JP2000344964A - Polyolefin resin - Google Patents

Abstract

(57) [Problem] To provide a polyolefin resin which has good stretchability at the time of forming a stretched film and the obtained stretched film has excellent heat resistance and rigidity, and a stretched film obtained by stretching such a polyolefin resin. I do. When the crystalline polyolefin resin has an elution temperature of 36 to 1 when measured by a temperature-increased fractional correlation molecular weight measurement method.
A polyolefin resin modifier containing a polyolefin having an active ingredient at a temperature of 04 ° C. and a molecular weight in the range of 100,000 to 1,000,000, and a crystallinity containing 4 to 20% by weight of the polyolefin resin effective ingredient. It is a polyolefin resin composition. Further, in addition to the polyolefin resin modifier, the elution temperature exceeds 116 ° C. and the molecular weight is 10,000 to 1
By providing a crystalline polyolefin resin composition containing 4 to 20% by weight of a polyolefin in the range of 10,000, a polyolefin resin composition having better film processing properties and a stretched film are provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyolefin resin modifier, in particular, a crystalline polyolefin resin used for a stretched film, for example, a polypropylene-based resin, having improved heat resistance such as film formability, stretchability, and low heat shrinkage. And a modified polyolefin resin composition, and a stretched film comprising the resin composition.

[0002]

2. Description of the Related Art Stretched polyolefin films, particularly biaxially stretched polyolefin films, are widely used as packaging materials due to their excellent mechanical and optical properties. As a production method, a sequential biaxial stretching method by a tenter method is generally used.

In recent years, the production equipment for biaxially stretched polyolefin films has been increased in size and speed, and with general conventional polyolefin resins, the mechanical load of the stretching apparatus during film formation has increased, the film thickness accuracy has been reduced, Further, problems such as occurrence of tearing in stretching of the film have occurred. Therefore, various methods for improving the stretchability have been proposed. For example, Japanese Unexamined Patent Publication No. 9-32014 proposes a technique that contains a specific amount of amorphous formed and broadens the stereoregularity distribution. However, there is still room for improvement as a stretched polyolefin film having good film-forming properties even at the time of high-speed film formation and having excellent mechanical properties and heat resistance.

[0004]

Therefore, there has been a demand for the development of a polyolefin resin having good stretchability that can cope with an increase in the size and speed of production equipment for a stretched polyolefin film. Accordingly, an object of the present invention is to provide a wide temperature control range in which a film can be formed during stretching, a small mechanical load, excellent precision in thickness and thinness of a formed film, excellent stretchability, and no occurrence of stretching tear. An object of the present invention is to obtain a polyolefin resin composition suitable for a monoaxially or biaxially stretched film that can be stably produced and has good heat resistance such as a formed film heat shrinkage and a stretched film composed of the polyolefin resin composition. Another object of the present invention is to provide means for solving the problem of how to achieve the object.

[0005]

Means for Solving the Problems The present inventors have intensively studied to solve the above objects and problems. As a result, when the crystalline polyolefin resin contains a specific amount of polyolefin present at a specific elution temperature and in a specific molecular weight range, as measured by a temperature-increased fractional correlation molecular weight measurement method, the formation of a stretchable film In the process, the temperature control range of film formation is wide, the mechanical load in stretching is reduced, the film breakage is small, the thickness and thinness of the drawn film are excellent, and the heat resistance such as heat shrinkage is good. The inventors have found that the present invention has been completed.

That is, the present invention provides (1) an elution temperature of 36 to 104 ° C.
And (2) a crystal containing 4 to 20% by weight of a polyolefin resin effective component as an active ingredient, the polyolefin resin having a molecular weight in the range of 100,000 to 1,000,000. It is a functional polyolefin resin composition.

Further, the present invention relates to (3) In addition to the above polyolefin resin modifier, the elution temperature exceeds 116 ° C. and the molecular weight is 10,000 to 10 Polyolefins in the range of 10,000
By providing a crystalline polyolefin resin composition containing 20% by weight, a polyolefin resin composition having better film processing characteristics is provided.

Further, the present invention also provides a stretched film comprising the polyolefin resin composition shown in the above (2) and (3).

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the temperature-assisted fractionation correlation molecular weight measurement method is a temperature-assisted fractionation method
on Fractionation (TREF method) and molecular weight distribution measurement (Siz
e Exclusion Chromatography (SEC method) is an analysis method linked online, and is also simply abbreviated to TREF / SEC method. In the TREF / SEC method, a polyolefin (polypropylene resin, etc.) crystallized in a solution is dissolved in a solvent at different temperatures, and the molecular weight distribution and the elution amount (concentration) of the polyolefin are continuously measured at each melting temperature. This is a method for evaluating the composition distribution of the polyolefin.

That is, an inert carrier such as diatomaceous earth or silica beads is used as a filler, and a sample solution having an arbitrary concentration obtained by dissolving a sample polyolefin in a solvent consisting of ortho-dichlorobenzene is injected into the TREF column. After the temperature of the TREF column is lowered and the sample is attached to the surface of the packing material, the column temperature is raised stepwise to an arbitrary temperature, a solvent composed of ortho-dichlorobenzene is passed, and elution is performed at the temperature. The resulting polyolefin component is continuously introduced into a high-temperature SEC column, and the polyolefin elution amount (% by weight) and the molecular weight distribution are measured.

By this operation, the composition distribution of the polyolefin can be seen in a graph drawn by the elution temperature and the molecular weight distribution (a crystallinity-molecular weight correlation diagram is shown by a contour line or a bird's-eye view).

The projection of the elution temperature shows the crystallinity distribution. Since the elution temperature increases as the elution component becomes more easily crystallized, the relationship between the elution temperature and the elution amount (% by weight) of the polymer should be determined. Thus, the distribution of crystallinity of the polymer can be known.

In the above method, it is necessary that the temperature drop rate of the TREF column is adjusted to a rate required for crystallization of the crystalline portion contained in the polyolefin of the sample at a predetermined temperature. May be determined in advance by an experiment. Usually, the rate of decrease in the temperature of the column is determined in the range of 5 ° C./min or less.

In the present invention, the crystalline polyolefin resin composition contains 4 to 20% by weight, preferably 4 to 20% by weight of a component having an elution temperature of 36 to 104 ° C. and a molecular weight of 100,000 to 1,000,000 by the TREF / SEC method. Is 5-18% by weight,
An important point is that it is preferably present as an active ingredient in an amount of 6 to 15% by weight. If the amount of the above-mentioned active ingredient in the crystalline polyolefin is less than 4% by weight, the stretchability in stretching during film formation decreases, the temperature range in which film formation can be performed is narrowed, and the mechanical load increases, and the film breaks during stretching. And the film thickness thinness accuracy also deteriorates. On the other hand, if it exceeds 20% by weight, the heat shrinkage of the stretched film increases, and the heat resistance decreases.

Further, regarding the above-mentioned active ingredient, a preferable embodiment is that the elution temperature range by the TREF / SEC method is 40.
It is preferable that the molecular weight of the eluted component be 100,000 to 1,000,000 in the temperature range of -88 ° C, more preferably 44-68 ° C.

In short, it is important that these active ingredients be present in the crystalline polyolefin resin composition of the present invention in an amount of 4 to 20% by weight, and the means for doing so is not particularly limited. For example, a polyolefin containing more than 20% by weight to 100% by weight of the active ingredient is produced as a modifier for a crystalline polyolefin resin (hereinafter referred to as a modifier A), and this is mechanically combined with the crystalline polyolefin resin. When a method of mixing, or a crystalline polyolefin resin is obtained by polymerization, by appropriately selecting a catalyst used for polymerization, a method of producing a crystalline polyolefin resin and the active ingredient at the time of polymerization and obtaining a mixture is used. Can be That is,
In order to easily obtain the crystalline polyolefin resin composition of the present invention, the former is preferable, but in order to obtain a uniform mixture of the modifier of the present invention and the crystalline polyolefin resin, the latter method may be effective. Many.

In the present specification, regardless of the method of mixing the active ingredient for the modifier and the crystalline polyolefin resin, those in which both are substantially uniformly integrated are referred to as the polyolefin resin composition of the present invention.

In the present invention, the crystalline polyolefin resin to be modified by mixing a modifier may be a propylene homopolymer or a propylene-α-olefin containing an α-olefin other than propylene as a copolymerization component. Examples include olefin copolymers and mixtures thereof.

In the propylene-α-olefin copolymer, the content of monomer units based on one or more α-olefins other than propylene is 10 mol% or less, and more preferably 5 mol% or less. It is preferably an α-olefin copolymer or a mixture thereof. α
-As the olefin, ethylene, butene-1, pentene-1,3-methyl-1-butene, hexene-1,3-
Methyl-1-pentene, 4-methyl-1-pentene, heptene-1, octene-1, nonene-1, decene-1,
Dodecene-1, tetradecene-1, hexadecene-1,
2-20 carbon atoms such as octadecene-1 and eicosene-1
Α-olefins can be exemplified. Further, the propylene-α-olefin copolymer may be any of a random copolymer and a block copolymer, and among them, a random copolymer is preferred.

When the crystalline polyolefin resin is a propylene homopolymer or a propylene-α-olefin copolymer and the content of α-olefins other than propylene is less than 1 mol%, 13C-NM exhibiting its crystallinity is obtained.
Although the isotactic pentad fraction by R is not particularly limited, it is preferably 0.80 to 0.99, more preferably 0.85 to 0.98, and further more preferably 0.87 to 0.98. More preferably, it is 0.97. What is the isotactic pentad fraction here?
A. Macromolecules, 13 , 267, (198) by A. Zambelli et al.
This is the fraction in which five propylene units quantified based on the assignment of the peaks of the 13C-NMR spectrum published in 0) continuously take the same configuration.

Of course, the crystalline polyolefin resin used in the present invention is not limited to the above-mentioned polypropylene-based resin, but may be any other olefin polymer or copolymer other than the polypropylene-based resin. The target is a polyolefin resin having an amount of 30% or more, preferably 40% or more.

Although the physical properties of the polyolefin resin composition of the present invention are not particularly limited, the melt flow rate (MFR) is usually determined in consideration of the moldability into a film.
It is preferably in the range of 0.1 to 20 g / 10 minutes, and more preferably in the range of 1 to 10 g / 10 minutes. The weight average molecular weight (Mw) is 200,000 to 800,000,
Preferably, the range of 250,000 to 450,000 is suitable. Ratio (Mw) between weight average molecular weight (Mw) and number average molecular weight (Mn)
/ Mn) is preferably in the range of 2 to 20, considering the ease of film formation and the increase in melt tension to improve workability, and more preferably 4 to 20.
More preferably, it is in the range of 10 to 10.

The above-mentioned molecular weight distribution was obtained by calculating the elution profile measured by SEC method at 145 ° C. using ortho-dichlorobenzene as a solvent, and calculating the weight-average and number-average molecular weight calculated from a general-purpose calibration curve of polypropylene under the measurement conditions. Obtained from. Further, the melting point is preferably 130 ° C. or higher, more preferably in the range of 135 to 170 ° C., and further preferably in the range of 140 to 160 ° C. Here, the melting point of the polyolefin resin is a peak temperature of a crystal melting curve at the time of temperature rise measured by a differential scanning calorimeter (hereinafter simply referred to as DSC).

TREF of the above polyolefin resin composition
The peak temperature of the elution curve obtained by the method is 100 to 1 in consideration of the rigidity and heat resistance of the stretched film obtained by film formation.
A range of 30 ° C is preferable, a range of 110 to 125 ° C is more preferable, and a range of 115 to 120 ° C is particularly preferable. In addition, TREF referred to here is to dissolve polyolefin (polypropylene resin or the like) crystallized in a solution in a solvent at a different temperature, and to continuously measure the elution amount (concentration) of the polyolefin at each dissolution temperature. This is a method for evaluating the crystallinity distribution of polyolefin.

That is, an inert carrier such as diatomaceous earth or silica beads is used as a filler, and a sample solution having an arbitrary concentration obtained by dissolving a sample polyolefin in a solvent composed of ortho-dichlorobenzene is injected into the TREF column. After the temperature of the TREF column is lowered and the sample adheres to the surface of the packing material, the column temperature is linearly increased to an arbitrary temperature, a solvent consisting of ortho-dichlorobenzene is passed, and the column is eluted at the same temperature. The elution amount (% by weight) of the resulting polyolefin component is measured. By this operation, the crystallinity distribution of the polyolefin with respect to the elution temperature can be seen.

In this method, the rate of temperature decrease of the TREF column needs to be adjusted to a rate necessary for crystallization of the crystalline portion contained in the polyolefin of the sample at a predetermined temperature. May be determined in advance by an experiment. Usually, the rate of decrease in the temperature of the column is determined in the range of 5 ° C./min or less.

TREF of the above polyolefin resin composition
The elution component at 0 ° C. or lower in the / SEC method is not particularly limited, but is 10% by weight or less in consideration of the film surface properties such as blocking resistance, scratch resistance, and slipperiness of the formed polyolefin film. And more preferably 7% by weight or less,
It is particularly preferred that the content be 5% by weight or less.

Further, the molecular weight of the components eluted at 0 ° C. in the TREF / SEC method of the above polyolefin resin composition is not particularly limited, but in consideration of bleeding out to the film surface and generation of fish eyes, etc.
The molecular weight at the peak top position of the molecular weight distribution curve of the eluted component at 0 ° C. obtained by the SEC measurement is preferably 10,000 to 400,000, and more preferably 150,000 to 300,000.

The polyolefin resin composition of the present invention has a T
Components having an elution temperature of 36 to 104 ° C and a molecular weight of 100,000 to 1,000,000 by REF / SEC method are 4 to 20% by weight.
Within the range, excellent thickness and thinness precision and stretchability can be obtained. However, in order to further improve the heat resistance such as the heat shrinkage of the formed stretched film, the elution temperature by the TREF / SEC method is 116 ° C. , And preferably contains 4 to 20% by weight of a polyolefin component having a molecular weight of 10,000 to 100,000, more preferably 5 to 15% by weight, and still more preferably 6 to 10% by weight. Is particularly preferred. Such a polyolefin component is also a polymer or copolymer composed of the same olefins as the modifier.

Hereinafter, the present invention will be described in more detail.

First, the modifier A of the present invention comprises TREF / S
Elution temperature by EC method is 36 to 104 ° C, molecular weight is 10
Components in the range of １００1,000,000, that is, 20
% By weight to 100% by weight.
0-100% by weight, preferably 50-100% by weight.
More preferably, it is contained by weight%. Further, the elution temperature according to the TREF / SEC method is 40 to 8
Component having a molecular weight in the range of 100 to 1,000,000 at 8 ° C.
0% by weight, and the elution temperature is preferably 44 to
Components having a molecular weight in the range of 100 to 1,000,000 at 68 ° C
Most preferably, it contains 100% by weight.

As the modifier A, a crystalline polyolefin resin generally having lower crystallinity than the crystalline polyolefin resin is used without any limitation as long as the content of the active ingredient is more than 20% by weight to 100% by weight. be able to. Examples of the modifier A include an α-olefin homopolymer, a copolymer of two or more α-olefins, a mixture of these polymers, and the like. The α-olefin copolymer may be any of a random copolymer and a block copolymer, and among them, a random copolymer is preferred.

As the α-olefin, ethylene,
Propylene, butene-1, pentene-1, 3-methyl-
Examples thereof include 1-butene, hexene-1, 3-methyl-1-pentene, 4-methyl-1-pentene, heptene-1, octene-1, and nonene-1.

Among these modifiers A, propylene homopolymer, ethylene-propylene copolymer, ethylene-propylene
1-hexene copolymer, ethylene-1-octene copolymer, propylene-1-butene copolymer, propylene-1
-Hexene copolymers, propylene-ethylene-1-butene copolymers, and mixtures thereof are preferably used.

The melt flow rate of the modifier A is not particularly limited, but is preferably 1 to 20 g / 10 minutes. The weight average molecular weight (Mw) is preferably in the range of 100,000 to 400,000. Further, the molecular weight distribution (Mw / Mn)
Is preferably in the range of 1.5 to 15.

Further, the melting point of the modifier A is not particularly limited, but it is preferable that at least one melting peak exists in the range of 60 to 150 ° C.

The elution components of the modifier A at 0 ° C. or lower in the TREF / SEC method are not particularly limited, but the blocking resistance, scratch resistance, and slip resistance of the formed polyolefin film are not limited. It is preferably 5% by weight or less in consideration of film surface properties such as
The content is more preferably 4% by weight or less, and further preferably 3% by weight or less.

[0038] The modifier A may be obtained by any method. For example, a method of individually polymerizing the respective elution components constituting the modifier A and mixing them, obtaining a state in which the polypropylene component and the propylene-ethylene random copolymer component are arranged in one molecular chain, and / or There is a method of obtaining a so-called block copolymer which can achieve a state in which a molecular chain composed of a polypropylene component and a molecular chain composed of a propylene ethylene random copolymer component alone can be microscopically mixed to the extent that mechanical mixing cannot achieve. The modifier A obtained as a block copolymer has an excellent effect of improving stretchability and is preferable for obtaining a more transparent stretched film.

The production method for obtaining the modifier A as a block copolymer is not particularly limited as long as it satisfies the requirements of the present invention. For example, it can be suitably produced 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 or a non-coordinating ionized compound (hereinafter abbreviated as component [II]), a polypropylene component (a) is prepared. A method of producing the copolymer component (b) of propylene and ethylene stepwise is exemplified.

As the component [I], compounds 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 _1m ) ( _{C 5 H 4-n R 2n} ) MX 1 X 2 (1) ( wherein, M represents a group IVb transition metal atom of the periodic _{table. (C 5 H 4-m} R 1m), (C 5 H _4-n R _2n ) 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; 1 to 20 hydrocarbon groups, silicon-containing hydrocarbon groups, or two carbon atoms on a cyclopentadienyl ring to form one or more hydrocarbon rings optionally substituted with hydrocarbons Hydrocarbon group.

Q is (C_FiveH_4-mR_1m) And (C_FiveH_4-n
R_2nA) a divalent, hydrocarbon group,
Unsubstituted silylene group or hydrocarbon-substituted silylene group
You. X ₁And X_TwoCan be the same or different
Represents a hydrogen, halogen or hydrocarbon group. ) Key
Laral compounds can be suitably used.

More preferably, in the formula (1), M is a zirconium or hafnium atom, R ₁ and R ₂ are the same or different, a hydrocarbon group having 1 to 20 carbon atoms, and X ₁ and X ₂ are the same or different. Chiral metallocene compounds in which different halogen atoms or hydrocarbon groups Q are hydrocarbon-substituted silylene groups are preferred.

A specific example of the component [I] is 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, compounds obtained by replacing zirconium in the above compounds with hafnium are also preferably used. Further, 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. The aluminoxane compound has the general formula (2)
Alternatively, an aluminum compound represented by (3) is preferable.

[0047]

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[0048]

Embedded image

In the general formula (2) or (3), R is an alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and methyl, ethyl, propyl, butyl and isobutyl are preferred. No. 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, and 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, a method in which copper sulfate hydrate having water of crystallization is used. , Aluminum sulfate hydrate, a method of reacting adsorbed water with a trialkylaluminum in a hydrocarbon solvent using a hydrous silica gel or the like.

As the non-coordinating ionized compound, any known non-coordinating ionizing compound other than the aluminoxane compound can be used without 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 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 (4) 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 can be mentioned. Among them, tris (pentafluoro) borane is preferably used.

Examples of the boron-containing ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

Specifically, trialkyl-substituted ammonium salts include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, trimethylammonium (p -Tolyl) boron, trimethylammoniumtetra (o-tolyl) boron, tributylammoniumtetra (pentafluorophenyl) boron, tripropylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (m, m-dimethylphenyl) Boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (o-tolyl) boron, and the like,
N, N-dialkylanilinium salts include N, N-
Dimethylanilinium tetra (phenyl) boron, N,
N-diethylanilinium tetra (phenyl) boron,
N, N-2,4,6-pentamethylanilinium tetra (phenyl) boron and the like, and dialkylammonium salts include di (1-propyl) ammoniumtetra (pentafluorophenyl) boron and dicyclohexylammoniumtetra (phenyl) ) Boron and the like, and examples of triarylphosphonium salts include triphenylphosphonium tetra (phenyl) boron and tri (methylphenyl) phosphonium tetra (phenyl)
Boron and tri (dimethylphenyl) phosphonium tetra (phenyl) boron.

Among the above-mentioned boron atom-containing Lewis acids or boron atom-containing ionic compounds, triphenylcarbonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, 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 per mol of the transition metal in the component [I].
More preferably, it is 1 to 50,000 mol, and still more preferably, 10 to 30,000 mol. When the non-coordinating ionized compound is used as the component [II], the amount of the component [II] used (the molar amount of the Group 3B atom in the component [II]) is determined by the amount of the transition metal in the component [I]. For 1 mole,
0.01 to 10,000 mol is preferable, more preferably 0.1 to 5,000 mol, and still more preferably 1 to 3,
000 moles are preferred.

In the process for preparing a polypropylene component (a) and a copolymer component (b) of propylene and ethylene in the presence of a catalyst consisting of the components [I] and [II], if necessary, an organoaluminum may be used. Compounds (hereinafter abbreviated as component [III]) can also be used in combination. Ingredient [II
I] 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 general formula (5) include trimethylaluminum, triethylaluminum, trin-propylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum trin-hexylaluminum Trialkylaluminums such as tri-n-octylaluminum and tri-n-decylaluminum; dialkylaluminum monohalides such as diethylaluminum monochloride, diethylaluminum monobromide and diethylaluminum monofluoride; methylaluminum sesquichloride; ethylaluminum sesquichloride Chloride, ethylaluminum dichlorides, alkylaluminum halides, diethylaluminum monoethoxy , Alkoxy aluminum such as ethylaluminum ethoxide. 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 preferably 1 to 50,000 mol, more preferably 5 to 5 mol, per 1 mol of the transition metal atom in the component [I]. 〜１０10,000 mol. Particularly preferably, it is 10 to 5,000 mol.

The component [I] and / or the component [II]
It is also possible to use by supporting on a fine particle carrier (hereinafter abbreviated as component [IV]). When the above-mentioned 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 greatly 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 properties of the carrier vary depending on the kind and the production method, but the carrier preferably used in the present invention has a particle size of 10%.
３００300 μm, more preferably 20-200 μm, specific surface area is preferably 50-1000 m ³ / g, more preferably 100-700 m ³ / g, and pore volume is preferably 0.3-3.0 cm ³ / g. Preferably 0.5 to
2.5 cm ³ / g.

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

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 metallocene compound [I] to be used per 1 g of the fine particle carrier [IV] is 0.005 to 5% by transition metal atom.
A ratio of 1 mmol, preferably 0.05-0.5 mmol is desirable. When an aluminoxane compound is used as the component [II], the metallocene compound [I]
The amount of the aluminoxane compound used is preferably 1 to 200 mol, more preferably 15 to 150 mol, per 1 mol of the transition metal atom in the component [I], in terms of the molar amount of Al atoms. .

When a non-coordinating ionized compound is used, the amount of the non-coordinating ionized compound relative to the metallocene compound [I] is determined by the amount of 5A in the non-coordinating ionized compound.
It is preferably 0.1 to 20 mol per mol of the transition metal atom in the component [I] in terms of the molar amount of the group atom,
More preferably, it is 1 to 15 mol.

In order to obtain the obtained polymer with more excellent particle properties, the following method can be adopted. That is,
In the presence of the components [I], [II], [IV] and, if necessary, the components [III], first, the olefin is prepolymerized. Component in prepolymerization [II
The use amount of [I] is not particularly limited, but is preferably 1 to 50,0 based on 1 mol of the transition metal atom in the component [I].
00 mole, more preferably 5 to 10,000 mole. Particularly preferably, it is 10 to 5,000 mol.

The above components used in the prepolymerization may be added one by one successively, or a mixture thereof may be added all at once. Preferably, the components [I] and [I] are added to the catalyst component [IV].
V] 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 random copolymer with a higher bulk specific gravity.

The olefin used for preparing the prepolymerized catalyst component includes 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
Α-olefins such as hexadecene, 1-octadecene and 1-eicosene; cyclopentene, cycloheptene,
Such as norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene; And cyclic olefins.

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-pentene.

In the prepolymerization, it is preferable that the olefin is substantially homopolymerized in an amount of 95 mol% or more.

The polymerization amount of the olefin firstly applied in the prepolymerization of the present invention depends on the catalyst components [I], [II] and [I
V], preferably from 0.1 to 1 per gram of catalyst formed from
000 g, more preferably from 1 to 50 g.

Further, particularly preferred embodiments of the prepolymerization include the following [I], [II],
In the presence of each component of [IV] and if necessary [III],
First, a method in which propylene is prepolymerized to obtain a first prepolymerization catalyst, and then the prepolymerization of 1-butene is further carried out in a stepwise manner in the presence of the first prepolymerization catalyst and the above-mentioned component [III] is preferred. Used.

The amount of component [III] used in the prepolymerization 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 component [I]. 〜１０10,000 mol. More preferably, it is 10 to 5,000 mol. After obtaining the first prepolymerization catalyst by the above prepolymerization of propylene, usually,
It is desirable that unreacted propylene and component [III] used as required be removed by washing and subjected to the subsequent prepolymerization.

In each prepolymerization step, propylene and 1-butene each contain 95 mol% or more, preferably 98 mol%.
It is preferable to carry out substantially the above homopolymerization.

The polymerization amount of propylene initially applied in the prepolymerization is 0.1 to 1000 g, preferably 1 to 10 g per gram of the catalyst formed from the catalyst components [I], [II] and [IV]. Can be selected from the range of
-The polymerization amount of butene depends on the catalyst components [I], [II], [II]
0.1 to 1000 g per 1 g of the catalyst formed from I],
Preferably, it may be selected from the range of 1 to 500 g. The ratio of propylene polymerization amount to 1-butene polymerization amount is 0.001 to 10 by weight ratio of propylene polymerization amount / 1-butene polymerization amount.
0, preferably in the range of 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, particularly 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. 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.

The modifier A is produced by carrying out the polymerization of the polypropylene component and the polymerization of the copolymer component of propylene and ethylene stepwise in the presence of the above-mentioned catalyst component. The polymerization order is not particularly limited, but it is preferable to produce the polypropylene component (a) in the first step and the copolymer component (b) of propylene and ethylene in the second step to produce a polymer with good particle properties. Preferred for.

The polymerization conditions are not particularly limited as long as the effect is recognized, but the following conditions are generally preferred.

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

In the polymerization of the polypropylene component (a),
Hydrogen can also be allowed to coexist 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.

Next, random copolymerization of propylene and ethylene is performed. In the random copolymerization of propylene and ethylene, in the case of slurry polymerization using propylene itself as a solvent, ethylene gas is supplied following the propylene polymerization, and in the case of gas phase polymerization, a mixed gas of propylene and ethylene is supplied. It is implemented by doing.

In the random copolymerization of propylene and ethylene, it is preferable to carry out one-stage random copolymerization after propylene polymerization, but it is also possible to produce by varying the ethylene supply concentration in multiple stages. The polymerization temperature of the random copolymerization of propylene and ethylene is preferably in the range of 0 to 100 ° C, preferably 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 and ethylene may be any of a batch system, a semi-batch system and a continuous system, 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 modifier A of the present invention can be obtained by evaporating the monomers from the polymerization system. This modifier A can be subjected to known washing or countercurrent washing with a hydrocarbon having 7 or less carbon atoms.

The method for producing the polyolefin resin composition of the present invention by mixing the modifier A with the crystalline polyolefin resin as described above is not particularly limited. For example, a powder blending method or a pellet blending method using a tumbler, Henschel mixer, or the like can be used.

When the polyolefin resin composition of the present invention is produced by polymerization in the course of producing the active ingredient of the modifier A and the crystalline polyolefin resin, for example, a polypropylene resin having a different stereoregularity is used. A method of mixing several kinds of polymerizable catalyst components to polymerize propylene can be mentioned. In particular, a method of polymerizing propylene by mixing two or more kinds of a solid titanium catalyst component, an organoaluminum compound, and an electron donor that provides a polypropylene resin having a different stereoregularity can be suitably used.

In this method, as the electron donor, those generally known in the polymerization of propylene can be used without any limitation, but the organosilicon compounds represented by the following general formulas (V) and (VI) can be used. When used in combination, the elution temperature by the TREF / SEC method within the range of the present invention is 36 to
104 ° C, a component having a molecular weight in the range of 100,000 to 1,000,000
It is particularly preferable because a composition containing up to 20% by weight can be easily obtained.

[0099]

Embedded image

(R ₃ ) _n -Si- (OC ₂ H ₅ ) _4-n (VI) (where R ₁ , R ₂ and R ₃ are the same or different hydrocarbon groups, and n is 0 or 1) Is.)

As the above-mentioned solid titanium catalyst component, a compound known to be used for the polymerization of propylene can be used without any limitation. In particular, a solid titanium catalyst component having high catalytic activity and containing titanium, magnesium and halogen as components is preferable. Such a catalyst component is obtained by supporting a titanium halide, particularly titanium tetrachloride, on various magnesium compounds, especially magnesium chloride.

As the organoaluminum compound, a compound known to be used for the polymerization of propylene can be employed without any limitation.

For example, trimethylaluminum, triethylaluminum, tri-n-propylaluminum,
Tri-n-butyl aluminum, tri-isobutyl aluminum, tri-n-hexyl aluminum, tri-n
Trialkylaluminums such as -octylaluminum and tri-n-decylaluminum; diethylaluminum monohalides such as diethylaluminum monochloride; alkylaluminum halides such as methylaluminum dichloride and ethylaluminum dichloride.

In addition, monoethoxydiethylaluminum,
Alkoxy aluminums such as diethoxy monoethyl aluminum can be used. Among them, triethylaluminum is most preferred.

The amount of the organoaluminum compound to be used is preferably from 10 to 1,000, more preferably from 50 to 500, in terms of aluminum / titanium (molar ratio) based on titanium atoms in the solid titanium catalyst component.

In the organosilicon compounds represented by formulas (V) and (VI), R ₁ , R ₂ and R ₃
May be a chain, branched, or cyclic aliphatic hydrocarbon group or an aromatic hydrocarbon group, and the number of carbon atoms is not particularly limited.

Examples of suitable hydrocarbon groups in the present invention include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl,
1 to 1 carbon atoms such as t-butyl group, pentyl group and hexyl group
C6 alkyl groups such as vinyl group, propenyl group and allyl group; C2-6 alkynyl groups such as ethynyl group and propynyl group; cyclopentyl group, cyclohexyl group, cycloheptyl group and the like Carbon number 5
And a cycloalkyl group of 7 to 7; an aryl group having 6 to 12 carbon atoms such as a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. Among them, R3 is preferably a linear alkyl group, alkenyl group, or aryl group. N is 0 or 1.

Examples of the organosilicon compound preferably used in the present invention are as follows.

Examples of the organosilicon compound represented by the general formula (V) include dimethyldimethoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, divinyldimethoxysilane, diallyldimethoxysilane,
Di-1-propenyldimethoxysilane, diethynyldimethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, cyclohexylmethyldimethoxysilane, tert-butylethyldimethoxysilane, ethylmethyldimethoxysilane, propylmethyldimethoxysilane, cyclohexyltrimethoxysilane,
Examples thereof include diisopropyldimethoxysilane, dicyclopentyldimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, and allyltrimethoxysilane.

Examples of the organosilicon compound represented by the general formula (VI) include, for example, tetraethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, pentyltriethoxysilane, and isopropyltriethoxysilane. Ethoxysilane, 1-propenyltriethoxysilane, isopropenyltriethoxysilane, ethynyltriethoxysilane,
Octyltriethoxysilane, dodecyltriethoxysilane, phenyltriethoxysilane, allyltriethoxysilane and the like can be mentioned.

The amount of the organosilicon compounds represented by the general formulas (V) and (VI) is set to 0.1 in terms of Si / Ti (molar ratio) with respect to Ti atoms of the solid titanium catalyst component.
It is preferably from 1 to 500, and more preferably from 1 to 100. Further, the use ratio of these two kinds of organosilicon compounds needs to be (V) :( VI) = 1: 5-1: 25 in a molar ratio, and may be 1: 10-10: 20. preferable. When the use ratio of the organosilicon compounds (V) and (VI) is less than 1: 5, the elution peak width of the obtained polypropylene resin by TREF becomes narrow, that is, when the elution temperature is 36 to 104 ° C. Since the amount of the component is low, the stretchability at the time of film formation is reduced, the mechanical load is increased, and the stretch of the film is easily broken.

The order of addition of the above-mentioned components is not particularly limited, and the organosilicon compounds represented by the general formulas (V) and (VI) may be mixed and supplied simultaneously or separately. These can also be supplied after contacting or mixing with the organoaluminum compound in advance.

The other polymerization conditions are not particularly limited as long as the effects of the present invention are recognized, but generally the following conditions are preferred. The polymerization temperature is from 20 to 200 ° C, preferably from 50 to 200 ° C.
The temperature is 150 ° C., and hydrogen can be allowed to coexist as a molecular weight regulator. The polymerization can be performed by slurry polymerization, solventless polymerization, gas phase polymerization, or the like, and may be any of batch, semi-batch, and continuous methods.
It can be performed in stages. Before the polymerization of propylene, preliminary polymerization of propylene or another monomer may be performed. Further, the above polymerization may be performed in multiple stages.

In the present invention, the polypropylene resin composition obtained by the above method can be used alone, or can be used by blending with another polypropylene resin. Of course, it is also possible to blend the polypropylene resin compositions obtained by the above method.

In the present invention, the polyolefin resin composition obtained as described above may be used as it is or by appropriately selecting a polyolefin resin composition having an elution temperature of 36 to 104 ° C. by TREF / SEC and a molecular weight of 100 to 1,000,000. Can be made into a polyolefin resin composition containing 4 to 20% by weight. Alternatively, the polyolefin resin composition of the present invention having a desired composition can be obtained by further mixing a modifier A or a crystalline polyolefin resin with the resin composition.

The polyolefin resin composition of the present invention having an elution temperature by TREF / SEC exceeding 116 ° C. and containing 4 to 20% by weight of a component having a molecular weight in the range of 10,000 to 100,000 is the same as described above. It is possible to obtain. The elution temperature by the TREF / SEC method is 116
C. and a molecular weight in the range of 10,000 to 100,000
It can also be produced by mixing a modifier (hereinafter, referred to as a modifier B) and a modifier A containing more than 0% by weight to 100% by weight with a crystalline polyolefin resin.

The modifier B is a highly crystalline polypropylene resin. The melt flow rate of the modifier B is not particularly limited, but is preferably in the range of 5 to 100 g / 10 min, and more preferably 30 to 80 g / 10 min in consideration of the moldability into a film. More preferably, it is within the range. Also, the weight average molecular weight (M
w) is suitably in the range of 50,000 to 800,000, preferably 100,000 to 300,000.

Molecular weight distribution (Mw / Mn) of the above modifier B
Is not particularly limited, but is preferably from 1.5 to 40, and more preferably from 2 to 10 in consideration of the ease of forming a film and the increase in melt tension to improve workability. More preferred.

Although the melting point of the modifier B is not particularly limited, it is preferably 150 ° C. or higher,
More preferably, it is in the range of 55 to 170 ° C.

The peak top temperature of the elution curve of the above modifier B by the TREF method is preferably 110 or more and 115 to 130 ° C. in consideration of the rigidity and heat resistance of the stretched film obtained by forming the film. More preferably, it is within the range.

The components eluted at 0 ° C. or lower in the TREF / SEC method of the above-mentioned modifier B are not particularly limited, but include those such as blocking resistance, scratch resistance, and slip resistance of the formed polyolefin film. Considering the film surface properties, the content is preferably 5% by weight or less, more preferably 3% by weight or less.

[0122] Further, the modifying agent B is, if the content of a propylene homopolymer and propylene -α-olefin copolymer other than propylene α- olefin is less than 1 mol%, ¹³ C indicating the crystallinity Although the isotactic pentad fraction by -NMR is not particularly limited, it is preferably 0.80 to 1 and 0.93 to
More preferably, it is 0.99.

Further, a modifier (referred to as modifiers A and B) in which the modifier A and the modifier B were previously mixed at a ratio of 20 to 80 or 80 to 20 was obtained, and this was mixed with a crystalline polyolefin. It is also possible to mix with resin.

The weight ratio (B / A) of each active ingredient of the modifier A and the modifier B mixed in the crystalline polyolefin resin is as follows:
Preferably in the range of 0.5-2, more preferably 0.8-
The range is 1.5. By setting the content in this range, it is possible to improve the stretchability in film formation, that is, to increase the range of the temperature at which film formation is possible in stretching, reduce the mechanical load, reduce film breakage, and improve the accuracy of thickness and thickness.

The polyolefin resin composition used in the present invention may contain, if necessary, an antioxidant, a chlorine scavenger, a heat stabilizer, an antistatic agent, an antifogging agent, an ultraviolet absorber, a lubricant,
Additives such as a nucleating agent, an anti-blocking agent, a pigment, other resins and fillers may be blended as long as the effect is not impaired.

The polyolefin resin composition of the present invention can be used for the production of any molded product and exhibits excellent extrusion characteristics and stretchability. Particularly, when the film is formed by a stretching process for obtaining a stretched film. It has a remarkable effect.

The stretched polyolefin film of the present invention may be any of a biaxially stretched film and a uniaxially stretched film. The thickness of the stretched film is not particularly limited, but is preferably in the range of 3 to 150 μm for a biaxially stretched film and 10 to 254 μm for a uniaxially stretched film. The stretched polyolefin film of the present invention is stretched in at least one direction. Of course, it may be stretched biaxially. Although the stretching ratio is not particularly limited, it is generally 4 to 10 times in the uniaxial direction,
In the case of biaxial stretching, it is general that the film is further stretched in a direction perpendicular to that direction in a range of 4 to 15 times.

One or both surfaces of the stretched polyolefin film of the present invention may be subjected to a surface treatment such as a corona discharge treatment, if necessary. Further, a layer made of another resin having a lower melting point than the polyolefin resin used in the present invention may be laminated on one side or both sides for the purpose of imparting a function such as heat sealability. The method of laminating other resins is not particularly limited, but a co-extrusion method, a laminating method and the like are preferable.

As the method for producing a stretched polyolefin film of the present invention, a known method can be employed without any limitation. For example, as a method of manufacturing a stretched film by a sequential biaxial stretching method by a tenter method, the above polypropylene composition is formed into a sheet or film by a T-die method, an inflation method, and the like, and then supplied to a longitudinal stretching apparatus and heated. The film is longitudinally stretched 3 to 10 times at a roll temperature of 120 to 170 ° C., and then a tenter temperature of 130 to 130 is applied using a tenter.
A method in which the film is laterally stretched 4 to 15 times at 180 ° C. is preferable.

Although the above molding conditions are not particularly limited, in order to obtain a good stretched film having good thickness / thin accuracy and fusing sealability, it is required that the longitudinal stretching be performed at 145 to 170 ° C. 3 to 5 times.
In the horizontal stretching, it is preferable to stretch 4 to 12 times at 155 to 180 ° C. Furthermore, if necessary, 0 to 2
A method of performing heat treatment at 80 to 180 ° C. while allowing 5% relaxation can be given. Of course, after these stretching, stretching may be performed again.
Stretching methods such as rolling can be combined. Also, a stretched film can be obtained by stretching only uniaxially.

[0131]

As described above, the polyolefin resin composition of the present invention comprises:
When forming a stretched film, the temperature control range in which the film can be formed is wider than that of conventionally known polyolefin resins, the mechanical load during stretching is small, the thickness and thinness of the formed film are excellent, the stretchability is good, and the stretching is performed. It is hard to break. Therefore, it is a polyolefin resin suitable for producing a stretched film that can be stably operated continuously for a long time at high speed. further,
The heat resistance such as the heat shrinkage of the formed stretched film is good. Such effects indicate that the polyolefin resin composition of the present invention is excellent as a polyolefin resin composition for a stretched film, and has extremely high industrial value.

[0132]

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.

(1) TREF / SEC The molecular weight distribution curve, the weight average molecular weight and the elution amount of the elution temperature range by TREF / SEC were measured using a multipurpose liquid chromatograph manufactured by Uniflows Co., Ltd. in the TREF / SEC mode under the following conditions. Measured.

Solvent: ortho-dichlorobenzene TREF column: 4.6 mmφ × 150 mm Filler: Chromosolve P Flow rate: 1.0 ml / min Crystallization conditions: 140 ° C. to 0 ° C. (Cooling rate: 2.0 ° C.)
/ Hour) Temperature rise condition: 4 ° C step Total 36 fractions (0,4,4)
8, 12, 16, 20, 24, 28, 32, 36, 4
0,44,48,52,56,60,64,68,7
2,76,80,84,88,92,96,100,1
04, 108, 112, 116, 120, 124, 12
8, 132, 136, 140) SEC column: SHOdex UT 807 + 806M ×
Two SEC thermostat: 145 ° C Detector: Infrared detector for high temperature liquid chromatography Measurement wave number: 3.41 μm Sample concentration: 0.4 wt% Injection amount: 500 μl

In this case, after the sample solution was introduced into the TREF column at 140 ° C., the liquid feeding was stopped, and the temperature was reduced from 140 ° C. to 0 ° C.
The temperature is lowered at 2 ° C./hour until the sample polymer is crystallized on the filler surface. After holding at 0 ° C. for 30 minutes, the components dissolved at 0 ° C. are introduced into the SEC column at 1.0 ml / min, and SEC measurement is performed. In the meantime, in the TREF constant temperature bath, the temperature is rapidly raised to the next measurement temperature (4 ° C.) and kept until the SEC measurement is completed. Similarly, a component dissolved at 4 ° C. is introduced into an SEC column to perform SEC measurement. Thereafter, SEC measurement is repeatedly performed up to the set temperature.

(2) TREF The elution temperature measured by TREF was measured in a TREF mode under the following conditions using a multipurpose liquid chromatograph manufactured by Uniflows.

Solvent: ortho-dichlorobenzene TREF column: 4.6 mmφ × 150 mm Filler: Chromosolve P Flow rate: 1.0 ml / min Crystallization conditions: 140 ° C. to 0 ° C. (Cooling rate: 2.0 ° C.)
/ Hour) Temperature rise condition: Continuous temperature rise 40 ° C / hr (Temperature range 0 ° C)
Detector: infrared detector for high temperature liquid chromatography Measurement wave number: 3.41 μm Sample concentration: 0.4 wt% Injection amount: 500 μl

As in the TREF / SEC measurement, the sample is crystallized, kept at 0 ° C. for 30 minutes, and the concentration of the dissolved component is detected at 0 ° C. Thereafter, while elevating the TREF column temperature linearly at a predetermined rate, the concentration is detected by flowing the solvent, and the elution amount with respect to the elution temperature is obtained.

(3) Melt flow rate (MFR) Measured according to JIS K7210.

(4) Molecular weight distribution High-temperature GPC apparatus SSC-7100 manufactured by Senshu Kagaku Co., Ltd.
And the weight average molecular weight and the number average molecular weight calculated from the elution profile measured under the following conditions.

Solvent: ortho-dichlorobenzene Flow rate: 1.0 ml / min Column temperature: 145 ° C. Detector: high-temperature differential refraction detector Column: SHOdex UT807 (1), 806M (2),
802.5 (1 piece) Sample concentration: 0.1 wt% Injection volume: 0.50 ml

(5) Pentad fraction Measured under the following conditions using JNM-GSX-270 ( ^13C- nuclear resonance frequency 67.8 MHz) manufactured by JEOL Ltd.

Measurement mode: 1H-complete decoupling Pulse width: 7.0 microseconds (C45 degrees) Pulse repetition time: 3 seconds Integration count: 50,000 times Solvent: Mixed solvent of ortho-dichlorobenzene / deuterated benzene (90/10 (% By volume) Sample concentration: 120 mg / 2.5 ml Solvent Measurement temperature: 120 ° C

In this case, the pentad fraction is 13 C-NM
It was determined by measuring the splitting peak in the methyl group region of the R spectrum. The peak of the methyl group region was assigned to A.I. Zambelli et al [Macromol
ecules 13, 267 (1980)].

(6) DSC Measurement The melting point was measured under the following conditions using a DSC6200R apparatus manufactured by Seiko Instruments Inc.

Heating rate: 10 ° C./min (Temperature range 230 to
(30 ° C) Temperature drop rate: 10 ° C / min (Temperature range -30 to 2)
30 ° C)

Example 1 (Adjustment of solid titanium catalyst)
It carried out according to the method of Example 1 of Unexamined-Japanese-Patent No. 58-83006. That is, 9.5 g (100 mmol) of anhydrous magnesium chloride, 100 ml of decane and 2
-47 ml of ethylhexyl alcohol (300 mmo
l) was heated and stirred at 125 ° C. for 2 hours, and 5.5 g (37.5 mmol) of phthalic anhydride was added to the solvent.
The mixture was further stirred and mixed at 125 ° C. for 1 hour to obtain a uniform solution.

After cooling to room temperature, the whole amount was charged dropwise over 1 hour into 400 ml (3.6 mmol) of titanium tetrachloride kept at -20 ° C. Thereafter, the temperature of the mixture was raised to 110 ° C. over 2 hours, and when the temperature reached 110 ° C., 5.4 ml of diisobutyl phthalate (25 m
mol) was added and kept under stirring at 110 ° C. for 2 hours. After completion of the reaction for 2 hours, a solid portion was collected by hot filtration, and the solid portion was resuspended in 2000 ml of titanium tetrachloride, and then heated 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 solid titanium catalyst prepared by the above production method was stored as a heptane slurry. The composition of the solid titanium catalyst was 2.1% by weight of titanium, 57.0% by weight of chlorine, 18.0% by weight of magnesium, and 21.9% by weight of diisobutyl phthalate.

(Preliminary polymerization) In a 10-L polymerization vessel purged with nitrogen, 2000 ml of purified n-hexane, 500 mmol of triethylaluminum, 25 mmol of cyclohexylmethyldimethoxysilane, and 50 mmol of the solid titanium compound subjected to the contact treatment in terms of titanium atoms. After charging, propylene was continuously introduced into the polymerization reactor for 1 hour so that the amount became 2 g per 1 g of the solid titanium catalyst component.
The temperature during this period was kept at 15 ° C.

After one hour, the reaction was stopped, and the inside of the reactor was sufficiently purged with nitrogen. The solid part of the obtained slurry was washed five times with purified n-hexane to obtain a prepolymerized catalyst (titanium-containing polypropylene). As a result of the analysis, 1.7 g of propylene was polymerized per 1 g of the solid titanium catalyst.

(Main Polymerization) Content of Nitrogen-substituted 200
Into a 0 L polymerization vessel, 500 kg of propylene was charged, 1752 mmol of triethylaluminum, and cyclohexylmethyldimethoxysilane as an organosilicon compound.
After charging 5 mmol, 350 mmol of tetraethoxysilane and 10 L of hydrogen, the internal temperature of the polymerization vessel was raised to 65 ° C. 4.38 mmol of the prepolymerized catalyst obtained by the above prepolymerization was charged with titanium atoms, then the internal temperature of the polymerization vessel was raised to 70 ° C., and propylene and ethylene were copolymerized for 2 hours.

After completion of the polymerization, unreacted propylene was purged, and the obtained white granular polymer was dried under reduced pressure at 70 ° C. for 1 hour. Tables 1 and 2 show the structural characteristics of the obtained polyolefin resin a.

(Granulation) 0.1 part by weight of 2,6-di-t-butylhydroxytoluene as an antioxidant and 100 parts by weight of the polyolefin resin a powder obtained in the above (main polymerization), and a chlorine scavenger Add calcium stearate to 0.
1 part by weight, 0.2 parts by weight of stearyl diethanolamide as an antistatic agent, and spherical polymethyl methacrylate particles having an average particle size of 1.5 μm as an antiblocking agent.
After adding 1 part by weight and mixing with a Henschel mixer for 5 minutes, the mixture was added to an extruder having a screw diameter of 65 mmφ using an extrusion granulator.
The mixture was extruded at 0 ° C., and the pellets were granulated to obtain raw material pellets.

(Formation of Biaxially Stretched Film) A film forming experiment of a biaxially stretched film was performed using the obtained raw material pellets by the following method. Raw material pellets, screw diameter 90m
Using a m-diameter T-die sheet extruder, the sheet was extruded at 280 ° C., and a 1 mm thick sheet was formed with a cooling roll at 30 ° C. Next, the raw sheet was stretched 5.6 times between rolls in the machine direction (MD) using a tenter-type sequential biaxial stretching apparatus, and subsequently in a tenter at 165 ° C. in the transverse direction (T).
After stretching by 10 times at mechanical magnification in D), the film was relaxed by 4% and heat-treated to form a biaxially stretched polyolefin film having a thickness of 20 μm at a speed of 50 m / min.

At the time of film formation, the roll preheating temperature for longitudinal stretching was changed, and the temperature range in which film formation was possible (lower limit temperature to upper limit temperature) was evaluated. The roll preheating temperature was lowered, and the lower limit temperature at which stable film formation was possible for 10 minutes without causing whitening of the film, unevenness in thickness, thinness of the film, and the like was defined as the lower limit temperature at which film formation was possible.

Further, the preheating temperature of the roll is increased, and the upper limit temperature at which stable film formation can be performed for 10 minutes without causing whitening, thickness unevenness, etc. of the film due to melting of the surface of the longitudinally stretched sheet is set to the upper limit temperature at which the film can be formed. And The difference between the upper limit temperature at which the film could be formed and the lower limit temperature at which the film could be formed was defined as the temperature range over which the film could be formed.

The mechanical load (current value, unit ampere) applied to the longitudinal stretching and the transverse stretching at the center temperature of the temperature range.
The film formability (stretchability) was evaluated by In addition, the influence of the stretching unevenness on the thickness and thinness accuracy was evaluated according to the following criteria based on the thickness pattern of the film measured using an infrared thickness measuring machine WEB GAGE manufactured by Yokogawa Electric Corporation installed between the tenter and the winding machine. .

A: less than ± 0.5 μm ○: ± 0.5 μm or more and less than 1.0 μ Δ: ± 1.0 μm or more and less than 1.5 μ ×: ± 1.5 μm or more

Further, continuous operation was carried out for 5 hours, and the number of film stretching tears in the tenter was evaluated. One side of the formed film was subjected to a corona discharge treatment of 30 W min / m ² according to a conventional method, and was wound up. After the obtained stretched film was aged at 40 ° C. for 3 days, the heat shrinkage (heat resistance) was measured by the following method.

Using the MD and TD of the film in the length direction, a sample was cut out into a tape shape having a length of 600 mm and a width of 15 mm, and a mark was placed at a position of 500 mm length (50 mm from both ends). After standing for a minute,
The film sample was taken out, cooled at room temperature for 15 minutes, the length between marks was measured, and the heat shrinkage was measured by the following equation. Heat shrinkage (%) = {(L _O −L _S ) / L _O } × 100 where L _O : length between marks before heat shrink (500 mm) L _S : length between marks after heat shrink (Mm) film forming temperature range, mechanical load in longitudinal and transverse stretching, number of times of film stretching torn in continuous operation for 5 hours,
Table 3 shows the results of the heat shrinkage of the MD and TD of the thickness precision, the stretched film.

Example 2 In the main polymerization, homopolymerization of propylene was carried out using 27 mmol of cyclohexylmethyldimethoxysilane and 285 mmol of ethyltriethoxysilane as organosilicon compounds, and polyolefin resin b shown in Table 1 was obtained. The procedure was the same as in Example 1. The results are shown in Tables 1, 2, and 3.

Comparative Example 1 In the main polymerization, propylene homopolymerization was performed using 164 mmol of cyclohexylmethyldimethoxysilane alone as an organosilicon compound to obtain polypropylene (polyolefin resin c) as shown in Table 1. Performed similarly to 1. The results are shown in Tables 1, 2, and 3.

Comparative Examples 2 and 3 Polyolefin resins d and e were obtained in the same manner as in Comparative Example 1, except that copolymerization with ethylene was carried out. The results are shown in Tables 1, 2, and 3.

Comparative Example 4 In the main polymerization, propylene was homopolymerized using t-butylethyldimethoxysilane as the organosilicon compound. Otherwise in the same manner as in Comparative Example 1, a polyolefin resin f was obtained. The results are shown in Tables 1, 2, and 3.

Example 3 In the main polymerization, copolymerization with ethylene was carried out. Otherwise in the same manner as in Comparative Example 1, a polyolefin resin g shown in Table 1 was obtained.

Comparative Example 1
Using the polyolefin resin c obtained in the above, the blending amounts were as shown in Table 2. Other than that, it carried out similarly to Example 1. The results are shown in Tables 2 and 3.

Examples 4 and 5 The same procedures as in Example 3 were carried out except that the amounts shown in Table 2 were used. The results are shown in Tables 2 and 3.

Example 6 The propylene-ethylene copolymer (Sanyo Kasei Biscol 660 (polyolefin resin h)) shown in Table 1 and the polyolefin resin d obtained in Comparative Example 2 were used, and the blending amounts shown in Table 2 were used. Other than that, it carried out similarly to Example 1. The results are shown in Tables 2 and 3.

Example 7 Production Method of Polyolefin Resin i (Preparation of Supported Metallocene Catalyst) Silica-supported methylaluminoxane (MAO on SiO ₂ , manufactured by Whitco, 25 wt% -Al product) was added to 10 g of rac-dimethylsilylenebis-1- ( 100 ml of toluene solution of 2-methylbenzindenyl) zirconium dichloride (0.0
05 mmol / ml toluene solution) at room temperature.
Stirred for 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) 600 kg of propylene was inserted into a polymerization tank having an internal volume of 2 m ³ , and triisobutylaluminum 6
12 mmol were introduced. Thereafter, the internal temperature of the polymerization tank was reduced to 55
The temperature was raised to ° C. Next, ethylene gas is added at a gas phase concentration of 6.
After supplying so as to be 0 mol%, 10 g of the metallocene catalyst supported on the silica gel was charged. Subsequently, the internal temperature of the autoclave is raised to 60 ° C., and ethylene gas is supplied while maintaining the ethylene gas phase concentration at a constant level.
Polymerization was carried out for hours.

After completion of the polymerization, unreacted propylene was purged and dried at 50 ° C. for 1 hour to obtain 175 kg of a white granular polymer. Table 1 shows the structural characteristics of the obtained propylene-ethylene copolymer (polyolefin resin i).
It was shown to.

The above polyolefin resin i and Comparative Example 2
The procedure was performed in the same manner as in Example 1 except that the blending amount shown in Table 2 was used using the polyolefin resin d obtained in the above. The results are shown in Tables 2 and 3.

Example 8 Method for Producing Polyolefin Resin j (Polymerization) (Pre-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 a metallocene catalyst supported on silica gel obtained in the same manner as in Example 7 [Preparation of supported metallocene catalyst] 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 in a gas phase concentration of 1%.
The copolymerization was carried out for 70 minutes while supplying the solution to a concentration of 0.1 mol% and further keeping the gas phase concentration of ethylene constant. After completion of the polymerization, unreacted propylene is purged, and 5
By drying at 0 ° C. for 1 hour, 135 kg of a white granular polymer was obtained. Table 1 shows the structural characteristics of the obtained polyolefin resin j.

The above polyolefin resin j and Comparative Example 2
The procedure was performed in the same manner as in Example 1 except that the blending amount shown in Table 2 was used using the polyolefin resin d obtained in the above. The results are shown in Tables 2 and 3.

Example 9 175 kg of a white granular polymer was obtained in the same manner as in Example 8, except that the gas phase ethylene concentration in the second-stage polymerization was changed to 17.2 mol%. Table 1 shows the structural characteristics of the obtained polyolefin resin k.

The procedure was carried out in the same manner as in Example 1, except that the polyolefin resin k and the polyolefin resin d obtained in Comparative Example 2 were used and the amounts shown in Table 2 were used. Table 2 shows the results.
3 is shown.

Examples 10 to 12 A commercially available propylene-butene copolymer (polyolefin resin 1) shown in Table 1 and the polyolefin resin d obtained in Comparative Example 2 were used, except that the blending amounts shown in Table 2 were used. , And in the same manner as in Example 1. The results are shown in Tables 2 and 3.

Comparative Example 5 The same procedure as in Example 1 was carried out, except that the olefin resin 1 used in Example 10 and the polyolefin resin c obtained in Comparative Example 1 were used and the amounts shown in Table 2 were used. The results are shown in Tables 2 and 3.

Examples 13 and 14 The same procedures as in Example 1 were carried out, except that the olefin resin 1 used in Example 10 and the polyolefin resin c obtained in Comparative Example 1 were used and the amounts shown in Table 2 were used. Was. The results are shown in Tables 2 and 3.

Comparative Example 6 The procedure of Example 1 was repeated, except that the olefin resin 1 used in Example 10 and the polyolefin resin c obtained in Comparative Example 1 were used and the amounts shown in Table 2 were used. The results are shown in Tables 2 and 3.

Examples 15 to 17 The same procedure as in Example 1 was carried out except that the polyolefin resin j obtained in Example 8 and the polyolefin resin c obtained in Comparative Example 1 were used and the amounts shown in Table 2 were used. Was. The results are shown in Tables 2 and 3.

Example 18 The procedure of Example 1 was repeated, except that the polyolefin resin k obtained in Example 9 and the polyolefin resin c obtained in Comparative Example 1 were used in the amounts shown in Table 2. The results are shown in Tables 2 and 3.

Examples 19 and 20 The same procedures as in Example 1 were carried out except that the polyolefin resin k obtained in Example 9 and the polyolefin resin f obtained in Comparative Example 4 were used in the amounts shown in Table 2. Was. The results are shown in Tables 2 and 3.

Comparative Example 7 Commercially available elastomer (polyolefin resin m) shown in Table 1
And using the polyolefin resin f obtained in Comparative Example 4, Table 2
The procedure was performed in the same manner as in Example 1 except that the amounts were as shown in Table 1. The results are shown in Tables 2 and 3.

Examples 21 and 22 (Preparation of solid titanium catalyst)
It carried out according to the method of Example 1 of Unexamined-Japanese-Patent No. 58-83006.

That is, anhydrous magnesium chloride 0.95
g (10 mmol), 10 ml of decane and 4.7 ml (30 mmol) of 2-ethylhexyl alcohol in 125
After heating and stirring at 2 ° C. for 2 hours, 0.55 g (6.75 mmol) of phthalic anhydride was added to the solvent, and the mixture was further stirred and mixed at 125 ° C. for 1 hour to obtain a homogeneous solution. After cooling to room temperature, the whole amount was dropped into 40 ml (0.36 mmol) of titanium tetrachloride kept at -20 ° C over 1 hour.

Thereafter, the temperature of the mixture was raised to 110 ° C. over 2 hours. When the temperature reached 110 ° C., 0.54 ml (2.5 mmol) of diisobutyl phthalate was added, and the mixture was heated to 110 ° C. for 2 hours. And kept under stirring.
After completion of the reaction for 2 hours, a solid portion was collected by hot filtration, and the solid portion was resuspended in 200 ml of titanium tetrachloride, and then heated again at 110 ° C. for 2 hours.

After the completion of the reaction, the 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 solid titanium catalyst prepared by the above manufacturing method was stored as a heptane slurry. The composition of the solid titanium catalyst was 2.1% by weight of titanium, 57.0% by weight of chlorine, and 1% of magnesium.
8.0% by weight and 21.9% by weight of diisobutyl phthalate.

(Preliminary polymerization) 200 ml of purified n-hexane, 50 mmol of triethylaluminum, 10 mmol of didiclope, and 5 mmol of a solid titanium compound component subjected to a contact treatment were charged into a 1 L polymerization vessel subjected to nitrogen substitution in terms of titanium atoms. Thereafter, propylene was continuously introduced into the polymerization reactor for 30 minutes so that the amount became 2 g per 1 g of the solid titanium catalyst component. The temperature during this period was kept at 10 ° C. After 30 minutes, the reaction was stopped, and the inside of the reactor was sufficiently purged with nitrogen. The solid part of the obtained slurry was washed five times with purified n-hexane to obtain a prepolymerized catalyst (titanium-containing polypropylene). As a result of the analysis, 1.7 g of propylene was polymerized per 1 g of the solid titanium catalyst.

(Main polymerization) Nitrogen-substituted content 400
100 kg of propylene was charged into a polymerization vessel of L, 75 mmol of triethylaluminum, and 37.5 mmol of didicopentyldimethoxysilane as an organosilicon compound.
l, and after charging hydrogen gas, the internal temperature of the polymerization vessel was raised to 65
The temperature was raised to ° C. 0.25 mmol of the prepolymerized catalyst obtained by the above prepolymerization was charged as titanium atoms, and then the internal temperature of the polymerization vessel was raised to 70 ° C., and polymerization was performed for 6 hours.

After the completion of the polymerization, 50 ml of methanol as a polymerization terminator was added to stop the reaction. Then, 30 kg of liquid propylene was added to the polymerization tank, and the mixture was stirred for 1 hour, allowed to stand still to precipitate polymer particles, and The propylene portion was withdrawn from the top of the polymerization tank with a withdrawal nozzle. The polymer slurry in the polymerization tank was sent to a flash tank and separated from unreacted propylene to obtain a white granular polymer. Table 1 shows the structural characteristics of the obtained polyolefin resin n.

Polyolefin resin used in Example 10
The procedure was performed in the same manner as in Example 1 except that the above-mentioned polyolefin resin n and the polyolefin resin d obtained in Comparative Example 2 were used, and the amounts shown in Table 2 were used. Table 2 shows the results.
3 is shown.

Example 23 Using the polyolefin resin k obtained in Example 9 and the polyolefin resin n obtained in Example 21 shown in Table 1 and the polyolefin resin c obtained in Comparative Example 1, the amounts shown in Table 2 were used. Except having performed, it carried out similarly to Example 1. The results are shown in Tables 2 and 3.

Examples 24 to 26 (Preparation of Solid Titanium Catalyst)
It carried out according to the method of Example 1 of Unexamined-Japanese-Patent No. 7-292029.

That is, 10 g of diethoxymagnesium and 80 ml of toluene were charged into a 200-ml round bottom flask equipped with a stirrer and sufficiently replaced with nitrogen gas, to obtain a suspended state. Next, 20 ml of titanium tetrachloride was added to the suspension, and the temperature was raised. When the temperature reached 80 ° C., 2.7 ml of di-n-butyl phthalate was added, and the temperature was further raised to 110 ° C. Thereafter, the mixture was reacted while stirring at a temperature of 110 ° C. for 2 hours. After the reaction, 9
After washing twice with 100 ml of toluene at 0 ° C., 20 ml of fresh titanium tetrachloride and 80 ml of toluene were added.
The temperature was raised to 0 ° C., and the reaction was carried out with stirring for 2 hours.

After the reaction, n-heptane 100 at 40 ° C.
After washing 10 times with ml, a solid titanium catalyst was obtained. The solid-liquid in the solid titanium catalyst was separated, and the content of titanium in the solid was measured to be 2.91% by weight.

Then, prepolymerization and main polymerization were carried out in the same manner as in Example 21 to obtain a white granular polymer. Table 1 shows the structural characteristics of the obtained polyolefin resin o.

The polyolefin resin k obtained in Example 9 and the polyolefin resin o obtained in Example 9 shown in Table 1 and the polyolefin resin d obtained in Comparative Example 2 were used, and the blending amounts shown in Table 2 were used. Performed similarly to 1. The results are shown in Tables 2 and 3.

[0201]

[Table 1]

[0202]

[Table 2]

[0203]

[Table 3]

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Paper junior high school 1-1 Mikage-cho, Tokuyama-shi, Yamaguchi Prefecture Tokuyama Co., Ltd. F-term (reference) BC01 4J002 BB011 BB032 BB033 BB042 BB043 BB121 BB122 BB123 BB141 BB142 BB143 BB151 BB152 BB153 BB172 BB173 GG02

Claims (4)

[Claims] 1. A modifier for a polyolefin resin containing, as an active ingredient, a polyolefin having an elution temperature of 36 to 104 ° C. and a molecular weight in the range of 100,000 to 1,000,000 as measured by a temperature-increased fractional correlation molecular weight measurement method. . 2. The composition according to claim 1, which contains 4 to 20% by weight of the active ingredient.
A crystalline polyolefin resin composition containing. 3. The active ingredient according to claim 1, which has an elution temperature of more than 116 ° C. and a molecular weight of 10,000 to 100,000 when measured by 4 to 20% by weight of a temperature-sensitive fractional correlation molecular weight measuring method. A polyolefin resin composition comprising 4 to 20% by weight of a certain polyolefin and the balance being a crystalline polyolefin resin. 4. A stretched film comprising the polyolefin resin composition according to claim 2.