JP2000351879A - Propylene random copolymer composition and film made thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a propylene random copolymer composition which is useful for preparing a film which is excellent in heat sealability and has slipperiness and antiblocking properties necessarey for high-speed bag making by compounding a nucleating agent into a random copolymer of propylene and ethylene and/or 1-butene so as to give a composition having specified caloric properties. SOLUTION: This composition satisfies the conditions: that the peak top temperature Tc ( deg.C) at the highest temperature side in a crystallization curve obtained with a differential scanning calorimeter and the peak top temperature Tm ( deg.C) at the lowest temperature side in a melting curve satisfy the realtion represented by the formula: Tc>=0.75×Tm-5; and that the amount W0 (wt.%) of a component eluted in the temperature range of lower than 0 deg.C in the temperature-rise fractionation chromatograph is 6 wt.% or lower. Preferably, the nucleating agent is compounded in an amount of 0.001-5 wt.% of the random copolymer. Preferably, the random copolymer has a melt index of 0.1-200 g/10 min or has a stereoregularity index P measured by 13C-NMR of 98 mol% or higher.

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 composition and a film comprising the same, and more particularly, to a propylene random copolymer composition of propylene and ethylene and / or 1-butene. The present invention relates to a product and a film formed from the product. 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 Films of a crystalline propylene-based polymer composition are widely used as packaging films because 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 heated Is performed by an operation called heat sealing for melting and bonding. In recent years, these series of bag making and packaging processes have been made to form films at a high speed in order to improve productivity, and there is a strong demand for the development of materials having excellent heat sealability. In addition, in order to perform these secondary processing steps smoothly, it is required that packaging films have excellent slipping properties and antiblocking properties as essential properties. Furthermore, in recent years, large-scale film formation has been promoted in order to increase the productivity of film formation, and as a result, film conditions have changed from the past, but even in such a case, the film quality does not deteriorate. Has been requested.

However, heat sealing a propylene homopolymer film requires a high temperature and a long time of pressurization. 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, a large amount of a comonomer such as ethylene, 1-butene, and other α-olefins is used in order to obtain a sufficient heat sealing property improving effect. Copolymerization was required. Also, these comonomers are often concentrated in low molecular weight components, and have become tacky components with poor crystallinity (hereinafter referred to as sticky components). Therefore, the rigidity, which is the original feature 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 the film cannot be put to practical use. .

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 is not 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 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 use and a 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. In addition, it is possible to obtain a film having both the slip property and the anti-blocking property required for high-speed bag making. Further, even if the film forming speed is increased, the deterioration of the film quality is extremely small. It is an object of the present invention to provide a propylene-based random copolymer composition having an improved and a film comprising the same.

[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). Therefore, the present inventors have conducted intensive studies on the film properties of a propylene-based polymer produced by using the above-mentioned catalyst component, and as a result, a composition obtained by blending a nucleating agent with a propylene-based random copolymer among them was obtained. The inventors have found that the above object of the invention is satisfied at a very high level, and have completed the present invention.

That is, the present invention provides the following propylene random copolymer composition and a film comprising the same. 1. A propylene-based random copolymer composition comprising (i) a random copolymer of propylene, ethylene and / or 1-butene, and (ii) a nucleating agent, wherein the composition is a differential scanning calorimeter (DSC). ), The peak top temperature Tc (° C.) on the highest temperature side in the crystallization curve and the peak top temperature Tm (° C.) on the lowest temperature side in the melting curve are represented by the following formula (1): Tc ≧ 0.75 × Tm -5 A propylene-based random copolymer characterized by satisfying (1) and having an amount W0 (% by weight) eluted in a range of 0 ° C. or less in a temperature rising fractionation chromatograph of 6% by weight or less. Composition. 2. (I) a random copolymer of propylene, ethylene and 1-butene, wherein the propylene random copolymer is obtained by mixing (ii) a nucleating agent with a propylene random copolymer satisfying the following conditions: Composition. The sum of the ¹³ content of ethylene units of C-NMR copolymer as measured by α content (mol%) and ¹³ were determined by C-NMR copolymer of 1-butene units beta (mol%) (Α + β) is 0.1 to 15 mol%, and the main elution peak temperature of the temperature-raising fractionation chromatograph is Tpt
(Tpt−5) ° C. to (Tpt + 5)
The amount Wpt (wt%) eluted in the temperature range of 2 ° C. is 2
0% by weight or more, and the amount W0t (% by weight) eluted in a temperature range of 0 ° C. or less in a temperature rising fractionation chromatograph and the above (α + β) satisfy the following equations (2) to (4). When 0.1 ≦ (α + β) <2, W0t ≦ 1 (2) When 2 ≦ (α + β) <12, W0t ≦ (α + β) / 2 (3) 12 ≦ (α + β) ≦ When 15, W0t ≦ 6 (4) (I) A random copolymer of propylene and ethylene, wherein the random copolymer of propylene and (ii) a nucleating agent is blended with a random copolymer of propylene satisfying the following conditions: The content γ (% by weight) of ethylene units in the copolymer measured by ¹³ C-NMR is 0.2 to 10% by weight, and the main elution peak temperature of the temperature rising fractionation chromatograph is Tpr
(Tpr-5) ° C. to (Tpr + 5)
The amount Wpr (% by weight) eluted in the temperature range of 2 ° C. is 2
0% by weight or more, and the amount W0r (% by weight) eluted in a temperature range of 0 ° C. or less in a temperature-raising fractionation chromatograph satisfies the relationship of the following formula (5). W0r ≦ (3 + 2γ) / 4 (5)

[0008] 4. The propylene-based random copolymer composition according to any one of the above items 1 to 3, wherein the amount of the component (ii) is 0.001 to 5 parts by weight per 100 parts by weight of the component (i). 5. In the component (i), the melt index MI (g
/ 10 min) is 0.1 to 200 g / 10 min. 6. In the component (i), the stereoregularity index P (mol%) in the copolymer measured by ¹³ C-NMR is 98 mol%.
The propylene-based random copolymer composition according to any one of the above items 1 to 5, which is as described above. 7. A film comprising the propylene-based random copolymer composition according to any one of the above 1 to 6. 8. 7. A multilayer film comprising the propylene-based random copolymer composition according to any one of the above 1 to 6 as at least one layer component.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The propylene random copolymer composition of the first invention of the present application comprises (i) propylene, ethylene and / or 1
A propylene-based random copolymer composition obtained by mixing (ii) a nucleating agent with a random copolymer with butene, and the highest temperature in a crystallization curve measured by a differential scanning calorimeter (DSC) -Side peak top temperature Tc (° C.) and the lowest temperature-side peak top temperature Tm in the melting curve
(° C.) satisfies the following equation (1): Tc ≧ 0.75 × Tm−5 (1) and elutes in a temperature rising fractionation chromatograph in a range of 0 ° C. or less W0 (weight%). Is not more than 6% by weight.

First, the propylene random copolymer which is the component (i) of the present invention includes a copolymer of propylene and ethylene, a copolymer of propylene and 1-butene, propylene, ethylene and 1-butene. And may be one kind or a mixture of two or more kinds. This is because low-temperature heat sealability becomes unsatisfactory with a propylene homopolymer. In addition,
The method for producing the propylene random copolymer (i) will be described later.

The propylene random copolymer composition of the present invention is obtained by blending the component (i) with the nucleating agent of the component (ii). The nucleating agent will also be described later. Further, the propylene random copolymer composition of the present invention needs to satisfy the above formula (1). If the formula (1) is not satisfied, the effect of improving the moldability and the film properties will be small. It is more preferable that the following formula (6) is satisfied, and it is more preferable that the following formula (7) is satisfied. Tc ≧ 0.75 × Tm (6) Tc ≧ 0.75 × Tm + 5 (7) Furthermore, the propylene-based random copolymer composition of the present invention has a temperature of 0 ° C. or lower in a fractionated chromatograph at elevated temperature. It is necessary that the amount W0 (% by weight) eluted in the range is 6% by weight or less. When W0 exceeds 6% by weight, the film, fiber, sheet, molded product and the like become sticky. Further, appearance troubles due to bleeding of additives and low molecular weight components occur, which is not preferable. It is more preferably at most 5% by weight, further preferably at most 4% by weight.

Next, the second invention of the present application relates to (i) a random copolymer of propylene, ethylene and 1-butene, which satisfies the following conditions: It is a propylene-based random copolymer composition containing an agent. The second invention has a meaning as a more specific example of the first invention. The sum of the ¹³ content of the ethylene units in the copolymer as measured by C-NMR alpha content (mol%) and ¹³ C-NMR by measured copolymer of 1-butene units beta (mol%) ( α + β) is from 0.1 to 15 mol%, and
(Tpt−5) ° C. to (Tpt + 5)
The amount Wpt (wt%) eluted in the temperature range of 2 ° C. is 2
0% by weight or more, and the amount W0t (% by weight) and (α + β) eluted in a temperature range of 0 ° C. or less in a temperature-raising fractionation chromatograph satisfy the following equations (2) to (4). When 0.1 ≦ (α + β) <2, W0t ≦ 1 (2) When 2 ≦ (α + β) <12, W0t ≦ (α + β) / 2 (3) 12 ≦ (α + β) ≦ 15, W0t ≦ 6 (4) Hereinafter, the above and the above will be described in detail. The sum of the ¹³ content of the ethylene units in the copolymer as measured by C-NMR alpha content (mol%) and ¹³ C-NMR by measured copolymer of 1-butene units beta (mol%) ( α + β) is 0.1 to 15 mol%. Preferably,
4 to 14 mol%. More preferably, it is 6 to 13 mol%.

Preferably, (α-β) satisfies the relationship of the following equation (8). −5 ≦ (α−β) ≦ 5 (8) More preferably, 0.5 ≦ (α / β) ≦ 2, and more preferably α ≧ 6 and 1 ≦ (α / β). β) ≦
2 is satisfied. If (α + β) is less than 0.1 mol%, the effect of improving the heat sealability cannot be expected, and if it exceeds 15 mol%, the rigidity of the film becomes unsatisfactory. If the relationship of the above formula (8) is not satisfied, that is, if (α−β) <− 5, 1-butene may be liquefied in the reactor in the gas phase polymerization, and lumps may be easily generated. . If (α-β)> 5, the effect of 1-butene unit to suppress the bleeding of the tacky component becomes small, and in particular, the antiblocking property may be easily reduced with time. Tpt is the main elution peak temperature of the temperature rising fractionation chromatograph.
(Tpt−5) ° C. to (Tpt + 5)
The amount Wpt (wt%) eluted in the temperature range of 2 ° C. is 2
0% by weight or more. Preferably, the relationship of the following expression (9) is satisfied. 90−7 (α + β) ≦ Wpt (9) More preferably, Wpt is 30% by weight or more and satisfies the relationship of the following formula (10). 100-7 (α + β) ≦ Wpt (10) When Wp is less than 20% by weight, the tail of the main elution peak greatly extends to the high temperature side and / or the low temperature side,
A component on the low temperature side is not preferable because it makes the film sticky, and a component on the high temperature side is not preferable because heat sealing property is insufficient and transparency depends on molding conditions.

In the propylene random copolymer of the component (i) of the present invention, the component on the high temperature side of the main elution peak contributes to the moldability and rigidity such as chill roll release, so that it is more than absent at all. Is preferably present, and it is preferable that the amount WHt (% by weight) and (α + β) eluted in a temperature range of (Tpt + 5) ° C. or more satisfy the relationship of the following formula (11). 0.1 ≦ WHt ≦ (α + β) (11) More preferably, 0.1 ≦ WHt ≦ (α + β) -3 (12) More preferably, 0.5 ≦ WHt ≦ (α + β) − 5 (13). The amount W0t (% by weight) eluted in the temperature range of 0 ° C. or lower in the temperature rising fractionation chromatograph and (α + β) satisfy the following equations (2) to (4). When 0.1 ≦ (α + β) <2, W0t ≦ 1 (2) When 2 ≦ (α + β) <12, W0t ≦ (α + β) / 2 (3) 12 ≦ (α + β) ≦ In the case of 15, W0t ≦ 6 (4) Preferably, the following relationships (14) to (16) are satisfied.

When 0.1 ≦ (α + β) <4, W0t ≦ 1 (14) When 4 ≦ (α + β) <14, W0t ≦ (α + β−2) / 2 (15) 14 When ≦ (α + β) ≦ 15, W0t ≦ 6 (16) More preferably, the following relationships (17) and (18) are satisfied. When 0.1 ≦ (α + β) <4, W0t ≦ 0.5 (17) When 4 ≦ (α + β) ≦ 15, W0t ≦ (α + β-3) / 2 (18) W0 and If (α + β) does not satisfy the above relations (2) to (4), the 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.

In the present invention, the amount of the boiling diethyl ether extractable component (Et (% by weight)) in the propylene-based random copolymer and (α + β) satisfy the following equations (19) and (20). Is preferred. When 0.1 ≦ (α + β) <12, Et ≦ 0.2 (α + β) +0.6 (19) When 12 ≦ (α + β) ≦ 15, Et ≦ 3 (20) More preferably Satisfies the relationship of the following equations (21) and (21). When 0.1 ≦ (α + β) <10, Et ≦ 0.2 (α + β) +0.3 (21) When 10 ≦ (α + β) ≦ 15, Et ≦ 2.3 (22) More preferably, the relationship of the following equations (23) and (24) is satisfied. Et ≦ 0.2 (α + β) when 0.1 ≦ (α + β) <10, (23) Et ≦ 2 when 10 ≦ (α + β) ≦ 15 (24) Et and (α + β) Satisfying the above relationship is preferable because the film does not become sticky. The method for producing the propylene random copolymer of the component (i) will be described later. The propylene-based random copolymer composition of the present invention is obtained by blending the component (i) with the nucleating agent of the component (ii). The nucleating agent will also be described later.

Finally, the third invention of the present application relates to (i) a random copolymer of propylene and ethylene, which is a propylene random copolymer satisfying the following conditions:
(Ii) A propylene-based random copolymer composition containing a nucleating agent. This third invention has a meaning as a more specific example of the first invention. The content γ (% by weight) of ethylene units in the copolymer measured by ¹³ C-NMR is 0.2 to 10% by weight.
Preferably it is 0.5-9% by weight, more preferably 1-8% by weight, most preferably 3-7% by weight.

If the content of the ethylene unit is too small, the effect of improving the heat sealing property cannot be expected. If the content of the ethylene unit is too large, the rigidity of the film becomes unsatisfactory, which is not preferable. The propylene random copolymer of the component (i) of the present invention has a melting point Tmr (° C.) of the copolymer measured by a differential scanning calorimeter (DSC).
And γ preferably satisfy the relationship of the following formula (25): Tmr ≦ 160−5γ (25) More preferably, Tmr ≦ 160−6γ (26) is there.

If this relationship is not satisfied, the heat sealability tends to be insufficient and the antiblocking property may be low. When the main elution peak temperature of the temperature rising fractionation chromatograph is Tpr (° C.),
The elution amount Wpr (% by weight) in the temperature range of (Tpr-5) ° C to (Tpr + 5) ° C is 20% by weight or more. Preferably, 20 ≦ Wpr and (80−15γ) ≦ Wpr (27), and more preferably, 30 ≦ Wpr and (90−12γ) ≦ Wpr (28).

When the Wpr is less than 20% by weight, the tail of the main elution peak is greatly extended to the high temperature side and / or the low temperature side, and the low temperature side component is obtained by sticking the formed film. The components on the high-temperature side are not preferred because they make the heat sealing property insufficient and increase the dependence of transparency on molding conditions. In addition, the propylene random copolymer of the component (i) of the present invention has a higher amount than the none at all because the component on the high temperature side of the main elution peak contributes to moldability and rigidity such as chill roll release. Is preferable, and the propylene random copolymer of the present invention satisfies the relationship of the following formula (29) with the amount (WHr (% by weight)) eluted in a temperature range of (Tpr + 5) ° C. or higher. Is preferred. 0.1 ≦ WHr ≦ 3γ (29) More preferably, WHr ≦ (3γ−3) and (3γ−15) ≦ WHr (30). The amount W0r (% by weight) eluted in the temperature range of 0 ° C. or lower in the temperature-raising separation chromatograph satisfies the relationship of the following formula (5). W0r ≦ (3 + 2γ) / 4 (5) Preferably, W0r ≦ (2 + 2γ) / 4 (31) is satisfied.

When W0r does not satisfy the relationship of (5),
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. In the propylene random copolymer of the component (i) of the present invention, the amount of the boiling diethyl ether extractable component Er (% by weight) in the copolymer is 2.5% by weight or less, and Er and γ are as follows. It is preferable that the relationship of Expression (32) is satisfied. Er ≦ (2γ + 15) / 10 (32) More preferably, Er ≦ (γ + 5) / 5 (33).

In this case, the formed film is preferable because it does not become sticky. Furthermore, the propylene random copolymer of the component (i) of the first to third inventions of the present application has a melt index MI (g / 10 min) of 0.1 to 20.
It is preferably 0 g / 10 min. It is more preferably 1 to 40 g / 10 min, and still more preferably 2 to 10 g / 10 min.
２０20 g / 10 min. If the MI is out of this range, the moldability may be poor.

The first to third inventions of the present invention have a
Propylene random copolymer, ¹³By C-NMR
The measured stereoregularity index P (mol%) in the copolymer is 9
It is preferably at least 8 mol%. More preferably 9
8.5 mol% or more. Stereoregularity is less than 98 mol%
Is insufficient, the rigidity and anti-blocking property of the film are insufficient.
It can be confusing.

Further, the propylene random copolymer of the component (i) of the first to third inventions of the present invention has a weight average molecular weight Mw and a number average molecular weight Mn measured by gel permeation chromatography (GPC). Ratio (Mw / Mn)
Is preferably 2 to 6. In this case, transparency and moldability of the film are also excellent, which is preferable. More preferably, it is 2.5-5.

Next, a method for producing the propylene random copolymer of the component (i) of the first to third aspects of the present invention will be described. The propylene random copolymer of the component (i) of the present invention is obtained by subjecting the magnesium compound and the titanium compound (A) to a temperature of 120 ° C. or more and 150 ° C. or less in the presence of an electron-donating compound and, if necessary, a silicon compound. After the contact, the solid catalyst component is washed with an inert solvent at a temperature of 100 ° C. or more and 150 ° C. or less, (B) an organoaluminum compound, and if necessary, (C) an electron donating compound as a third component. Can be produced by copolymerizing propylene and ethylene using a catalyst consisting of

Hereinafter, each catalyst component, a preparation method, a polymerization method, and the like will be described. Each catalyst component (A) Solid catalyst component The solid catalyst component contains magnesium, titanium and an electron donor, and includes the following (a) magnesium compound, (b) titanium compound, (c) electrophilic compound and It is formed from a solid catalyst component comprising a silicon compound (d), if necessary.

(A) Magnesium compound The magnesium compound is not particularly limited, but is generally
Formula (I) MgR¹R^Two ... It is preferable to use a magnesium compound represented by the following formula (I).
it can. In the above general formula (I), R¹And R^Two
Is a hydrocarbon group, OR^ThreeGroup (R ^ThreeIs a hydrocarbon group) or
Indicates a halogen atom. Where R¹And R^TwoThe hydrocarbon
As the elementary group, an alkyl group having 1 to 12 carbon atoms, cyclo
When an alkyl group, an aryl group, an aralkyl group, etc.^ThreeBase
As R^ThreeIs an alkyl group having 1 to 12 carbon atoms,
Roalkyl, aryl, aralkyl, etc.
Examples of chlorine atoms include chlorine, bromine, iodine, and fluorine.
Can be Also, R¹And R^TwoAre the same but different
May be.

Specific examples of the magnesium compound represented by the above general formula (I) include dimethylmagnesium, diethylmagnesium, diisopropylmagnesium, dibutylmagnesium, dihexylmagnesium, dioctylmagnesium, ethylbutylmagnesium, diphenylmagnesium, dicyclohexylmagnesium and the like. Alkylmagnesium, arylmagnesium; alkoxymagnesium such as dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, dihexyloxymagnesium, dioctoxymagnesium, diphenoxymagnesium, dicyclohexyloxymagnesium, etc .; alloxymagnesium; ethylmagnesium 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 dyed and 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, and fluorine. Examples of the alcohol 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. ) May be contacted with a halide. Examples of the halide include silicon tetrachloride, silicon tetrabromide, tin tetrachloride, tin tetrabromide, and hydrogen chloride.
Among them, silicon tetrachloride is preferred from the viewpoint of polymerization activity and stereoregularity. R ⁴ is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-
Alkyl groups such as butyl group, isobutyl group, hexyl group, octyl group and cyclohexyl group; alkenyl groups such as propenyl group and butenyl group; aryl groups such as phenyl group, tolyl group and xylyl group; phenethyl group and 3-phenylpropyl group And the like.

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,
Two or more kinds may be used in combination. Further, it may contain halogen such as iodine or other elements such as silicon or aluminum, and may contain an electron donor such as alcohol, ether or ester.

(B) Titanium compound The titanium compound is not particularly limited, but may have 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 preferred, and a chlorine atom is particularly preferred. R ⁵ is a hydrocarbon group, which may be a saturated group or an unsaturated group, may have a linear or branched chain, or may be a cyclic group; and furthermore, sulfur, nitrogen, oxygen, It may contain a hetero atom such as silicon or phosphorus. Preferably 1 to 1 carbon atoms
Zero hydrocarbon groups, particularly alkyl groups, alkenyl groups, cycloalkenyl groups, aryl groups, aralkyl groups, and the like are preferable, and linear or branched alkyl groups are particularly preferable. Or different they the same as each other if the OR ⁵ there is a plurality. Specific examples of R ⁵ include methyl group, ethyl group, n- propyl group, an isopropyl group, n-
Butyl, sec-butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, allyl, butenyl, cyclopentyl, cyclohexyl, cyclohexenyl Group, phenyl group, tolyl group, benzyl group, phenethyl group and the like. p shows the integer of 0-4.

Specific examples of the titanium compound represented by the general formula (II) include tetramethoxytitanium, tetraethoxytitanium, tetra-n-propoxytitanium, tetraisopropoxytitanium, tetra-n-butoxytitanium,
Tetraalkoxy titanium such as tetraisobutoxytitanium, tetracyclohexyloxytitanium, and tetraphenoxytitanium; titanium tetrahalide such as titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide; methoxytitanium trichloride, ethoxytitanium trichloride, and propoxy Trihalogenated alkoxytitaniums such as titanium trichloride, n-butoxytitanium trichloride, ethoxytitanium tribromide; dimethoxytitanium dichloride, diethoxytitanium dichloride, diisopropoxytitanium dichloride, di-n-propoxytitanium dichloride, diethoxytitaniumdichloride Dihalogenated dialkoxytitanium such as bromide; trimethoxytitanium chloride, triethoxytitanium chloride, triisopropoxytitanium chloride, tri-n-propoxytitanium chloride De, etc. monohalogenated trialkoxy titanium such as 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 alcohols, phenols, ketones, aldehydes, esters of organic acids and inorganic acids, and ethers such as monoether, diether and polyether. And nitrogen-containing electron donating compounds such as ammonia, amines, nitriles and isocyanates. Among 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.

Specifically, phthalic acid, naphthalene-1,
2-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, 5,6,7,8-tetrahydronaphthalene-1,2
Methyl, ethyl, n- of dicarboxylic acids such as -dicarboxylic acid, 5,6,7,8-tetrahydronaphthalene-2,3-dicarboxylic acid, indane-4,5-dicarboxylic acid and indane-5,6-dicarboxylic acid; Propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methyl Pentyl, 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-ethylhexyl, 2-methylpentyl, 3-methylpentyl, 2-ethylpentyl,
Examples thereof include dialkyl esters such as 3-ethylpentyl. Among these, 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. Specific examples thereof include di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, and diethyl phthalate. 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 formula (III), X ² represents a halogen atom, of 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 have a linear or branched chain, or may have a cyclic structure, and furthermore, sulfur, nitrogen, oxygen, It may contain a hetero atom such as silicon or phosphorus. 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 methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl, Examples include n-octyl group, n-decyl group, allyl group, butenyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group, phenyl group, tolyl group, benzyl group, phenethyl group and the like. 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, Examples thereof include propoxytrichlorosilane, dipropoxydichlorosilane, and tripropoxychlorosilane. Among these, silicon tetrachloride is particularly preferred. These silicon compounds may be used alone or in combination of two or more.

(B) Organoaluminum Compound The (B) organoaluminum compound used in the production of the crystalline polypropylene of the present invention is not particularly limited. Aluminoxanes and mixtures thereof 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 Donor Compound) To produce the propylene random copolymer of the present invention,
(C) An electron donating compound is used. 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 these, from the viewpoint of polymerization activity and stereoregularity, it is preferable to use an organic silicon compound having a Si-OC bond, ethers and esters, and particularly to use an organic silicon compound having a Si-OC bond. Is preferred.

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-
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 can be mentioned. Further, the following general formula (IV) as an organosilicon compound

[0043]

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(Wherein, R ^{7 to} R ^{9 each} represent a hydrogen atom or a hydrocarbon group, which may be the same or different, 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, or 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, Branched hydrocarbon groups such as isobutyl group, t-butyl group and 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.

R ¹⁰ and R ¹¹ are linear hydrocarbon groups such as methyl group, ethyl group and n-propyl group; and branched hydrocarbon groups such as isopropyl group, isobutyl group, t-butyl group and texyl group. And 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. Of these, preferably those having 1 to 6 carbon atoms
Linear hydrocarbon group, particularly preferably a methyl group,
It is an ethyl group.

R ¹² and R ¹³ are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl,
Examples thereof include a linear or branched alkyl group such as an n-pentyl group, an n-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 above general formula (IV) include neopentyl n
-Propyldimethoxysilane, neopentyl n-butyldimethoxysilane, neopentyl n-pentyldimethoxysilane, neopentyl n-hexyldimethoxysilane, 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-cyclohexylhexyl n-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 Pentyl dimethoxy silane, diisoheptyl dimethoxy silane, diisohexyl dimethoxy silane and the like can be mentioned.

Specific examples of particularly preferred compounds include neopentyl n-propyldimethoxysilane, neopentyl n-pentyldimethoxysilane, isopentylneopentyldimethoxysilane, diisopentyldimethoxysilane, diisoheptyldimethoxysilane, and diisohexyldimethoxysilane. Specific examples of more preferable compounds include neopentyl n-pentyldimethoxysilane and diisopentyldimethoxysilane. The silicon compound represented by the general formula (IV) can be synthesized by an arbitrary method. A typical synthetic route is as follows.

[0050]

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

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 can be mentioned.

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. Examples include 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; 1,1-dimethoxy-2,3 , 4,5-tetrachlorocyclopentadiene, 9,9-dimethoxyfluorene, dimethoxymethane derivatives such as diphenyldimethoxymethane, and the like.

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. Furthermore, when a silicon compound is used, it is usually 0.00
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 brought into contact with each other at 120 to 150 ° C., preferably 125 to 150 ° C., after adding all the components.
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, so that the titanium compound is sufficiently supported on the magnesium compound serving as a catalyst carrier. When a solvent is used in the contacting operation, it is usually 5,000 ml or less, preferably 10 to 10 mol per 1 mol of the titanium compound.
Use 1,000 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 was 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 or filtration is preferable. There are no particular restrictions on the amount of the inert solvent used, the washing time, and the number of washings.
00-100,000 ml, preferably 10
The reaction is usually performed for 1 minute to 24 hours, preferably for 10 minutes to 6 hours, using a solvent of 00 to 50,000 ml. 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, etc.
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.

Polymerization Method The amount of the catalyst component used in producing the propylene random copolymer (i) constituting the present invention is not particularly limited, but the solid catalyst component (A) is The amount is usually in the range of 0.00005 to 1 mmol per liter of reaction volume in terms of titanium atom. The organoaluminum compound (B) has an aluminum / titanium atomic ratio of usually 1 An amount is used such that it is in the range of ~ 1000, preferably 10-500. If the 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
An amount is used such that it is in the range of 2.0, more preferably in the range of 0.05 to 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 polymerization of the propylene random copolymer of the component (i) constituting the present invention, first, if desired, an olefin prepolymerization is carried out in view of polymerization activity, stereoregularity and polymer powder form. Thereafter, the main polymerization may be performed. In this case, the (A) solid catalyst component,
In the presence of a catalyst obtained by mixing (B) an organoaluminum compound and, if necessary, (C) an electron-donating compound at a predetermined ratio, an olefin is usually used in an amount of 1 to 100.
At normal pressure to 50 kg / cm ² at a temperature in the range of
Prepolymerization is performed at a pressure of about G, and then propylene and ethylene as a comonomer are fully polymerized in the presence of a catalyst and a prepolymerized 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 above 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, etc., and further to any of batch polymerization and continuous polymerization. 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 a range of 40 to 90 ° C. The polymerization time depends on the polymerization temperature of the raw materials propylene / ethylene, propylene / 1-butene, and propylene / ethylene / 1-butene, and cannot be determined unconditionally. 10
It is about an hour. The mixing ratio of the raw materials depends on the polymerization temperature, pressure, and the like, and cannot be unconditionally determined.
0.1-20 mol% of ethylene (remaining propylene), 1-
Butene 0.1-20 mol% (remaining propylene), ethylene 0.1-20 mol%, 1-butene 0.1-20 mol%
(Remaining propylene). The molecular weight can be adjusted by adding a chain transfer agent, preferably by adding hydrogen. Further, an inert gas such as nitrogen may be present.

Polymerization can be carried out in two or more stages under different polymerization conditions. Further, the present invention comprises (i)
In the polymerization for producing the propylene-based random copolymer as the component, as for the catalyst component, the component (A), the component (B), and the component (C) are mixed at a predetermined ratio, contacted, and immediately. Polymerization may be carried out by introducing propylene and ethylene, or after contact and aging for about 0.2 to 3 hours, polymerization may be carried out by introducing propylene and ethylene. Further, this catalyst component can be supplied by suspending it in an inert solvent, propylene or the like.

In the propylene random copolymer of the component (i) constituting 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.

Next, the nucleating agent of the component (ii) blended in the propylene random copolymer of the component (i) will be described. ( Ii) The nucleating agent for the component (ii) is not particularly limited.
It can be suitably selected from organic phosphoric acid nucleating agents, sorbitol nucleating agents, aromatic carboxylic acid nucleating agents, high melting point polymer nucleating agents, inorganic nucleating agents, rosin acid nucleating agents, and amide nucleating agents. . The nucleating agent will be described in order. Organic phosphoric acid nucleating agent As the organic phosphoric acid nucleating agent, for example, the following general formula (VI)

[0068]

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[0069] (wherein, R ¹⁵ is oxygen, sulfur or a hydrocarbon group having 1 to 10 carbon atoms, R ^16, R ¹⁷ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, R ^16, R ¹⁷ may be the same or different, and R ¹⁶ may be linked to each other, R ^{17 to} each other or R ¹⁶ and R ¹⁷ may be bonded to form a ring;
Is a 1 to 3 valent metal atom, and r is an integer of 1 to 3. )).

Specific examples of the compound represented by the general formula (VI) include sodium-2,2'-methylene-
Bis (4,6-di-tert-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis (4,6
-Di-t-butylphenyl) phosphate, lithium-
2,2'-methylene-bis- (4,6-di-t-butylphenyl) phosphate, lithium-2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2 , 2'-ethylidene-bis (4
-I-propyl-6-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4-methyl-6-t-butylphenyl) phosphate, lithium-
2,2′-methylene-bis (4-ethyl-6-t-butylphenyl) phosphate, calcium-bis [2,
2′-thiobis (4-methyl-6-t-butylphenyl) phosphate], calcium-bis [2,2′-thiobis (4-ethyl-6-t-butylphenyl) phosphate], calcium-bis [2 2'-thiobis-
(4,6-di-t-butylphenyl) phosphate],
Magnesium-bis [2,2′-thiobis (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2′-thiobis- (4-t-octylphenyl) phosphate], sodium-2 , 2'-butylidene-bis (4,6-di-methylphenylphosphate, sodium-2,2'-butylidene-bis (4,6
-Di-t-butylphenyl) phosphate, sodium-2,2'-t-octylmethylene-bis (4,6-di-methylphenyl) phosphate, sodium-2,
2'-t-octylmethylene-bis (4,6-di-t-
Butylphenyl) phosphate, calcium-bis-
(2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate), magnesium-bis [2,
2'-methylene-bis (4,6-di-t-butylphenyl) phosphate], barium-bis [2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate], sodium- 2,2'-methylene-bis (4
-Methyl-6-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis (4-ethyl-6
-Tert-butylphenyl) phosphate, sodium (4,4'-dimethyl-5,6'-di-tert-butyl-
2,2′-biphenyl) phosphate, calcium-bis [(4,4′-dimethyl-6,6′-di-tert-butyl-2,2′-biphenyl) phosphate], sodium-2,2′-ethylidene -Bis (4-m-butyl-6-
t-butylphenyl) phosphate, sodium-2,
2'-methylene-bis (4,6-di-methylphenyl)
Phosphate, sodium-2,2'-methylene-bis (4,6-di-ethylphenyl) phosphate, potassium-2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, calcium- Screw [2
2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2 ′
-Ethylidene-bis (4,6-di-t-butylphenyl) phosphate], barium-bis [2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], aluminum-tris [ 2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate], aluminum-tris [2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], Bis (2,4,8,10-tetra-t-butyl-
6-hydroxy-12H-dibenzo [d, g] [1,
3,2] dioxophosphin-6-oxide) ammonium hydroxide salt and a mixture of two or more thereof. In particular, sodium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate, bis (2,4,8,10-tetra-t-butyl-
6-hydroxy-12H-dibenzo [d, g] [1,
3,2] Dioxophosphosine-6-oxide) ammonium hydroxide salt is preferred. Further, as the organic phosphoric acid-based nucleating agent, the following general formula (VII)

[0071]

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(Wherein R ¹⁸ is hydrogen or C 1 -C 10)
Wherein M is a monovalent to trivalent metal atom,
s is an integer of 1 to 3. ) Can also be mentioned. Specific examples of the compound represented by the general formula (VII) include sodium-bis (4-t-butylphenyl) phosphate and sodium-bis (4-
Methylphenyl) phosphate, sodium-bis (4
-Ethylphenyl) phosphate, sodium-bis (4-i-propylphenyl) phosphate, sodium-bis (4-t-octylphenyl) phosphate,
Potassium-bis (4-t-butylphenyl) phosphate, calcium-bis (4-t-butylphenyl) phosphate, magnesium-bis (4-t-butylphenyl) phosphate, lithium-bis (4-t-butylphenyl) phosphate , Aluminum-bis (4-t-
Butylphenyl) phosphate and mixtures of two or more of these. Particularly, sodium-bis (4-t-butylphenyl) phosphate is preferable. Sorbitol nucleating agent As the sorbitol nucleating agent, for example, the following general formula (VI
II)

[0073]

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(Wherein each R ¹⁹ may be the same or different, and includes hydrogen, halogen such as chlorine, or a compound having 1 to 1 carbon atoms.
10 hydrocarbon groups. t and u are each 0 to 5
Is an integer. )). Specific examples of the compound represented by the general formula (VIII) include 1,3,2,4-dibenzylidene sorbitol, 1,3-benzylidene-2,4-p-methylbenzylidene sorbitol, -Benzylidene-2,4
-P-ethylbenzylidene sorbitol, 1,3-p-
Methylbenzylidene-2,4-benzylidenesorbitol, 1,3-p-ethylbenzylidene-2,4-benzylidenesorbitol, 1,3-p-methylbenzylidene-2,4-p-ethylbenzylidenesorbitol,
1,3-p-ethylbenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3,2,4-di (p-
Methylbenzylidene) sorbitol, 1,3,2,4-
Di (p-ethylbenzylidene) sorbitol, 1,3,
2,4-di (pn-propylbenzylidene) sorbitol, 1,3,2,4-di (pi-propylbenzylidene) sorbitol, 1,3,2,4-di (pn-butylbenzylidene) ) Sorbitol, 1,3,2,4-di (ps-butylbenzylidene) sorbitol,
3,2,4-di (pt-butylbenzylidene) sorbitol, 1,3,2,4-di (2 ′, 4′-dimethylbenzylidene) sorbitol, 1,3,2,4-di (p-
Methoxybenzylidene) sorbitol, 1,3,2,4
Di (p-ethoxybenzylidene) sorbitol, 1,
3-benzylidene-2-p-chlorobenzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4
-Benzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-p-ethylbenzylidene sorbitol, 1,3-p-methylbenzylidene -2,4-p-chlorobenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-
Chlorbenzylidene sorbitol and 1,3,2,4
-Di (p-chlorobenzylidene) sorbitol and a mixture of two or more thereof, and in particular, 1,3,2,4-dibenzylidene sorbitol,
3,2,4-di (p-methylbenzylidene) sorbitol, 1,3,2,4-di (p-ethylbenzylidene) sorbitol, 1,3-p-chlorobenzylidene-2,4
-P-methylbenzylidene sorbitol, 1,3,2
4-Di (p-chlorobenzylidene) sorbitol and mixtures of two or more thereof are preferred. As the sorbitol nucleating agent, the following general formula (IX)

[0075]

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(Wherein each R ²⁰ may be the same or different and is an alkyl group having 1 or 2 carbon atoms). Aromatic carboxylic acid nucleating agent As the aromatic carboxylic acid nucleating agent, the following formula (X)

[0077]

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The aluminum hydroxy-di p represented by the formula
-T-butylbenzoate and the like. High melting point polymer nucleating agent Examples of high melting point polymers include polyvinylcyclohexane,
Examples thereof include polyvinylcycloalkane such as polyvinylcyclopentane, poly3-methylpentene-1, poly3-methylptene-1, and polyalkenylsilane.

Inorganic nucleating agents : inorganic nucleating agents include silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon,
Aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc,
Clay, mica, asbestos, glass fiber, glass flake, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder,
Molybdenum sulfide and the like can be given. In particular, talc is preferred.

[0080] As the rosin acid type nucleating agent rosin acid type nucleating agent, such as sodium rosin acid salts, potassium rosin acid salts, rosin acid metal salts such as magnesium rosin acid salts are used. The rosin acid metal salt is a reaction product of the rosin acid and the metal compound, and is a mixture of the rosin acid metal salt and the unreacted rosin acid, and both the unreacted rosin acid-free rosin acid metal salt. Means Examples of the metal compound that reacts with rosin acid to form a metal salt include compounds that have a metal element such as sodium, potassium, and magnesium and that form a salt with the rosin acid. Chloride, nitrate, acetate, sulfate, carbonate, hydroxide and the like.

Examples of the rosin acids include natural rosins such as gum rosin, tall oil rosin, and wood rosin; disproportionated rosin, hydrogenated rosin, dehydrogenated rosin, polymerized rosin, α,
Various modified rosins such as β-ethylenically unsaturated carboxylic acid modified rosin; purified products of the natural rosin, purified products of the modified rosin, and the like. Natural rosins usually contain a plurality of resin acids, such as pimaric acid, sandaracopimaric acid, parastolic acid, isopimaric acid, abietic acid, dehydroabietic acid, neoabietic acid, dihydropimaric acid, dihydroabietic acid, and tetrahydroabietic acid. Have been.

The unsaturated carboxylic acid used for preparing the α, β-ethylenically unsaturated carboxylic acid-modified rosin is, for example, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid. , Acrylic acid, methacrylic acid and the like. Preferred examples of the rosin acid metal salt include the following general formulas (XIa) and (XIb)

[0083]

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(R ²¹ , R ²² and R ²³ may be the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, M is a metal ion having 1 to 3 valences, and v is It is the same integer as the valence of the metal ion M, and is an integer of 1 to 3.). Specific examples of the alkyl group of R ^{21 to} R ²³ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group,
Examples thereof include alkyl groups having 1 to 8 carbon atoms such as various pentyl groups, various heptyl groups, and various octyl groups, and these groups have a substituent such as a hydroxyl group, a carboxyl group, an alkoxy group, and a halogen. May be.

Specific examples of the cycloalkyl group represented by R ^{21 to} R ²³ include a cycloalkyl group having 5 to 8 carbon atoms such as a cyclopentyl group, a cyclohexyl group and a cycloheptyl group. Hydroxyl group,
It may have a substituent such as a carboxyl group, an alkoxy group and a halogen. Examples of the aryl group of R ^{21 to} R ²³ include an aryl group having 6 to 10 carbon atoms such as a phenyl group, a tolyl group, and a naphthyl group. These groups include a hydroxyl group, a carboxyl group, an alkoxy group, It may have a substituent such as halogen.

In the above R ^{21 to} R ²³ , a compound in which R ²¹ is an isopropyl group and R ²² and R ²³ are methyl groups is more preferable. M is a monovalent to trivalent metal ion, specifically, lithium, sodium, potassium,
Monovalent metal ions such as rubidium and cesium; divalent metal ions such as beryllium, magnesium, calcium, strontium, barium and zinc; and trivalent metal ions such as aluminum. Among them, monovalent or divalent metal ions are preferable, and sodium ions, potassium ions, and magnesium ions are more preferable.

Specific examples of the compound (XIa) include, for example, lithium dehydroabietic acid, sodium dehydroabietic acid, potassium dehydroabietic acid, beryllium dehydroabietic acid, magnesium dehydroabietic acid, calcium dehydroabietic acid, zinc dehydroabietic acid, dehydroabietic acid. Examples thereof include metal salts of dehydroabietic acid such as aluminum abietic acid, and sodium dehydroabietic acid, potassium dehydroabietic acid, and magnesium dehydroabietic acid are preferably used.

Specific examples of the compound (XIb) include, for example, lithium dihydroabietic acid, sodium dihydroabietic acid, potassium dihydroabietic acid, beryllium dihydroabietic acid, magnesium dihydroabietic acid, calcium dihydroabietic acid, zinc dihydroabietic acid, and dihydroabieticin. Metal salts of dihydroabietic acid such as aluminum phosphate;
Sodium dihydroabietic acid, potassium dihydroabietic acid and magnesium dihydroabietic acid are preferably used.

Amide-based nucleating agent JP-A-6-240058, JP-A-6-25659
U.S. Pat. No. 5,086,049; dicarboxylic acid amide compounds described in JP-A-5-262936;
For example, a tricarballylic acid amide compound described in JP-A-78374, a sulfur-containing amide described in JP-B-4-34568, and the like can be used.

The component (ii) may be used alone or
You may use it in combination of 2 or more types. By incorporating the above nucleating agent, high-speed molding can be performed without deteriorating the properties of the film. (Ii) The amount of the component is
0.001 to 5 parts by weight, more preferably 0.001 to 1 part by weight, particularly preferably 0.1 to 1 part by weight, based on 100 parts by weight of the propylene random copolymer of the component (i).
005 to 0.5 parts by weight. If that amount is too small,
The above effects may not be sufficient, and if the amount is too large, the effect corresponding to the amount may not be obtained.

The propylene random copolymer composition of the present invention may further contain, if necessary, additives such as an antioxidant, a neutralizing agent, an antiblocking agent and a slipping agent in addition to the component (ii). Can be blended. As a preferred antioxidant, pentaerythrityl-tetrakis [3
-(3,5-di-t-butyl-4-hydroxyphenyl) propionate ("Irganox 1010", manufactured by Ciba Specialty Chemicals), octadecyl-3- (3,5-di-t-butyl-4) -Hydroxyphenyl) propionate (“Irganox 1076”,
Ciba Specialty Chemicals), 1,3,5
-Trimethyl-2,4,6-tris (3,5-di-t-
Butyl-4-hydroxybenzyl) benzene (“Irganox 1330”, manufactured by Ciba Specialty Chemicals), tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate (“Irganox 3114”) , Ciba Specialty Chemicals)
Phenolic antioxidants such as tris (2,4-di-t)
-Butylphenyl) phosphite ("Irgafos 16
8 ", manufactured by Ciba Specialty Chemicals), tetrakis (2,4-di-t-butylphenyl) 4,4'-
Examples thereof include phosphorus-based antioxidants such as biphenylene-di-phosphite ("P-EPQ", manufactured by Ciba Specialty Chemicals).

Preferred neutralizing agents are calcium stearate, zinc stearate, magnesium stearate, Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ .3.5H ₂ O
( "DHT-4A", manufactured by Kyowa Chemical Industry Co., Ltd.) hydrotalcites, such _{as, [Li 2 Al 4 (OH} ) 12] CO 3 · 3
Examples thereof include lithium aluminum composite hydroxide salts such as H ₂ O (“Mizukarak”, manufactured by Mizusawa Chemical Industry Co., Ltd.). Preferred examples of the antiblocking agent include synthetic silica-based compounds such as "Sylysia" (manufactured by Fuji Silysia) and "Mizukasil" (manufactured by Mizusawa Chemical Industry). As a preferred slip agent, erucamide,
Fatty acid amides such as oleic acid amide, stearic acid amide, behenic acid amide, ethylenebisstearic acid amide, ethylenebisoleic acid amide, stearyl erucic acid amide, and oleyl palmitic acid amide can be mentioned.

Further, the propylene random copolymer composition of the present invention contains an antistatic agent, an antifogging agent, a weathering agent, a coloring agent, a drip-free agent, a flame retardant, a flame retardant auxiliary, an antibacterial agent, an inorganic Or you may mix well-known additives, such as an organic filler. The film according to the fourth invention of the present application 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, various additives can be formulated as needed in the powder of the propylene-based random copolymer, extruded and granulated by a kneader, pelletized, and formed into a T-die cast film. In general, the thickness of the propylene-based random copolymer of the present invention is controlled to be 10 to 50 even by a T-die casting method even at a high-speed film forming condition of a take-up speed of 50 m / min or more.
A film of 0 μm can be obtained. In addition, since it has the above-mentioned preferable characteristics, it can be suitably used as at least one layer component in the production of 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.
The method is not particularly limited to this, and any film forming method may be used as long as a film can be manufactured by a melt extrusion molding method.

[0094]

[Production Example 1]

(Preparation of magnesium compound) The reaction layer equipped with a stirrer (internal volume 80 liters) was sufficiently replaced with nitrogen gas, 20 liters of dehydrated ethanol, 1.06 kg of metallic magnesium and 106 g of iodine were added, and the system was refluxed under stirring. The reaction was allowed to proceed until the generation of hydrogen gas from inside was stopped, and a solid reaction product was obtained. The reaction product containing the solid reaction product was dried under reduced pressure to obtain a target magnesium compound (a solid catalyst support).

(Preparation of Solid Catalyst Component) 4.0 kg of the magnesium compound was put into a reaction layer equipped with a stirrer (internal volume: 80 liters), which was purged with nitrogen.
20 liters of heptane were added. Heat to 40 ° C, add 600 ml of silicon tetrachloride, stir for 20 minutes, and di-
850 ml of n-butyl phthalate were added. The temperature of the solution was raised to 70 ° C., and then titanium tetrachloride was added to 19.
25 liters were charged. The internal temperature was set to 125 ° C., and the reaction was carried out for 2 hours. Thereafter, washing was performed sufficiently using 125 ° C. dehydrated n-heptane. Then add titanium tetrachloride to 30.5
0 liter was added, the internal temperature was set to 125 ° C., and a contact reaction was performed for 2 hours. Thereafter, washing was carried out sufficiently using dehydrated n-heptane at 125 ° C. to obtain a solid catalyst component.

(Preliminary polymerization) The above solid catalyst component was added to a reaction layer equipped with a stirrer (internal volume: 80 liters) replaced with nitrogen.
Then, 8.4 liters of dehydrated n-heptane was 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 therethrough at normal pressure and reacted for 2 hours. Thereafter, the solid component was sufficiently washed with dehydrated n-heptane to obtain a catalyst component.

(Polymerization) The above catalyst component was added to a polymerization tank equipped with a stirrer having an internal volume of 200 liters in terms of titanium atoms in the component in an amount of 3 parts.
The amount of triethylaluminum was 4 mmol / kg (polymer) and the amount of dicyclopentyldimethoxysilane was 0.4 mmol / kg (polymer). The polymerization temperature was 75 ° C and the polymerization pressure (total pressure). Propylene, ethylene and 1 kg at 24 kg / cm ² G
-Butene was reacted. At this time, the ethylene supply amount was adjusted so as to have a predetermined ethylene content, the 1-butene supply amount was adjusted so as to have a predetermined 1-butene content, and the hydrogen supply amount of the molecular weight regulator was further adjusted so as to have a predetermined molecular weight. . When the gas composition in the polymerization apparatus at this time was analyzed by gas chromatography, the ethylene concentration was 3.5 mol%,
Butene concentration is 3.5 mol%, hydrogen concentration is 11.0 mol%
Met. Table 1 shows the results of the evaluation of the obtained propylene-based random copolymer powder in accordance with the following “Resin Property Evaluation Method”.

[Production Example 2] (Preparation of magnesium compound) Same as Production Example 1. (Preparation of solid catalyst component) Same as in Production Example 1. (Preliminary polymerization) Same as in Production Example 1. (Polymerization) The above catalyst component was added to a polymerization tank equipped with a stirrer having an internal volume of 200 liters in an amount of 3 mmol / k in terms of titanium atoms in the component.
g (polymer), triethylaluminum was supplied at 4 mmol / kg (polymer), and dicyclopentyldimethoxysilane was supplied at 1 mmol / kg (polymer).
Propylene and ethylene were reacted at ² G. At this time, the ethylene supply amount was adjusted so as to have a predetermined ethylene content, and the hydrogen supply amount of the molecular weight regulator was adjusted so as to have a predetermined molecular weight. When the gas composition in the polymerization apparatus at this time was analyzed by gas chromatography, the ethylene concentration was 5.0 mol% and the hydrogen concentration was 8.5 mol%. Table 2 shows the results of the evaluation of the powder of the obtained propylene-based random copolymer in accordance with the “resin property evaluation method” described below.

[Production Example 3] (Preparation of magnesium compound) Same as Production Example 1. (Preparation of solid catalyst component) The magnesium compound was added to a reaction layer equipped with a stirrer (internal volume: 80 liters), which had been replaced with nitrogen.
0 kg was added, and 20 liters of dehydrated n-heptane was further added. Heat to 40 ° C and silicon tetrachloride 600
Then, the mixture was stirred for 20 minutes, and 850 ml of di-n-butyl phthalate was added. The temperature of the solution was raised to 70 ° C., and then 19.25 liters of titanium tetrachloride were added. The internal temperature was 110 ° C., and the reaction was carried out for 2 hours.
Thereafter, the substrate was sufficiently washed with dehydrated n-heptane at 80 ° C. Further, 30.50 liters of titanium tetrachloride was added, the internal temperature was set to 110 ° C., and a contact reaction was performed for 2 hours. Thereafter, washing was performed sufficiently using dehydrated n-heptane at 80 ° C. to obtain a solid catalyst component.

(Preliminary polymerization) The above solid catalyst component was added to a reaction layer equipped with a stirrer (internal volume: 80 liters) replaced with nitrogen.
Then, 8.4 liters of dehydrated n-heptane was 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 therethrough at normal pressure and reacted for 2 hours. Thereafter, the solid component was sufficiently washed with dehydrated n-heptane to obtain a catalyst component.

(Polymerization) The above-mentioned catalyst component was added to a 200-liter polymerization tank equipped with a stirrer in terms of titanium atoms in the component.
The amount of triethylaluminum was 4 mmol / kg (polymer) and the amount of dicyclopentyldimethoxysilane was 0.4 mmol / kg (polymer). The polymerization temperature was 75 ° C and the polymerization pressure (total pressure). Propylene, ethylene and 1 kg at 24 kg / cm ² G
-Butene was reacted. At this time, the ethylene supply amount was adjusted so as to have a predetermined ethylene content, the 1-butene supply amount was adjusted so as to have a predetermined 1-butene content, and the hydrogen supply amount of the molecular weight regulator was further adjusted so as to have a predetermined molecular weight. . Further, when the gas composition in the polymerization apparatus at this time was analyzed by gas chromatography, the ethylene concentration was 5.4 mol%,
The butene concentration was 1.3 mol% and the hydrogen concentration was 9.5 mol%. Table 1 shows the results of the evaluation of the obtained propylene-based random copolymer powder in accordance with the following “Resin Property Evaluation Method”.

[0102]

[Table 1]

[0103]

[Table 2]

Example 1 100 parts by weight of the propylene-based random copolymer obtained in Production Example 1 was mixed with bis (2,4,8,10-tetra-t-butyl-6-hydroxy-) as a nucleating agent. 12H-dibenzo [d, g] [1,3,2] dioxophosphin-6-oxide) ammonium hydroxide salt (Adegastab NA-21, manufactured by Asahi Denka Co., Ltd.)
0.1 part by weight of Irganox 1010 (manufactured by Ciba Specialty Chemicals), 0.1 part by weight of Irgafos 168 (manufactured by Ciba Specialty Chemicals) as antioxidants, 0.23 parts by weight of a silica compound (manufactured by Fuji Silysia Ltd.) as a blocking agent, 0.1 parts by weight of calcium stearate as a neutralizing agent, and 0.05 parts by weight of erucamide as a lubricant are added. Mod of Toshiba Machine Co., Ltd.
It pelletized with the el35B extruder. Table 3 shows the results of the evaluation of the pellets in accordance with the following "method for evaluating the properties of the copolymer composition". 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 243 ° C. at the exit of the T-die, a chill roll temperature of 40 ° C., and a take-up speed of 125 m / min. Molded. Table 3 shows the results of evaluation of the obtained films in accordance with the following “Method of evaluating film quality”.

Example 2 In Example 1, sodium-2,2'-methylenebis (2,4-di-t-butylphenyl) phosphate (Adegas Tab NA-11, manufactured by Asahi Denka Co., Ltd.) was used as a nucleating agent. The same procedure was performed except that 0.05 part by weight was added. The results are shown in Table 3. [Example 3] In Example 1, 1,3,3
The same procedure was performed except that 0.2 parts by weight of 2,4-dibenzylidene sorbitol (manufactured by Shin Nippon Riken Co., Ltd., Gelol MD) was added. The results are shown in Table 3.

Example 4 The same procedure was performed as in Example 1, except that the propylene random copolymer produced in Production Example 2 was used. The results are shown in Table 3. [Comparative Example 1] The same operation as in Example 1 was carried out except that the propylene random copolymer produced in Production Example 3 was used. The results are shown in Table 3.

Reference Example 1 The procedure of Example 1 was repeated, except that no nucleating agent was used. As a result, the chill roll release property of the ear part was deteriorated, and a clean film could not be obtained. Some of the results are shown in Table 3. Reference Example 2 The same operation as in Example 4 was carried out except that no nucleating agent was used. As a result, the chill roll release property of the ear part was deteriorated, and a clean film could not be obtained. Some of the results are shown in Table 3.

[0108]

[Table 3]

[0109]

[Table 4]

[Resin Characteristic Evaluation Method] (1) Comonomer Content, Stereoregularity Index Content of ethylene unit in propylene-based tertiary random copolymer of propylene, ethylene and 1-butene α (mol%) ) And the content β (mol%) of the 1-butene unit were determined by Kang-Bo from the ¹³ C-NMR spectrum.
ng Leeet. al, Polymer J .; , 2
8, 696-702 (1996). α = (Ety / S) × 100 β = (Bu / S) × 100 where S = Pro + Ety + Bu Pro = ｛a + (b + d + e) / 2 + (h + i + m + r
+ S + t)｝ / 3 Ety = {(d + e) / 2 + (j + k + L + p + q)}
/ 2Bu = {b / 2 + (c + f + n + o + u)} / 4 The above a, b, c, etc. are the signal intensities shown in Table 4 below. For example, a is the signal intensity of the number a in the table.

[0111]

[Table 5]

Referring to JP-A-8-208909, the stereoregularity index P was obtained from the ¹³ C-NMR spectrum.
(Mol%) was calculated from the following equation. This Pt value is the isotactic fraction of triad units in the region where the propylene units and / or 1-butene units of the copolymer molecular chain are head-to-tail bonded. Pt = {r / (r + s + t-hi)} × 100 where r, s, t, etc. are the signal intensities shown in Table 4 above. For example, r is the signal intensity of the number r in the table. Propylene random copolymer of propylene and ethylene The content γ (% by weight) of ethylene units in the propylene random copolymer was calculated from the respective signal intensities according to the following formula. Table 5 shows the assignment of each signal. P represents a propylene unit and E represents an ethylene unit. Therefore, P
PP indicates that three propylene units are continuous, and EEE indicates that three ethylene units are continuous.

[0113]

[Table 6]

Γ = 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) (10) Here, for example, I (1) is the signal intensity of signal number 1 in Table 5.

The stereoregularity index P (mol%) was calculated from the following equation. Pr = ｛I (11) / (I (11) + I (12) + I (13) −I (4) −
I (5))｝ × 100 This Pr 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 represented by T
The signal intensity of methyl carbon of the propylene unit in the EPE chain appearing in the rr region is substituted by the signal intensity of Tδδ (signal 4) by the signal intensity of βδ (signal 5).

The ¹³ C-NMR spectra were measured using a JNM-EX400 type NMR apparatus manufactured by JEOL Ltd. under the following conditions. 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: 4 Seconds Number of accumulations: 4,000 (2) Temperature rise separation chromatography (TREF) (Wpt,
(WHt, W0t, Wpr, WHr, W0r (% by weight)) The sample solution was 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, and the sample was used as a filler. Adsorb. 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. A) 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: Barco 500 μl loop a) Measurement conditions Solvent: o-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 filling Agent: Chromosolve P (30-60 mesh) Column temperature distribution: within ± 2.0 ° C

(3) Peak top temperature (Tct, Tcr (° C.)) and melting point (Tmt, Tcr) on the highest temperature side in the crystallization curve of the copolymer by differential scanning calorimetry (DSC)
mr (° C.)) It was measured using a DSC7 differential scanning calorimeter manufactured by PerkinElmer. A 10 mg sample was previously melted at 230 ° C. for 3 minutes in a nitrogen atmosphere, and then melted at 10 ° C./min for 20 minutes.
The peak top temperature on the highest temperature side in the crystallization exothermic curve obtained by lowering the temperature to ° C was defined as (Tct, Tcr (° C)). Furthermore, after keeping at this temperature for 3 minutes, 10 ° C./m
The peak top temperature of the maximum peak of the melting endothermic curve obtained by raising the temperature in was defined as the melting point (Tmt, Tmr (° C.)).

(4) Extraction amount of boiling diethyl ether in the copolymer (Et, Er (% by weight)) 3 g of a pellet pulverized to a size of 1 mmφ mesh path was put on a cylindrical filter paper, and diethyl ether as an extraction solvent was put in a flat bottom flask. Add 160 ml and reduce the reflux frequency to 1
Soxhlet extraction is performed for 10 hours at a time of about 5 min. After completion of the extraction, diethyl ether was recovered by a rotary evaporator, and further dried by a vacuum dryer until a constant weight was obtained to obtain a boiling diethyl ether extraction amount. (5) Melt index MI (g / 10 min) According to JIS K7210, temperature 230 ° C, load 2,
Measured at 160 g. (6) Molecular weight distribution (Mw / Mn) Gel permeation chromatography was measured under the following conditions. The ratio between the weight average molecular weight Mw and the number average molecular weight Mn was determined as a molecular weight distribution (Mw / Mn). Column: TOSO BMHHR-H (S) HT Solvent: 1,2,4-trichlorobenzene Column temperature: 145 ° C. Flow rate: 1.0 ml / min Calibration curve: Universal Calibration Detector: RI (Waters 150C) Analysis program: HT -GPC (Ver 1.0)

"Copolymer Composition Characteristic Evaluation Method" (1) The peak top temperature Tc (° C.) on the highest temperature side in the crystallization curve of the copolymer composition by a differential scanning calorimeter (DSC) and the melting curve Peak top temperature Tm (° C.) on the lowest temperature side It was measured using a DSC7 type differential scanning calorimeter manufactured by PerkinElmer. A 10 mg sample was previously melted at 230 ° C. for 3 minutes in a nitrogen atmosphere, and then melted at 10 ° C./min for 20 minutes.
The peak top temperature on the highest temperature side in the crystallization exothermic curve obtained by lowering the temperature to ° C was defined as Tc (° C). Further, after maintaining at this temperature for 3 minutes, the peak top temperature of the lowest temperature side peak of the melting endothermic curve obtained by increasing the temperature at 10 ° C./min was defined as Tm (° C.). (2) Extraction amount of boiling diethyl ether in the copolymer composition E (% by weight) Same as the above “Resin property evaluation method”.

[Evaluation Method of Film Quality] All of the formed films were annealed at a temperature of 40 ° C. for 24 hours, and further adjusted at a temperature of 23 ± 2 ° C. and a humidity of 50 ± 10% for 16 hours or more. The measurement was performed under the same temperature and humidity conditions. (1) Heat seal temperature Measured in accordance with 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, 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

(2) Anti-blocking property With respect to the two films, one metal roll surface and the other anti-metal roll surface were brought into close contact with each other under the following conditions.
Fix each to a 10 × 10 cm jig, 10 × 10 cm
Was measured by a peel test under the following conditions. Adhesion condition: temperature 50 ° C, 7 days, load 15g / cm ² ,
Area 10 × 10 cm Peeling test conditions: test speed; 20 mm / min, load cell; 2 kg

(3) Slip Property (Static Friction Coefficient) After a film-covered threat is allowed to stand on a film-covered glass plate, the glass plate is tilted to tilt the glass plate when the threat starts to slide. The evaluation was made by the tan of the angle θ. 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 Surface pressure: 15 g / cm ² (4) Transparency (haze) Measured according to JIS K 7105 did.

(5) Impact resistance Evaluation was made by a film impact tester manufactured by Toyo Seiki Seisaku-sho, Ltd., based on the impact breaking strength using a 1/2 inch impact head. (6) Tensile modulus Measured under the following conditions by a tensile test in accordance with JIS K 7127. Cross head speed: 500 mm / min Load cell: 10 kg Measurement direction: machine direction (MD) In Table 3, in Comparative Example 1, bleeding occurred, the slip property and anti-blocking property were significantly reduced as compared with the examples, and the tensile strength was increased. The modulus of elasticity also decreases, and the heat sealability is low. Further, in the reference example, a clear film could not be obtained as in the example under the severe film forming conditions described above, and it can be seen that the effect of the nucleating agent is exhibited in the present invention.

[0126]

According to the propylene-based random copolymer composition of the present invention, excellent heat-sealing properties are exhibited without impairing desirable properties such as rigidity, transparency and moisture-proofness inherent in a polypropylene film. In addition, a film having both slip properties and anti-blocking properties required for high-speed bag making can be obtained. Further, even when the film forming speed is increased, the deterioration of the film quality is extremely small, and further, the moldability and the film characteristics are improved.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/098 C08K 5/098 5/20 5/20 5/49 5/49 C08L 23/14 C08L 23 / 14 23/22 23/22 F-term (reference) 4F071 AA20 AA87 AA88 AE22 AH04 BB06 BC01 4F100 AA20H AH02H AH03H AH08H AH10H AK04A AK04J AK07A AK07J AK09A AK09J AK80AJA03 CA04 J04 JL01 JL12 JN01 YY00A YY00H 4J002 AF023 BB111 BB112 BB173 BK003 CP033 DE076 DE136 DE146 DE236 DJ006 DJ016 DJ036 DJ046 DL006 EG046 EL106 EW046 FA046 FD030 FD203 FD206 GF00

Claims (8)

[Claims] 1. A propylene-based random copolymer composition comprising (i) a random copolymer of propylene, ethylene and / or 1-butene, and (ii) a nucleating agent, comprising: Top temperature Tc (° C.) on the highest temperature side in the crystallization curve, measured by a scanning calorimeter (DSC)
And peak top temperature Tm on the lowest temperature side in the melting curve
(° C.) satisfies the following formula (1): Tc ≧ 0.75 × Tm−5 (1), and the amount W0 (% by weight) that elutes in the range of 0 ° C. or lower in the temperature-raising fractionation chromatograph Is 6% by weight or less. 2. A propylene random copolymer of (i) propylene, ethylene and 1-butene, wherein the propylene-based random copolymer satisfies the following conditions (a) to (c) and a nucleating agent is blended. -Based random copolymer composition. The sum of the ¹³ content of ethylene units of C-NMR copolymer as measured by α content (mol%) and ¹³ were determined by C-NMR copolymer of 1-butene units beta (mol%) (Α + β) is 0.1 to 15 mol%, and the main elution peak temperature of the temperature-raising fractionation chromatograph is Tpt
(Tpt−5) ° C. to (Tpt + 5)
The amount Wpt (wt%) eluted in the temperature range of 2 ° C. is 2
0% by weight or more, and the amount W0t (% by weight) eluted in a temperature range of 0 ° C. or less in a temperature rising fractionation chromatograph and the above (α + β) satisfy the following equations (2) to (4). When 0.1 ≦ (α + β) <2, W0t ≦ 1 (2) When 2 ≦ (α + β) <12, W0t ≦ (α + β) / 2 (3) 12 ≦ (α + β) ≦ In the case of 15, W0t ≦ 6 (4) 3. A random copolymer of propylene and ethylene which is a random copolymer of propylene and ethylene which satisfies the following conditions (1) to (3): Polymer composition. The content γ (% by weight) of ethylene units in the copolymer measured by ¹³ C-NMR is 0.2 to 10% by weight, and the main elution peak temperature of the temperature rising fractionation chromatograph is Tpr
(Tpr-5) ° C. to (Tpr + 5)
The amount Wpr (% by weight) eluted in the temperature range of 2 ° C. is 2
0% by weight or more, and the amount W0r (% by weight) eluted in a temperature range of 0 ° C. or less in a temperature-raising fractionation chromatograph satisfies the relationship of the following formula (5). W0r ≦ (3 + 2γ) / 4 (5) 4. The compounding amount of the component (ii) is (1)
The propylene random copolymer composition according to any one of claims 1 to 3, which is 0.001 to 5 parts by weight based on 00 parts by weight. 5. The component (i) having a melt index MI (g / 10 min) of 0.1 to 200 g / 10 m.
The propylene random copolymer composition according to any one of claims 1 to 4, which is in. 6. The component according to claim 1, wherein the component (i) has a stereoregularity index P (mol%) of 98 mol% or more in the copolymer measured by ¹³ C-NMR. Propylene random copolymer composition. 7. A film comprising the propylene random copolymer composition according to claim 1. 8. A multilayer film comprising the propylene random copolymer composition according to claim 1 as at least one component.