JP2001064336A - Propylene-based resin composition and its preparation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a propylene-based resin composition which shows excellence in transparency and flexibility, has sufficient mechanical strength, hardly produces a wrinkle and shows no tackiness. SOLUTION: This resin composition comprises a polypropylene component and a copolymer component of propylene, ethylene and butene-1 or a copolymer component of propylene and butene-1 and is characterized in that (I) an eluting fraction up to 80 deg.C (hereinafter referred to as a middle temperature eluting component) is 50 to 99 wt.% of the total weight, an eluting fraction above 80 deg.C (hereinafter referred to as a high temperature eluting component) is 50 to 1 wt.% of the total weight and an eluting fraction up to 0 deg.C (hereinafter referred to as a low temperature eluting component) is not more than 10 wt.% of the total weight measured by means of a temperature increase elution separation method using o-dichlorobenzene as a solvent and that (II) the ethylene unit content of the middle and low temperature eluting components is from not less than 0 wt.% to not more than 10 wt.% and the butene-1 unit content of the same is from not less than 3 wt.% to not more than 40 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a propylene-based resin composition having excellent transparency and flexibility, sufficient mechanical strength and no stickiness, a method for producing the same, and a flexible film made of the same.

[0002]

2. Description of the Related Art Conventionally, in the field of various packaging films for textiles, foods, daily necessities, etc., particularly in the field where transparency, flexibility and the like are required, vinylon films and soft vinyl chloride films to which a plasticizer is added are used. Used. Although these films are excellent in flexibility, transparency, glossiness and texture, vinylon film is easily changed in quality due to moisture, and in a soft vinyl chloride film,
Due to the hygienic problems caused by bleed-out of plasticizers and environmental problems such as generation of harmful gases during waste combustion, the above-mentioned problems are maintained while maintaining the excellent characteristics of vinylon films and soft vinyl chloride films. There is a demand for the development of a flexible film that solves the above problem.

[0003] Polypropylene has attracted attention as a clean material because it does not deteriorate in quality due to moisture and does not generate harmful gases during combustion. However, polypropylene resin film is a conventional vinylon film,
There was a problem that the flexibility was inferior to the soft vinyl chloride film and wrinkles were easily generated.

As a method for obtaining a flexible polypropylene film, a method using a copolymer of propylene and an α-olefin such as a copolymer of propylene and ethylene or a terpolymer of propylene, ethylene and butene-1 (Japanese Patent Publication No. 4
JP-A-68033) and a method using a blend of a propylene-based resin and a low-crystalline or non-crystalline olefin-based polymer (JP-A-54-48846). In the case, when the content of olefins to be copolymerized is increased to impart flexibility, the amount of by-products of the non-crystalline polymer is significantly increased, causing a sticky feeling or a problem that heat resistance is significantly reduced due to a lowered melting point. there were.

In the method using a blend of a propylene-based resin and a low-crystalline or non-crystalline olefin-based polymer, it is difficult to uniformly mix the propylene-based resin and the olefin-based polymer. However, there was a problem that transparency was poor.

As means for solving such a problem, Japanese Patent No. 2677920 and Japanese Patent Application Laid-Open No. 7-11835
No. 4 discloses that a propylene-based copolymer having a specific composition exhibits good flexibility and transparency.

[0007] However, the propylene-based polymer obtained by the above method has a sticky feeling,
Since many non-crystalline components, which are factors inhibiting transparency, are mixed, there is still room for improvement in stickiness and transparency, and further improvement has been desired.

In Japanese Patent Application No. 10-366652,
A propylene-based resin composition having a specific crystallinity distribution in which components eluted at a temperature of up to 0 ° C. by a temperature raising fractionation method using an o-dichlorobenzene solvent is 10% by weight or less is shown. However, the propylene-based resin composition obtained by the above method has no sticky feeling,
Although exhibiting good flexibility and transparency, there is still room for improvement in terms of low mechanical strength and easy wrinkling, and further improvement has been desired.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a vinylon film and a soft vinyl chloride film which have excellent flexibility, transparency, mechanical strength, and hardly cause wrinkles, and have no sticky feeling. Another object of the present invention is to provide a resin composition having no physical property change due to humidity, environmental and hygienic problems, and a flexible film made of the same.

[0010]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have found that a copolymer of propylene, ethylene and butene-1 having a limited amount of non-crystalline components. Or a propylene-based resin composition comprising a low-crystalline copolymer of propylene and butene-1 in a specific amount has been successfully developed, and it has been found that such a composition satisfies all of the above objects. Was completed.

That is, the present invention comprises (I) o-dichlorobenzene comprising a polypropylene component and a copolymer of propylene with ethylene and butene-1, or a polypropylene component and a copolymer of propylene with butene-1. Components eluted at temperatures up to 80 ° C. (hereinafter referred to as “medium and low temperature eluting components”) are eluted at a temperature of 80 ° C. or more by 50 to 99% by weight of the total components by a temperature rising elution fractionation method (TREF) using a solvent. Ingredients (hereinafter referred to as hot eluting ingredients)
Is 50 to 1% by weight of the whole, and a component eluted at a temperature up to 0 ° C. (hereinafter referred to as a low-temperature eluting component) is 1% of the whole.
0% by weight or less, and (II) the content of ethylene units in the above-mentioned medium / low temperature elution component is 0% by weight or more and 10% by weight or less, and the butene-1 unit content is 3% by weight or more and 40% by weight or less. A propylene-based resin composition characterized in that:

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The propylene resin composition of the present invention comprises a polypropylene component and propylene and ethylene and butene-1, or a copolymer component of a polypropylene component and propylene and butene-1.

The ratio of the above-mentioned polypropylene component to the copolymer component of propylene and ethylene or butene-1 or the ratio of the propylene to butene-1 copolymer component is determined by temperature-elevation elution fractionation using o-dichlorobenzene as a solvent ( (Hereinafter referred to as TREF) method.

[0015] That is, the polypropylene component mainly consists of the elution component at 80 ° C or higher in the elution curve by the TREF method. Also, propylene and ethylene and butene
The copolymer component 1 or the propylene and butene-1 copolymer component mainly consists of components that elute at temperatures up to 80 ° C.

Here, the TREF method is described, for example, in Journal.
of Applied Polymer Science; Applied Polymer Sympos
ium 45, 1-24 (1990). That is, a high-temperature polymer solution is introduced into a column filled with a diatomaceous earth filler, and the column temperature is gradually decreased to crystallize the filler surface in order from the component having the highest crystallinity. By gradually raising,
This is a method in which components are eluted in ascending order of crystallinity and the eluted polymer components are collected. With this method, the crystallinity distribution of the polymer can be measured.

In the present invention, the advantages of the present invention, namely, excellent transparency and flexibility, sufficient mechanical strength, less wrinkling, and no stickiness are characteristic of the polypropylene component and propylene. TRE which indirectly indicates the constituent ratio of a copolymer component of ethylene and butene-1 or a copolymer component of propylene and butene-1
The ratio of the eluting components (the distribution of crystallinity) measured by the method F and the constituent ratios of propylene, ethylene and butene-1 in the low- and mid-temperature eluting components are extremely important.

In the propylene resin composition of the present invention, the components eluted at 80 ° C. or higher (hereinafter, referred to as high-temperature components) have a propylene unit content of 97 to 100% by weight. Specifically, the high-temperature eluting component contains 3% by weight or less, preferably 1.5% by weight or less, more preferably 1% by weight or less of a monomer unit composed of a propylene homopolymer or an α-olefin or ethylene other than propylene. It is a random copolymer of not more than weight%. In the above random copolymer, when the amount of such monomer units other than propylene exceeds 3% by weight, the heat resistance of the product is reduced.

The α-olefin has 4 to 4 carbon atoms.
Although an α-olefin of 18 can be used, it is preferably an α-olefin having 4 to 8 carbon atoms, particularly 1-butene,
-Hexene and 1-octene can be suitably used.

In the propylene resin composition of the present invention, the proportion of the high-temperature eluting component is 1 to 50% by weight, preferably 3 to 30% by weight, more preferably 5 to 20% by weight. That is, when the proportion of the high-temperature eluting component is lower than 1% by weight, the balance between heat resistance and rigidity and flexibility is deteriorated, and when it is 50% by weight or more, transparency is remarkably deteriorated.

In the propylene resin composition of the present invention, a component eluted at a temperature up to 80 ° C. by the TREF method (hereinafter referred to as a medium-low temperature elution component) imparts flexibility and sufficient mechanical strength to a product. Necessary for the production, the ethylene unit content is 0 to 10% by weight, butene-1
A content of 3 to 40% by weight, preferably an ethylene unit content of 0 to 8% by weight, a butene-1 content of 5 to 35% by weight,
More preferably, ethylene and / or butene-1 mainly composed of low-crystalline propylene containing ethylene and butene-1 units having an ethylene unit content of 0 to 5% by weight and a butene-1 content of 7 to 30% by weight. It is composed of a copolymer or a propylene / butene-1 copolymer. The copolymer is a copolymer obtained by randomly copolymerizing propylene and ethylene and butene-1 or propylene and butene-1 in order to more effectively impart sufficient mechanical strength and flexibility to the product. Is preferred.

When the composition ratio of ethylene unit and butene-1 unit of the above-mentioned medium- and low-temperature eluting components is out of the above range, TR
Even if the composition ratio of each elution component indicated by EF is within the range of the present invention, sufficient mechanical strength cannot be imparted to the product.

In the propylene-based resin composition of the present invention, the amount of the components eluted at a low temperature is 50 to 99% by weight, preferably 70 to 97% by weight, and more preferably 80 to 95% by weight. When the content of the medium- and low-temperature eluting components is less than 50% by weight, the flexibility of the product is low, resulting in poor transparency. On the other hand, if the content of the medium-to-low temperature elution component is more than 99% by weight, the mechanical strength decreases.

One of the features of the propylene resin composition of the present invention is that the amount of components eluted up to 0 ° C. (hereinafter referred to as low temperature components) is small. That is, such 0 ° C
It is important that the amount of the eluted components up to 10% by weight, preferably 8% by weight or less, more preferably 6% by weight or less of the whole (the total amount of the medium- and low-temperature eluted components and the high-temperature eluted components). When the amount of the eluted component exceeds 10% by weight, the transparency of the product deteriorates, and sufficient mechanical strength cannot be imparted to the product.

The propylene-based resin composition of the present invention is not particularly limited as long as it satisfies the above-mentioned constitutions. For example, it is measured by a differential scanning calorimeter (hereinafter, referred to as DSC) of the high-temperature eluting components. The measured melting point is 120 to improve the transparency and heat resistance of the product film.
It is preferable that it is -170 degreeC, and it is more preferable that it is 130-155 degreeC.

The molecular weight distribution (Mw / Mn) of the propylene resin composition of the present invention measured by gel permeation chromatography (GPC) is 5 or less in order to improve blocking resistance of the film product. , Preferably 4
Hereinafter, it is more preferably 3 or less.

The intrinsic viscosity [η] measured with a Ubbelohde viscometer in tetralin at 135 ° C. is 0.1 in order to improve moldability and blocking resistance of the product.
5 to 5.0 dl / g, preferably 0.5 to 3.0 dl / g
g, more preferably 0.8 to 2.0 dl.

Further, the propylene resin composition of the present invention has a temperature of 230 ° C. and a temperature of 2.1 ° C. according to ASTM-D1238.
The melt flow rate measured under a load of 6 kg is 0.01 to 50 g / 10 min, preferably 0.1 to 30 g / 10 min, and more preferably, considering moldability.
Those having a concentration of 0.5 to 20 g / 10 minutes are preferred.

Further, the calorific value of the endothermic peak measured by DSC is preferably 80 mJ / mg or less, preferably 70 mJ or less, more preferably 50 mJ or less, for further improving the transparency of the product.

The propylene resin composition of the present invention may contain, for example, 5% by weight in addition to the above-mentioned polypropylene component and copolymer component as a resin component, as long as the effect of the propylene resin composition of the present invention is not impaired. A polymer of another α-olefin may be contained as a component in the following range. Examples of the α-olefin include 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene,
1-heptene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 3-ethyl-1-hexene, 4
-Ethyl-1-hexene, 1-octene, 1-decene,
1-dodecene, 1-tetradecene, 1-hexadecene,
Examples thereof include 1-octadecene and 1-eicosene.

The propylene resin composition used in the present invention may be obtained by any method.

For example, a method of separately polymerizing a high-temperature eluting component and a medium-low-temperature eluting component and mixing them may be used.
A state in which a random copolymer component of ethylene and butene-1 or propylene and a random copolymer component of butene-1 are arranged in one molecular chain and / or a polypropylene component and propylene and ethylene and butene-1
A so-called block that can achieve a state in which a molecular chain composed of each of a random copolymer component of propylene and a random copolymer component of propylene and butene-1 alone can not be achieved by mechanical mixing. The method of obtaining as a copolymer is preferable because a propylene-based resin composition capable of forming a film having better transparency is obtained.

The production method for obtaining the propylene resin composition of the present invention as a block copolymer is not particularly limited as long as it satisfies the requirements of the present invention.
It can be suitably manufactured by the following method.

That is, in the presence of a catalyst comprising a metallocene compound (hereinafter abbreviated as component [I]), an aluminoxane compound and / or a non-coordinating ionized compound (hereinafter abbreviated as component [II]), a polypropylene component (A) is prepared. ) And a copolymer component of propylene, ethylene and butene-1, or a copolymer component (B) of propylene and butene-1 in a stepwise manner.

As the component [I], any compound known to be used for the polymerization of olefins can be used without any limitation. Among them, the following general formula (1) Q (C ₅ H _4-m R ¹ _m ) _{(C 5 H 4-n R} 2 n) MX 1 X 2 (1) ( wherein, M represents a periodic table group IVb transition metal _{atoms. (C 5 H 4-m} R 1 m), (C ₅ H _4-n R ² _n ) represents a substituted cyclopentadienyl group, m and n are integers of 1 to 3, R ¹ and R ² may be the same or different, hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group or a hydrocarbon cyclopentadienyl bound to two carbon atoms on the ring by one or may be more substituted by a hydrocarbon group, a hydrocarbon group to form a hydrocarbon ring .Q is a _{(C 5 H 4-m R} 1 m) and _{(C 5 H 4-n R} 2 n) crosslinkable a group, Valence, hydrocarbon group, .X ¹ and X ² is an unsubstituted silylene group or hydrocarbon-substituted silylene group may be the same or different and hydrogen also be halogen or chiral represented by.) Indicating a hydrocarbon group Compounds can be suitably used.

More preferably, in the above formula (1),
M is a zirconium or hafnium atom, and R ¹ and R ² are the same or different and have 1 to 20 carbon atoms, X ¹
And a chiral metallocene compound wherein X ² is the same or different halogen atom or hydrocarbon group, and Q is a hydrocarbon-substituted silylene group.

As a specific example of the component [I], rac-
Dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl)
Zirconium dichloride, rac-dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ′,
5′-dimethylcyclopentadienyl) zirconium dimethyl, rac-dimethylsilylene (2,3,5-trimethylcyclopentadienyl) (2 ′, 4 ′, 5′trimethylcyclopentadienyl) zirconium dichloride, rac-dimethyl Silylene (2,3,5-trimethylcyclopentadienyl) (2 ′, 4′5 ′, 5′-trimethylcyclopentadienyl) zirconium dimethyl, rac-dimethylsilylenebis (2-methyl-indenyl) zirconium dichloride, rac-diphenylsilylenebis (2-methyl-indenyl) zirconium dichloride, rac-dimethylsilylenebis (2-
Methyl-indenyl) zirconium dimethyl, rac-
Diphenylsilylenebis (2-methyl-indenyl) zirconium dimethyl, rac-dimethylsilylenebis (2-methyl-4,5,6,7-tetrahydroindenyl) zirconium dichloride, rac-diphenylsilylenebis (2-methyl-4, 5,6,7-tetrahydroindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-4,5,6,7-tetrahydroindenyl) zirconium dimethyl, rac
-Diphenylsilylenebis (2-methyl-4,5,6,
7-tetrahydroindenyl) zirconium dimethyl,
rac-dimethylsilylenebis (2,4-dimethyl-indenyl) zirconium dichloride, rac-diphenylsilylenebis (2,4-dimethyl-indenyl) zirconium dichloride, rac-dimethylsilylenebis (2,4-dimethyl-indenyl) zirconium dimethyl Rac-diphenylsilylenebis (2,4-dimethyl-indenyl) zirconium dimethyl, rac-dimethylsilylenebis (2-methyl-4-isopropylindenyl) zirconium dichloride, rac-diphenylsilylenebis (2-methyl-4-isopropyl) Indenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-4-isopropylindenyl) zirconiumdimethyl, rac-diphenylsilylenebis (2-methyl -4-isopropylindenyl) zirconium dimethyl, rac-dimethylsilylenebis (2-methyl-4,6-diisopropylindenyl) zirconium dichloride, rac-diphenylsilylenebis (2-methyl-4,6-diisopropylindenyl) zirconium Dichloride, rac-dimethylsilylenebis (2-methyl-4,6-diisopropylindenyl) zirconium dimethyl, rac-diphenylsilylenebis (2-methyl-4,6-diisopropylindenyl) zirconium dimethyl, rac-dimethylsilylenebis ( 2-methyl-4-t-butylindenyl) zirconium dichloride, rac-diphenylsilylenebis (2-methyl-4-t-butylindenyl) zirconium dichloride, rac-dimethylsilyl Renbisu (2
-Methyl-4-t-butylindenyl) zirconium dimethyl, rac-diphenylsilylenebis (2-methyl-4-t-butylindenyl) zirconium dimethyl,
rac-dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, rac-
Diphenylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dimethyl, rac-diphenylsilylenebis (2-methyl-4-phenylindene) Nil) zirconium dimethyl, rac-dimethylsilylenebis (2-
Methyl-4-naphthylindenyl) zirconium dichloride, rac-diphenylsilylenebis (2-methyl-4-naphthylindenyl) zirconium dichloride, rac-dimethylsilylenebis (2-methyl-4-
Naphthylindenyl) zirconium dimethyl, rac-
Diphenylsilylenebis (2-methyl-4-naphthylindenyl) zirconium dimethyl, rac-dimethylsilylenebis (2-methyl-benzindenyl) zirconium dichloride, rac-diphenylsilylenebis (2-methyl-benzindenyl) zirconium dichloride, rac-dimethyl Silylene bis (2-methyl-
Benzindenyl) zirconium dimethyl, rac-diphenylsilylenebis (2-methyl-benzindenyl) zirconium dimethyl, and the like.

Further, a compound in which zirconium is replaced by hafnium is also preferably used.

The above metallocene compounds can be used in combination.

As the component [II], known compounds can be used without any limitation. Among them, the following compounds can be preferably used. As the aluminoxane compound, an aluminum compound represented by the general formula (2) or (3) is preferable.

[0041]

Embedded image

[0042]

Embedded image In the general formula (2) or (3), R has 1 carbon atom.
To 6, preferably 1 to 4, alkyl groups, such as a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group. Among them, particularly preferred is a methyl group, which may partially contain an alkyl group having 2 to 6 carbon atoms. m is an integer of 4 to 100, preferably 6 to
80, particularly preferably 10 to 60.

As the method for producing the aluminoxane compound, various known methods may be employed, for example, a method in which a trialkylaluminum is directly reacted with water in a hydrocarbon solvent. Examples thereof include a method of reacting adsorbed water and trialkylaluminum in a hydrocarbon solvent using copper sulfate hydrate having water of crystallization, aluminum sulfate hydrate, silica gel impregnated with water, or the like.

As the non-coordinating ionized compound, known compounds can be used without any particular limitation. In particular, an ionized compound containing a boron atom can be suitably used.

Specific examples of the ionizable compound containing a boron atom include a Lewis acid containing a boron atom and an ionic compound containing a boron atom.

Examples of the above-mentioned Lewis acid containing a boron atom include compounds represented by the general formula (4).

BR ₃ (4) In the above general formula, R is a phenyl group or a fluorine which may have a substituent such as fluorine, a methyl group and a trifluoromethyl group.

Specific examples of the compound represented by the general formula include trifluoroborane, triphenylborane, tris (4-fluorophenyl) borane, tris (3,5
-Difluorophenyl) borane, tris (4-fluoromethylphenyl) borane, tris (pentafluorophenyl) borane, tris (p-tolyl) borane, tris (o-tolyl) borane, tris (3,5-dimethylphenyl) borane And the like. Among them, tris (pentafluorophenyl) borane is preferably used.

The boron-containing ionic compound is a salt of a cationic compound and a boron-containing anionic compound, and includes a trialkyl-substituted ammonium salt, an N, N-dialkylanilinium salt, a dialkylammonium salt, and a triarylphosphonate. Phonium salts and the like can be mentioned. Examples of the trialkyl-substituted ammonium salt include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, and tri (n
-Butyl) ammonium tetra (phenyl) boron, trimethylammonium tetra (p-tolyl) boron, trimethylammonium tetra (o-tolyl) boron, tributylammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p
-Dimethylphenyl) boron, tributylammoniumtetra (m, m-dimethylphenyl) boron, tributylammoniumtetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammoniumtetra (o-tolyl) boron and the like. , N, N-dialkylanilinium salts include N, N-dimethylaniliniumtetra (phenyl) boron, N, N-diethylaniliniumtetra (phenyl) boron, N, N-2,
4,6-pentamethylanilinium tetra (phenyl)
Examples of the dialkylammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron. Examples of the triarylphosphonium salt include triphenylammonium. Examples thereof include phosphonium tetra (phenyl) boron, tri (methylphenyl) phosphonium tetra (phenyl) boron, and tri (dimethylphenyl) phosphonium tetra (phenyl) boron.

Further, triphenylcarbonium tetrakis (pentafluorophenyl) borate, N, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate and ferrocenium tetra (pentafluorophenyl) borate can also be mentioned. Among them, triphenylcarbonium tetrakis (pentafluorophenyl) borate and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate are preferably used.

The amounts of component [I] and component [II] used are arbitrary. However, when an aluminoxane compound is used as component [II], the amount of component [II] used (Al atom in component [II]) Is preferably 0.1 to 100,000 mol, more preferably 1 to 50,000 mol, and still more preferably 10 to 100 mol, per 1 mol of the transition metal in the component [I].
30,000 moles are preferred. When the non-coordinating ionized compound is used as the component [II], the amount of the component [II] used (the molar amount of the boron atom in the component [II]) is 1 mol of the transition metal in the component [I]. For 0.01 to 10,
000 mol is preferred, and more preferably 0.1 to 50,000.
00 mol, more preferably 1 to 3000 mol, is suitable.

The polypropylene component (A) and the copolymer component (B) of propylene and ethylene and / or an α-olefin of C4 to C18 (B) are added stepwise in the presence of a catalyst comprising the components [I] and [II]. In the production method, if necessary, an organoaluminum compound (hereinafter referred to as component [III]
May be used together. Component [III] is a compound represented by the general formula (5).

AlR _m X _3-m (5) (wherein, R represents a hydrocarbon group such as an alkyl group or an aryl group having 1 to 10 carbon atoms or an alkoxy group. X represents a halogen atom. , The valence of Al is an integer of 1 to 3.) Specific examples of the compound represented by the above general formula include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, and tri-n-butylaluminum. Trialkyl aluminums such as triisobutylaluminum tri-n-hexylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, diethylaluminum monochloride, diethylaluminum monobromide,
Dialkylaluminum monohalides such as diethylaluminum monofluoride, methylaluminum sesquichloride, ethylaluminum sesquichloride,
Alkyl aluminum halides such as ethylaluminum dichlorides, alkoxyaluminums such as diethylaluminum monoethoxide and ethylaluminum diethoxide are exemplified. Among them, trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum are preferably used.

The amount of the component [III] is not particularly limited, but is generally 1 to 50,000 mol, preferably 5 to 5 mol, per 1 mol of the transition metal atom in the component [I].
10,000 moles. More preferably 10 to 5,
000 mol.

The component [I] and / or the component [II] can be used by being supported on a fine particle carrier (hereinafter abbreviated as the component [IV]). When the catalyst component is supported on a carrier,
The particle properties of the obtained polymer are improved, and process suitability in resin production such as prevention of polymerization scale in a reactor can be significantly improved.

As the fine particle carrier, those having a function as a carrier can be used without any limitation, and inorganic oxides are particularly preferable.

Specifically, SiO ₂ , Al ₂ O ₃ , MgO,
ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO,
ThO ₂ or the like or a mixture thereof, for example, SiO ₂ —Al
₂ O ₃ , SiO ₂ -MgO, SiO ₂ -TiO ₂ , SiO _2-
V ₂ O ₅ , SiO ₂ —Cr ₂ O ₃ , SiO ₂ —TiO ₂ —Mg
O or the like can be suitably used. Among these, a carrier containing at least one component selected from the group consisting of SiO ₂ and Al ₂ O ₃ as a main component is more preferable.

The inorganic fine particle carrier is usually 150 to 1000
C., preferably at 200 to 800.degree.

Although the properties of the carrier vary depending on the kind and the production method, the carrier preferably used in the present invention has a specific surface area of 50 to 1000 m ³ / g, preferably 100 to 700 m ³ / g.
m ³ / g.

The particle size of these carriers is generally from 0.1 to 50.
0 μm, preferably 1 to 200 μm, more preferably 10 to 100 μm. If the particle size is small, the resulting particles become a finely powdered polymer, and if the particle size is too large, the particles become coarse and handling of the powder becomes difficult.

The pore volume of these carriers is usually 0.1 to 5 c
m ³ / g, preferably 0.3 to ³ cm ³ / g. The pore volume can be measured by a BET method, a mercury intrusion method, or the like.

The amount of the component [I] to be used per 1 g of the component [IV] is 0.005 to 1 mmol, preferably 0.05 to 0.5 mmol of transition metal atoms. When an aluminoxane compound is used as the component [II], the amount of the aluminoxane compound used relative to the component [I] is converted to the molar amount of Al atoms, and is calculated as 1 mole of the transition metal atom in the component [I]. 1 to 200 moles,
Preferably it is 15 to 150 mol.

When a non-coordinating ionized compound is used, the amount of the non-coordinating ionized compound used with respect to the component [I] is converted into the molar amount of boron atoms in the non-coordinating ionized compound. It is 0.1 to 20 mol, preferably 1 to 15 mol, per 1 mol of the transition metal atom in [I].

In order to obtain the obtained polymer with more excellent particle properties, the following method can be adopted.

That is, the component [I], the component [II], and the component [I
V] and optionally component [III] in the presence of
First, olefin prepolymerization is performed. The amount of the component [III] to be used in the prepolymerization is not particularly limited, but generally, is based on 1 mol of the transition metal atom in the component [I].
1 to 50,000 mol, preferably 5 to 10,000.
00 mole. More preferably, it is 10 to 5,000 mol. Each of the above components used in the prepolymerization may be added one by one sequentially, or a mixture thereof may be added all at once. Preferably, the components [I] and [II] are added to the catalyst component [IV].
Is brought into contact in advance. More preferably, a method of supporting the component [II] on the catalyst component [IV] and then supporting the component [I] is effective for obtaining a block copolymer with a higher bulk specific gravity.

The olefin used in the prepolymerization is ethylene; propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 4,4-dimethyl- 1-pentene,
1-heptene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 3-ethyl-1-hexene, 4
-Ethyl-1-hexene, 1-octene, 1-decene,
1-dodecene, 1-tetradecene, 1-hexadecene,
Α-olefins such as 1-octadecene and 1-eicosene; cyclopentene, cycloheptene, norbornene,
5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,2
Cyclic olefins such as 3,4,4a, 5,8,8a-octahydronaphthalene; Further, styrene, dimethylstyrenes, allylnorbornane, allylbenzene, allylnaphthalene, allyltoluenes, vinylcyclopentane, vinylcyclohexane, vinylcyclopeptane, diene and the like can also be used. Preferably,
Ethylene, propylene, 1-butene, 1-pentene, 3
-Methyl-1-butene, 1-hexene, 4-methyl-1
-Pentene, 4,4-dimethyl-1-pentene, 1-heptene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 3-ethyl-1-hexene, 4-ethyl-1-hexene , 1-octene, 1-decene, cyclopentene and vinylcyclohexane, particularly preferably ethylene, propylene, 1-butene, 1-heptene, 3-methyl-1-butene, 1-hexene and 4-methyl-1-. Penten. Prepolymerization is 95 olefins
It is preferable to conduct substantially homopolymerization of at least mol%. The polymerization amount of the olefin firstly applied in the prepolymerization of the present invention is 0.1 to 1000 g, preferably 1 to 1000 g per 1 g of the catalyst formed from the catalyst components [I], [II] and [IV].
What is necessary is just to select from the range of 50 g. Further, as a particularly preferred embodiment of the prepolymerization, in the above prepolymerization,
First, propylene is prepolymerized in the presence of each of the components [I], [II], [IV] and, if necessary, [III] to obtain a first prepolymerization catalyst, and then the first prepolymerization catalyst And a method in which the prepolymerization of 1-butene is further carried out stepwise in the presence of the above component [III]. The amount of the component [III] used in the prepolymerization is not particularly limited, but is generally 1 to 50,000 mol, preferably 5 to 1 mol, per 1 mol of the transition metal atom in the component [I].
0.000 mole. More preferably, 10 to 5,0
00 mole. After the first pre-polymerization catalyst is obtained by the above-mentioned pre-polymerization of propylene, it is usually desirable to remove the unreacted propylene and the component [III] used as necessary by washing, and to provide them for the subsequent pre-polymerization. 95% by mole of propylene and 1-butene in each prepolymerization stage
As described above, it is preferable to carry out substantially homopolymerization of 98 mol% or more. The polymerization amount of propylene which is firstly applied in the preliminary polymerization depends on the catalyst components [I], [II] and [I
V], from 0.1 to 1000 g / g of catalyst formed from
Preferably, the amount may be selected from the range of 1 to 10 g.
0.1 to 10 per 1 g of the catalyst formed from [I] and [III]
00 g, preferably in the range of 1 to 500 g. The ratio of the propylene polymerization amount to the 1-butene polymerization amount is 0.00% by weight of the propylene polymerization amount / 1-butene polymerization amount.
It is suitably in the range of 1 to 100, preferably 0.005 to 10.

In the prepolymerization, slurry polymerization is usually preferably applied. As a solvent, a saturated aliphatic hydrocarbon or an aromatic hydrocarbon such as hexane, heptane, cyclohexane, benzene or toluene is used alone, or a mixed solvent thereof is used. Can be used. Each prepolymerization temperature is -2
The temperature is preferably from 0 to 100 ° C, especially from 0 to 60 ° C, and each stage of the prepolymerization may be carried out under different temperature conditions. The pre-polymerization time may be appropriately determined according to the pre-polymerization temperature and the amount of polymerization in the pre-polymerization, and the pressure in the pre-polymerization is not limited, but in the case of slurry polymerization, generally, the pressure is from atmospheric pressure to 5 kg / cm. ^{About 2} .

Each of the prepolymerizations may be carried out in any of batch, semi-batch, and continuous methods.

After completion of each prepolymerization, it is preferable to wash a saturated aliphatic hydrocarbon or an aromatic hydrocarbon such as hexane, heptane, cyclohexane, benzene, and toluene alone or with a mixed solvent thereof. Usually, 5 to 6 times are preferable.

In the method of obtaining the propylene resin composition of the present invention as a block copolymer of propylene, propylene-ethylene and butene-1 or propylene and butene-1 by polymerization, the propylene resin composition may be used in the presence of the above-mentioned catalyst component. Component and propylene and ethylene and butene-1 copolymer component or propylene and butene-
The polymerization of one copolymer component is performed stepwise. The polymerization order is not particularly limited, but the polypropylene component is used in the first stage and propylene and ethylene and butene-1 are used in the second stage.
It is preferred to produce a copolymer component having good particle properties or a copolymer component of propylene or butene-1.

The polymerization conditions are not particularly limited as long as the effects of the present invention are recognized, but the following conditions are generally preferred.

The polymerization of the polypropylene component may be carried out by supplying propylene alone or a mixture of propylene and another α-olefin and / or ethylene within a range satisfying the requirements of the present invention. The polymerization temperature in the polymerization of the polypropylene component is preferably from 0 to 100 ° C, preferably from 20 to 80 ° C.

In the above polymerization, hydrogen can be used as a molecular weight regulator. Further, any method such as slurry polymerization, gas phase polymerization, and solution polymerization using the monomer itself used as the solvent for the polymerization may be used. Considering the simplicity of the process, the reaction rate, and the particle properties of the produced copolymer, slurry polymerization using propylene itself as a solvent is a preferred mode.

The polymerization system may be any of a batch system, a semi-batch system and a continuous system. Further, the polymerization can be carried out in two or more stages having different conditions such as hydrogen concentration and polymerization temperature.

Subsequent to the polymerization for obtaining the polypropylene component, random copolymerization of propylene with ethylene and butene-1 or propylene with butene-1 is carried out. The random copolymerization of propylene with ethylene and butene-1 or propylene and butene-1 is carried out by a slurry polymerization using propylene itself as a solvent.
Alternatively, by supplying only liquefied butene-1, or in the case of gas phase polymerization, propylene and ethylene and butene-
1 or a mixed gas of propylene and butene-1.

In the random copolymerization of propylene and ethylene and butene-1 or propylene and butene-1 according to the present invention, it is preferable to carry out one-stage random copolymerization following the propylene polymerization. Can be changed in multiple stages. The polymerization temperature of the random copolymerization of propylene with ethylene and butene-1 or propylene and butene-1 is 0 to 1
It is preferable to adopt from the range of 00 ° C, preferably from 20 to 80 ° C. If necessary, hydrogen can be used as a molecular weight regulator, and the polymerization can be carried out by changing the hydrogen concentration at that time in multiple steps or continuously.

The random copolymerization of propylene with ethylene and butene-1 or propylene with butene-1 may be any of batch, semi-batch and continuous methods, and the polymerization may be carried out in multiple stages. Further, the polymerization in this step may employ any method of slurry polymerization, gas phase polymerization, and solution polymerization.

After the completion of the main polymerization, the propylene resin of the present invention can be obtained by evaporating the monomers from the polymerization system. This propylene-based resin can be subjected to known washing or countercurrent washing with a hydrocarbon having 7 or less carbon atoms.

The propylene resin composition of the present invention contains an antistatic agent, an antifogging agent, an antiblocking agent, an antioxidant, a heat stabilizer, a chlorine scavenger, a weathering agent, a lubricant, a neutralizing agent, and a coloring agent. Known additives such as a nucleating agent, an inorganic or organic filler, and the like may be added. In this case, these additives may be mixed with the resin composition and then pelletized by an extruder for use. Further, in addition to the above additives, an organic peroxide may be added to perform thermal decomposition, and the molecular weight may be adjusted within a range that satisfies the requirements of the present invention.

The propylene-based resin composition of the present invention is excellent in flexibility and transparency, has sufficient mechanical strength, is hardly wrinkled, and has a remarkable effect of remarkably reducing stickiness that has not been achieved in the past. Therefore, it is suitable as a film, especially as a soft film. The use of the film is not particularly limited, and it is used for packaging of food, clothing, stationery, miscellaneous goods, etc., but among those uses, it has sufficient mechanical strength, is hardly wrinkled, and is transparent after time. Since there is no change in sex, it can be suitably used for clothing and textile applications.

As a method for forming the propylene-based resin composition into a film, a known film forming method can be employed without any particular limitation. The molding temperature at that time is usually 200 to 300 ° C., preferably 2 to 30, taking into account the occurrence of melt fracture, the moldability of the film, and the thermal degradation of the resin.
The temperature is preferably from 20 to 270 ° C. As a method of forming the film, any forming method such as a non-stretched film, a uniaxially stretched film, a biaxially stretched film, a calender molding and an inflation molding by a T die can be used.

In the present invention, the term “film” does not have a strict meaning with respect to the thickness, but is a generic term including a sheet, and is generally 10 to 1000 μm.
The degree is preferably used.

The flexible film made of the propylene-based resin composition obtained by the present invention has high transparency and good heat sealability. Therefore, the film is made of another thermoplastic film such as a polypropylene film or a polyethylene film. , Polyethylene terephthalate film, polyamide film, polyvinyl chloride film,
By laminating on a surface layer such as an ethylene-vinyl acetate copolymer film, heat sealability can be improved without impairing the physical properties of the thermoplastic resin film.

In particular, the propylene homopolymer and propylene are compatible with a polypropylene resin film obtained by copolymerizing ethylene and / or an α-olefin other than propylene, for example, ethylene or 1-butene in an amount of 5 mol% or less. By laminating the above films, a film having excellent transparency and easy heat sealing properties is provided.

A low-density polyethylene, a linear low-density polyethylene, a copolymer of propylene and another α-olefin, and laminated on a film of a relatively low crystalline resin or a soft resin such as ethylene-vinyl acetate. By doing
The heat sealing property of the soft resin film can be improved.

When the soft film made of the propylene resin composition of the present invention is used for the surface layer, the layer structure of the laminated film is not particularly limited as long as the soft film made of the propylene resin composition of the present invention is the surface layer. The soft film layer (A) made of the propylene-based resin composition of the present invention and the thermoplastic resin film layer (B) are not limited to a two-layer structure, but may be a layer (A), a layer (B), or a layer (A). It may have a three-layer structure as described above, and may be appropriately configured in consideration of physical properties such as rigidity and flexibility of the film. Further, another layer (C) may be laminated.

The raw material of the other layer (C) is not particularly limited, and various resins can be adopted according to the purpose.

The above laminated film has an overall thickness of 1
It is preferably from 0 to 100 μm, particularly preferably from 20 to 60 μm.
More preferably, it is in the range of μm.

The thickness of each layer laminated is the same as that of layer (A)
Has a thickness of preferably 0.5 to 30 μm, more preferably 1 to 10 μm.

The layer (B) has a thickness of 5 to 70 μm.
m, more preferably 10 to 50 μm.

The thickness of the other layer (C) is not particularly limited, but is preferably 2 to 30 μm.

The raw materials of each layer of the laminated film may contain, if necessary, additives such as an antioxidant, a lubricant, an antiblocking agent, an antistatic agent and an antifogging agent within a range that does not impair the effects of the present invention. It can also be added.

The laminated film may simply be an extruded unstretched film or a uniaxially or biaxially stretched stretched film.

The method for producing the laminated film is not particularly limited, but may be a co-extrusion T-die method, a co-extrusion inflation method,
An extrusion lamination method, a dry lamination method and a sand lamination method are used, and among them, an extrusion lamination method and a co-extrusion T-die method are particularly preferably used.

In the case of manufacturing by the above-mentioned extrusion T-die method, for example, a crystalline polyolefin film is used for the layer (B), a soft film made of the propylene resin composition of the present invention is used for the layer (A), and if necessary, When a crystalline polyolefin film is used for the layer (C), melt extrusion is performed using a plurality of extruders, before or after the die, or inside the die, so that the layer (A) / the layer (B) / the layer (C). It can be manufactured by a co-extrusion laminating method of laminating.

The conditions for forming the laminated film are not particularly limited. Generally, the resin temperature is 190 to 300 ° C., the air gap is 60 to 200 mm, and the cooling roll temperature is 10 to 7 mm.
It is preferable to carry out at 0 ° C. at a film forming speed of 50 to 500 m / min.

The laminated film may be used as it is, but is preferably subjected to a corona discharge treatment in order to improve the adhesion to the printing ink.

The conditions of the corona discharge treatment are not particularly limited, but the adhesiveness of the obtained laminated film to printing ink,
Alternatively, from the viewpoint of preventing the generation of offensive odor due to the damage of the corona discharge treatment, the wetting tension of the film surface is 31 to 43.
Dynes / cm, preferably 33 to 38 dynes / c
m.

The use of the laminated film in which the propylene-based resin composition layer of the present invention is laminated is not particularly limited, and the laminated film is used for packaging foods, clothing, stationery, miscellaneous goods, and the like. Since no deterioration in transparency occurs, it can be suitably used especially for food applications.

The propylene-based resin composition of the present invention can be mixed with a known polypropylene-based resin as a heat-sealing property improving agent to obtain a film having good heat-sealing property. The polypropylene resin used is a propylene homopolymer, and the propylene unit is 5
Propylene containing 0 mol or more, other α-olefin and / or a random or block copolymer of ethylene and a mixture thereof or a polypropylene resin thereof and other thermoplastic resin mixed,
Olefin random copolymer, for example, propylene-ethylene copolymer, propylene-ethylene-butene-
Particularly excellent improvement effects are exhibited for copolymers having a low melting point, such as copolymer 1 and propylene-α-olefin copolymer.

The mixing ratio of the polypropylene resin 10
It is usually in the range of 1 to 100 parts by weight, preferably 2 to 60 parts by weight based on 0 parts by weight.

The method of mixing the heat-sealing property improver comprising the propylene-based resin composition of the present invention with a known polypropylene-based resin is not limited at all. For example, a powder blending method using a tumbler or a Henschel mixer or a pellet blending method Can be mentioned. The resulting mixture of the heat-resistant polypropylene-based resin composition, if necessary, an antioxidant, a hydrochloric acid absorber, an anti-agglomeration agent, a heat stabilizer, an ultraviolet absorber, a lubricant,
Various additives such as a weather resistance stabilizer, an antistatic agent, a nucleating agent, a pigment and a filler can also be blended. The mixing ratio is appropriate, and the method of preparation can be used without any limitation to conventionally known methods.

As a method of forming the mixture of the propylene-based resin composition into a product film, a known film forming method can be employed without any particular limitation. The molding temperature at that time is usually 200 to 30 in consideration of the occurrence of melt fracture, the moldability of the film, the thermal deterioration of the resin, and the like.
The temperature is preferably 0 ° C, preferably 220 to 270 ° C. As a method of forming the film, any forming method such as a non-stretched film, a uniaxially stretched film, a biaxially stretched film, a calender molding and an inflation molding by a T die can be used. Further, the mixture of the above-mentioned polypropylene-based resin composition may be used as a single-layer film, or may be used as a heat seal layer of a multilayer film. Further, the film surface may be subjected to a corona treatment.

The propylene-based resin composition obtained according to the present invention is also suitable as a stretchability improving agent when the propylene-based polymer is formed into a biaxially stretched film by being blended with the propylene-based polymer. Can be used for

Specific examples of the propylene-based polymer include polypropylene, propylene and α-olefins having 3 to 20 carbon atoms such as ethylene, 1-butene, 1-hexene and 4-methyl-1-pentene. Can be exemplified.

The mixing ratio of the polypropylene resin 10
It is usually in the range of 1 to 20 parts by weight, preferably 2 to 10 parts by weight based on 0 parts by weight.

The resulting mixture of the propylene polymer composition and the propylene polymer of the present invention may contain, if necessary, an antioxidant, a hydrochloric acid absorber, a coagulation inhibitor, a heat stabilizer, an ultraviolet absorber, a lubricant, Various additives such as a weather resistance stabilizer, an antistatic agent, a nucleating agent, a pigment and a filler can also be blended. The mixing ratio is appropriate, and the method of preparation can be used without any limitation to conventionally known methods.

As a method of forming the mixture of the propylene resin composition into a product film, a known film forming method can be employed without any particular limitation.

Further, the propylene-based resin composition obtained by the present invention is excellent in flexibility, transparency, tensile elongation, heat resistance and has no sticky feeling. Can be suitably used in the field of For example, in the field of injection molding, there are bumpers, mat guards, lamp packings for automobile parts, and in the field of home appliances, various packings, ski shoes, grips, and roller skates. On the other hand, in the field of extrusion molding, there are various types of automotive interior materials, home appliances and electric wire materials, various insulating sheets, covering materials for cords, and waterproof sheets, waterproof materials, joint materials, stretch films for packaging, etc. in the field of civil engineering and construction materials. it can.

The molding method is not particularly limited, and can be suitably used for various applications by any molding method such as extrusion molding, injection molding, press molding, and vacuum molding.

When forming, various stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, anti-agglomeration agents, lubricants, plasticizers,
Pigments, inorganic or organic fillers can also be included. Examples of these additives include 2,6-di-t-butyl-p-cresol, tetrakis [methylene-3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate] methane, 4,4'-butylidenebis (6-t-butyl-m-cresol), tocophenols, ascorbic acid, dilaurylthiodipropionate, phosphoric acid stabilizer, fatty acid monoglyceride, N, N
-(Bis-2-hydroxyethyl) alkylamine, 2
-(2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, calcium stearate, magnesium oxide, magnesium hydroxide, alumina, aluminum hydroxide, silica, hydrotalcite, talc , Clay, gypsum, glass fiber, titania, calcium carbonate, carbon black, petroleum resin,
Mention may be made of polybutene, wax, synthetic or natural rubber.

[0112]

As will be understood from the above description, TR
A polypropylene-based resin composition whose crystallinity distribution and composition as measured by the EF method have a specific mode is excellent in transparency and flexibility, has sufficient mechanical strength, hardly generates wrinkles, and has a sticky feeling. Therefore, it can be suitably used as a transparent soft film.

Further, it is suitably used in various fields in which conventional thermoplastic elastomers are used.

[0114]

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

The methods for measuring various physical properties of the polymers obtained in the following Examples and Comparative Examples are as follows.

(1) Melt flow rate (abbreviated as MFR) It conformed to ASTM D1238.

(2) Bulk density According to ASTM D1895.

(3) Melting point Using DSC-6200R manufactured by Seiko Electronics Co., Ltd., about 5 mg of a sample was packed in an aluminum pan, heated to 200 ° C. at 10 ° C./min, held at 200 ° C. for 5 minutes, and then 20 ° C./min. The temperature was lowered to room temperature by heating at a temperature of 10 ° C./min.

(4) Ethylene and butene-1 content The ¹³ C-NMR spectrum was measured using JEOL GSX-270.

(5) Molecular weight distribution Using a 150C type gel permeation chromatography (GPC) manufactured by Waters, column GMH6HT
(Manufactured by Tosoh Corporation). The molecular weight distribution (Mw / Mn) was determined from the ratio between the obtained weight average molecular weight (Mw) and number average molecular weight (Mn).

(6) TREF (Temperature Rise Elution Fractionation) Elution Curve An automatic TREF device (SSC-73) manufactured by Senshu Kagaku
00, ATREF) under the following conditions.

Solvent: orthodichlorobenzene Flow rate: 150 ml / hour Heating rate: 4 ° C./hour Detector: infrared detector Measurement wave number: 3.41 μm Column: “Packed column 30” manufactured by Senshu Kagaku
Φ ”, 30 mmΦ × 300 mm Concentration: 1 g / 120 ml Injection volume: 100 ml In this case, the sample solution is introduced into the column at 145 ° C., and then gradually cooled to −10 ° C. at a rate of 2 ° C./hour to fill the sample polymer. After adsorbing on the surface of the agent, the concentration of the polymer eluted at each temperature by raising the column temperature under the above conditions at the same time as starting to flow the solvent is measured with an infrared detector. A curve was obtained.

(7) Transparency (haze value) Based on JIS K6714.

(8) Flexural modulus According to ASTM D-790.

(9) Vicat softening temperature Measured under a load of 250 g according to JIS K7206.

(10) 1% Modulus Measured according to JIS K7127.

(11) Stress at 10% strain JIS No. 4 test piece (dumbbell type, measuring part width 10 mm)
The distance between chucks is 20 mm and the pulling speed is 20 mm /
The stress at the time of tensile strain of 10% per minute was measured.

(12) Blocking property Two films (12 × 12 cm) were superposed and
After applying a load of kg for 24 hours at a temperature of 40 ° C., 4 ×
A sample was cut out to 4 cm, and a tensile tester (speed: 1
(00 mm / min).

(13) Evaluation of Surface Adhesion By injection molding, 50 mm long × 40 mm wide × 10 m thick
m flat plate, and superimpose two flat plates, 3kg
After leaving for 3 days at 40 ° C. under a load of f, the two superposed flat plates are pulled in a direction perpendicular to the adhesive surface at a test speed of 300 mm / min, and the maximum stress when peeled off It was evaluated (see FIG. 1).

(14) Texture The texture and the difficulty of wrinkling of the film were evaluated as texture based on the following criteria.

A: The touch was soft and wrinkles were hardly generated.

；: The touch was soft, but wrinkles were easily generated.

Δ: The touch was slightly hard.

X: The touch was hard and wrinkles were easily generated.

[0135] Example 1 [Preparation of supported metallocene catalyst] silica gel support methylaluminoxane (MAO on SiO _2, Uittoko Co., 25 wt% -Al product) in 10 g rac- dimethylsilylene-bis-1- (2-methylindenyl) 100 ml of a toluene solution of zirconium dichloride (0.005 m
(mol / ml toluene solution) and stirred at room temperature for 30 minutes. Next, the reaction mixture was filtered, and the obtained solid was washed twice with 50 ml of toluene and dried under reduced pressure to obtain a metallocene catalyst supported on silica gel. 0.045 mmol of metallocene was supported per 1 g of the catalyst.

[Polymerization] (Preliminary stage, polymerization of propylene) 400 kg of propylene was inserted into a polymerization tank having an internal volume of 2 m ³ , and 612 mmol of triisobutylaluminum was introduced. Thereafter, the internal temperature of the polymerization tank was raised to 55 ° C. Next, 15 g of the metallocene catalyst supported on the silica gel was charged. Subsequently, the internal temperature of the autoclave was raised to 60 ° C., and polymerization was performed for 30 minutes.

(Second stage, propylene, ethylene and butene
1) After the polymerization in the first stage, 4.7 mol% of ethylene gas in gas phase concentration and 12.0 mol% of liquefied butene-1 in gas phase concentration are supplied, and furthermore, the gas phase concentration of ethylene is increased. The copolymerization was carried out for 110 minutes while supplying so as to keep the temperature constant. After completion of the polymerization, unreacted propylene was purged and dried at 50 ° C. for 1 hour to obtain 100 kg of a white granular polymer.

Analysis of the eluted component at 80 ° C. or higher and the eluted component at a temperature lower than 80 ° C. by TREF of the obtained polymer revealed that the melting point of the component at 80 ° C. or higher was 146 ° C.

Further, the eluted components at a temperature lower than 80 ° C. had an ethylene content of 2.5 wt% and a butene-1 content of 25.3 wt%.

Table 1 shows the MFR, molecular weight distribution, bulk density, amount of TREF eluting component, amount of high temperature eluting component and melting point, component amount of medium and low temperature eluting component, and ethylene and butene-1 content of the obtained polymer.

FIG. 2 shows an elution curve of the obtained polymer by the TREF method.

[Evaluation of physical properties] 100 parts by weight of the obtained polymer was mixed with 2,6-di-t-butyl-p- as an antioxidant.
After adding 0.1 part by weight of cresol and 0.05 part by weight of calcium stearate as a chlorine scavenger and mixing with a Henschel mixer for 5 minutes, the screw diameter was 65 mmΦ.
The pellets were extruded at 230 ° C. using an extrusion granulator (1), and the pellets were granulated to obtain raw material pellets, which were subjected to physical property measurement. The haze value is a value of a 3 mm-thickness test piece for transparency evaluation obtained by injection molding. Table 2 shows the results.

Example 2 The polymerization time in the former stage of Example 1 was 10 minutes, the gas phase ethylene concentration in the latter stage polymerization was 4.6 mol%, and gas phase butene-1 was used.
The procedure was performed in the same manner as in Example 1 except that the concentration was 12.5 mol% and the polymerization time was 130 minutes. The results are shown in Tables 1 and 2.

Example 3 The polymerization time in the former stage of Example 1 was 40 minutes, the gas phase ethylene concentration in the latter stage polymerization was 4.7 mol%, and gas phase butene-1 was used.
Example 1 was repeated except that the concentration was 13.1 mol% and the polymerization time was 100 minutes. The results are shown in Tables 1 and 2.

Example 4 The polymerization time in the former stage of Example 1 was 50 minutes, the gas phase ethylene concentration in the latter stage polymerization was 4.8 mol%, and gas phase butene-1 was used.
Example 1 was repeated except that the concentration was 13.2 mol% and the polymerization time was 90 minutes. The results are shown in Tables 1 and 2.

Example 5 The same procedure as in Example 1 was conducted except that the polymerization time in the former stage of Example 1 was changed to 15 minutes, the concentration of gas-phase butene-1 in the latter stage polymerization was changed to 12.6 mol%, and the polymerization time was changed to 125 minutes. Was. The results are shown in Tables 1 and 2.

Example 6 The polymerization time in the former stage of Example 1 was 35 minutes, the gas phase ethylene concentration in the latter stage polymerization was 7.7 mol%, and gas phase butene-1 was used.
The procedure was performed in the same manner as in Example 1 except that the concentration was 12.0 mol% and the polymerization time was 105 minutes. The results are shown in Tables 1 and 2.

Example 7 The polymerization time in the former stage of Example 1 was 45 minutes, the gas phase ethylene concentration in the latter stage polymerization was 12.1 mol%,
Example 1 was repeated except that the concentration was 18.8 mol% and the polymerization time was 95 minutes. The results are shown in Tables 1 and 2.

Example 8 The polymerization time in the former stage of Example 1 was 60 minutes, the gas phase ethylene concentration in the latter stage polymerization was 13.2, the gas phase butene-1 concentration was 7.6 mol%, and the polymerization time was 80 minutes. Other than that, it carried out similarly to Example 1. The results are shown in Tables 1 and 2.

Example 9 [Preparation of supported catalyst metallocene catalyst] The same procedure as in Example 1 was carried out.

[Preliminary polymerization] 200 ml of purified heptane, 50 mmol of triisobutylaluminum and 5 mmol of a supported metallocene catalyst component were charged in a 1 L autoclave subjected to N ₂ substitution in terms of Zr atom, and propylene was added to 1 g of the supported metallocene catalyst component. On the other hand, it was introduced into the reactor continuously for 1 hour so that the amount became 5 g, and prepolymerization was performed. The temperature during this period was kept at 15 ° C.

After 1 hour, the introduction of propylene was stopped, and the inside of the reactor was sufficiently purged with N ₂ . The solid component of the resulting slurry was washed six times with formed heptane.

[Polymerization] Using the above prepolymerized catalyst, the polymerization was carried out in the same manner as in [Polymerization] of Example 1. Table 1 shows the results.

[Evaluation of Physical Properties] The evaluation was performed in the same manner as in Example 1. Table 2 shows the results.

Example 10 [Preparation of supported metallocene catalyst] The procedure of Example 1 was repeated.

[Preliminary Polymerization] 200 ml of purified heptane, 50 mmol of triisobutylaluminum, and 5 mmol of a supported metallocene catalyst component were charged in a 1 L autoclave subjected to N ₂ substitution in terms of Zr atom, and then propylene was added to 1 g of the supported metallocene catalyst component. On the other hand, it was introduced into the reactor continuously for 1 hour so that the amount became 5 g, and prepolymerization was performed.

The temperature during this period was kept at 15 ° C.
One hour later, the introduction of propylene was stopped, and the inside of the reactor was sufficiently replaced with N ₂ . The solid component (first prepolymerization catalyst) of the obtained slurry was washed six times with purified heptane.

Further, this first prepolymerized catalyst was charged into a 1 L autoclave having N ₂ substitution, and purified heptane 2
After adding 00 ml and 50 mmol of triisobutylaluminum, 1-butene was continuously introduced into the reactor for 1 hour so as to be 20 g per 1 g of the supported metallocene catalyst component, and prepolymerized. The temperature during this period was 15 ° C.
Held.

The solid portion of the obtained slurry was washed six times with purified heptane to obtain a prepolymerized catalyst comprising a metallocene-containing polyolefin.

[Polymerization] The polymerization was carried out in the same manner as in [Polymerization] of Example 1 using the above prepolymerized catalyst.

Table 1 shows the results.

[Evaluation of Physical Properties] The evaluation was performed in the same manner as in Example 1. Table 2 shows the results.

Example 11 [Polymerization] (Preliminary stage, polymerization of propylene) 250 g of propylene was charged into an autoclave having an internal volume of 2 L, and a toluene solution of methylaluminoxane (PMAO-S, manufactured by Tosoh Akzo Co., Ltd.)
3.1 mmol-Al / ml). Thereafter, the internal temperature of the autoclave was raised to 55 ° C. Then, 0.5 ml of a toluene solution (PMAO-S, manufactured by Tosoh Akzo, 3.1 mmol-Al / ml) of methylaluminoxane preactivated for 15 minutes at room temperature and rac
-Dimethylsilylenebis-1- (2-methylbenzindenyl) zirconium dichloride 0.3 mg of the whole mixed solution was charged. Subsequently, the internal temperature of the autoclave was raised to 60 ° C.
And the polymerization was carried out for 30 minutes.

(Second stage, propylene, ethylene and butene
(1) Copolymerization) After performing the polymerization at the first stage, ethylene gas was supplied at a gas phase concentration of 4.8 mol%, and liquefied butene-1 was supplied at a gas phase concentration of 11.9 mol. The copolymerization was carried out for 110 minutes while feeding so as to keep it constant. After the completion of the polymerization, unreacted propylene was purged and dried at 50 ° C. for 1 hour to obtain 100 g of a white bulk polymer. Table 1 shows the results.

[Evaluation of Physical Properties] The evaluation was performed in the same manner as in Example 1. Table 2 shows the results.

Example 12 [Polymerization] The procedure of Example 11 was repeated except that the metallocene used in Example 11 was 0.03 mg of dimethylsilylenebis (2-methyl-4-naphthyl-indenyl) zirconium dichloride. White massive polymer 10
5 g were obtained. The results are shown in Tables 1 and 2.

Example 13 [Production of Random Copolymer] 250 g of propylene was inserted into a polymerization tank having an inner volume of 2 L, and 1.2 mmol of triisobutylaluminum was introduced. Thereafter, the internal temperature of the polymerization tank was reduced to 5
The temperature was raised to 5 ° C, and ethylene gas was 5.0 mol in gas phase concentration.
%, Liquefied butene-1 in gas-phase butene concentration of 12.2 mol
%. Next, 20 mg of the metallocene catalyst supported on the silica gel was charged. Subsequently, the internal temperature of the autoclave was raised to 60 ° C., and polymerization was carried out for 120 minutes while supplying ethylene so as to keep the gas phase concentration constant. After the polymerization is completed, unreacted propylene is purged, and 50
Drying at 1 ° C. for 1 hour gives a white bulk polymer 15
0 g was obtained. The bulk density could not be measured because of the bulk.

[Blend with Crystalline Polypropylene] Crystalline polypropylene (propylene homopolymer, MFR
= 2.0 g / 10 min, Mw / Mn = 6.2, melting point = 16
(3 ° C.) 20 parts by weight and 80 parts by weight of the above random copolymer (freeze-ground bulk polymer) were blended. Table 1 shows the results of the obtained blend.

[Evaluation of Physical Properties] The evaluation was performed in the same manner as in Example 1. Table 2 shows the results.

Comparative Example 1 [Preparation of catalyst] The catalyst was prepared according to the method described in JP-A-58-83006.
The method was carried out according to the method of Example 1 of Japanese Patent Application Laid-Open Publication No. Hei 9 (1994) -189, No. That is, 0.95 g (10 mmol) of anhydrous magnesium chloride, decane 1
0 ml and 4.7 ml of 2-ethylhexyl alcohol
(30 mmol) was heated and stirred at 25 ° C. for 2 hours.

To this solution was added 0.55 g of phthalic anhydride.
(6.75 mmol) was added, and the mixture was further stirred and mixed at 125 ° C. for 1 hour to obtain a homogeneous solution. After cooling to room temperature, 40 ml of titanium tetrachloride (0.
36 mmol) over 1 hour.

Thereafter, the temperature of the mixed solution was raised to 110 ° C. over 2 hours. When the temperature reached 110 ° C., 0.54 ml of diisobutyl phthalate was added, and the mixture was kept under stirring at 110 ° C. for 2 hours. . After completion of the reaction for 2 hours, the mixture was filtered to collect a solid portion, and the solid portion was resuspended in 200 ml of TiCl ₄ , and then heated again at 110 ° C. for 2 hours.

After the completion of the reaction, a heating reaction was performed again at 110 ° C. for 2 hours. After completion of the reaction, a solid portion was collected again by hot filtration, and sufficiently washed with decane and hexane until no free titanium compound was detected in the washing solution. The composition of the solid Ti catalyst was 2.1% by weight of titanium, 57% by weight of chlorine, 18.0% of magnesium, and 2 parts of diisobutyl phthalate.
It was 1.9% by weight.

[Preliminary polymerization] 1 L inner volume with N ₂ substitution
200 ml of purified n-hexane, 50 mmol of triethylaluminum, 10 mmol of diphenyldimethoxysilane, 50 mmol of ethyl iodide, and 5 mmol of solid Ti catalyst component in terms of Ti atom were charged into the autoclave, and then 3 g of propylene was added to 1 g of the solid catalyst component. For 30 minutes continuously into the autoclave as described above. The temperature during this period was kept at 15 ° C.

After 30 minutes, the reaction was stopped, and the inside of the autoclave was sufficiently replaced with N ₂ . The solid part of the obtained slurry was washed four times with purified n-hexane to obtain a titanium-containing polypropylene. As a result of the analysis, 2.1 g of propylene was polymerized per 1 g of the solid Ti catalyst component.

[Polymerization] (Preliminary stage, polymerization of propylene) 200 kg of propylene was charged into a polymerization tank having an internal volume of 2 m ³ , 612 mmol of triethylaluminum, 306 mmol of cyclohexylmethyldimethoxysilane and 306 mmol of hydrogen gas were introduced. The internal temperature of the polymerization tank was raised to 55 ° C. Next, 16.4 mm of titanium-containing polypropylene was used as Ti atoms.
and the polymerization was started. Subsequently, the internal temperature of the autoclave was raised to 60 ° C., and polymerization was performed for 15 minutes.

(Second stage, propylene, ethylene and butene
1) After the polymerization in the first stage was performed, 2.5 mol% of ethylene gas was vapor phase concentration, and liquefied butene-1 was vapor phase concentration.
Was supplied to a concentration of 33.2 mol%, and copolymerization was carried out for 125 minutes while further supplying ethylene so as to keep the gas phase concentration constant.

After completion of the polymerization, unreacted propylene was purged and dried at 50 ° C. for 1 hour to obtain 104 kg of a white granular polymer. Table 1 shows the results.

[Evaluation of Physical Properties] The evaluation was performed in the same manner as in Example 1. Table 2 shows the results.

Comparative Example 2 In Example 1, the polymerization amount was changed to 300
kg, the first-stage polymerization for 12 minutes and the second-stage polymerization for gas-phase butene-
The procedure was performed in the same manner as in Example 1 except that the polymerization time was 128 minutes at a concentration of 29.3 mol%. The results are shown in Tables 1 and 2.

Comparative Example 3 The amount of propylene introduced was changed to 550 k
g, the first-stage polymerization for 70 minutes, the second-stage polymerization for ethylene gas phase concentration of 16.2 mol% and butene-1 gas phase concentration of 0.5 mol
The procedure was performed in the same manner as in Example 1 except that 1% and the polymerization time were 70 minutes. The results are shown in Tables 1 and 2.

Comparative Example 4 In the [polymerization] of Example 1, the polymerization time of the first stage was 25 minutes, the polymerization of the second stage was 34.1 mol% of ethylene gas phase concentration, 12.5 mol% of butene-1 gas phase concentration, and the polymerization time was 115 minutes. The procedure was performed in the same manner as in Example 1 except that the amount was changed to minutes. Tables 1 and 2 show the results.
Shown in

Comparative Example 5 The procedure of Example 1 was repeated, except that the polymerization time in the first stage was changed to 5 minutes, and the polymerization time in the second stage was changed to 135 minutes. The results are shown in Tables 1 and 2.

Comparative Example 6 In the [polymerization] of Example 1, the polymerization time in the former stage was 70 minutes,
The procedure was carried out in the same manner as in Example 1 except that the polymerization time in the latter stage was changed to 70 minutes. The results are shown in Tables 1 and 2.

[0185]

[Table 1]

[0186]

[Table 2] Evaluation of physical properties of film Example 14 [Pelletizing] 0.1 part by weight of 2,6-di-t-butyl-p-cresol as an antioxidant and calcium stearate as a chlorine scavenger were added to 5 kg of the polymer obtained in Example 1. After adding 0.05 parts by weight, 0.15 parts by weight of Syloid 55 (average particle size: 2.73 μm) as an antiblocking agent, and 0.06 parts by weight of erucamide as a lubricant, mixing with a Henschel mixer for 5 minutes, Screw diameter 65
Extruded pellets were granulated at 230 ° C. using a mmΦ single screw extruder to obtain raw material pellets.

[Preparation of film]
It was supplied to a 40 mmΦ extruder heated at 0 ° C., extruded from a T-die die, and cast with a casting roll adjusted to a surface temperature of 40 ° C. to obtain a 40 μm-thick unstretched film. Table 3 shows the physical properties of the obtained film.

Examples 15 to 24 Using the polymers obtained in Examples 2 to 13, Example 14
An unstretched film was obtained in the same manner as described above. Table 3 shows the physical properties of the obtained film.

Comparative Examples 7 to 13 Using the polymers obtained in Comparative Examples 1 to 7, non-stretched films were obtained in the same manner as in Example 12. Table 3 shows the physical properties of the obtained film.

Comparative Example 14 Propylene-ethylene copolymer (MFR; 7.0 g / 1)
0 min, ethylene content; 3.5% by weight, melting point: 145
° C) ethylene-butene-1 copolymer (MI; 7.0, 1-butene content; 100 parts by weight as a soft resin;
A non-stretched film was obtained in the same manner as in Example 14 using a resin mixed with 100 parts by weight of (12 mol%). The physical properties of the obtained film are shown in Table 3 (in Table 3, PP + EB
R).

Comparative Example 15 A propylene-butene-1 copolymer (M
I; 7.0 g / 10 min, butene-1 content; 23 mol%) in the same manner as in Example 14 to obtain a non-stretched film. Table 3 shows the physical properties of the obtained film. (Table 3
In some cases, it is described as PB copolymer)

[0192]

[Table 3]

[Brief description of the drawings]

FIG. 1 is a view showing a method for evaluating the adhesiveness of a propylene-based resin composition in the present invention.

FIG. 2 is a flowchart showing a typical polymerization method of the present invention.

FIG. 3 is a flowchart showing a typical polymerization method of the present invention.

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4F071 AA20 AA75 AA84 AF43Y AH04 BA01 BB04 BB07 BB08 BB09 BC01 4J026 HA02 HA04 HA20 HA27 HA32 HA34 HA35 HB02 HB03 HB04 HB20 HB34 HB35 HB45 HE01 4J0ABA02A00A01B BB01B BB02B BC12B BC13B BC15B BC16B BC17B BC18B BC19B CA24C CA25C CA26C CA27C CA28C CA29C DA01 DA02 DA03 DA04 DA06 EB02 EB04 EB05 EB08 EB09 EB10 EB18 EB21 EC01 EC03 GA19

Claims (5)

[Claims] (1) a polypropylene component and a copolymer component of propylene, ethylene and butene-1 or a copolymer component of propylene and butene-1;
-Components eluted at a temperature up to 80 ° C (hereinafter referred to as “medium and low temperature eluting components”) are eluted at a temperature of 80 ° C or higher by 50 to 99% by weight of the whole by a temperature rising elution fractionation method using a dichlorobenzene solvent. Ingredients (hereinafter referred to as hot eluting ingredients)
Is 50 to 1% by weight of the whole, and a component eluted at a temperature up to 0 ° C. (hereinafter referred to as a low-temperature eluting component) is 1% of the whole.
0% by weight or less, and (II) the content of ethylene units in the medium and low temperature elution component is 0% by weight or more and 10% by weight or less, and the butene-1 unit content is 3% by weight or more and 40% by weight or less. A propylene-based resin composition characterized by the following. 2. The propylene-based resin composition according to claim 1, wherein the melting point of the high-temperature eluting component measured by a thermal differential scanning calorimeter is 130 to 155 ° C. 3. The propylene resin composition according to claim 1, wherein the polypropylene component and the copolymer component are block copolymers. 4. The method according to claim 3, wherein the polypropylene component and the copolymer component are produced stepwise in the presence of a catalyst comprising a metallocene compound, an aluminoxane compound and / or a non-coordinating ionized compound. A method for producing a block copolymer. 5. A flexible film comprising the propylene resin composition according to claim 1.