to 9% by weight, more preferably 1 to 8% by weight, most preferably 3 to 7% by weight. If the ethylene unit content is less than 0.2% by weight,
The effect of improving heat sealability cannot be expected. 10% by weight
If it exceeds, the rigidity of the film becomes unsatisfactory, which is not preferable.

In the propylene random copolymer of the present invention, the melting point (Tm (° C.)) of the copolymer measured by a differential scanning calorimeter (DSC) and α satisfy the relationship of the following formula (2). Tm ≦ 160−5α (2) More preferably, Tm ≦ 160−6α (5) is satisfied.

When this relationship is not satisfied, the heat sealing property tends to be insufficient and the anti-blocking property may be low. Tp is the main elution peak temperature of the fractionated chromatograph
(C), the amount (Wp (% by weight)) eluted in the temperature range of (Tp-5) C to (Tp + 5) C is 20.
% By weight or more. Preferably, 20 ≦ Wp and (80−15α) ≦ Wp (6), and more preferably, 30 ≦ Wp and (90−12α) ≦ Wp (7).

[0012] When Wp is less than 20% by weight, the bottom of the main elution peak is greatly extended to the high temperature side and / or the low temperature side, and the component on the low temperature side is obtained by sticking the formed film. The components on the high-temperature side are not preferred because they cause insufficient heat sealing properties and increase the dependence of transparency on molding conditions. In addition, the propylene random copolymer of the present invention had a certain amount of the component on the high-temperature side of the main elution peak, which did not exist at all because it contributed to moldability and rigidity such as chill roll release. More preferably, the propylene random copolymer of the present invention elutes in a temperature range of (Tp + 5) ° C. or higher (W
H (% by weight) and α preferably satisfy the relationship of the following expression (3). 0.1 ≦ WH ≦ 3α (3) More preferably, WH ≦ (3α−3) and (3α−15) ≦ WH (8) are satisfied.

The amount eluted (W0 (% by weight)) in the temperature range of 0 ° C. or lower in the temperature-raising fractionation chromatograph and α satisfy the following formula (1). W0 ≦ (3 + 2α) / 4 (1) Preferably, W0 ≦ (2 + 2α) / 4 (9) is satisfied.

When W0 does not satisfy the relationship (1), the formed film becomes sticky, and troubles due to bleeding of additives, low molecular weight components and the like are likely to occur, which is not preferable. The propylene random copolymer of the present invention has a boiling diethyl ether extractable component amount (E (% by weight)) in the copolymer of 2.5% by weight or less, and
And α preferably satisfy the relationship of the following equation (4). E ≦ (2α + 15) / 10 (4) More preferably, E ≦ (α + 5) / 5 (10) is satisfied. In this case, it is preferable that the formed film does not become sticky.

The propylene random copolymer of the present invention has a melt index (MI (g / 10 mi)
n)) is preferably from 0.1 to 200 g / 10 min. It is more preferably 1 to 40 g / 10 min, and still more preferably 2 to 20 g / 10 min.
If the melt index is out of this range, the moldability may be poor.

The propylene random copolymer of the present invention preferably has a stereoregularity index (P (mol%)) of 98 mol% or more in the copolymer measured by ¹³ C-NMR. More preferably, it is 98.5 mol% or more. If the stereoregularity index P is less than 98 mol%, the rigidity and antiblocking properties of the formed film may be insufficient. The above α, Tm, Wp, WH, W0
, E, MI and P can be determined by the measuring method described in the embodiment. 2. Method for producing propylene-based random copolymer The propylene-based random copolymer of the present invention is prepared by subjecting (A) a magnesium compound and a titanium compound to 120 ° C. or higher in the presence of an electron-donating compound and optionally a silicon compound.
After contact at a temperature of 50 ° C or less, 100 ° C or more
Propylene by using a solid catalyst component consisting of one washed with an inert solvent at a temperature of 0 ° C. or lower, (B) an organoaluminum compound and, if necessary, (C) a catalyst consisting of an electron-donating compound as a third component. It can be produced by copolymerizing ethylene.

Hereinafter, each catalyst component, a preparation method, a polymerization method, and the like will be described. [I] Each catalyst component (A) Solid catalyst component The solid catalyst component contains magnesium, titanium and an electron donor. The following (a) magnesium compound, (b) titanium compound, and (c) And a solid catalyst component comprising a silicon compound (d) if necessary. (A) Magnesium Compound The magnesium compound is not particularly limited, but a magnesium compound represented by the general formula (I) MgR ¹ R ² ... (I) can be preferably used.

In the above general formula (I), R¹and
R^TwoIs a hydrocarbon group, OR^ThreeGroup (R ^ThreeIs a hydrocarbon group)
Or a halogen atom. Where R¹And R^TwoCharcoal
Examples of the hydride group include an alkyl group having 1 to 12 carbon atoms,
A cycloalkyl group, an aryl group, an aralkyl group, etc.
^ThreeAs a group, R^ThreeIs an alkyl group having 1 to 12 carbon atoms,
A cycloalkyl group, an aryl group, an aralkyl group, etc.
Chlorine, bromine, iodine, fluorine, etc.
Can be mentioned. Also, R¹And R^TwoAre the same
May also be different.

Specific examples of the magnesium compound represented by the above general formula (I) include dimethyl magnesium, diethyl magnesium, diisopropyl magnesium, dibutyl magnesium, dihexyl magnesium, dioctyl magnesium, ethyl butyl magnesium, diphenyl magnesium, dicyclohexyl magnesium and the like. Alkyl magnesium, aryloxy magnesium, dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium, dibutoxy magnesium, dihexyloxy magnesium, dioctoxy magnesium, diphenoxy magnesium, dicyclohexyloxy magnesium, etc. Chloride, butylmagnesium chloride, hex Le chloride, isopropyl magnesium chloride, isobutyl magnesium chloride, t- butyl magnesium chloride, phenyl magnesium bromide, benzyl magnesium chloride,
Alkyl magnesium halides such as ethyl magnesium bromide, butyl magnesium bromide, phenyl magnesium chloride and butyl magnesium iodide, aryl magnesium halides; butoxymagnesium chloride, cyclohexyloxymagnesium chloride, phenoxymagnesium chloride, ethoxymagnesium bromide, butoxymagnesium bromide, ethoxymagnesiumiodide Examples thereof include alkoxymagnesium halides such as dyde, allyloxymagnesium halides; and magnesium halides such as magnesium chloride, magnesium bromide, and magnesium iodide.

Among these magnesium compounds, from the viewpoint of polymerization activity and stereoregularity, magnesium halide, alkoxymagnesium, alkylmagnesium,
Alkyl magnesium halides can be suitably used. The above magnesium compound can be prepared from metallic magnesium or a compound containing magnesium.

One example is a method in which halogen and alcohol are brought into contact with metallic magnesium.
Here, examples of the halogen include iodine, chlorine, bromine, and fluorine. Of these, iodine is preferred. Examples of alcohols include methanol, ethanol, propanol, butanol, cyclohexanol, octanol and the like.

As another example, Mg (OR ⁴ ) ₂
In magnesium represented alkoxy compound (wherein, R ⁴
Represents a hydrocarbon group having 1 to 20 carbon atoms. ) Is contacted with a halide. Examples of the halide include silicon tetrachloride, silicon tetrabromide, tin tetrachloride, tin tetrabromide, and hydrogen chloride. Among these, silicon tetrachloride is preferred from the viewpoint of polymerization activity and stereoregularity. R ⁴ is an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a hexyl group or an octyl group; an alkenyl group such as a cyclohexyl group, an allyl group, a propenyl group or a butenyl group. Aryl groups such as phenyl, tolyl, and xylyl groups; aralkyl groups such as phenethyl and 3-phenylpropyl; Among them, an alkyl group having 1 to 10 carbon atoms is particularly preferable.

Further, the magnesium compound is silica,
It may be supported on a support such as alumina or polystyrene. The above magnesium compounds may be used alone or in combination of two or more. Further, it may contain halogen such as iodine, other elements such as silicon and aluminum, and may contain an electron donor such as alcohol, ether and ester. (B) Titanium compound The titanium compound is not particularly limited, but is represented by the general formula (I)
I) A titanium compound represented by TiX ¹ _p (OR ⁵ ) _4-p (II) can be preferably used.

In the above formula (II), X ¹ represents a halogen atom, among which a chlorine atom and a bromine atom are preferable, and a chlorine atom is particularly preferable. R ⁵ is a hydrocarbon group, which may be a saturated group or an unsaturated group, a linear group, a branched group, or a cyclic group; , Oxygen, silicon, phosphorus and the like. Preferably a hydrocarbon group having 1 to 10 carbon atoms, particularly an alkyl group,
An alkenyl group, a cycloalkenyl group, an aryl group, an aralkyl group and the like are preferable, and a linear or branched alkyl group is particularly preferable. When a plurality of —OR ⁵ are present, they may be the same or different. Specific examples of R ⁵ include methyl group, ethyl group, n- propyl group, an isopropyl group, n- butyl group, sec- butyl group, an isobutyl group, n- pentyl group, n- hexyl, n- heptyl, n-octyl group, n-decyl group, allyl group, butenyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group, phenyl group, tolyl group, benzyl group,
And a phenethyl group. p shows the integer of 0-4.

Specific examples of the titanium compound represented by the above general formula (II) include tetramethoxytitanium, tetraethoxytitanium, tetra-n-propoxytitanium, tetraisopropoxytitanium, tetra-n-butoxytitanium and tetraisotitanium. Tetraalkoxy titanium such as butoxytitanium, tetracyclohexyloxytitanium, and tetraphenoxytitanium; titanium tetrahalide such as titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide; methoxytitanium trichloride, ethoxytitanium trichloride, and propoxytitanium trichloride Chloride, n-butoxytitanium trichloride,
Trihalogenated alkoxytitaniums such as ethoxytitanium tribromide; dimethoxytitanium dichlorides such as dimethoxytitanium dichloride, diethoxytitanium dichloride, diisopropoxytitanium dichloride, di-n-propoxytitanium dichloride, diethoxytitanium dibromide; trimethoxy Titanium chloride, triethoxytitanium chloride, triisopropoxytitanium chloride, tri-
Monohalogenated trialkoxy titanium such as n-propoxy titanium chloride and tri-n-butoxy titanium chloride can be exemplified. Among these, a titanium compound having a high halogen content, particularly titanium tetrachloride, is preferred from the viewpoint of polymerization activity. These titanium compounds may be used alone or in combination of two or more. (C) Electron-donating compound Examples of the electron-donating compound include oxygen-containing compounds such as alcohols, phenols, ketones, aldehydes, esters of organic or inorganic acids, and ethers such as monoether, diether and polyether. Examples include electron donors and nitrogen-containing electron donating compounds such as ammonia, amines, nitriles, and isocyanates. Examples of the organic acid include a carboxylic acid, and specifically, malonic acid and the like.

Of these, esters of polycarboxylic acids are preferred, and esters of aromatic polycarboxylic acids are more preferred. From the viewpoint of polymerization activity, monoesters and / or diesters of aromatic dicarboxylic acids are particularly preferred. Further, an aliphatic hydrocarbon in which the organic group in the ester portion is linear, branched or cyclic is preferable. In particular,
Phthalic acid, naphthalene-1,2-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, 5,6,7,8-tetrahydronaphthalene-1,2-dicarboxylic acid, 5,6
7,8-tetrahydronaphthalene-2,3-dicarboxylic acid, indane-4,5-dicarboxylic acid, indane-5,
Methyl and ethyl dicarboxylic acids such as 6-dicarboxylic acid,
n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, 1-methylbutyl,
-Methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1-methylpentyl, 2-methylpentyl,
3-methylpentyl, 4-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, 2-
Methylhexyl, 3-methylhexyl, 4-methylhexyl, 2-ethylhexyl, 3-ethylhexyl, 4-
Examples thereof include dialkyl esters such as ethylhexyl, 2-methylpentyl, 3-methylpentyl, 2-ethylpentyl, and 3-ethylpentyl. Among them, phthalic acid diesters are preferable, and a linear or branched aliphatic hydrocarbon having 4 or more carbon atoms in the organic group in the ester portion is preferable.

As specific examples, di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, diethyl phthalate and the like can be preferably mentioned. These compounds may be used alone or in combination of two or more. (D) Silicon compound In the preparation of the solid catalyst component, in addition to the components (a), (b) and (c), the component (d) may optionally have the following general formula (III), Si (OR ⁶ ) _{^{q X 2 4-q ...... (}} III) (R 6 is a hydrocarbon group, X ² is a halogen atom, q is 0 to 3
Indicates an integer. ) Can be used. By using a silicon compound, the catalytic activity and stereoregularity can be improved, and the amount of fine powder in the produced polymer can be reduced.

In the above general formula (III), X ² represents a halogen atom, among which a chlorine atom and a bromine atom are preferred, and a chlorine atom is particularly preferred. R ⁶ is a hydrocarbon group, which may be a saturated group or an unsaturated group, may be a linear group, a branched group, or a cyclic group; , Oxygen, silicon, phosphorus and the like.
Preferably, a hydrocarbon group having 1 to 10 carbon atoms, particularly an alkyl group, an alkenyl group, a cycloalkenyl group, an aryl group and an aralkyl group are preferred. When a plurality of —OR ⁶ are present, they may be the same or different. Specific examples of R ⁶ include a methyl group, an ethyl group, n-
Propyl group, isopropyl group, n-butyl group, sec-
Butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, allyl, butenyl, cyclopentyl, cyclohexyl, cyclohexenyl, phenyl, Examples include a tolyl group, a benzyl group, and a phenethyl group. q shows the integer of 0-3.

Specific examples of the silicon compound represented by the above general formula (III) include silicon tetrachloride, methoxytrichlorosilane, dimethoxydichlorosilane, trimethoxychlorosilane, ethoxytrichlorosilane, diethoxydichlorosilane, triethoxychlorosilane, Propoxytrichlorosilane, dipropoxydichlorosilane,
Tripropoxychlorosilane and the like can be mentioned. Among these, silicon tetrachloride is particularly preferred. These silicon compounds may be used alone or in combination of two or more. (B) Organoaluminum Compound (B) The organoaluminum compound used in the production of the crystalline polypropylene of the present invention is not particularly limited, but has an alkyl group, a halogen atom, a hydrogen atom, an alkoxy group, aluminoxane, and the like. Can be preferably used. Specifically, trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum,
Trialkylaluminums such as trioctylaluminum; dialkylaluminum monochlorides such as diethylaluminum monochloride, diisopropylaluminum monochloride, diisobutylaluminum monochloride and dioctylaluminum monochloride; alkylaluminum sesquihalides such as ethylaluminum sesquichloride; methylaluminoxane and the like A chain aluminoxane and the like can be mentioned. Among these organic aluminum compounds, trialkyl aluminum having a lower alkyl group having 1 to 5 carbon atoms, particularly trimethyl aluminum, triethyl aluminum, tripropyl aluminum and triisobutyl aluminum are preferred. These organoaluminum compounds may be used alone or in combination of two or more. (C) Third Component (Electron-donating Compound) In preparing the catalyst for polymerization of crystalline polypropylene of the present invention, (C) an electron-donating compound is used as necessary. As the (C) electron donating compound, an organosilicon compound having a Si—O—C bond, a nitrogen-containing compound, a phosphorus-containing compound, and an oxygen-containing compound can be used. Among them, from the viewpoint of polymerization activity and stereoregularity, Si—O—C
It is preferable to use an organic silicon compound having a bond, ethers and esters, and it is particularly preferable to use an organic silicon compound having a Si—O—C bond.

Specific examples of the organosilicon compound having a Si—O—C bond include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, Triethylethoxysilane, ethylisopropyldimethoxysilane, propylisopropyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, isopropylisobutyldimethoxysilane, di-
t-butyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, t-butyldimethoxysilane
Butylpropyldimethoxysilane, t-butylisopropyldimethoxysilane, t-butylbutyldimethoxysilane, t-butylisobutyldimethoxysilane, t-butyl (s-butyl) dimethoxysilane, t-butylamyldimethoxysilane, t-butylhexyldimethoxysilane , T-butylheptyldimethoxysilane, t-butyloctyldimethoxysilane, t-butylnonyldimethoxysilane, t-butyldecyldimethoxysilane, t-butyl
Butyl (3,3,3-trifluoromethylpropyl) dimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylpropyldimethoxysilane, cyclopentyl-t
-Butyldimethoxysilane, cyclohexyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclohexyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, bis (2,3
-Dimethylcyclopentyl) dimethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane,
Methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, t-butyltrimethoxysilane,
s-butyltrimethoxysilane, amyltrimethoxysilane, isoamyltrimethoxysilane, cyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, norbornanetrimethoxysilane, indenyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, cyclopentyl (t- Butoxy) dimethoxysilane, isopropyl (t-butoxy) dimethoxysilane, t-butyl (isobutoxy) dimethoxysilane, t
-Butyl (t-butoxy) dimethoxysilane, texyltrimethoxysilane, texylisopropoxydimethoxysilane, texyl (t-butoxy) dimethoxysilane, texylmethyldimethoxysilane, texylethyldimethoxysilane, texylisopropyldimethoxysilane, Texylcyclopentyldimethoxysilane, texylmyristyldimethoxysilane, texylcyclohexyldimethoxysilane, and the like.

Further, the following general formula (IV):

[0032]

Embedded image

(Wherein, R ^{7 to} R ^{9 each} represent a hydrogen atom or a hydrocarbon group, which may be the same or different from each other, or may be bonded to an adjacent group to form a ring. ¹⁰ and R ¹¹ represent a hydrocarbon group, which may be the same or different, and may be bonded to an adjacent group to form a ring, and R ¹² and R ¹³ have 1 to 1 carbon atoms.
And 20 alkyl groups, which may be the same or different from each other. m is an integer of 2 or more, and n is an integer of 2 or more. ) Can be used.

In the above general formula (IV), specifically, R ^{7 to} R ⁹ represent a hydrogen atom, a linear hydrocarbon group such as a methyl group, an ethyl group or an n-propyl group, an isopropyl group, Isobutyl group, t-butyl group, branched hydrocarbon groups such as texyl group, cyclobutyl group, cyclopentyl group,
Examples include a saturated cyclic hydrocarbon group such as a cyclohexyl group and an unsaturated cyclic hydrocarbon group such as a phenyl group and a pentamethylphenyl group. Among them, hydrogen and a straight-chain hydrocarbon group having 1 to 6 carbon atoms are preferable, and hydrogen, a methyl group and an ethyl group are particularly preferable.

In the above general formula (IV), R ¹⁰ and R ¹¹ are linear hydrocarbon groups such as methyl group, ethyl group, n-propyl group, isopropyl group, isobutyl group, t-butyl group, A branched hydrocarbon group such as a texyl group,
Examples include saturated cyclic hydrocarbon groups such as cyclobutyl group, cyclopentyl group and cyclohexyl group, and unsaturated cyclic hydrocarbon groups such as phenyl group and pentamethylphenyl group. These may be the same or different. Among these, a linear hydrocarbon group having 1 to 6 carbon atoms is preferable, and a methyl group and an ethyl group are particularly preferable.

In the above formula (IV), R ¹² and R ¹³ represent methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s
ec-butyl group, t-butyl group, n-pentyl group, n-
Examples thereof include linear or branched alkyl groups such as a hexyl group and an n-octyl group. These may be the same or different. Among these, a linear hydrocarbon group having 1 to 6 carbon atoms is preferable, and a methyl group is particularly preferable.

Preferred examples of the silicon compound represented by the general formula (IV) include neopentyl n-propyldimethoxysilane, neopentyl n-butyldimethoxysilane, neopentyl n-pentyldimethoxysilane, and neopentyl n-hexyldimethoxysilane. Silane, neopentyl n-heptyldimethoxysilane, isobutyl n-propyldimethoxysilane, isobutyl n-
Butyldimethoxysilane, isobutyl n-pentyldimethoxysilane, isobutyl n-hexyldimethoxysilane, isobutyl n-heptyldimethoxysilane, 2-cyclohexylpropyl n-propyldimethoxysilane,
2-cyclohexylbutyl n-propyldimethoxysilane, 2-cyclohexylpentyl n-propyldimethoxysilane, 2-cyclohexylhexyln-propyldimethoxysilane, 2-cyclohexylheptyl n-propyldimethoxysilane, 2-cyclopentylpropyln
-Propyldimethoxysilane, 2-cyclopentylbutyl n-propyldimethoxysilane, 2-cyclopentylpentyl n-propyldimethoxysilane, 2-cyclopentylhexyl n-propyldimethoxysilane, 2-cyclopentylheptyl n-propyldimethoxysilane,
Isopentyl n-propyldimethoxysilane, isopentyl n-butyldimethoxysilane, isopentyl n-pentyldimethoxysilane, isopentyl n-hexyldimethoxysilane, isopentyl n-heptyldimethoxysilane, isopentylisobutyldimethoxysilane, isopentylneopentyldimethoxysilane, diiso Pentyldimethoxysilane, diisoheptyldimethoxysilane, diisohexyldimethoxysilane and the like can be mentioned.
Specific examples of particularly preferred compounds include neopentyl n
-Propyldimethoxysilane, neopentyl n-pentyldimethoxysilane, isopentylneopentyldimethoxysilane, diisopentyldimethoxysilane, diisoheptyldimethoxysilane, diisohexyldimethoxysilane.Examples of more preferred compounds include neopentyl. n-pentyldimethoxysilane and diisopentyldimethoxysilane.

The silicon compound represented by the above general formula (IV) can be synthesized by any method. A typical synthetic route is as follows.

[0039]

Embedded image

In this synthetic route, the starting compound [1]
Is commercially available or can be obtained by known alkylation, halogenation and the like. The compound [1] can be subjected to a known Grignard reaction to obtain an organosilicon compound represented by the general formula (IV). Each of these organosilicon compounds may be used alone,
Two or more kinds may be used in combination.

Specific examples of the nitrogen-containing compound include 2,6
-Diisopropylpiperidine, 2,6-diisopropyl-4-methylpiperidine, N-methyl2,2,6,6-
2,6-substituted piperidines such as tetramethylpiperidine; 2,5 such as 2,5-diisopropylazolidine and N-methyl 2,2,5,5-tetramethylazolidine
-Substituted azolidines; substituted methylenediamines such as N, N, N ', N'-tetramethylmethylenediamine, N, N, N', N'-tetraethylmethylenediamine;
Substituted imidazolidines such as 1,3-dibenzylimidazolidine and 1,3-dibenzyl-2-phenylimidazolidine are exemplified.

Specific examples of the phosphorus-containing compound include triethyl phosphite, tri n-propyl phosphite, triisopropyl phosphite, tri n-butyl phosphite, triisobutyl phosphite, diethyl n-butyl phosphite, and diethyl phenyl phosphite. Phosphites such as fight; Specific examples of the oxygen-containing compound include 2,6-substituted tetrahydrofurans such as 2,2,6,6-tetramethyltetrahydrofuran and 2,2,6,6-tetraethyltetrahydrofuran;
And dimethoxymethane derivatives such as -dimethoxy-2,3,4,5-tetrachlorocyclopentadiene, 9,9-dimethoxyfluorene and diphenyldimethoxymethane. [II] Preparation of Solid Catalyst Component The method for preparing the solid catalyst component (A) includes the above (a) magnesium compound, (b) titanium compound,
The (c) electron donor and, if necessary, the (d) silicon compound may be brought into contact by a usual method except for the temperature, and the contact procedure is not particularly limited. For example, each component may be contacted in the presence of an inert solvent such as a hydrocarbon,
Each component may be diluted with an inert solvent such as a hydrocarbon in advance and contacted. Examples of the inert solvent include aliphatic hydrocarbons such as octane, decane, and ethylcyclohexane, alicyclic hydrocarbons, and mixtures thereof.

Here, the titanium compound is usually added in an amount of 0.1 to 1 mol of magnesium of the above magnesium compound.
5 to 100 moles, preferably 1 to 50 moles are used.
If the molar ratio is outside the above range, the catalytic activity may be insufficient. The above electron donor is used in an amount of usually 0.01 to 10 mol, preferably 0.05 to 1.0 mol, per 1 mol of magnesium of the above magnesium compound.
Use 0 moles. If the molar ratio deviates from the above range, catalytic activity and stereoregularity may be insufficient. Further, when a silicon compound is used, it is usually used in an amount of 0.001 mol per mol of magnesium of the above magnesium compound.
It is used in an amount of 1 to 100 mol, preferably 0.005 to 5.0 mol. If the molar ratio deviates from the above range, the effect of improving catalytic activity and stereoregularity may not be sufficiently exhibited, and the amount of fine powder in the produced polymer may increase.

The above components (a) to (d) are contacted at 120 to 150 ° C., preferably 125 to 150 ° C. after all the components have been added.
This is performed in a temperature range of 140 ° C. If the contact temperature is outside the above range, the effect of improving the catalytic activity and stereoregularity will not be sufficiently exhibited. The contact is usually performed for 1 minute to 24 hours, preferably for 10 minutes to 6 hours. The pressure at this time is
When using a solvent, depending on its type, contact temperature, etc.
The range varies, but is usually 0-50 kg / cm
² G, preferably in the range of 0 to 10 kg / cm ² G. In addition, during the contact operation, it is preferable to perform stirring in view of uniformity of contact and contact efficiency.

Further, it is preferable that the contact with the titanium compound is performed twice or more to sufficiently support the magnesium compound serving as a catalyst carrier. When a solvent is used in the contacting operation, it is usually 5000 ml or less, preferably 10 to 1 mol per mol of the titanium compound.
Use 000 ml of solvent. If this ratio deviates from the above range, contact uniformity and contact efficiency may be deteriorated.

The solid catalyst component obtained by the above contact is 1
Wash with an inert solvent at a temperature of 00-150 ° C, preferably 120-140 ° C. When the washing temperature is outside the above range, the effect of improving the catalytic activity and stereoregularity is not sufficiently exhibited. As the inert solvent, for example, octane, aliphatic hydrocarbons such as decane, methylcyclohexane, alicyclic hydrocarbons such as ethylcyclohexane, toluene,
Aromatic hydrocarbons such as xylene, tetrachloroethane,
Halogenated hydrocarbons such as chlorofluorocarbons or mixtures thereof can be mentioned. Of these, aliphatic hydrocarbons are preferably used.

The washing method is not particularly limited, but a method such as decantation and filtration is preferred. There are no particular restrictions on the amount of the inert solvent used, the washing time, and the number of washings.
100 to 100000 ml, preferably 100
Use 0-50,000 ml of solvent, usually 1
The reaction is performed for a period of from minutes to 24 hours, preferably from 10 minutes to 6 hours.
If the ratio deviates from the above range, the cleaning may be incomplete.

The range of the pressure at this time varies depending on the type of the solvent, the washing temperature, and the like.
g / cm ² G, preferably in the range of 0 to 10 kg / cm ² G. In addition, during the washing operation, it is preferable to perform stirring in view of uniformity of washing and washing efficiency. In addition,
The obtained solid catalyst component can be stored in a dry state or in an inert solvent such as a hydrocarbon. [III] Polymerization Method The amount of the catalyst component used in producing the crystalline polypropylene of the present invention is not particularly limited, but the solid catalyst component of the component (A) is converted to a titanium atom by a reaction volume. The amount is usually in the range of 0.00005 to 1 mmol per liter, and the organoaluminum compound (B) has an aluminum / titanium atomic ratio of usually 1 to 1000, preferably 10 to 500. The amount used is such that If this atomic ratio is outside the above range, the catalytic activity may be insufficient. When an electron donating compound such as an organosilicon compound is used as the third component (C), the molar ratio of (C) the electron donating compound / (B) the organoaluminum compound is usually 0.001 to 5.0,
Preferably 0.01 to 2.0, more preferably 0.05
An amount is used such that it is in the range of ~ 1.0. If the molar ratio is outside the above range, sufficient catalytic activity and stereoregularity may not be obtained. However, when pre-polymerization is performed, it can be further reduced.

In the present invention, from the viewpoints of polymerization activity, stereoregularity, and polymer powder form, if desired, the olefin may be preliminarily polymerized before the main polymerization. In this case, the olefin is usually added in the presence of a catalyst obtained by mixing (A) the solid catalyst component, (B) the organoaluminum compound and, if necessary, (C) the electron donating compound at a predetermined ratio. At a temperature in the range of -100 ° C, pre-polymerization is carried out at normal pressure to a pressure of about 50 kg / cm ² G, and then propylene is main-polymerized in the presence of a catalyst and a pre-polymerized product.

As the olefin used for the prepolymerization, an α-olefin represented by the general formula (V) R ¹⁴ —CH ＝ CH ₂ (V) is preferable. In the general formula (V), R ¹⁴ is a hydrogen atom or a hydrocarbon group, and the hydrocarbon group may be a saturated group or an unsaturated group.
Specifically, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene,
1-decene, 3-methyl-1-pentene, 4-methyl-
Examples thereof include 1-pentene, vinylcyclohexane, butadiene, isoprene, and piperylene. These olefins may be used alone or in combination of two or more. Among the olefins, ethylene and propylene are particularly preferred.

The type of polymerization in this main polymerization is not particularly limited, and can be applied to any of solution polymerization, slurry polymerization, gas phase polymerization, bulk polymerization, and the like. It is applicable to two-stage polymerization and multi-stage polymerization under different conditions. Further, regarding the reaction conditions, the polymerization pressure is not particularly limited, and is usually from atmospheric pressure to 80 kg / c from the viewpoint of polymerization activity.
m ² G, preferably ^{2 to} 50 kg / cm ² G, the polymerization temperature is usually 0 to 200 ° C., preferably 20 to 90 ° C.,
More preferably, it is appropriately selected within the range of 40 to 90 ° C. The polymerization time depends on the polymerization temperature of propylene as a raw material and cannot be determined unconditionally.
0 hour, preferably about 10 minutes to 10 hours.

The molecular weight can be adjusted by adding a chain transfer agent, preferably by adding hydrogen. Also,
An inert gas such as nitrogen may be present. Polymerization can be carried out in two or more stages under different polymerization conditions. Further, in the present invention, for the catalyst component,
After the components (A), (B) and (C) are mixed at a predetermined ratio and brought into contact with each other, propylene may be immediately introduced to carry out the polymerization. After aging for about an hour, propylene may be introduced for polymerization. Further, this catalyst component can be supplied by suspending it in an inert solvent, propylene or the like.

In the present invention, the post-treatment after the polymerization can be carried out by a conventional method. That is, in the gas phase polymerization method, after polymerization, the polymer powder derived from the polymerization vessel,
In order to remove the olefins and the like contained therein, it may be passed through a nitrogen gas stream or the like, or may be pelletized by an extruder as desired. , A small amount of water, alcohol and the like can also be added. In the bulk polymerization method, after the polymerization, the monomer can be completely separated from the polymer led out of the polymerization vessel and then pelletized. 3. Film The film of the present invention is a film formed using the propylene-based random copolymer. The method for producing the film is not particularly limited, and a usual T-die casting method or the like is used. That is, the propylene random copolymer powder is formulated with various additives as necessary, extruded and granulated by a kneader, pelletized,
Die casting can be performed. Usually, the thickness of the propylene-based random copolymer of the present invention is 10 to 500 μm by the T-die casting method even under a high-speed film forming condition at a take-up speed of 50 m / min or more.
Can be obtained. Further, since it has the above-mentioned preferable characteristics, it can be suitably used as at least one layer component when producing a laminated film by a co-extrusion film forming method. The film forming method is preferably a T-die casting film forming method in which high-speed film forming is performed by a large film forming machine, but is not particularly limited thereto, and any method can be used as long as a film can be manufactured by a melt extrusion molding method. A film forming method may be used.

Various additives used as desired include antioxidants, neutralizing agents, slip agents, antiblocking agents, antifogging agents, and antistatic agents. These additives may be used alone or in a combination of two or more. For example, examples of the antioxidant include a phosphorus-based antioxidant, a phenol-based antioxidant, and a sulfur-based antioxidant.

Specific examples of the phosphorus-based antioxidant include trisnonylphenyl phosphite, tris (2,4-di-
t-butylphenyl) phosphite, distearylpentaerythritol diphosphite, bis (2,4-di-
t-butylphenyl) pentaerythritol phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl Phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4-biphenylene-di-phosphonite,
ADK STAB 1178 (Asahi Denka Co., Ltd.), Sumilizer TNP (Sumitomo Chemical Co., Ltd.), JP-135 (Johoku Chemical Co., Ltd.), ADK STAB 2112 (Asahi Denka Co., Ltd.), J
PP-2000 (Johoku Chemical Co., Ltd.), Weston 61
8 (GE (product)), ADK STAB PEP-24G (Asahi Denka (product)), ADK STAB PEP-36 (Asahi Denka (product)), ADK STAB HP-10 (Asahi Denka (product)),
Sandstab P-EPQ (Sand (product)), Phosphite 168 (Ciba Specialty Chemicals (product)) and the like.

Specific examples of the phenolic antioxidant include 2,6-di-t-butyl-4-methylphenol,
n-octadecyl-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate, tetrakis [methylene-3- (3,5-di-t-butyl-4-
Hydroxyphenyl) propionate] methane, tris (3,5-di-t-butyl-4-hydroxybenzyl)
Isocyanurate, 4,4'-butylidenebis- (3-
Methyl-6-t-butylphenol), triethylene glycol-bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate], 3,9-
Bis {2- [3- (3-t-butyl-4-hydroxy-
5-methylphenyl) propionyloxy] -1,1-
Dimethylethyl {-2,4,8,10-tetraoxaspiro [5,5] undecane, Sumilizer BHT (Sumitomo Chemical Co., Ltd.), Yoshinox BHT (Yoshitomi Pharmaceutical Co., Ltd.), Antage BHT (Kawaguchi Chemical Co., Ltd.) ), Irganox 1076 (manufactured by Ciba Specialty Chemicals), Irganox 1010 (manufactured by Ciba Specialty Chemicals), Adekastab AO-60 (manufactured by Asahi Denka), Sumilizer BP-101 (manufactured by Sumitomo Chemical) ), Tominox TT (Yoshitomi Pharmaceutical Co., Ltd.), TT
HP (Toray Co., Ltd.), Irganox 3114 (Chivas Specialty Chemicals Co., Ltd.), ADK STAB AO
-20 (Asahi Denka Co., Ltd.), ADK STAB AO-40 (Asahi Denka Co., Ltd.), Sumilizer BBM-S (Sumitomo Chemical Co., Ltd.), Yoshinox BB (Yoshitomi Pharmaceutical Co., Ltd.), Antage W-300 (Kawaguchi Chemical (manufactured)), Irganox 245 (Ciba Specialty Chemicals (manufactured)), ADK STAB AO-70 (Asahi Denka (manufactured)), Tominox 917 (Yoshitomi Pharmaceutical (manufactured)), ADK STAB AO-80
(Asahi Denka Co., Ltd.), Sumilizer GA-80 (Sumitomo Chemical Co., Ltd.) and the like.

Specific examples of the sulfur-based antioxidant include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate. Pentaerythritol tetrakis (3-laurylthiopropionate),
Sumilizer TPL (Sumitomo Chemical Co., Ltd.), Yoshinox DLTP (Yoshitomi Pharmaceutical Co., Ltd.), Antiox L (Nippon Oil & Fats Co., Ltd.), Sumilizer TPM (Sumitomo Chemical Co., Ltd.), Yoshinox DMTP (Yoshitomi Pharmaceutical Co., Ltd.) ,
Antiox M (Nippon Oil & Fats), Sumilizer T
PS (Sumitomo Chemical Co., Ltd.), Yoshinox DSTP (Yoshitomi Pharmaceutical Co., Ltd.), Antiox S (Nippon Oil & Fats Co., Ltd.),
ADK STAB AO-412S (Asahi Denka Co., Ltd.), SEE
NOX 412S (Cipro Kasei Co., Ltd.), Sumilizer TDP (Sumitomo Chemical Co., Ltd.) and the like.

Among these, preferred phenolic antioxidants include Irganox 1010 (product of Ciba Specialty Chemicals, Inc.): Substance name: pentaerythrityl-tetrakis [
3- (3,5-Di-t-butyl-4-hydroxyphenyl) propionate] Ciba Specialty Chemicals (Irganox 1076): Substance: Octadecyl-3- (3,5-di-
t-Butyl-4-hydroxyphenyl) propionate Irganox 1330 (manufactured by Ciba Specialty Chemicals): Substance: 1,3,5-trimethyl-2,4
6-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene Irganox 3114 (manufactured by Ciba Specialty Chemicals): Substance: Tris (3,5-di-t-butyl-)-
4-hydroxybenzyl) isocyanurate and the like. Preferred phosphorous antioxidants include Irgafos 16 (manufactured by Ciba Specialty Chemicals).
8: Substance name: tris (2,4-di-t-butylphenyl) phosphite chivas specialty chemicals (manufactured by P-EPQ): substance name: tetrakis (2,4-di-
(t-butylphenyl) 4,4'-biphenylene-di-phosphite and the like.

When an antioxidant is used in the present invention
Is based on 100 parts by weight of the propylene random copolymer.
It may be added in an amount of about 0.001 to 1 part by weight. to this
This is preferable because yellowing and the like can be prevented. As a neutralizer
Calcium stearate, zinc stearate,
Magnesium thearate, hydrotalcites (eg
For example, DHT-4A manufactured by Kyowa Chemical Industry Co., Ltd .: Composition formula: Mg
_4.5 Al_Two(OH)₁₃CO_Three・ 3.5H_TwoO), Lichiu
Aluminum hydroxide (for example, Mizusawa Chemical Industries
Mizukarak (product name): Composition formula: [Li_TwoAl_Four(O
H)₁₂] CO_Three・ MH_TwoO, especially m ≒ 3)
Good.

As the anti-blocking agent, a synthetic silica-based anti-blocking agent “Sylysia” manufactured by Fuji Silysia (manufactured by) and a synthetic silica-based anti-blocking agent “Mizukasil” manufactured by Mizusawa Chemical Industries (manufactured by) are particularly preferable. As slip agents, erucamide, oleamide,
Stearic acid amide, behenic acid amide, ethylene bis stearic acid amide, ethylene bis oleic acid amide,
Stearyl erucamide and oleyl palmitamide are particularly preferred.

In the present invention, various additives are added in an amount of 0.00% by weight based on 100 parts by weight of the propylene random copolymer.
About 1 to 1 part by weight may be added. The following examples can be given as specific examples of the additive formulation. Example of additive formulation (A) Antioxidant Irganox 10 from Ciba Specialty Chemicals
10: 1000 ppm Irgafos 16 from Ciba Specialty Chemicals
8: 1000 ppm Neutralizing agent Calcium stearate: 1000 ppm Antiblocking agent Silica-based antiblocking agent manufactured by Fuji Silysia Ltd .: 10
00 ppm slip agent erucamide: 250 ppm Additive Formulation Example (B) Antioxidant Ciba Specialty Chemicals Irganox 10
10: 1000 ppm Irgafos 16 from Ciba Specialty Chemicals
8: 1000 ppm Neutralizing agent Calcium stearate: 1000 ppm Antiblocking agent Silica-based antiblocking agent of Fuji Silysia Ltd .: 23
00 ppm slip agent erucamide: 500 ppm

[0062]

[Example 1]

(Preparation of magnesium compound) The reaction layer equipped with a stirrer (internal volume 80 L) was sufficiently replaced with nitrogen gas, and dehydrated ethanol 2
0L, 1.06kg of metallic magnesium and 106 of iodine
g, and the mixture was reacted with stirring under reflux conditions until hydrogen gas was no longer generated from the inside of the system to obtain a solid reaction product. The reaction product containing the solid reaction product was dried under reduced pressure to obtain a target magnesium compound (a solid catalyst carrier). (Preparation of solid catalyst component) 4.0 kg of the magnesium compound was added to a reaction layer equipped with a stirrer (internal volume: 80 L) which was replaced with nitrogen.
, And 20 L of dehydrated heptane was further added. Heat to 40 ° C and add 600 ml of silicon tetrachloride,
Then, 850 ml of di-n-butyl phthalate was added. The temperature of the solution was raised to 70 ° C., and then 19.25 L of titanium tetrachloride was charged. The internal temperature was set to 125 ° C., and a contact reaction was performed for 2 hours. Thereafter, washing was sufficiently performed using dehydrated heptane at 125 ° C. 30.50 L of titanium tetrachloride
In addition, the internal temperature was set to 125 ° C., and a contact reaction was performed for 2 hours. Thereafter, the solid was thoroughly washed with 125 ° C. dehydrated heptane to obtain a solid component [A]. (Preliminary polymerization) Nitrogen-replaced reaction layer with stirrer (internal volume 8
0 L), 1.0 kg of the solid component [A] was charged, and 8.4 L of dehydrated heptane was further added. The mixture was heated to 40 ° C., and 43 ml of triethylaluminum and 116 ml of dicyclopentyldimethoxysilane were added. Propylene was allowed to flow at normal pressure and reacted for 2 hours. Thereafter, the solid component was sufficiently washed with dehydrated heptane to obtain a catalyst component. (Polymerization) The above solid catalyst component was added to a polymerization tank with a stirrer having an internal volume of 200 L in an amount of 3 mmol / kg in terms of titanium atoms in the component.
-4 mmol / kg of triethylaluminum with PP
1 mm of dicyclopentyldimethoxysilane with PP
ol / kg-PP, and the polymerization temperature is 80 ° C.
Propylene and ethylene were reacted at a polymerization pressure (total pressure) of 28 kg / cm ² G. 1. Adjust the ethylene concentration in the polymerization apparatus to 2.
The polymerization was carried out with 5 mol% and a hydrogen concentration of 5.0 mol%. As a result, the ethylene content of 2 wt% and the M.P. A propylene-based random copolymer having an I of 7.1 was obtained. (Pelletization and film formation) Table 3 shows the results of the evaluation of the powder of the propylene-based random copolymer thus obtained in accordance with the following "resin property evaluation method". Further, the powder of the propylene-based random copolymer includes the above (A)
Additive prescription, Toshiba Machine Co., Ltd. Model35
It pelletized with the B extruder. The pellets of the obtained propylene-based random copolymer were formed into a film having a thickness of 30 μm using a 75 mmφ extruder manufactured by Mitsubishi Heavy Industries, under the conditions of a resin temperature of 265 ° C., a chill roll temperature of 25 ° C., and a take-up speed of 150 m / min at the T-die outlet. Molded. Table 3 shows the results of the evaluation of the obtained film in accordance with the following “Method of evaluating film quality”. "Resin Characteristics Evaluation method" ¹³ spectra measured ¹³ C-NMR of C-NMR in accordance α and P is manufactured by JEOL Ltd. of JNM-E
It measured using the X400 type NMR apparatus on condition of the following.

NMR measurement conditions Sample concentration: 220 mg / NMR solvent 3 ml NMR solvent: 1,2,4-trichlorobenzene / benzene-d6 = 90/10 (volume ratio) Measurement temperature: 130 ° C. Pulse width: 45 ° Pulse repetition time Table 4 shows the assignment of each signal of the obtained propylene random copolymer. Chemical shift values are signal (1),
(11), (12), and (13) are shown in the calculation range, and other signals are shown in the peak top position. Table 2 shows all signals in the calculation range. In addition, P shows a propylene unit and E shows an ethylene unit. Therefore, PPP indicates that three propylene units are continuous, and EEE indicates that three ethylene units are continuous.

[0064]

[Table 1]

[0065]

[Table 2]

The content (α (% by weight)) of ethylene units in the propylene-based random copolymer was calculated from the respective signal intensities according to the following equation. α = 2X / (300-X) X = Et / S × 100 Et = IEEE + 2/3 (IPEE + IEPE) +1/3 (IPPE
+ IPEP) S = IEPE + IPPE + IEEE + IPPP + IPEE + IPEP IEPE = I (4) IPPP = I (8) IPPE = I (5) IPEE = I (9) IEEE = I (7) / 2 + I (6) / 4 + I (6) (10) Here, for example, I (1) is the signal intensity of signal number (1) in Table 1 or Table 2. The stereoregularity index (P (mol%)) was calculated from the following equation. P = I (11) / (I (11) + I (12) + I (13) -I (2) -I
(4)) × 100 This P value is an isotactic fraction of triad units in the propylene chain region of the copolymer molecular chain. In this equation, the signal intensity of the methyl carbon of the propylene unit at the center of the PPE chain appearing in the mr region is Sα
It is substituted by the signal intensity of γ (2nd signal). The signal intensity of the methyl carbon of the propylene unit in the EPE chain appearing in the rr region is substituted by the signal intensity of Tδδ (the fourth signal). Temperature rising fractionation chromatography (TREF) A sample solution is introduced into a TREF column adjusted to a temperature of 135 ° C, and then gradually cooled to 0 ° C at a rate of 5 ° C / hr to adsorb the sample to the filler. Then the column was moved to speed 4
The temperature was raised to 135 ° C. at 0 ° C./hr to obtain an elution curve.
The measuring device and the measuring conditions are shown below.

1) Measuring device TREF column: silica gel column (4.6φ × 150 mm) manufactured by GL Science Co., Ltd. Flow cell: optical path length 1 mm K manufactured by GL Science Co.
Br cell Liquid sending pump: SSC-3100 pump manufactured by Senshu Kagaku Co., Ltd. Valve oven: Model 55 manufactured by GL Sciences Inc.
4 oven TREF oven: GL Science's two-line temperature controller: Rigaku Corporation REX-C100 temperature controller Detector: Infrared detector for liquid chromatography FOXBORO's MIRAN 1A CVF 10-way valve: Barco's electric Valve loop: 500 μL loop manufactured by Barco 2) Measurement conditions Solvent: ortho-dichlorobenzene Sample concentration: 7.5 g / L Injection volume: 500 μL Pump flow rate: 2.0 mL / min Detection wave number: 3.41 μm Column packing : Chromosolve P (30 to 60 mesh) Column temperature distribution: within ± 2.0 ° C Melting point (Tm (° C)) of copolymer by differential scanning calorimeter (DSC) DSC7 type differential scanning calorimeter manufactured by PerkinElmer It was measured using a meter. A sample of 10 mg was previously melted at 230 ° C. for 3 minutes in a nitrogen atmosphere, and then melted at 10 ° C./min.
Cool to 0 ° C. After holding at this temperature for 3 minutes, 1
The peak top temperature of the maximum peak of the melting endothermic curve obtained by raising the temperature at 0 ° C./min was defined as the melting point. Extraction amount of boiling diethyl ether in copolymer (E (% by weight)) 3 g of pellets pulverized to a size of 1 mmφ mesh path were put in a cylindrical filter paper, 160 ml of diethyl ether as an extraction solvent was put in a flat-bottomed flask, and the reflux frequency was 1 Times / 5m
soxhlet extraction for about 10 hours. After completion of the extraction, diethyl ether was recovered by a rotary evaporator, and further dried to a constant weight by a vacuum drier to obtain a boiling diethyl ether extraction amount. Melt index (MI (g / 10 min)) According to JIS K7210, temperature 230 ° C, load 216
It was measured at 0 g. "Evaluation method of film quality" All the films formed were annealed for 24 hours at a temperature of 40 ° C.
After conditioning for 16 hours or more at 3 ± 2 ° C. and 50 ± 10% humidity, measurement was performed under the same temperature and humidity conditions. Heat seal temperature Measured according to JIS Z-1707. Specifically, after sealing with a heat seal bar calibrated by a surface thermometer under the following conditions, and leaving it at room temperature for 24 hours, the peel strength was measured by a T-type peeling method at room temperature with a peeling rate of 200 mm / min. . The heat sealing temperature is defined as the temperature at which the peel strength becomes 300 g / 15 mm.
It was calculated from the peel strength curve.

Sealing conditions Sealing surface: metal roll surface / metal roll surface Sealing area: 15 × 10 mm Sealing pressure: 2.0 kg / cm ² Sealing time: 1 second Sealing temperature: Several points so that heat sealing temperature can be interpolated Blocking property With respect to the two films, one metal roll surface and another anti-metal roll surface were brought into close contact with each other under the following conditions.
Fix each to a 10 x 10 cm jig, 10 x 10 cm
Was measured by a peel test under the following conditions.

Adhesion conditions Part 1: Temperature 60 ° C., 3 hours, load 36 g / cm ² , area 10 × 10 cm Part 2: Temperature 50 ° C., 7 days, load 15 g / cm ² , area 10 × 10 cm Speed: 20 mm / min Load cell: 2 kg Slip property After a film-covered threat is allowed to stand on a film-covered glass plate, the glass plate is tilted, and the glass plate tilt angle θ when the threat slides out. The tan was evaluated. For the measurement, a friction angle measuring device manufactured by Toyo Seiki Seisaku-sho, Ltd. was used. The conditions are shown below.

Measurement surface: metal roll surface / metal roll surface Tilt speed: 2.7 ° / sec Thread weight: 1 kg Thread cross-sectional area: 65 cm ² Inter-surface pressure: 15 g / cm ² Transparency (haze) Measured according to JIS K7105. . Impact resistance was evaluated by the impact breaking strength using a 1/2 inch impact head in a film impact tester manufactured by Toyo Seiki Seisaku-sho, Ltd. Tensile modulus Measured under the following conditions by a tensile test in accordance with JIS K7127.

Crosshead speed: 500 mm / min Load cell: 10 kg Measurement direction: machine direction (MD) [Comparative Example 1] In the preparation of the solid catalyst component, the contact reaction temperature was changed from 125 ° C. to 110 ° C.
The same procedure as in Example 1 was performed, except that the washing process using 5 ° C. dehydrated heptane was changed to use 80 ° C. dehydrated heptane. The results are shown in Table 3. [Example 2] The ethylene concentration in the polymerization apparatus was adjusted to 5.0 mol%, the hydrogen concentration was adjusted to 8.5 mol%, the additive formulation was changed to the above (B), and a 75 mmφ extruder manufactured by Mitsubishi Heavy Industries was used. Resin temperature 243 ° C, chill roll temperature 40
Film thickness 30 µm under the conditions of ° C and a take-off speed of 125 m / min.
Example 1 was performed except that the film was formed. The results are shown in Table 3. Example 3 The same procedure as in Example 2 was carried out except that the ethylene concentration in the polymerization apparatus was changed to 7.5 mol% and the hydrogen concentration was changed to 12.2 mol%. The results are shown in Table 3. [Comparative Example 2] In the preparation of the solid catalyst component, the contact reaction temperature was changed from 125 ° C to 110 ° C.
The same operation as in Example 2 was performed, except that the washing process using 5 ° C. dehydrated heptane was changed to use 80 ° C. dehydrated heptane. The results are shown in Table 3. [Example 4] The ethylene concentration in the polymerization apparatus was set to 2.7 mol%.
And the stereoregularity index P was obtained from the following equation. The results are shown in Table 4. P = I (11) / (I (11) + I (12) + I (13) -I (4) -I
(5)) × 100 This P value is the isotactic fraction of triad units in the propylene chain region of the copolymer molecular chain. In this equation, the signal intensity of methyl carbon of the propylene unit at the center of the PPE chain appearing in the mr region is Tβ
It is substituted by the signal intensity of δ (5th signal). Further, the signal intensity of the methyl carbon of the propylene unit in the EPE chain appearing in the rr region is substituted by the signal intensity of Tδδ (4th signal). The method of calculating P includes the method described in the first embodiment and the method described in the present embodiment, but substantially the same result is obtained in many cases. If they are different,
It is more appropriate to use the calculation method of the present embodiment. [Example 5] The ethylene concentration in the polymerization apparatus was 5.3 mol%.
Were performed in the same manner as in Example 2 except that the calculation method of P was changed in the same manner as in Example 4. The results are shown in Table 4. [Example 6] The ethylene concentration in the polymerization apparatus was set to 7.9 mol%.
Were performed in the same manner as in Example 2 except that the calculation method of P was changed in the same manner as in Example 4. The results are shown in Table 4.

[0072]

[Table 3]

[0073]

[Table 4]

[0074]

The propylene random copolymer of the present invention has a relatively wide molecular weight distribution and composition distribution,
And because it has the characteristic that there is little sticky component, without deteriorating the inherent properties of polypropylene such as rigidity, transparency and moisture resistance, excellent heat sealability is exhibited, and the slip property required for high-speed bag making and A film having both anti-blocking properties can be obtained, and a film with extremely small deterioration in quality can be produced even when the film forming speed is increased.

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Claims (8)

[Claims] 1. A random copolymer of propylene and ethylene, which satisfies the following: The ethylene unit content (α (% by weight)) in the copolymer measured by ¹³ C-NMR is 0.2 to 10% by weight. Tp is the main elution peak temperature of the fractionated chromatograph
(C), the amount (Wp (% by weight)) eluted in the temperature range of (Tp-5) C to (Tp + 5) C is 20.
% By weight or more. The amount (W0 (% by weight)) eluted in the temperature range of 0 ° C. or lower in the temperature rising fractionation chromatograph and α satisfy the relationship of the following formula (1). W0 ≦ (3 + 2α) / 4 (1) 2. The melting point (Tm (° C.)) and α of the copolymer measured by a differential scanning calorimeter (DSC) are represented by the following formula (2).
The propylene-based random copolymer according to claim 1, which satisfies the following relationship: Tm ≦ 160−5α (2) 3. The amount of elution (WH (% by weight)) and α in the temperature range of (Tp + 5) ° C. or more, where Tp (° C.) is the main elution peak temperature of the temperature-increased fractionation chromatograph, is represented by the following formula (3) The propylene random copolymer according to claim 1 or 2, which satisfies the relationship of (1) or (2). 0.1 ≦ WH ≦ 3α (3) 4. The method according to claim 1, wherein the amount of the boiling diethyl ether extractable component (E (% by weight)) in the copolymer is 2.5% by weight or less, and E and α satisfy the relationship of the following formula (4). 4. The propylene-based random copolymer according to any one of items 1 to 3. E ≦ (2α + 15) / 10 (4) 5. The melt index (MI (g / 10 m)
The propylene random copolymer according to any one of claims 1 to 4, wherein (in)) is from 0.1 to 200 g / 10 min. 6. The propylene random copolymer according to claim 1, wherein a stereoregularity index (P (mol%)) in the copolymer measured by ¹³ C-NMR is 98 mol% or more. Polymer. 7. The propylene-based random copolymer according to claim 1, wherein α is 3 to 7% by weight. 8. A film comprising the propylene-based random copolymer according to claim 1.