JPH08291236A - Polypropylene composition - Google Patents

Abstract

PURPOSE: To obtain a polypropylene composition improved in transparency, image clarity and fusion sealability and having excellent moldability without getting worse in thin and dense accuracy caused by drawing unevenness in a drawing process and produce a polypropylene drawn film. CONSTITUTION: This composition comprises 100 pts.wt. of (A) a crystalline polypropylene having 105-125 deg.C peak temperature (Tp) in an elusion curve by a temperature raising elusion fractionation method and 9-17 deg.C elusion temperature difference (σ) calculated from the elusion curve at 90wt.% elusion and at 20wt.% elusion and 0.00001-1.0 pts.wt. of (B) a crystalline nucreating agent such as di(p-methyl-benzylidene)sorbitol, talc, polycyclopentene, poly-3-methyl-1- butene, etc. The polypropylene drawn film is produced by drawing a sheet consisting of the polypropylene composition at least in >= one axial direction.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel polypropylene composition and a stretched film comprising the polypropylene composition. More specifically, the present invention relates to a polypropylene composition that gives a stretched film having good moldability and having significantly improved transparency and image clarity, and a stretched film made of the polypropylene composition.

[0002]

2. Description of the Related Art Polypropylene stretched films, particularly polypropylene biaxially stretched films, are widely used for packaging materials and the like because of their excellent mechanical and optical properties. However, due to the high crystallinity of polypropylene, these polypropylene stretched films are generally inferior in transparency and image clarity to other highly transparent thermoplastic resins such as polystyrene and polyvinyl chloride.

Several means have been proposed so far in an attempt to improve the transparency of a polypropylene stretched film. For example, polypropylene-based organic crystal nucleating agents such as sorbitol derivatives, alkali metal salts or aluminum salts of aromatic carboxylic acids (for example, JP-A-58-58).
80392, JP 55-12460 A).
Or addition of an inorganic crystal nucleating agent such as talc having a fine particle size (Japanese Patent Laid-Open No. 3-166244), or a branched α-olefin polymer having 5 or more carbon atoms (Japanese Patent Publication No. 45-32430), vinylcycloalkane. Polymer (Japanese Patent Publication No. 3-422)
98) and the like are included to improve the transparency and image clarity of the film.

[0004]

However, when these crystalline nucleating agents are contained in crystalline polypropylene, the raw sheet obtained by extrusion molding becomes hard when the polypropylene stretched film is formed, and the film is not stretched. There was a problem in the formability of the stretched film due to the deterioration of the thickness accuracy and the breakage of the stretch due to the uneven stretching.

Further, the inclusion of these crystal nucleating agents raises the crystallization temperature of the polypropylene composition, and when the formed stretched film is made into a bag by fusing seal, the fusing seal strength (the bag breaking strength of the fusing seal part). There was a problem that it decreased.

Therefore, the object of the present invention is to provide excellent transparency,
Having image clarity, and when forming a stretched film, uneven stretching or tearing of the film during stretching does not occur,
It is an object of the present invention to provide a polypropylene composition which has so-called good moldability and has improved melt-sealing performance of a molded stretched film, and a stretched film made of the polypropylene.

[0007]

From these viewpoints, the present inventors have conducted diligent studies on a polypropylene stretched film having improved transparency, image clarity, stretched film moldability and fusing sealability, and as a result, surprising In particular, by using a polypropylene composition containing a small amount of a crystal nucleating agent in crystalline polypropylene having a specific crystallinity distribution, the transparency, image clarity and fusing sealing property of the obtained polypropylene stretched film are remarkably improved. Further, they have found that the polypropylene composition is excellent in moldability without causing deterioration in thickness accuracy and stretching breakage due to uneven stretching during stretched film molding, and completed the present invention.

That is, according to the present invention, (A) the peak temperature of the elution curve by the temperature rising elution fractionation method is 105 to 125 ° C.,
To 100 parts by weight of crystalline polypropylene having a difference in elution temperature between 90% by weight elution and 20% by weight elution calculated from the elution curve (hereinafter, also simply referred to as elution temperature difference) of 9 to 17 ° C., B) A polypropylene composition comprising 0.00001 to 1 part by weight of a crystal nucleating agent, and a polypropylene stretched film comprising the polypropylene composition and stretched at least uniaxially.

In the present invention, the temperature rising elution fractionation method (hereinafter simply abbreviated as TREF) separates polyolefins by the difference in the melting temperature in a solvent and measures the elution amount (concentration) of the polyolefin at each melting temperature. Then, the crystallinity distribution of the polyolefin is evaluated. That is, diatomaceous earth, using an inert carrier such as silica beads as a packing material, and injecting into the column a sample solution of any concentration in which the sample polyolefin is dissolved in a solvent consisting of orthodichlorobenzene, and the temperature of the column is After adsorbing the sample on the packing surface by lowering the temperature, the temperature of the column is raised while passing the solvent consisting of ortho-dichlorobenzene through the column, and the concentration of the eluted polyolefin at each temperature is detected. Then, the crystallinity distribution of the polyolefin is measured from the value of the elution amount (% by weight) of the polyolefin and the temperature (° C) in the column at that time.

In the above method, the rate of decrease of the column temperature is the rate required for crystallization of the crystalline portion contained in the sample polyolefin, and the rate of increase of the column temperature is the dissolution of the sample at each temperature. Needs to be adjusted to a rate at which the temperature can be completed, and the rate of decrease and rate of increase of the temperature of the column may be determined in advance by experiments. Generally, the rate of decrease of the temperature of the column is determined in the range of 2 ° C./minute or less, and the rate of increase of the temperature of the column is determined in the range of 4 ° C./minute or less.

Here, the elution peak temperature (Tp) refers to the peak position (° C.) at which the elution amount is maximum in the elution curve showing the relationship between the elution temperature (° C.) and the elution amount (% by weight).
FIG. 1 is an elution curve showing the relationship between the elution temperature (° C.) and the elution amount (% by weight) of the crystalline polypropylene produced in Example 1 described later, where the temperature at the peak position indicated by point A. 118.4 ° C. is the elution peak temperature.

The elution temperature difference (σ) calculated from the elution curve is the elution temperature difference when the integrated elution amount is 20% by weight and 90% by weight, and is calculated by the following formula.

Σ = T (90) -T (20) where T (90) is the temperature (° C.) when the integrated elution amount is 90% by weight. T (20): The integrated elution amount is 20% by weight. Temperature (° C.) FIG. 2 is an integrated elution curve showing the relationship between the elution temperature (° C.) and the integrated elution amount (% by weight) of the crystalline polypropylene produced in Example 1 described later, where B Point is T (90)
Is 121.1 ° C, and C is 110.1 at T (20).
° C. Therefore, the elution temperature difference in this case is (12
1.1-110.1) results in 11.0 ° C.

Since the above-mentioned elution temperature depends on the crystallinity of the polymer, that is, the stereoregularity and the copolymer composition, TREF is used.
The crystallinity distribution of the polymer can be known by determining the relationship between the elution temperature and the elution amount (% by weight) of the polymer.

The crystalline polypropylene used in the present invention has a peak temperature (Tp) of the elution curve by TREF of 1
It is necessary to be in the range of 05 to 125 ° C., especially 1
It is preferably in the range of 10 to 120 ° C. That is, when the peak temperature of the elution curve is less than 105 ° C, the heat resistance and rigidity such as the heat shrinkage rate are lowered when the obtained molded product, particularly a stretched film is molded. Further, when the peak temperature exceeds 125 ° C., the moldability is lowered, and when forming a stretched film, the melt-cut sealing property is lowered, and the stretchability at the time of forming the stretched film is lowered, so that the stretched film is stretched. This is not preferable because the thickness accuracy of the film is deteriorated due to unevenness and the film often breaks due to stretching.

The difference in elution temperature ([sigma]) of the crystalline polypropylene used in the present invention needs to be in the range of 9 to 17 [deg.] C., particularly preferably 10 to 15 [deg.] C. When the elution temperature difference is less than 9 ° C., the moldability is lowered, and the fusion cut sealability with the stretched film is lowered,
The stretchability during forming a stretched film is lowered, and the unevenness of the stretch results in deterioration of the thickness accuracy of the film and tearing of the film frequently. Further, if the difference in the melting temperature exceeds 17 ° C., the heat resistance and rigidity such as the heat shrinkage rate of the obtained molded product, particularly the stretched film, are deteriorated, which is not preferable.

The crystalline polypropylene used in the present invention is so long as the peak temperature of the elution curve by TREF and the elution temperature difference satisfy the above range.
Although the effects of the present invention can be sufficiently achieved, further considering the heat resistance and rigidity such as the heat shrinkage rate of the stretched film obtained by using the polypropylene composition of the present invention, the integrated elution amount is 90% by weight. % Elution temperature (T (9
0)) is preferably 110 ° C. or higher, and more preferably 115 ° C. or higher.

The elution amount (a) of the crystalline polypropylene of the present invention at an elution temperature of 20 ° C. or lower is 5% by weight from the viewpoint of heat resistance such as heat shrinkage of the stretched film obtained by molding and prevention of blocking. The amount is preferably below, and more preferably 3.5% by weight or less. In addition,
The elution amount at an elution temperature of 20 ° C. or lower is an integrated elution amount (wt%) at an elution temperature of 20 ° C., and is the amount of a polymer component soluble in a solvent at 20 ° C. or lower.

The crystalline polypropylene used in the present invention may be a homopolymer of propylene as long as it has the above-mentioned characteristics, and propylene is used as a copolymerization component as long as the effect of the present invention is not impaired. Other α-olefins may be included. As α-olefins other than propylene, ethylene, butene-1, pentene-1,
3-methyl-1-butene, hexene-1,3-methyl-
1-pentene, 4-methyl-1-pentene, heptene-
Examples of the α-olefin having 2 to 20 carbon atoms include 1, octene-1, nonene-1, decene-1, dodecene-1, tetradecene-1, hexadecene-1, octadecene-1, eicosene-1. . These α-olefins may be contained alone or in combination as a copolymerization component. The ratio of the α-olefin to be contained varies depending on the kind, but it is generally preferable to select it in the range of 10 mol% or less in terms of the ratio in the copolymer. For example, when the α-olefin other than propylene is ethylene, the peak temperature of TREF (T
In order to make p) within the range of the present invention, it is preferable that the proportion of the ethylene component in the copolymer is 2.0 mol% or less.

The isotactic pentad fraction of the crystalline polypropylene used in the present invention is preferably 0.85 or more. The isotactic pentad fraction as used in the present invention means A. Zambilli et al., Macromolecules, 13 , 267 (19).
80) is the fraction in which 5 propylene units, which are quantified based on the attribution of the ¹³ C-NMR spectrum peaks, have the same consecutive configuration.

The molecular weight distribution represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the crystalline polypropylene used in the present invention is not particularly limited, Considering the case of film formation, it is preferably 3 to 20 in order to increase melt tension and improve workability. The molecular weight distribution is a value measured by gel permeation chromatography (hereinafter also referred to as GPC) using o-dichlorobenzene as a solvent,
The calibration curve used is calibrated with standard polystyrene.

The melt flow rate of the crystalline polypropylene used in the present invention is not particularly limited, but in consideration of the moldability for various stretched films, it is usually in the range of 0.01 to 100 g / 10 minutes. It is preferably used in the range of 0.1 to 50 g / 10 minutes.

In the present invention, the method for producing the crystalline polypropylene having the above characteristics is not particularly limited, but it is generally preferable to employ the following method. For example, a method of mixing several kinds of catalyst components capable of polymerizing crystalline polypropylene having different stereoregularity and polymerizing propylene can be mentioned. In particular, solid titanium catalyst component,
A method in which propylene is polymerized by mixing two or more kinds of electron donors that give an organoaluminum compound and a crystalline polypropylene having different stereoregularity can be preferably used. In this method, as the electron donor, those generally known in the polymerization of propylene can be used without any limitation. However, an organosilicon compound represented by the following general formula (I) and general formula (II) should be used in combination. However, a polypropylene having a wide crystallinity distribution, that is, having a difference (σ) in the elution temperature between 90% by weight elution and 20% by weight elution calculated from the elution curve by TREF in the range of 9 to 17 ° C. It is preferable for obtaining well.

[0024]

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(However, R ₁ , R ₂ and R ₃ are the same or different hydrocarbon groups, and n is 0 or 1.) The solid titanium catalyst component described above is used for the polymerization of propylene. Any known compound can be used without any limitation. In particular, a solid titanium catalyst component having high catalytic activity, which contains titanium, magnesium and halogen, is suitable. Such a catalyst component comprises titanium halide, especially titanium tetrachloride, supported on various magnesium compounds, especially magnesium chloride.

As the organoaluminum compound, compounds known to be used for propylene polymerization can be employed without any limitation. For example, trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum,
Tri-n-butyl aluminum, tri-isobutyl aluminum, tri-n-hexyl aluminum, tri-n
Examples include trialkylaluminums such as octylaluminum and tri-n-decylaluminum; diethylaluminum monohalides such as diethylaluminum monochloride; alkylaluminum halides such as methylaluminum sesquichloride ethylaluminum dichloride. Alternatively, alkoxyaluminums such as monoethoxydiethylaluminum and diethoxymonoethylaluminum can be used. Of these, triethylaluminum is most preferred. The amount of the organoaluminum compound used is 10 / aluminum / titanium (molar ratio) based on the titanium atom in the solid titanium catalyst component.
It is preferably 1000, more preferably 50 to 500.

In the organosilicon compounds represented by the above general formulas (I) and (II), R ₁ , R ₂ and R ₃
The hydrocarbon group represented by can be a chain, branched, or cyclic aliphatic hydrocarbon group, or an aromatic hydrocarbon group, and the carbon number thereof is not particularly limited. Examples of suitable hydrocarbon groups include methyl group, ethyl group, n-propyl group,
C1-C6 alkyl groups such as i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, pentyl group and hexyl group; vinyl group, propenyl group, allyl group, etc. An alkenyl group having 2 to 6 carbon atoms; an ethynyl group,
Alkynyl group having 2 to 6 carbon atoms such as propynyl group; cycloalkyl group having 5 to 7 carbon atoms such as cyclopentyl group, cyclohexyl group, cycloheptyl group; and 6 carbon atoms such as phenyl group, tolyl group, xylyl group and naphthyl group The aryl group of -12, etc. can be mentioned. Of these, R ₃ is preferably a linear alkyl group, alkenyl group, or aryl group. In addition, n is 0 or 1.

Examples of the organic silicon compounds that can be preferably used are as follows. Examples of the organosilicon compound represented by the general formula (I) include dimethyldimethoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, divinyldimethoxysilane, diallyldimethoxysilane, di-1-propenyldimethoxysilane, diethynyldimethoxysilane, and the like. Diphenyldimethoxysilane, methylphenyldimethoxysilane, cyclohexylmethyldimethoxysilane, tert-butylethyldimethoxysilane, ethylmethyldimethoxysilane, propylmethyldimethoxysilane, cyclohexyltrimethoxysilane, diisopropyldimethoxysilane, dicyclopentyldimethoxysilane, vinyltrimethoxysilane, Examples thereof include phenyltrimethoxysilane and allyltrimethoxysilane.

Examples of the organosilicon compound represented by the general formula (II) include tetraethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, pentyltriethoxysilane, and isopropyltriethoxysilane. Ethoxysilane, 1-propenyltriethoxysilane, isopropenyltriethoxysilane, ethynyltriethoxysilane,
Examples include octyltriethoxysilane, dodecyltriethoxysilane, phenyltriethoxysilane and allyltriethoxysilane.

The amount of the organosilicon compound represented by the general formula (I) or the general formula (II) used is 0. Si / Ti (molar ratio) based on the Ti atom of the solid titanium catalyst component.
1 to 500 is preferable, and 1 to 100 is more preferable. Further, the use ratio of these two kinds of organosilicon compounds needs to be (I) :( II) = 1: 5 to 1:25, and 1:10 to 1:20 in molar ratio. preferable. That is, the amount of the organosilicon compound (II) in the above usage ratio of the organosilicon compound (I) and (II) is 2
When it is more than 5, the peak temperature (Tp) of the elution curve by TREF of the obtained crystalline polypropylene is 105.
The temperature tends to be lower than 0 ° C, and it becomes difficult to obtain the crystalline polypropylene specified in the present invention. In addition, the cumulative elution amount of the obtained crystalline polypropylene is 90% by weight.
The temperature T (90) at which the temperature becomes equal to 110 ° C. is lower than 110 ° C., and the elution amount (a) at an elution temperature of 20 ° C. or lower exceeds 5 wt%. The heat resistance tends to decrease.

Further, the amount of the organosilicon compound (II) in the above use ratio of the organosilicon compound (I) and (II) is 5
When the amount is less than the above, the difference in the elution temperature (σ) between the 90 wt% elution and the 20 wt% elution calculated from the elution curve of the obtained crystalline polypropylene by TREF
Tends to be less than 9 ° C., and the stretchability at the time of molding decreases, resulting in deterioration of the thickness accuracy of the film and tearing of the film.

In the above-described method for producing crystalline polypropylene used in the present invention, the crystalline polypropylene having a peak temperature (Tp) of the elution curve by TREF exceeding 125 ° C. or the elution curve by TREF is 90. It is possible to effectively suppress the production amount of crystalline polypropylene in which the difference (σ) in the elution temperature between the time of elution by weight% and the time of elution at 20% by weight exceeds 17 ° C.

The order of adding the above-mentioned respective components is not particularly limited, and the organosilicon compounds represented by the general formula (I) and the general formula (II) may be mixed and supplied simultaneously or separately. Further, these may be supplied after being contacted or mixed with the organoaluminum compound in advance.

Other polymerization conditions can be arbitrarily changed within the range where the characteristics of the crystalline polypropylene specified in the present invention can be obtained, but the following conditions are generally preferable. That is, the polymerization temperature is 20 to 200 ° C., preferably 50.
The temperature is up to 150 ° C, and hydrogen can be allowed to coexist as a molecular weight modifier. Further, for the polymerization, slurry polymerization, solventless polymerization, gas phase polymerization, etc. can be applied, and batch type, semi-batch type,
Any of continuous methods may be used, and the polymerization may be carried out in two stages under different conditions. Also, propylene and other monomers may be prepolymerized before the polymerization of propylene. Further, the above-mentioned polymerization may be carried out in multiple stages.

In the polypropylene composition of the present invention, the crystalline polypropylene obtained by the above method is generally used alone, but other crystalline polypropylene may be blended and used. Of course, it is also possible to blend the crystalline polypropylenes obtained by the above method.

Furthermore, even in the method of polymerizing polypropylene using a metallocene-based catalyst composed of a metallocene compound and an organoaluminum compound, the present invention may be used in combination with two or more kinds of catalyst components capable of polymerizing crystalline polypropylene having different stereoregularity. The method of obtaining crystalline polypropylene having a wide crystallinity distribution specified in 1. is applied.

The crystal nucleating agent used in the polypropylene composition of the present invention may be any crystal nucleating agent used for crystalline polypropylene such as organic crystal nucleating agent, inorganic crystal nucleating agent and polymer crystal nucleating agent. It can be used without limitation. Among them, a molded product from which a polymer-based crystal nucleating agent is obtained, particularly a stretched film, has a large effect of improving transparency and image clarity, and there is no bleed-out from the stretched film, and therefore it is preferably used.

The content of the crystal nucleating agent used in the present invention in the crystalline polypropylene is in the range of 0.00001 to 1 part by weight based on the crystalline polypropylene. That is,
When the content of the crystal nucleating agent is less than 0.00001 parts by weight, the effect of improving the transparency and the image clarity of the obtained molded product cannot be seen. On the other hand, if the amount exceeds 1.0 part by weight, the melt-sealing property in the case of a stretched film is deteriorated or the moldability is deteriorated, and for example, the surface of the sheet is roughened during the molding of the stretched film, resulting in a poor image quality. Of the film, deterioration of thickness accuracy of the film, and breakage of the stretch.

Since the more preferable range of the content of the crystal nucleating agent varies depending on the kind of the crystal nucleating agent, it is preferable to determine it for each crystal nucleating agent, as will be described later.

Specific examples of the organic crystal nucleating agent used in the present invention include dibenzylidene sorbitol,
Sorbitol derivatives such as dimethylbenzylidene sorbitol, sodium p-tert-butylbenzoate, sodium β-naphthoate, sodium 1,2-cyclohexanedicarboxylate, aluminum dibenzoate, basic di-p-ter
Metal salts of aromatic carboxylic acids such as sodium salts and aluminum salts of aromatic carboxylic acids such as t-butyl benzoate, aromatic carboxylic acids, 2,2-methylenebis (4,6-di-tert-butylphenyl phosphate) ) Aromatic metal phosphates such as sodium can be mentioned. The content of the organic crystal nucleating agent in the crystalline polypropylene is in the range of 0.005 to 1 part by weight, particularly 0.01 to 0.5 part by weight, based on 100 parts by weight of the crystalline polypropylene. Further, it is preferably 0.05 to 0.3 parts by weight.

Specific examples of the above-mentioned inorganic crystal nucleating agent used in the present invention include talc and mica. The particle size of the inorganic crystal nucleating agent is 10 from the viewpoint of deterioration of the film appearance due to generation of fisheye.
It is preferably not more than μm, more preferably not more than 6.0 μm. The preferred content of the inorganic crystal nucleating agent in the crystalline polypropylene is in the range of 0.005 to 0.4 parts by weight with respect to 100 parts by weight of the crystalline polypropylene,
In particular, the amount is preferably 0.008 to 0.2 part by weight, more preferably 0.01 to 0.1 part by weight.

The above-mentioned polymer type crystal nucleating agent preferably used in the present invention is, for example, a cyclic olefin polymer, a fluorine-containing polymer, a branched α-olefin polymer having 5 or more carbon atoms, a vinylcycloalkane polymer. Examples include coalescing.

The above-mentioned cyclic olefin polymer is a polymer having a ring structure of a monomer having a polymerizable double bond in the ring, and is a homopolymer of a cyclic olefin monomer having 4 to 20 carbon atoms, A copolymer of olefin monomers, or a copolymer of 50 mol% or more of the above cyclic olefin monomers and 50 mol% or less of other monomers can be preferably used. In particular, specific examples of the cyclic olefin monomer that can be preferably used in the present invention include cyclobutene,
Cyclopentene, cyclopentadiene, 4-methylcyclopentene, 4,4-dimethylcyclopentene, cyclohexene, 4-methylcyclohexene, 4,4-dimethylcyclohexene, 1,3-dimethylcyclohexene,
1,3-cyclohexadiene, 1,4-cyclohexadiene, cycloheptene, 1,3-cycloheptadiene,
1.3.5-cycloheptatriene, cyclooctene,
1,5-cyclooctadiene, cyclododecene, etc. can be mentioned. Further, the ring of these cyclic olefins may be further substituted with a linear or branched alkyl group.

These cyclic olefin polymers are generally crystalline, and the higher the degree of crystallinity indicating the degree of crystallinity, the higher the transparency and the effect of improving the transparency, so the degree of crystallinity is 10%. Or more is preferable,
It is more preferably at least 30%, most preferably at least 50%. As the cyclic olefin polymer having such a high crystallinity, a homopolymer of the above-mentioned cyclic olefin monomer, or a block copolymer of cyclic olefin monomers with each other or with α-olefin can be preferably used. Further, the polymerization method of these cyclic olefin polymers is not particularly limited as long as the effects of the present invention are not impaired, and for example, the following polymerization methods are used. First, the catalyst is a metallocene-based catalyst, a vanadium-based catalyst, titanium trichloride or titanium tetrachloride, which is generally composed of a metallocene compound using a transition metal of Group IV of the periodic table and a coexisting system of methylaluminoxane or alkylaluminum or alkylaluminum halide. Examples of the catalyst include a titanium-based catalyst, an anionic polymerization catalyst, a radical polymerization catalyst, and the like, each of which is supported on a magnesium compound such as magnesium chloride, and these may be used alone or in combination. Among these, preferable catalysts are metallocene catalysts, vanadium catalysts, and titanium catalysts.
The method of polymerization is not particularly limited, such as gas phase polymerization, solution polymerization and bulk polymerization.

The content of the above-mentioned cyclic olefin polymer in the crystalline polypropylene is 100% by weight of the crystalline polyolefin 100.
It is in the range of 0.00001 to 0.1 parts by weight, preferably 0.00005 to 0.05 parts by weight, and more preferably 0.0001 to 0.02 parts by weight, based on parts by weight. Is more preferable.

The branched α-olefin polymer having 5 or more carbon atoms is a polymer of branched α-olefin monomer having a polymerizable double bond, and is a homopolymer of branched α-olefin monomer having 5 or more carbon atoms. A copolymer of the branched α-olefin monomers, and a copolymer of the branched α-olefin monomer in an amount of 50 mol% or more and another monomer of 50 mol% or less can be preferably used. Particularly, a branched α-olefin monomer which can be preferably used in the present invention has 5 to 5 carbon atoms.
10, specifically, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene. , 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3
-Ethyl-1-hexene and the like can be mentioned.

The above-mentioned vinyl cycloalkane polymer is a polymer of vinyl cycloalkane monomer having a polymerizable double bond, and is a polymer in which the cycloalkane structure is pendantly bonded from the main chain. Homopolymers of vinyl cycloalkane monomers, copolymers of the vinyl cycloalkane monomers with each other, and copolymers of 50 mol% or more of the vinyl cycloalkane monomers with 50 mol% or less of other monomers can be preferably used. Particularly, vinylcycloalkane monomers that can be preferably used in the present invention include
Specific examples thereof include vinylcyclobutane, vinylcyclopentane, vinyl-3-methylcyclopentane, vinylcyclohexane, vinyl-3-methylcyclohexane and vinylnorbornane.

These branched α-olefin polymers having 5 or more carbon atoms and vinylcycloalkane polymers are generally crystalline, and the higher the degree of crystallinity, which indicates the degree of crystallinity, the higher the effect of transparency and the improvement of image clarity. Therefore, it is preferable that the crystallinity is 10% or more.
It is more preferably 0% or more, and most preferably 40% or more. Examples of the branched α-olefin polymer and vinyl cycloalkane polymer having such a high crystallinity include homopolymers of the branched α-olefin monomer and vinyl cycloalkane monomer described above, or branched α-olefins having 5 or more carbon atoms. Between olefin monomers,
Block copolymers of vinyl cycloalkanes with each other or with other α-olefins can be preferably used.

The polymerization method of the branched α-olefin polymer having 5 or more carbon atoms and the vinyl cycloalkane polymer is not particularly limited, but for example, the following polymerization method is preferably used. First, a suitable catalyst is a titanium-based catalyst in which titanium trichloride, titanium tetrachloride or vanadium tetrachloride is supported on a magnesium compound such as magnesium chloride,
Vanadium-based catalysts, generally metallocene-based catalysts and the like consisting of a metallocene compound using a transition metal of Group IV of the periodic table and a coexisting system of methylaluminoxane or alkylaluminum or alkylaluminum halide, and the like, and these are used alone or in combination. May be done. The polymerization method is not particularly limited, such as gas phase polymerization, solution polymerization and bulk polymerization. Branched α with 5 or more carbon atoms
-The method of incorporating the olefin polymer and the vinylcycloalkane polymer into the crystalline polypropylene is such that, prior to the polymerization of the crystalline polypropylene, a branched α-olefin monomer having 5 or more carbon atoms or a vinylcycloalkane monomer is preliminarily polymerized. After that, a method in which a crystalline polymer structure portion is contained in the polypropylene molecular chain to obtain a polypropylene composition by homopolymerizing propylene or copolymerizing propylene with another α-olefin is particularly preferable.

The content of the branched α-olefin polymer having 5 or more carbon atoms in the crystalline polypropylene is 0.0001 to 1 with respect to 100 parts by weight of the crystalline polypropylene.
It may be in the range of parts by weight, but in particular 0.001 to 0.
It is preferably 5 parts by weight, and more preferably 0.005 to 0.
It is more preferably 2 parts by weight. The content of the vinyl cycloalkane polymer in the crystalline polypropylene is 100 parts by weight of the crystalline polypropylene.
It is in the range of 0.00001 to 0.1 part by weight, and particularly, 0.
It is preferably 0.0005 to 0.05 parts by weight, more preferably 0.0001 to 0.02 parts by weight.

As the above-mentioned fluorine-containing polymer, a homopolymer of a fluorine-containing monomer, a copolymer of fluorine-containing monomers, a copolymer of a fluorine-containing monomer and a hydrocarbon-based monomer, and particularly an α-olefin can be used. . Among them, specific examples of the fluorine-containing polymer that can be preferably used include, for example,
Tetrafluoroethylene polymer, 1-fluoroethylene polymer, 1,1-difluoroethylene polymer, trifluoroethylene polymer, 1-chloro-2,2-difluoroethylene polymer, chlorotrifluoroethylene polymer,
Hexafluoropropylene polymer, hexafluoropropylene oxoxide polymer, tetrafluoroethylene-methyl vinyl ether copolymer, trifluoroethylene-methyl vinyl ether copolymer, tetrafluoroethylene-perfluorovinyl ether copolymer, tetrafluoroethylene- Hexafluoropropylene copolymer and the like can be mentioned.

The above-mentioned fluoropolymers are generally crystalline, and the higher the degree of crystallinity, which represents the degree of crystallinity, the higher the transparency and the improvement in image clarity.
The crystallinity is preferably 50% or more, further 70
% Or more is more preferable. The particle size of the fluoropolymer is not particularly limited, but in order to obtain a stretched film having good transparency and image clarity, the average primary particle size is preferably 2 μm or less, and further 1 μm or less. Is more preferable.

The preferred content of the above-mentioned fluoropolymer in the crystalline polypropylene is the crystalline polypropylene 1
A range of 0.00001 to 0.1 parts by weight is selected with respect to 00 parts by weight, particularly preferably 0.0001 to 0.05 parts by weight, and further 0.001 to 0.02 parts by weight. More preferably.

The method of mixing the crystal nucleating agent with the crystalline polypropylene in the present invention is not particularly limited, and various mixing methods can be adopted. Specifically, a crystal nucleating agent is added to crystalline polypropylene, and mixed using a screw extrusion kneader such as a single-screw extruder or a twin-screw extruder, a Banbury mixer, a continuous mixer, or a mixing roll. When the crystal nucleating agent is a polymer crystal nucleating agent such as a cyclic olefin polymer, a branched α-olefin polymer having 5 or more carbon atoms, or a vinylcycloalkane polymer, a more preferable method is a polymer crystal nucleating agent. After pre-polymerization in advance, homopolymerization of propylene or propylene and other α-
Examples thereof include a method of forming a polypropylene composition containing a polymer crystal nucleating agent by copolymerizing with an olefin. Further, after obtaining a composition containing a high-molecular-weight crystal nucleating agent in a high concentration by the method as described above, the composition is used as a masterbatch with another crystalline polypropylene, and the dilution ratio is 2 to 1000. By diluting in the range of double (diluting the content of the polymer crystal nucleating agent to 0.5 to 0.001 times), the intended content of the polymer crystal nucleating agent can be obtained. The dilution ratio of the masterbatch is generally about 20 times, but in the present invention, it is possible to sufficiently improve the transparency and image clarity of the stretched film even at a considerably large dilution ratio of 100 times or more depending on the masterbatch concentration. it can.

In the polypropylene composition of the present invention, if necessary, an antioxidant, a chlorine scavenger, a heat resistance stabilizer, an antistatic agent, an antiblocking agent, an antifogging agent, an ultraviolet absorber, a lubricant, a pigment, and the like. Additives such as resins and fillers may be added as long as the effects are not impaired.

The polypropylene composition of the present invention can be used for the production of any molded product and exhibits excellent properties such as transparency and rigidity. In particular, a stretched film is molded by the polypropylene composition of the present invention. When it does, it exerts a remarkable effect.

The thickness of the polypropylene stretched film of the present invention is not particularly limited, but it is usually 3 to 150 μm for a biaxially stretched film and 10 to 25 for a uniaxially stretched film.
It is preferably 4 μm. The polypropylene stretched film of the present invention is stretched in at least a uniaxial direction. Of course, it may be biaxially stretched. Although the stretching ratio is not particularly limited, it is generally 4 to 10 times in the uniaxial direction, and in the case of biaxial stretching, it is generally stretched in the range of 4 to 15 times in the direction perpendicular thereto. Is.

The polypropylene stretched film of the present invention comprises
In order to obtain good fusing sealability and moldability, the plane orientation index is preferably 1 or less, more preferably in the range of 0.5 to 0.9, and further 0.6 to 0.8. Is most preferable. The above plane orientation index can be achieved by using the polypropylene composition of the present invention, and can be appropriately adjusted by changing the compounding ratio within the range of the composition.

The plane orientation index referred to in the present invention is an index representing the degree of plane orientation of the polypropylene crystal 010 plane, which is obtained by the X-ray diffraction method, to the plane parallel to the stretched film plane. Specifically, while rotating the polypropylene stretched film at a high speed around an axis perpendicular to the film surface, X-rays are made incident from a direction perpendicular to the film surface to measure the diffraction intensity, and the obtained X-ray diffraction intensity curve is shown. Amorphous peak and each crystalline peak are separated, and 111 reflection (2θ = 21.4 °) from polypropylene crystal (α crystal) and 04
It is calculated by the following formula from the ratio of the peak intensity of 0 reflection (2θ = 17.1 °).

[Face orientation index] = log {I (111) / I (040)} where I (111): 111 reflection peak intensity (counts) I (040): 040 reflection peak intensity (counts) 3 is the peak separation result of the X-ray diffraction curve of the polypropylene stretched film molded in Example 1 described later, where A
-B is I (040) with 511 counts, and C-D is I (11)
It is 2664 counts in 1). Therefore, the plane orientation index in this case is log (2664/511), which is 0.717.

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

As the method for producing the stretched polypropylene film of the present invention, known methods can be adopted without any limitation. For example, as a method for producing a stretched film by a sequential biaxial stretching method by a tenter method, the polypropylene composition is molded into a sheet or a film by a T-die method, an inflation method or the like, and then supplied to a longitudinal stretching device and heated. Longitudinal stretching of 3 to 10 times at a roll temperature of 120 to 170 ° C., and then using a tenter, a tenter temperature of 130 to
A method of transversely stretching 4 times to 15 times at 180 ° C. is preferable. The above-mentioned molding conditions are not particularly limited, but in order to reduce the plane orientation index of the stretched film to obtain a film having a good fusing and sealing property, it is preferable that the stretched film has a temperature of 3 to 15 at 145 to 170 ° C. in the longitudinal stretching.
It is preferable to stretch 5 times and 4 to 12 times in transverse stretching at 155 to 180 ° C. Further, a method of performing heat treatment at 80 to 180 ° C. while allowing 0 to 25% relaxation in the lateral direction as required can be mentioned. Of course, the stretching may be performed again after these stretchings, and in the longitudinal stretching, stretching methods such as multi-stage stretching and rolling can be combined. Also, a stretched film can be obtained by stretching only uniaxially.

[0063]

INDUSTRIAL APPLICABILITY The polypropylene composition of the present invention is remarkably improved in transparency, image clarity, melt-sealing property and heat resistance such as heat shrinkage of a stretched film to be molded, At this time, it is a polypropylene composition having excellent moldability that does not cause deterioration of thickness accuracy due to uneven drawing in the drawing process and drawing breakage, and its industrial value is extremely high.

[0064]

EXAMPLES In order to describe the present invention more specifically, examples and comparative examples will be described below, but the present invention is not limited to these examples. The polypropylene compositions and stretched films obtained in the following examples and comparative examples were evaluated by the following methods.

(1) Melt flow rate (MFR) It was measured according to JIS K 7210.

(2) Molecular weight distribution (Mw / Mn) High temperature GPC device SSC-7100 manufactured by Senshu Scientific Co., Ltd.
Was measured under the following conditions.

Solvent: Orthodichlorobenzene Flow rate: 1.0 ml / min Column temperature: 145 ° C. Detector: High temperature differential refraction detector Column: Showa Denko KK “SHODEX UT” 8
07,806M, 806M, 802.5 are connected in series and used Sample concentration: 0.1 wt% Injection volume: 0.50 ml (3) Pentad fraction JNM-GSX-270 ( ¹³ manufactured by JEOL Ltd.) C-nuclear resonance frequency 67.8 MHz) was used and measured under the following conditions.

Measurement mode: ¹ H-complete decoupling Pulse width: 7.0 microseconds (C45 degrees) Pulse repetition time: 3 seconds Accumulation number: 10000 times Solvent: Orthodichlorobenzene / deuterated benzene mixed solvent (90 / 10% by volume) Sample concentration: 120 mg / 2.5 ml Solvent measurement temperature: 120 ° C. In this case, the pentad fraction was determined by measuring the split peak in the methyl group region of the ¹³ C-NMR spectrum.
The attribution of the peak in the methyl group region is A. Zambel
li et al [Macromolecules 1
3, 267 (1980)].

(4) Temperature rising peak temperature (Tp) by elution fractionation method, difference in elution temperature between 90% by weight elution and 20% by weight elution (σ), and elution temperature at which cumulative elution amount becomes 90% by weight (T (90)) and elution temperature 20 ° C.
Elution amount below (a) Automatic TREF device SSC-730 manufactured by Senshu Scientific Co., Ltd.
It was measured under the following conditions using 0ATREF.

Solvent: Orthodichlorobenzene Flow rate: 150 ml / hour Temperature rising rate: 4 ° C./hour Detector: Infrared detector Measurement wave number: 3.41 μm Column: Senshu Kagaku "Packed Column 30"
φ ”, 30 mm φ × 300 mm Concentration: 1 g / 120 ml Injection volume: 100 ml In this case, the sample solution was introduced into the column at 145 ° C., and then slowly cooled down to 10 ° C. at a rate of 2 ° C./hour to fill the sample polymer. After adsorbing on the agent surface, the column temperature was raised under the above conditions, and the concentration of polymer eluted at each temperature was measured by an infrared detector.

(5) Plane orientation index An X-ray diffractometer JDX-3500 manufactured by JEOL Ltd. was used.
The measurement was performed under the following conditions.

Target: Copper (Cu-Kα line) Tube voltage-tube current: 40 kV-400 mA X-ray injection method: Vertical beam transmission method Monochromaticization: Graphite monochromator Divergence slit: 0.2 mm Light receiving slit: 0.4 mm Detector : Scintillation counter Measurement angle range: 9.0 to 31.0 ° Step angle: 0.04 ° Counting time: 4.0 seconds Sample rotation speed: 120 rotations / minute In this case, the stretched film was cut into 20 mm × 20 mm, and 60 sheets were piled up to have a thickness of about 3 mm, and the measurement was performed by mounting them on a permeation method rotary sample table attached to a wide-angle goniometer. For peak separation, after removing the background due to air scattering in the diffraction angle (2θ) range of 9 to 31 °, the amorphous peak and each crystalline peak are analyzed by the general peak separation method using the Gaussian function and Lorentz function. Separated. The plane orientation index was calculated from the peak intensity of 040 reflection and 111 reflection by the method described above.

(6) Haze Measured according to JIS K 6714.

(7) Image value An optical comb of 0.1 was used with an image measuring device manufactured by Suga Test Instruments Co., Ltd.
Using 25 mm, the comb direction was made parallel to the transverse stretching method of the stretched film, and the mapping value was measured.

(8) Fusing seal strength PP-500 type manufactured by Kyoeisha Co., Ltd., using a fusing seal machine equipped with a fusing blade for OPP film, a fusing seal temperature of 400.
Bag size 250 mm x under conditions of ℃ and bag making speed of 100 sheets / min
A 300 mm bag was made. The center of the fusing seal portion of the bag was cut into a width of 15 mm and a length of 200 mm, and a tensile test was performed at 100 mm / sec using an autograph manufactured by Shimadzu Corporation to measure the breaking strength and the breaking elongation of the fusing seal portion. This was repeated 10 times for each of the fusing seal portions on both sides of the bag, and the fusing seal strength (kgf) and the breaking elongation (%) were evaluated from the average values.

(9) Heat shrinkage ratio Measured according to JIS C 2318.

Example 1 (Preparation of titanium compound) The solid titanium component was prepared according to the method described in Example 1 of JP-A-58-38006. That is, anhydrous magnesium chloride 9.5
g, 100 ml of decane and 47 ml (300 mmol) of 2-ethylhexyl alcohol were heated and stirred at 125 ° C. for 2 hours, and then 5.5 g of phthalic anhydride (37.
(5 mmol) was added, and the mixture was stirred and mixed at 125 ° C. for 1 hour to obtain a uniform solution. After cooling to room temperature, -2
The whole amount was added dropwise to 400 ml (3.6 mmol) of titanium tetrachloride kept at 0 ° C over 1 hour. The temperature of this mixed solution was raised to 110 ° C. over 2 hours, and when it reached 110 ° C., 5.4 ml of diisobutyl phthalate (2
(5 mmol) was added and the mixture was kept under stirring at the same temperature for 2 hours. After the completion of the reaction for 2 hours, the solid portion was collected by hot filtration, and the solid portion was resuspended in 2000 ml of titanium tetrachloride, and then heated at 110 ° C. for 2 hours. After completion of the reaction, the solid portion was collected again by hot filtration, and thoroughly washed with decane and hexane until no free titanium compound was detected in the washing liquid. The solid titanium catalyst component prepared by the above production method was stored as a heptane slurry. The composition of the solid titanium catalyst component was 2.1% by weight of titanium, 57.0% by weight of chlorine, 18.0% by weight of magnesium and 2 parts of diisobutyl phthalate.
It was 1.9% by weight.

(Preliminary Polymerization) Purified hexane (6000 ml), triethylaluminum (100 mmol) and solid titanium catalyst component (10 mmol) in terms of titanium atom were charged into a 10 L polymerization reactor which had been subjected to nitrogen substitution, and then 10 g of titanium component was added as a whole. Was continuously introduced into the reactor for 1 hour so that the amount became 50 g. During this period, the temperature was kept at 10 ° C. After 1 hour, the introduction of propylene was stopped and the reactor was thoroughly replaced with nitrogen. The solid portion of the obtained slurry was washed 5 times with purified hexane to obtain a titanium-containing polypropylene.

(Main Polymerization of Propylene) 500 kg of propylene was charged into a 2000 L-content polymerization vessel subjected to nitrogen substitution, and 1.64 mol of triethylaluminum, 0.164 mol of ethyltriethoxysilane, and 0 of cyclohexylmethyldimethoxysilane. 0.0082 mol, 1 more hydrogen
After charging 0 L, the internal temperature of the polymerization vessel was raised to 65 ° C.
Titanium-containing polypropylene with titanium atom 0.0065
After charging 6 mol, the internal temperature of the polymerization vessel was raised to 70 ° C. and propylene polymerization was carried out for 1 hour. After 1 hour, unreacted propylene was purged to obtain a white granular polymer. The obtained polymer was dried under reduced pressure at 70 ° C.
The total polymer yield was 166 kg.

The obtained polypropylene has a melt flow rate (MFR), a pentad fraction, and a molecular weight distribution (Mw /
Mn), peak temperature (Tp) of elution curve by temperature rising elution fractionation method (TREF), difference in elution temperature between 90% by weight elution and 20% by weight elution (σ), and cumulative elution amount of 90% by weight Temperature (T (90)), elution temperature 20 ° C
The elution amount (a) below is shown in Table 1. Further, FIG. 1 shows an elution curve showing the relationship between the elution temperature (° C.) and the elution amount (wt%), and FIG. 2 shows an elution curve showing the relationship between the elution temperature (° C) and the cumulative elution amount (wt%). Indicated.

(Polymerization of cyclopentene) In a glass reactor equipped with a stirrer of 2000 ml, 500 ml of toluene, 500 mmol of methylaluminoxane and 0.5 mmol of dimethylsilylenebisindenylzirconium dichloride were introduced under a nitrogen atmosphere, and the system interior was adjusted to 60. The temperature was raised to ° C.
The polymerization was started by adding 100 ml of cyclopentene, and the polymerization was carried out at 60 ° C. for 4 hours. The reaction mixture containing the produced solid was added to a large amount of acidic methanol to terminate the polymerization. The obtained solid was filtered and dried under reduced pressure to obtain 63.5 g of polycyclopentene. The crystallinity determined by X-ray diffraction was 64%.

(Granulation) 100 parts by weight of the homopolypropylene powder obtained in the above (main polymerization of propylene) was added with 0.1 part by weight of 2,6-di-t-butylhydroxytoluene as an antioxidant, and chlorine was captured. 0.1 parts by weight of calcium stearate as an agent, 0.3 part by weight of stearyl diethanolamide as an antistatic agent, and 0.001 part by weight of the polycyclopentene obtained in the above (polymerization of cyclopentene) as a crystal nucleating agent were added. After mixing for 5 minutes with a mixer, an extrusion granulator having a screw diameter of 65 mmφ was used to extrude at 230 ° C. to granulate pellets to obtain raw material pellets.

(Molding of Biaxially Stretched Film) A molding experiment of a biaxially stretched film was carried out by the following method using the obtained polypropylene composition pellets. The polypropylene composition pellets were extruded at 280 ° C. using a T-die sheet extruder with a screw diameter of 90 mmφ, and a sheet having a thickness of 2 mm was formed with a cooling roll at 30 ° C. Then, this raw sheet was longitudinally stretched 4.2 times at 150 ° C. in the longitudinal direction by using a tenter type sequential biaxial stretching device, and subsequently 165
After transversely stretching in the tenter at 10 ° C. in the transverse direction by a mechanical ratio of 10 times, the mixture was heat-treated with a relaxation of 8% to form a biaxially stretched polypropylene film having a thickness of 50 μm at a speed of 16 m / min.

The influence of stretching unevenness on the thickness accuracy was evaluated according to the following criteria by the film thickness pattern measured using an infrared thickness measuring machine WEB GAGE manufactured by Yokogawa Electric Co., Ltd. installed between the tenter winders.

⊚: Less than ± 1.0 μm ◯: ± 1.0 μm or more and less than 1.5 μ Δ: ± 1.5 μm or more and less than 2.0 μ ×: ± 2.0 μm or more Further, continuous operation was performed for 5 hours and a tenter The number of film breaks was evaluated. Further, 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 wound. The obtained film was aged at 40 ° C. for 3 days, and then, haze (transparency), image value (image clarity), plane orientation index, fusing seal strength (fusing sealability),
The heat shrinkage (heat resistance) was measured. The results are shown in Table 2.
It was shown to. Further, FIG. 3 shows the result of peak separation of the X-ray diffraction curve of the stretched film.

Examples 2 and 3 The same procedure as in Example 1 was carried out except that the same homopolypropylene as in Example 1 was used and the polycyclopentene obtained in Example 1 was used in the blending amount shown in Table 1. The results are shown in Tables 1 and 2.

Comparative Example 1 Example 1 without adding polycyclopentene (crystal nucleating agent)
It carried out similarly to. The results are shown in Tables 1 and 2.

Comparative Examples 2 and 3 The same homopolypropylene as in Example 1 was used, and Example 1 was used.
The same procedure as in Example 1 was carried out except that the polycyclopentene obtained in 1 was used in the blending amount shown in Table 1. The results are shown in Table 1 and Table 2.
It was shown to.

Comparative Example 4 The procedure of Example 1 was repeated, except that 0.164 mol of cyclohexylmethyldimethoxysilane was used alone as the organosilicon compound to homopolymerize propylene. The results are shown in Tables 1 and 2.

Comparative Example 5 In the main polymerization of propylene, the content of ethylene component was 0.
Example 1 was repeated except that 5 mol% of a random copolymer of ethylene and propylene was polymerized. The results are shown in Tables 1 and 2.

Comparative Example 6 Ethyltriethoxysilane as an organosilicon compound
Example 1 was repeated except that 164 mol was used alone to homopolymerize propylene. The results are shown in Table 1,
The results are shown in Table 2.

Examples 4, 5 The amount of triethylaluminum used was 3.50 mol, 0.013 mol of cyclohexylmethyldimethoxysilane as an organosilicon compound and 0.2 of ethyltriethoxysilane.
62 mol was used (Example 4), and triethylaluminum was used in the same amount as described above, and 0.066 mol of cyclohexylmethyldimethoxysilane and 0.656 mol of ethyltriethoxysilane were used as the organosilicon compound (Example). Propylene was homopolymerized in the same manner as in Example 1 except for the above 5), and the same procedure as in Example 1 was carried out. The results are shown in Tables 1 and 2.

Comparative Examples 7 and 8 0.0033 mol of cyclohexylmethyldimethoxysilane and 0.099 mol of ethyltriethoxysilane were used as the organosilicon compound (Comparative Example 7), and 0.164 mol of cyclohexylmethyldimethoxysilane and ethyl were used. Propylene was homopolymerized in the same manner as in Example 4 except that 0.656 mol of triethoxysilane was used (Comparative Example 8), and the same procedure as in Example 1 was carried out. The results are shown in Tables 1 and 2.

[0094]

[Table 1]

[0095]

[Table 2]

Examples 6 and 7 Triethylaluminum was used in an amount of 1.64 mol, 0.0164 mol of diisopropyldimethoxysilane and 0.1% of pentyltriethoxysilane as an organosilicon compound.
Homopolymerization of propylene was carried out in the same manner as in Example 1 except that 64 mol was used (Example 6), 0.0164 mol of diphenyldimethoxysilane and 0.164 mol of octyltriethoxysilane were used (Example 7). Example 1
It carried out similarly to. The results are shown in Tables 3 and 4.

Comparative Examples 9 and 10 0.164 mol of diisopropyldimethoxysilane was used alone as the organosilicon compound (Comparative Example 9), and 0.164 mol of pentyltriethoxysilane was used alone (Comparative Example 10). Other than the above, homopolymerization of propylene was carried out in the same manner as in Example 6, and the same procedure as in Example 1 was carried out. The results are shown in Tables 3 and 4.

Example 8 As an organosilicon compound, 0.0492 mol of cyclohexylmethyldimethoxysilane and 0.04 mol of tetraethoxysilane were used.
A random copolymer of ethylene and propylene having an ethylene component content of 0.5 mol% was polymerized in the same manner as in Example 1 using 492 mol, and the same procedure as in Example 1 was carried out. The results are shown in Tables 3 and 4.

Example 9 As an organosilicon compound, 0.0492 mol of cyclohexylmethyldimethoxysilane and 0.04 mol of tetraethoxysilane were used.
In the same manner as in Example 1 using 492 mol, butene-
A random copolymer of butene-1 and propylene having a content of one component of 0.5 mol% was polymerized, and the same procedure as in Example 1 was carried out. The results are shown in Tables 3 and 4.

Example 10 (Polymerization of cyclobutene) In a glass reactor equipped with a 2000 ml stirrer, under a nitrogen atmosphere, 500 ml of toluene,
Methylaluminoxane (500 mmol) and dimethylsilylenebisindenylzirconium dichloride (0.5 mmol) were introduced, and the temperature of the system was raised to 60 ° C. Cyclobutene 2
Polymerization was started by adding 00 ml, and the polymerization was carried out at room temperature for 2 hours. The reaction mixture containing the produced solid was added to a large amount of acidic methanol to terminate the polymerization. The obtained solid was filtered and dried under reduced pressure to obtain 135 g of polycyclobutene. The crystallinity determined by X-ray diffraction is 68.
%Met.

The same procedure as in Example 1 was carried out except that the same crystalline polypropylene as in Example 8 was used and the polycyclobutene obtained above was blended in the amounts shown in Table 3. The results are shown in Table 3,
The results are shown in Table 4.

Example 11 Example 1 was repeated except that the same crystalline polypropylene as in Example 10 was used and polycyclobutene was blended in the amounts shown in Table 3.
The same procedure as in 0 was performed. The results are shown in Tables 3 and 4.

Example 12 Using a solid titanium catalyst component prepared in the same manner as in Example 1, prepolymerization of 3-methyl-1-butene was carried out as follows.

(Preliminary Polymerization of 3-Methyl-1-butene) Purified hexane 6000 was placed in a 10 L polymerization vessel subjected to nitrogen substitution.
ml, triethylaluminum 100 mmol, solid titanium catalyst component was charged in an amount of 10 mmol in terms of titanium atom, and 3-methyl-1-butene was added to the titanium component 10 g as a whole.
Was continuously introduced into the reactor for 2 hours so that the amount became 80 g. During this period, the temperature was kept at 20 ° C. After 2 hours, the introduction of 3-methyl-1-butene was stopped and the reactor was thoroughly replaced with nitrogen. The solid portion of the obtained slurry was washed 5 times with purified hexane to obtain a titanium catalyst component-containing 3-methyl-1-butene polymer. The weight of the 3-methyl-1-butene polymer at this time was 72 g. The crystallinity determined by X-ray diffraction was 60%.

(Main Polymerization) Nitrogen-substituted content of 200
A 0 L polymerization vessel was charged with 500 kg of propylene, 1.64 mol of triethylaluminum, and 0.049 of cyclohexylmethyldimethoxysilane as an organosilicon compound.
After charging 2 mol, 0.492 mol of tetraethoxysilane, and 10 L of hydrogen, the internal temperature of the polymerization vessel was raised to 65 ° C. The titanium-containing 3-methyl-1-butene was charged in an amount of 0.00656 mol of titanium atoms, and then the internal temperature of the polymerization vessel was adjusted to 7
The temperature was raised to 0 ° C., and propylene polymerization was carried out for 1 hour.
After 1 hour, unreacted propylene was purged to obtain a white granular polymer. The obtained polymer was dried under reduced pressure at 70 ° C. The total polymer yield was 143 kg. The content of the 3-methyl-1-butene polymer in the polypropylene containing the 3-methyl-1-butene polymer determined from the yield was 0.
It was 031 parts by weight. The polypropylene obtained had MFR, pentad fraction, Mw / Mn, Tp, σ, T9.
The results of 0 and a are shown in Table 3.

To 100 parts by weight of polypropylene powder containing 0.031 parts by weight of the 3-methyl-1-butene polymer (P-3MB-1) obtained above was added 2,6 as an antioxidant.
0.1 part by weight of di-t-butylhydroxytoluene,
0.1 parts by weight of calcium stearate as a chlorine scavenger and 0.3 parts by weight of stearyl diethanolamide as an antistatic agent were added, and pellets were granulated in the same manner as in Example 1 to obtain raw material pellets. A stretched film forming experiment was conducted in the same manner as in Example 1 using the polypropylene composition pellets. The results are shown in Tables 3 and 4.

Examples 13 and 14 Prepolymerization of 3-methyl-1-butene was carried out in the same manner as in Example 12 except that the amount of 3-methyl-1-butene introduced and the polymerization time were changed. The polypropylene containing 3-methyl-1-butene polymer shown in 1 was obtained. The crystallinity of the 3-methyl-1-butene polymer obtained at this time was 60% as in Example 12. The same procedure as in Example 12 was performed except that the polypropylene containing 3-methyl-1-butene polymer shown in Table 3 was used. The results are shown in Table 2.

Comparative Examples 11 and 12 This example was carried out in the same manner as in Example 12 except that polypropylene having the content of 3-methyl-1-butene polymer shown in Table 3 was polymerized. The results are shown in Table 2.

Comparative Example 13 Using the same titanium-containing 3-methyl-1-butene as in Example 12, in the main polymerization, 0.164 mol of cyclohexylmethyldimethoxysilane was used alone as the organosilicon compound to homopolymerize propylene. Except for the above, the same procedure as in Example 12 was carried out. The results are shown in Tables 3 and 4.

[0110]

[Table 3]

[0111]

[Table 4]

Example 15 (Preliminary Polymerization of 3-Methyl-1-Pentene) In a 10 L polymerization vessel subjected to nitrogen substitution, 6000 ml of purified hexane, 100 mmol of triethylaluminum, and 10 mmol of solid titanium catalyst component in terms of titanium atom were charged. After the addition, 3-methyl-1-pentene was added to 10 g of titanium component as a whole to 10 g.
It was continuously introduced into the reactor for 2 hours so that the amount became 0 g. During this period, the temperature was kept at 20 ° C. After 2 hours, the introduction of 3-methyl-1-pentene was stopped and the reactor was thoroughly replaced with nitrogen. The solid portion of the obtained slurry was washed 5 times with purified hexane to obtain a titanium-containing 3-methyl-1-pentene polymer. The weight of the 3-methyl-1-pentene polymer at this time was 83 g. The crystallinity determined by X-ray diffraction was 58%.

Using the titanium-containing 3-methyl-1-pentene polymer obtained above, main polymerization of propylene (propylene-ethylene copolymerization) was carried out in the same manner as in Example 8, and 3 shown in Table 5 was used. -Methyl-1-pentene polymer (P
A crystalline polypropylene having a content of -3MP-1) was obtained.
The procedure of Example 12 was repeated, except that 0.042 parts by weight of the polypropylene containing the 3-methyl-1-pentene polymer was used. The results are shown in Tables 5 and 6.

Example 16 (Preliminary Polymerization of Vinyl Cyclohexane) Purified hexane (6000 ml), triethylaluminum (100 mmol), and solid titanium catalyst component (10 mmol) in terms of titanium atom were charged in a 10 L polymerization reactor which had been subjected to nitrogen substitution. Cyclohexane was continuously introduced into the reactor for 2 hours so that the total amount of cyclohexane was 100 g per 10 g of titanium component. During this period, the temperature was kept at 20 ° C. After 5 hours, the introduction of vinylcyclohexane was stopped and the reactor was thoroughly replaced with nitrogen. The solid portion of the obtained slurry was washed 5 times with purified hexane to obtain a titanium-containing vinylcyclohexane polymer. At this time, the weight of the vinylcyclohexane polymer is 5
It was 9 g. Crystallinity calculated by X-ray diffraction is 43%
Met.

Using the titanium-containing vinylcyclohexane polymer obtained above, main polymerization of propylene (propylene-ethylene copolymerization) was carried out in the same manner as in Example 8, and Table 5
A crystalline polypropylene having the content of vinylcyclohexane polymer (PVCH) shown in was obtained. Example 12 was repeated except that the polypropylene containing 0.0005 parts by weight of this vinylcyclohexane polymer was used. The results are shown in Tables 5 and 6.

Example 17 To 100 parts by weight of the homopolypropylene powder obtained in Example 1, 0.1 parts by weight of 2,6-di-t-butylhydroxytoluene as an antioxidant and calcium stearate as a chlorine scavenger were added. 0.1 parts by weight, 0.3 parts by weight of stearyldiethanolamide as an antistatic agent, tetrafluoroethylene polymer (PEFE, manufactured by Asahi ICI, trade name "Fluon Lubricant L-171J", X-ray diffraction crystallization degree 78.7%, average primary particle size 0.2 μm)
Example 1 was repeated except that 0.003 parts by weight was added. The results are shown in Tables 5 and 6.

Examples 18 and 19 The same procedures as in Example 17 were carried out except that the same homopolypropylene as in Example 17 was used and the tetrafluoroethylene polymer was used in the blending amount shown in Table 5. The results are shown in Table 5 and Table 6.
It was shown to.

Comparative Examples 14 and 15 The same procedure as in Example 17 was carried out except that the same homopolypropylene as in Example 17 was used and the amount of tetrafluoroethylene polymer was changed as shown in Table 5. The results are shown in Table 5 and Table 6.
It was shown to.

Comparative Example 16 The procedure of Example 17 was repeated except that the homopolypropylene obtained in Comparative Example 4 was used. The results are shown in Tables 5 and 6.

Example 20 Crystalline polypropylene obtained in Example 8, tetrafluoroethylene polymer (PEFE, manufactured by Asahi ICI, trade name "Fluon Lubricant L-173J", X-ray diffraction crystallization degree 87.6% The average primary particle diameter was 0.2 μm), and the composition was the same as in Example 17, except that the formulation shown in Table 5 was used. The results are shown in Tables 5 and 6.

Example 21 The same procedure as in Example 17 was conducted except that the same crystalline polypropylene as in Example 20 was used and the amount of the tetrafluoroethylene polymer used in Example 20 was changed as shown in Table 5. The results are shown in Tables 5 and 6.

Example 22 In the main polymerization, 0.0492 mol of cyclohexylmethyldimethoxysilane and 0.492 mol of tetraethoxysilane were used as the organosilicon compound in the same manner as in Example 1 to obtain a propylene homopolymer. Polymerization powders of random copolymers having an ethylene content of 1.0 mol% obtained by polymerization in the same manner were blended in an amount of 50 wt% each, and the tetrafluoroethylene polymer used in Example 20 was used. Example 17 was repeated except that the compounding amount of The results are shown in Tables 5 and 6.

[0123]

[Table 5]

[0124]

[Table 6]

Example 23 The crystalline polypropylene obtained in Example 8 and di (p-methylbenzylidene) sorbitol (Me-D) as a crystal nucleating agent.
Example 17 except that BS) was used and the formulation of Table 7 was used.
It carried out similarly to. The results are shown in Tables 7 and 8.

Example 24 2,2-methylenebis (4,6-methylene phosphate) as a crystal nucleating agent
Di-tert-butylphenyl) sodium (PTBPN
Example 17 was carried out in the same manner as in Example 17 except that a) was used and the composition shown in Table 7 was used. The results are shown in Tables 7 and 8.

Example 25 Example 25 was effected in the same manner as in Example 17 except that aluminum-di-p-tert-butylbenzoate (Al-PTBBA) was used as a crystal nucleating agent and the composition shown in Table 7 was used. The results are shown in Table 7,
The results are shown in Table 8.

Comparative Example 17 The procedure of Example 17 was repeated, except that the amount of aluminum di-p-tert-butylbenzoate added was changed to that shown in Table 7. The results are shown in Tables 7 and 8.

Example 26 The same procedure as in Example 17 was carried out except that talc having an average particle size of 4.2 μm was used as a crystal nucleating agent and the formulation shown in Table 7 was used. The results are shown in Tables 7 and 8.

Example 27 Example 17 was carried out in the same manner as in Example 17 except that talc having an average particle size of 1.5 μm was used as the crystal nucleating agent and the composition shown in Table 7 was used. The results are shown in Tables 7 and 8.

Comparative Examples 18 and 19 The same procedure as in Example 17 was carried out except that the addition amount of talc having an average particle size of 4.2 μm was changed to that shown in Table 7. The results are shown in Tables 7 and 8.

Example 28 Using the homopolypropylene powder obtained in Example 7,
Heptane washing was performed by the following method.

(Heptane Washing) 5 L (about 5 times the amount) of normal heptane was added to 1 kg of homopolypropylene powder similar to that used in Example 7, and washing was carried out at 60 ° C. for 1 hour with stirring. A solid component insoluble in normal heptane was recovered and dried under reduced pressure at 70 ° C. The properties of the obtained polypropylene are shown in Table 7.

Example 1 was repeated except that the homopolypropylene washed by the above method was used. The results are shown in Tables 7 and 8.

Comparative Example 20 Using the homopolypropylene obtained in Comparative Example 7, Example 28
The same procedure as in Example 1 was performed except that the washing was performed in the same manner as in. The results are shown in Tables 7 and 8.

[0136]

[Table 7]

[0137]

[Table 8]

[Brief description of drawings]

FIG. 1 is an elution curve showing the relationship between the elution temperature (° C.) and the elution amount (% by weight) of the crystalline polypropylene of Example 1.

FIG. 2 is an elution curve showing the relationship between the elution temperature (° C.) and the integrated elution amount (% by weight) of the crystalline polypropylene of Example 1.

FIG. 3 X of polypropylene stretched film of Example 1
It is a line diffraction and the peak separation result.

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Claims (2)

[Claims] (A) The peak temperature of the elution curve by the temperature rise elution fractionation method is 105 to 125 ° C., and the difference in the elution temperature between 90% by weight elution and 20% by weight elution calculated by the elution curve is 100 parts by weight of crystalline polypropylene having a temperature of 9 to 17 ° C., and (B) a crystal nucleating agent of 0.00001 to
A polypropylene composition comprising 1 part by weight. 2. A polypropylene stretched film comprising the polypropylene composition according to claim 1.