JP2001064335A - 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, flexibility and impact resistance at a low temperature and shows no tackiness. SOLUTION: This resin composition comprises a polypropylene component and a copolymer component of propylene and ethylene and/or a 4C to 18C α-olefin and is characterized in that (I) an eluting fraction up to 80 deg.C is 50 to 99 wt.% of the total weight, an eluting fraction above 80 deg.C is 50 to 1 wt.% of the total weight and an eluting fraction up to 0 deg.C is not less 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) a toluene-soluble fraction measured at -40 deg.C is less than 5 wt.% of the total weight.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to transparency, flexibility,
The present invention relates to a propylene-based resin composition having excellent low-temperature impact resistance and no stickiness, a method for producing the same, and a use thereof.

[0002]

BACKGROUND OF THE INVENTION Olefin-based thermoplastic elastomers are:
Because it has an excellent balance between economy and performance, and can be lightened and recycled, it is widely used in various industrial parts, home electric parts, films and sheets, such as automobile parts such as bumpers.

[0003] Conventionally, in the production of olefin-based thermoplastic elastomers, ethylene-propylene rubber (hereinafter referred to as EPR) has been used.
That. ) Or ethylene-propylene terpolymer (hereinafter referred to as EPDM) and a thermoplastic resin such as polypropylene by an extruder, and a mechanical mixing method, and a method of producing both components by a series of polymerization to obtain a mixture of both components. (Polymerization method) is known. In the production by such a polymerization method, a two-stage polymerization method in which propylene is polymerized in the first step and ethylene and propylene are copolymerized in the second step is generally performed.

However, conventional EPR and EPDM
Is excellent in low-temperature impact resistance, but has a sticky feeling, and even a molded article made of a mixture of them and polypropylene has excellent low-temperature impact resistance, but has a sticky feeling and is white or milky white, It could not be used as a material for molded articles such as containers, sheets, films, etc., which required transparency.

Although the thermoplastic elastomer produced by the polymerization method has better transparency than that obtained by mechanical mixing, the resin obtained by this method also has a sticky feeling, The molded product was white or milky white, and could not be used in a field where transparency was required.

[0006]

Therefore, the mixture of EPR or EPDM and polypropylene has good properties such as flexibility and impact resistance at low temperature, and has excellent transparency and stickiness. The development of non-existent materials is a challenge.

[0007] To solve the above-mentioned problems, Japanese Patent No. 267
JP-A-7920 and JP-A-07-118354 disclose that a propylene-based copolymer having a specific composition exhibits good flexibility and transparency.

However, the propylene-based polymer obtained by the above method contains a large amount of non-crystalline components, which are factors that hinder transparency, in addition to low-crystalline components. There is still room for improvement in transparency, and further improvement has been desired.

In Japanese Patent Application No. 10-366652, o
-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 rising fractionation method using a dichlorobenzene solvent is 10% by weight or less of the whole is shown. However, although the propylene-based resin composition obtained by the above method exhibits good flexibility and transparency, there is still room for improvement in impact resistance at low temperatures, and impact resistance at low temperatures is required. In use, further improvements have been desired.

Accordingly, an object of the present invention is to provide a propylene-based resin composition having excellent low-temperature impact resistance, excellent transparency and flexibility, and having no stickiness.

[0011]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, propylene and ethylene and / or C4 to C4 having a limited amount of non-crystalline components.
We succeeded in developing a propylene-based resin composition comprising a specific amount of a low-crystalline copolymer component with a C18 α-olefin, and found that such a composition satisfies all of the above objects, and completed the present invention. did.

That is, the present invention comprises a polypropylene component and a copolymer component of propylene and ethylene and / or an α-olefin of C4 to C18, and (I) temperature-elevation elution fractionation using an o-dichlorobenzene solvent. According to the method, components eluted at temperatures up to 80 ° C (hereinafter referred to as “medium-low-temperature eluting components”) account for 50 to 99% by weight of the whole, and components eluted at a temperature of 80 ° C or higher (hereinafter referred to as “high-temperature eluting components”)
A component which is 50 to 1% by weight of the whole and elutes at a temperature of up to 0 ° C. (hereinafter referred to as a low-temperature eluting component) is 10% by weight or more of the whole, and was measured at a temperature of (II) -40 ° C. A propylene-based resin composition having a toluene-soluble content of less than 5% by weight of the whole.

[0013]

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 a copolymer component of propylene and ethylene and / or a C4-C18 α-olefin.

The above-mentioned polypropylene component and propylene,
The ratio of ethylene and / or C4-C18 to a copolymer component with an α-olefin is determined by an elution curve obtained by an elution curve obtained by a temperature rising elution fractionation (hereinafter referred to as TREF) method using o-dichlorobenzene as a solvent. It can be specified by quantity.

That is, the polypropylene component is mainly composed of a component eluted at 80 ° C. or higher in an elution curve by the TREF method. The copolymer component of propylene with ethylene and / or a C4 to C18 α-olefin is mainly composed of a component eluted at a temperature 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 characteristics of the present invention, which are excellent in impact resistance at low temperatures, transparency and flexibility and no stickiness, are characterized by a polypropylene component, propylene and ethylene and / or α of C4 to C18. -The ratio of the eluting component (crystallinity distribution) measured by the TREF method, which indirectly indicates the component ratio of the copolymer component with the olefin, and the non-soluble content indicated by the toluene soluble component at -40 ° C in the low-temperature eluting component. It is very important that the amount of the crystal component is low.

In the propylene resin composition of the present invention, the components eluted at 80 ° C. or higher (hereinafter, referred to as high temperature elution components) have a propylene unit content of 97 to 100% by weight. Specifically, the high-temperature eluting component is a homopolymer of propylene or a main component of propylene, and a monomer unit composed of α-olefin or ethylene other than propylene is 3% by weight or less, preferably 1.5% by weight. Below, more preferably 1% by weight or less of a random copolymer. 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 heat resistance is deteriorated, and when it is 50% by weight or more, the flexibility and the transparency are remarkably deteriorated.

In the propylene-based resin composition of the present invention, the components eluted at temperatures up to 80 ° C. by the TREF method (hereinafter referred to as “medium and low temperature elution components”) are components necessary for imparting flexibility to products. And 8 to less than 50% by weight, preferably 10 to 40% by weight, more preferably 15 to 30% by weight of ethylene and / or C
It is mainly composed of a low-crystallinity propylene-based copolymer containing 4-C18 α-olefin units. The copolymer is preferably a copolymer obtained by random copolymerization of propylene with ethylene and / or an α-olefin of C4 to C18 in order to more effectively impart flexibility to the product.

When the unit content of ethylene and / or a C4-C18 α-olefin in the above-mentioned medium- and low-temperature eluting components is less than 8% by weight, the product is inferior in flexibility and low-temperature impact resistance. %
Transparency decreases and stickiness increases.

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, when the content of the medium-to-low temperature elution component is more than 99% by weight, heat resistance is deteriorated.

The propylene-based resin composition of the present invention has a large amount of components eluted up to 0 ° C. (hereinafter referred to as low-temperature eluting components), and is a main factor in the development of stickiness represented by the amount of toluene soluble at −40 ° C. Another characteristic is that the amount of the non-crystalline component is small. That is, the amount of the eluted components up to 0 ° C. is 10% by weight or more, preferably 15% by weight or more, more preferably 20% by weight or more of the whole (the total amount of the medium- and low-temperature eluted components and the high-temperature eluted components), and −40. It is important that the toluene soluble matter is less than 5% by weight, preferably less than 4.5% by weight, more preferably less than 4% by weight. When the amount of the eluted components up to 0 ° C is less than 10% by weight, the impact resistance of the product at low temperature is inferior. When the amount of the soluble matter at -40 ° C in toluene is 5% by weight or more, the stickiness is increased, The object of the present invention cannot be achieved.

The propylene-based resin composition of the present invention is not particularly limited as long as it satisfies the above constitution. For example, the composition may be measured by a differential scanning calorimeter (hereinafter, referred to as DSC) of the high-temperature eluting component. 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 using 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, in order to improve the transparency of the product.

The propylene-based resin composition of the present invention comprises, in addition to the above-mentioned polypropylene component and a copolymer component of propylene and ethylene and / or an α-olefin of C4-18, as a resin component, As long as the effect of the composition is not impaired, for example, a range of 5% by weight or less, another α-olefin polymer may be contained as a component. As the α-olefin, 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, 1-octadecene, 1-eicosene and the like can be exemplified.

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. However, a polypropylene component and propylene may be mixed with ethylene and / or a C4-C18 α-olefin. In which the random copolymer component is arranged in one molecular chain, and / or a molecular chain consisting of a polypropylene component and a random copolymer component of propylene and ethylene and / or an α-olefin of C4 to C18, respectively. Can obtain a propylene-based resin composition that can achieve a micro-mixed state to the extent that cannot be achieved by mechanical mixing, that is, a method of obtaining a so-called block copolymer, which can be used as a film having better transparency. It is preferred.

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]) and 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 (B) of propylene and ethylene 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 an example of the specific 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.

Compounds obtained by replacing the above-mentioned zirconium with hafnium are also preferably used.

The above metallocene compounds can be used in combination.

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

[0042]

Embedded image

[0043]

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 adopted, 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 are used without any particular limitation. In particular, an ionized compound containing a boron atom can be suitably used.

Specific examples of the ionizing 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 boron-containing Lewis acid 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.

In the presence of a catalyst consisting of component [I] and component [II], a polypropylene component (A) and a copolymer component (B) of propylene and ethylene and / or a C4-C18 α-olefin are added stepwise. 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 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.

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 desirably 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 to be used for 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 prepolymerization may be carried out by 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 for obtaining the propylene resin composition of the present invention as a block copolymer comprising a polypropylene block and a copolymer block comprising propylene and ethylene and / or an α-olefin of C4 to C18 by polymerization, Propylene and ethylene and / or C4 in the presence of the catalyst component
The polymerization of the copolymer component with the α-olefin of C18 is performed stepwise. The polymerization order is not particularly limited, but it is preferable that the production of the polypropylene component in the first stage and the production of the copolymer component of propylene and ethylene and / or an α-olefin of C4 to C18 in the second stage have good particle properties. Preferred for producing polymers.

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 other 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.

Following the polymerization for obtaining the polypropylene component, propylene and ethylene and / or C4
Random copolymerization of C18 α-olefin is performed.
Propylene and ethylene and / or α of C4 to C18
-In the case of slurry polymerization using propylene itself as a solvent, the random copolymerization with olefin is carried out by ethylene gas and / or C4 to C18 following the propylene polymerization.
Propylene and ethylene and / or C4 to C4 in the case of gas phase polymerization.
This is carried out by supplying a mixed gas of 18 α-olefins.

In the random copolymerization of propylene with ethylene and / or a C4-C18 α-olefin of the present invention, it is preferable to carry out one-stage random copolymerization after propylene polymerization, but ethylene and / or C4-C1
No. 8 can be produced by changing the supply concentration of the α-olefin in multiple stages. The polymerization temperature of the random copolymerization of propylene with ethylene and / or a C4 to C18 α-olefin is 0 to 100 ° C, preferably 20 to 80 ° C.
It is preferable to adopt from the range. 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.

Propylene and ethylene and / or C4
-C18 random copolymerization of α-olefin is a batch type,
Either a semi-batch system or a continuous system may be used, 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 completion of the main polymerization, the propylene resin of the present invention can be obtained by evaporating the monomer 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 may contain commercially available additives such as an antioxidant, a heat stabilizer, and a chlorine scavenger. 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 transparency, has unprecedented excellent flexibility and impact resistance at a low temperature, and exhibits a remarkable effect of reducing stickiness. It is suitable as a soft film. The use of the film is not particularly limited, and is used for packaging of foods, clothing, stationery, miscellaneous goods, etc., but among those uses, the film is excellent in transparency, has no stickiness, and has excellent impact resistance at low temperatures. Therefore, it can be suitably used especially for food applications.

As the 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 film does not have a strict meaning with respect to the thickness in particular, but is a generic term including a sheet, and is generally 10 to 1000 μm.
The degree is preferably used.

The polypropylene-based resin composition may be used as a single-layer film, or may be used by laminating another resin to form a multilayer. The layer configuration is not particularly limited, and may be either a surface layer or an inner layer. There is no particular limitation on the resin used for lamination, but a propylene-based resin,
Examples include ethylene-based resins such as high-density polyethylene, low-density polyethylene, linear low-density polyethylene, ethylene-vinyl acetate copolymer, and ethylene-methacrylic acid copolymer. Further, the film surface may be subjected to a corona treatment.

Further, the propylene-based resin composition obtained by the present invention is excellent in flexibility, tensile elongation, heat resistance, impact resistance at low temperature, and has no sticky feeling. It can be suitably used in various fields. For example, in the field of injection molding, bumpers, mat guards, lamp packings,
In the field of home appliances, various packings, ski shoes, grips, and roller skates can be mentioned. 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 it can be suitably used for various applications by any molding method such as extrusion molding, injection molding, press molding, and vacuum molding.

When molding, 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.

Further, other resins can be added to the polypropylene resin composition of the present invention as long as the properties of the present invention are not significantly affected. For example, 90% mol or more of propylene and an α-olefin other than propylene such as 1-butene, 1-pentene, 1-hexene,
One or more kinds of 1 such as heptene and 4-methyl-1-pentene;
0 mol% or less of random copolymer, high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear polyethylene (LLDPE) obtained by copolymerizing ethylene and C4 to C10, ethylene-vinyl acetate copolymer (E
VA), ethylene methyl methacrylate copolymer (EM
MA), ethylene-propylene copolymer (EPR, EPDM), ethylene-butene-1
Olefin-based soft resin such as copolymer (EBM), propylene / butene-1 copolymer (PBM), styrene / butadiene block copolymer (SBR), petroleum resin / terpene resin or hydrogenated product thereof. Things can be used without restrictions.

In the present invention, the polypropylene resin composition to be used can be obtained by blending the above raw materials and the like, if necessary, followed by mixing and melt-kneading. The method of melt kneading is not particularly limited, and for example, using a screw extruder, a Banbury mixer, a mixing roll, etc., at 160 to 300 ° C., preferably 180 to 27 ° C.
It is good to carry out at a temperature of 0 ° C. Also, this melt kneading,
It can also be performed under a stream of an inert gas such as nitrogen gas.
Prior to melt-kneading, a known mixing device such as a tumbler or a Henschel mixer can be used without any limitation.

[0090]

As will be understood from the above description, TR
The crystallinity distribution measured by the EF method has a specific form,
A polypropylene-based resin composition in which the amount of the non-crystalline component represented by the amount of soluble components in toluene at 40 ° C. is limited is excellent in transparency, flexibility, impact resistance at a low temperature, and has no stickiness, so that it is a soft film. Can be suitably used.

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

[0092]

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) This was based on 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 Content A ¹³ C-NMR spectrum was measured using JEOL GSX-270.

(5) Molecular weight distribution Using a 150C gel permeation chromatography (GPC) manufactured by Waters, column GMH6HT was used.
(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 the condition of a load of 250 g according to JIS K7206.

(10) Young's modulus According to JIS K6758, the Young's modulus in the resin flow direction was measured.

(11) -30 ° C. Izod impact strength At −30 ° C., using an impact head having a diameter of 1 cm using a film impact tester manufactured by Toyo Seiki Co., Ltd.
It was calculated by dividing the energy value obtained under the condition of a capacity of 30 kg-cm by the thickness.

(12) Evaluation of Surface Adhesion By injection molding, the length was 50 mm × width 40 mm × thickness 10 m.
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).

(13) Amount of soluble matter in toluene at -40 ° C. 1 g of the polymer was added to 100 ml of toluene, and the temperature was raised to 100 ° C. with stirring. Then, stirring was further continued for 30 minutes to completely dissolve the polymer. It was left in a constant temperature room at 40 ° C. for 6 hours. The precipitate was separated by filtration in a -40 ° C constant temperature room, and the toluene solution was completely evaporated to obtain a soluble component.

-40 ° C. Toluene soluble matter (wt%) =
(Toluene soluble matter (g) / 1 g of polymer) × 100. Example 1 [Preparation of supported metallocene catalyst] silica gel support methylaluminoxane (MAO on SiO _2, Uittoko Co., 25 wt% -Al product) 10 g to rac- dimethylsilylene-bis-1- (2-methylindenyl) zirconium dichloride 100 ml of toluene solution (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] (First stage, polymerization of propylene) 600 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, 5 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 70 minutes.

(Second stage, copolymerization of propylene and ethylene)
After the polymerization in the first stage, ethylene gas was added at a gas phase concentration of 3%.
The copolymer was supplied to a concentration of 5.2 mol%, and copolymerization was carried out for 70 minutes while supplying the gas so as to keep the gas phase concentration of ethylene constant. After the polymerization is completed, unreacted propylene is purged,
By drying at 50 ° C. for 1 hour, 162 kg of a white granular polymer was obtained.

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 eluting component at a temperature lower than 80 ° C. had an ethylene content of 18.5 wt%, and no melting point peak was detected by DSC. Further, the soluble matter in toluene measured at -40 ° C was 1.9 wt%.

Table 1 shows the MFR, molecular weight distribution, bulk density, TREF elution component amount, high-temperature elution component amount and melting point, medium-low temperature elution component component and ethylene content of the obtained polymer, and toluene measured at -40 ° C. Shows the soluble content.

[Evaluation of physical properties] 100 parts by weight of the obtained polymer was added with 2,6-di-tert-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 30 minutes, the gas phase ethylene concentration in the latter stage polymerization was 35.5 mol%, and the polymerization time was 1
The procedure was performed in the same manner as in Example 1 except that the time was 10 minutes. The results are shown in Tables 1 and 2.

Example 3 The polymerization time in the former stage of Example 1 was 90 minutes, the gas phase ethylene concentration in the latter stage polymerization was 35.0 mol%, and the polymerization time was 5 minutes.
The procedure was performed in the same manner as in Example 1 except that the time was 0 minutes. The results are shown in Tables 1 and 2.

Example 4 The procedure of Example 1 was repeated except that the polymerization time in the former stage of Example 1 was changed to 110 minutes, the gas phase ethylene concentration in the latter polymerization was changed to 35.3 mol%, and the polymerization time was changed to 30 minutes. The results are shown in Tables 1 and 2.

Example 5 The polymerization time in the former stage of Example 1 was 80 minutes, the gas phase ethylene concentration in the latter stage polymerization was 40.3 mol%, and the polymerization time was 6 minutes.
The procedure was performed in the same manner as in Example 1 except that the time was 0 minutes. The results are shown in Tables 1 and 2.

Example 6 In the former stage of Example 1, the polymerization time was set to 60 minutes, the gas phase ethylene concentration in the latter stage polymerization was set to 16.0 mol%, and
Liquefied butene-1 is 5.0 mol% in gas phase butene-1 concentration
Example 1 except that the polymerization time was 80 minutes.
The same was done. The results are shown in Tables 1 and 2.

Example 7 In Example 1, the amount of propylene inserted was 350 kg, the polymerization time in the first stage was 14 minutes, and in the second stage polymerization, liquefied butene-1 was replaced with ethylene to 26 mol% in gas phase butene-1 concentration in place of ethylene. The procedure was performed in the same manner as in Example 1 except that the polymerization time was changed to 126 minutes. The results are shown in Tables 1 and 2.

Example 8 [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 in terms of Zr atom were charged into a 1 L autoclave substituted with N ₂ , 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] 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 9 [Preparation of supported catalyst 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 having been substituted with N _{2 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 part 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 10 [Polymerization] (Preliminary stage, polymerization of propylene) 450 g of propylene was charged into an autoclave having an inner 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 0.1 mg of a mixed solution was charged in its entirety. Subsequently, the internal temperature of the autoclave was raised to 60 ° C.
And the polymerization was carried out for 70 minutes.

(Second stage, copolymerization of propylene and ethylene)
After the polymerization in the first stage, ethylene gas was added at a gas phase concentration of 3%.
The copolymerization was carried out for 70 minutes while supplying the solution to a concentration of 5.5 mol% and further keeping the gas phase concentration of ethylene constant. After the polymerization is completed, unreacted propylene is purged,
By drying at 50 ° C. for 1 hour, 180 g of a white bulk polymer was obtained. 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] The procedure of Example 9 was repeated except that the metallocene used in Example 8 was 0.01 mg of dimethylsilylenebis (2-methyl-4-naphthyl-indenyl) zirconium dichloride. 165 g of white bulk polymer
I got The results are shown in Tables 1 and 2.

Example 12 [Production of random copolymer] 450 g of propylene was inserted into a polymerization tank having an internal 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 vaporized at a concentration of 35.4 mol.
It was fed to a concentration of 1%. Then, 5 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,
By drying at 50 ° C. for 1 hour, 160 g of a white bulk polymer 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 by 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.

0.55 g of phthalic anhydride was added to this solution.
(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] Inner volume 1 L 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) 600 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, 1.4 mmo of titanium-containing polypropylene was used as Ti atoms.
1 and the polymerization was started. Subsequently, the internal temperature of the autoclave was raised to 60 ° C., and polymerization was performed for 40 minutes.

(Second stage, copolymerization of propylene and ethylene)
After the polymerization at the first stage, ethylene gas was supplied to the gas phase at a concentration of 9.5 mol% in a gas phase concentration, and copolymerization was carried out for 100 minutes while supplying ethylene gas at a constant gas phase concentration.

After completion of the polymerization, unreacted propylene was purged and dried at 50 ° C. for 1 hour to obtain 155 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 The procedure of Example 1 was repeated, except that the polymerization time in the first stage was changed to 50 minutes, and the polymerization time in the second stage was changed to 90 minutes. The results are shown in Tables 1 and 2.

Comparative Example 3 In the [polymerization] of Example 1, the polymerization time in the former stage was 90 minutes,
The latter polymerization time was 50 minutes, and the ethylene gas phase concentration was 49.8.
The procedure was performed in the same manner as in Example 1 except that mol% was used. The results are shown in Tables 1 and 2.

Comparative Example 4 The polymerization time of the former stage in [Polymerization] of Example 1 was changed to 10 minutes,
The polymerization time in the latter stage was 130 minutes, and the ethylene gas phase concentration was 32.
The procedure was performed in the same manner as in Example 1 except that 1 mol% was used. The results are shown in Tables 1 and 2.

Comparative Example 5 The polymerization time of the former stage was changed to 120 in [polymerization] of Example 1.
Minutes, the subsequent polymerization time is 20 minutes, and the ethylene gas phase concentration is 3 minutes.
The procedure was performed in the same manner as in Example 1 except that the content was 2.1 mol%.
The results are shown in Tables 1 and 2.

[0155]

[Table 1]

[0156]

[Table 2] Evaluation of physical properties of film Example 13 [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 fed 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 150 μm-thick non-stretched film. Table 3 shows the physical properties of the obtained film.

Examples 14 to 24 Using the polymers obtained in Examples 2 to 12, Example 13
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 11 Using the polymers obtained in Comparative Examples 1 to 5, unstretched films were obtained in the same manner as in Example 13. Table 3 shows the physical properties of the obtained film.

Comparative Example 12 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 12 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 13 A propylene-butene-1 copolymer (M
I; 7.0 g / 10 min, butene-1 content; 23 mol%) to obtain a non-stretched film in the same manner as in Example 12. Table 3 shows the physical properties of the obtained film. (Table 3
In some cases, it is described as PB copolymer)

[0162]

[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.

Continued on the front page F-term (reference) 4F071 AA15 AA20 AA75 AA80 AA84 AF05Y AH07 BA01 BB07 BB08 BB09 BC01 BC08 4J026 HA04 HA27 HA32 HA35 HA38 HB02 HB03 HB04 HB27 HB32 HB35 HB48 HE06 4J0BA02ABAB BC13B BC15B BC16B BC17B BC19B BC24B BC25B CA25C CA26C CA27C CA28C CA29C DA01 DA02 DA03 DA04 DA05 DA06 EA02 EB04 EC01 ED01 ED03 ED04 ED05 EF01

Claims (5)

[Claims] (1) a polypropylene component and a copolymer component of propylene and ethylene and / or an α-olefin of C4 to C18, and (I) a temperature-elevating elution fractionation method using an o-dichlorobenzene solvent; The components eluted at temperatures up to 100 ° C. (hereinafter referred to as “medium and low temperature elution components”) account for 50 to 99% by weight, and the components eluted at a temperature of 80 ° C. or higher (hereinafter referred to as “high temperature elution components”) account for 50 to 1% by weight. %, And the components eluted at a temperature of up to 0 ° C. (hereinafter referred to as low-temperature elution components) are 10% by weight or more of the whole, and (II) the total amount of the toluene-soluble components measured at a temperature of −40 ° C. Less than 5% by weight of the propylene-based resin composition. 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, which is a block copolymer comprising a polypropylene block and a copolymer block comprising propylene and ethylene and / or an α-olefin of C4 to C18. . 4. A polypropylene component and a copolymer component of propylene and ethylene and / or an α-olefin of C4 to C18 in the presence of a catalyst comprising a metallocene compound, an aluminoxane compound and / or a non-coordinating ionized compound, respectively. 4. The method for producing a block copolymer according to claim 3, wherein the block copolymer is produced. 5. A flexible film comprising the propylene resin composition according to claim 1.