JPH07309912A - Polypropylene resin and stretched film - Google Patents

Abstract

(57) [Summary] [Objective] When a stretched film is formed, a polypropylene resin having high rigidity and heat resistance and having good stretchability during film formation is obtained. [Constitution] Melt flow rate is 0.1 to 10 g / 10
Min, temperature rise The peak temperature (Tp) of the elution curve by the elution fractionation method is 105 to 125 ° C., preferably 110 to 12
A polypropylene resin suitable for a biaxially stretched film having a dissolution peak width (σ) of 0 ° C. or more, preferably 9.0 ° or more, and preferably 10 ° or more, and a stretched film made of the polypropylene resin.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polypropylene resin and a stretched film made of the polypropylene resin. Specifically, when forming a uniaxially or biaxially stretched film, the uniaxially stretchable film has a wide temperature control range, a small mechanical load during stretching, little film breakage due to stretching, and good heat resistance such as heat shrinkage. It also relates to a polypropylene resin suitable for a biaxially stretched film and a stretched film made of the polypropylene resin.

[0002]

2. Description of the Related Art Biaxially oriented polypropylene films are widely used because of their excellent physical properties such as mechanical strength and transparency. The manufacturing method thereof is generally a biaxial stretching method using a tenter method.

In recent years, the production facilities for biaxially oriented polypropylene films have become larger and faster, and with conventional conventional polypropylene resins, the mechanical load of the stretching device during film formation has increased, and the accuracy of the film thickness has decreased. Furthermore, problems such as stretching breakage of the film have occurred.

[0004]

Therefore, there has been a demand for the development of a polypropylene resin which can cope with an increase in the size and speed of production equipment for a biaxially oriented polypropylene film. That is, during stretching, the temperature control range in which the film can be formed is wide, the mechanical load is small, the thickness accuracy of the formed film is excellent, the stretchability is good, and stretching tear does not occur, etc. Alternatively, a polypropylene resin suitable for a biaxially stretched film has been desired.

[0005]

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems, and as a result, a wide crystallinity distribution of polypropylene resin is effective for film-forming property. Low crystalline components (eluting components on the low temperature side of the elution peak in the temperature rising elution fractionation method) work effectively to reduce stretchability and mechanical load during stretching, and highly crystalline components (eluting in the temperature rising elution fractionation method) The inventors have found that the peak high-temperature-side elution component) effectively acts to maintain the heat resistance such as the rigidity and the heat shrinkage rate of the film obtained by film formation, and completed the present invention, resulting in the proposal thereof.

That is, in the present invention, the melt flow rate is 0.1 to 10 g / 10 minutes, the peak temperature (Tp) of the elution curve by the temperature rising elution fractionation method is 105 to 125 ° C., and the elution peak width (σ) is 9. It is a polypropylene resin characterized by being 0 degree or more.

The melt flow rate of the polypropylene resin of the present invention must be 0.1 to 10 g / 10 minutes,
It is preferably in the range of 1.0 to 5.0 g / 10 minutes. When the melt flow rate is less than 0.1 g / 10 minutes, the viscosity of the molten polypropylene resin becomes high, and the mechanical load of the extruder at the time of sheet forming by extrusion, which is the first step in the production of biaxially stretched film, increases. This makes extrusion molding difficult. The melt flow rate is 10
When it exceeds g / 10 minutes, the melt tension of the polypropylene resin decreases, so the sheet thickness accuracy decreases during sheet formation by extrusion, which is the first step in the production of biaxially stretched film, and the biaxial stretching causes The thickness accuracy of the manufactured film is deteriorated. When the range of the melt flow rate of the polypropylene resin used in the present invention is expressed by weight average molecular weight, it is 250,000 to 800,000, preferably 3
It will be in the range of 0,000 to 450,000.

The temperature rising elution fractionation method referred to in the present invention (hereinafter referred to as
Abbreviated as TREF. ) Is a method of separating polyolefin such as polypropylene resin by its crystallinity distribution, that is, the difference in the dissolution temperature in a solvent. Specifically, chromosolve was used as the packing material, the sample solution was introduced into the column, the sample was adsorbed on the packing material surface, and then the temperature of the column was increased while allowing the solvent to pass through, and elution was performed at each temperature. It can be measured by detecting the incoming polymer concentration.

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 polypropylene resin produced in Example 1 described later, where the temperature 118 at the peak position indicated by point A is 118. The elution peak temperature (Tp) is 0.4 ° C.

The elution peak width (σ) is a temperature difference in which the integrated elution amount is 20% by weight to 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. 2 is a dissolution curve showing the relationship between the dissolution temperature (° C.) and the cumulative dissolution amount (% by weight) of the polypropylene resin produced in Example 1 described later, where point B is 12 at T (90)
The temperature is 1.1 ° C, and the C point is 110.1 ° C at T (20). Therefore, the elution peak width (σ) in this case is (1
21.1-110.1) results in 11.0 degrees.

Since the elution temperature depends on the crystallinity of the polymer, that is, the stereoregularity and the copolymerization composition, the distribution of the crystallinity of the polymer is obtained by determining the relationship between the elution temperature and the elution amount (% by weight) of the polymer by TREF. You can know.

The peak temperature (Tp) of the elution curve by TREF of the polypropylene resin of the present invention is 105 to 125 ° C.
The range is 110 to 120 ° C., and the range is preferably 110 to 120 ° C. If the elution peak temperature is less than 105 ° C, the rigidity and heat resistance of the biaxially stretched film decrease. Also, 1
If the temperature exceeds 25 ° C, the stretchability during stretching during film formation will decrease, the mechanical load will increase, and stretch breakage of the film will frequently occur.

Further, the TR of the polypropylene resin of the present invention
The elution peak width (σ) by EF must be 9.0 degrees or more, and is preferably 10.0 degrees or more. When the elution peak width (σ) is less than 9.0 degrees, the stretchability is deteriorated, the mechanical load is increased, and stretching breakage of the film frequently occurs, which is not preferable.

The polypropylene resin of the present invention is TREF.
When the peak temperature and the elution peak width of the elution curve by the above, the effect of the present invention can be sufficiently achieved, further, the rigidity and biaxially stretched film obtained using the polypropylene resin of the present invention and Considering heat resistance, the elution temperature (T (9
0)) is preferably 110 ° C. or higher, and more preferably 115 ° C. or higher.

The elution amount (a) at an elution temperature of 20 ° C. or lower is preferably 5.0% by weight or less from the viewpoint of heat resistance and blocking prevention of the obtained biaxially stretched film, and further 3. It is more preferably 5% by weight or less. 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 polypropylene resin used in the present invention may be a homopolymer of propylene, or may contain an α-olefin other than propylene as a copolymerization component within a range that does not impair the effects of the present invention. Good. Examples of α-olefins other than propylene include 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,
Examples of the α-olefin having 2 to 20 carbon atoms include 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 content ratio varies depending on the type of monomer other than propylene, but in general, it is preferably 5 mol% or less in terms of the ratio in the copolymer. For example, α other than propylene
-When the olefin is ethylene, the proportion of the ethylene component in the copolymer is preferably 1.0 mol% or less so that the peak temperature (Tp) of TREF falls within the range of the present invention.

The method for producing the polypropylene resin of the present invention is not particularly limited, but it is generally preferable to employ the following method. For example, a method of mixing propylene by mixing several kinds of catalyst components capable of polymerizing polypropylene resins having different stereoregularity can be mentioned. In particular, a method of polymerizing propylene by mixing two or more kinds of electron donors that give a solid titanium catalyst component, an organoaluminum compound, and a polypropylene resin 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, polypropylene having a wide crystallinity distribution, that is, a polypropylene having a peak width (σ) of the elution curve by TREF of 9.0 degrees or more is preferable because it can be obtained with a smaller amount of atactic component.

[0019] _{(R 3) n -Si- (OC} 2 H 5) 4-n (II) ( where, R _1, R ₂ and R ₃ is a hydrocarbon group having same or different, n is 0 or 1. ) As the solid titanium catalyst component described above, a compound known to be used for propylene polymerization 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 adopted 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 dichloride and 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 to 1 in terms of aluminum / titanium (molar ratio) with respect to titanium atoms in the solid titanium catalyst component.
It is preferably 000, 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 in the present invention include methyl group, ethyl group, n
-Propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, and other alkyl groups having 1 to 6 carbon atoms; vinyl group, propenyl group An alkenyl group having 2 to 6 carbon atoms such as allyl group; an alkynyl group having 2 to 6 carbon atoms such as ethynyl group and propynyl group; a cycloalkyl group having 5 to 7 carbon atoms such as cyclopentyl group, cyclohexyl group and cycloheptyl group An aryl group having 6 to 12 carbon atoms such as a phenyl group, a tolyl group, a xylyl group and a naphthyl group. Of these, R ₃ is preferably a linear alkyl group, alkenyl group, or aryl group. N is 0 or 1
Is.

Examples of the organosilicon compound preferably used in the present invention 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 isopropyltrisilane. 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 Si / Ti (molar ratio) of Ti atom of the solid titanium catalyst component, respectively.
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. When the use ratio of the organosilicon compounds (I) and (II) is more than 1:25, the elution peak temperature (Tp) by TREF of the obtained polypropylene resin is 10
The temperature is less than 5 ° C., the temperature T (90) when the integrated elution amount is 90% by weight is less than 110 ° C., and the elution amount (a) at an elution temperature of 20 ° C. or less exceeds 5% by weight. The heat resistance of the stretched film is lowered. When the use ratio of the organosilicon compounds (I) and (II) is less than 1: 5, the elution peak width (σ) by TREF of the obtained polypropylene resin is less than 9.0 degrees, and the film formation At that time, the stretchability is lowered, the mechanical load is increased, and the film is broken due to stretching.

The order of adding the above-mentioned respective components is not particularly limited, and the organosilicon compounds represented by the general formulas (I) and (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 are not particularly limited as long as the effects of the present invention are recognized, but the following conditions are generally preferable. The polymerization temperature is 20 to 200 ° C, preferably 50 to
The temperature is 150 ° C., and hydrogen can coexist as a molecular weight modifier. For the polymerization, slurry polymerization, solventless polymerization, gas phase polymerization, etc. can be applied, and any of batch, semi-batch and continuous methods can be used.
It can also be performed in stages. 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 present invention, the polypropylene resin obtained by the above-mentioned method can be used alone, or can be used by blending with other polypropylene resin. Of course, it is also possible to blend the polypropylene resins obtained by the above method.

Further, also in the method of polymerizing polypropylene using a metallocene catalyst composed of a metallocene compound and alumoxane, polypropylene having a wide crystallinity distribution is used by combining two or more kinds of catalyst components capable of polymerizing polypropylene resins having different stereoregularity. The method of obtaining

In the polypropylene resin used in the present invention, if necessary, an antioxidant, a chlorine scavenger, a heat stabilizer, an antistatic agent, an antifogging agent, an ultraviolet absorber, a lubricant, a nucleating agent, an antiblocking agent. Additives such as agents, pigments, and other resins may be blended within a range that does not impair the effect.

The polypropylene resin of the present invention is suitable as a material for stretched films. The stretched film may be either uniaxially stretched or biaxially stretched. The thickness of the stretched film is not particularly limited, but is usually 3 to 150.
It is preferably in the range of μm. Further, one or both surfaces of the 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 polypropylene resin of 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 film of the present invention, known methods can be adopted without any limitation. For example,
The sequential biaxial stretching method by the tenter method is as follows. After the polypropylene resin raw material is formed into a sheet or film by a T-die method, an inflation method or the like, it is supplied to a longitudinal stretching device and heated at a heating roll temperature of 120 to 170 ° C. for 4 hours. Longitudinal stretching of 10 times, followed by a tenter with a tenter temperature of 130 to 1
This is a method of transversely stretching 4 to 15 times at 80 ° C., and while allowing a relaxation of 0 to 25% in the transverse direction as necessary, 80
The method of heat-treating at -180 degreeC can be mentioned. Of course, the stretching may be carried out again after these stretchings, and in the longitudinal stretching, stretching methods such as multi-stage stretching and rolling can be combined.

[0032]

EFFECT OF THE INVENTION The polypropylene resin of the present invention has a wider temperature adjustment range in which a stretchable film can be formed, as compared with conventionally known polypropylene resins, has a small mechanical load during stretching, and can be stretched. It is less likely to tear and has excellent stretchability during stretching, enabling long-term continuous operation. Further, the stretched film made of the polypropylene resin of the present invention has excellent thickness accuracy and good heat resistance such as heat shrinkage. Such effects indicate that the polypropylene resin of the present invention is extremely excellent as a polypropylene resin for a stretched film suitable for high-speed film formation.

[0033]

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.

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

(2) Weight average molecular weight 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: SHODEX UT Sample concentration: 0.1 wt% Injection volume: 0.50 ml (3) Pentad Fraction It was measured under the following conditions using JNM-GSX-270 ( ¹³ C-nuclear resonance frequency 67.8 MHz) manufactured by JEOL Ltd.

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) Elevation of temperature Peak temperature (Tp) by elution fractionation method, elution peak width (σ), elution temperature (T (90)) at which cumulative elution amount becomes 90% by weight, and elution temperature of 20 ° C. or less Elution amount in (a) It was measured under the following conditions using an automatic TREF device SSC-7300ATREF manufactured by Senshu Scientific Co., Ltd.

Solvent: Orthodichlorobenzene Flow rate: 150 ml / hour Temperature rising rate: 4 ° C./hour Detector: Infrared detector Measurement wave number: 3.41 μm Column: 30 mmφ × 300 mm Filler: Chromosolve P 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 gradually cooled to 10 ° C. at a rate of 2 ° C./hour to adsorb the sample polymer on the surface of the packing material, and then the column temperature was changed. By raising the temperature under the above conditions, the concentration of the polymer eluted at each temperature was measured with an infrared detector.

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 (3 g of phthalic anhydride was added to this solvent.
7.5 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, 400 ml of titanium tetrachloride kept at -20 ° C
The entire amount was charged dropwise into (3.6 mmol) 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 (25 mmol) of diisobutyl phthalate was added, and the mixture was maintained at the same temperature for 2 hours with stirring. After the reaction for 2 hours,
The solid part was collected by hot filtration, and the solid part was collected to 2000 m.
After resuspending with 1 liter of titanium tetrachloride, heating reaction was performed again at 110 ° C. for 2 hours. After the reaction was completed, 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 and 57.
It was 0% by weight, 18.0% by weight of magnesium and 21.9% by weight of diisobutyl phthalate.

(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 vessel subjected to nitrogen substitution, and then propylene was added to 10 g of titanium component as a whole. It 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) Content of 200 after nitrogen substitution
After charging 500 kg of propylene into a 0 L polymerization vessel, charged with 1.64 mol of triethylaluminum, 0.164 mol of ethyltriethoxysilane, 0.0082 mol of cyclohexylmethyldimethoxysilane, and 10 L of hydrogen, the internal temperature of the polymerization vessel was changed. The temperature was raised to 65 ° C. Titanium-containing polypropylene with titanium atom 0.00656mo
Then, the internal temperature of the polymerization vessel was raised to 70 ° C., and 1
Propylene polymerization was carried out for an 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 melt flow rate (MFR) of the obtained polypropylene resin, the weight average molecular weight, the pentad fraction, the copolymerization composition, the peak temperature (Tp) of the elution curve by the temperature rising elution fractionation method (TREF), the elution peak width ( σ), the temperature at which the cumulative elution amount becomes 90% by weight (T (9
0)) and the elution amount (a) at an elution temperature of 20 ° C. or less are shown in Table 1. Further, FIG. 1 shows an elution curve showing the relationship between the elution temperature (° C.) and the elution amount (% by weight), and FIG. 2 shows the elution temperature (° C.).
The elution curve showing the relationship between the cumulative elution amount (wt%) is shown.

(Granulation) To 100 parts by weight of polypropylene powder obtained from the polymerization machine, 0.1 parts by weight of 2,6-di-t-butylhydroxytoluene and calcium stearate were added, mixed with a Henschel mixer, and screwed. Extrude at 230 ° C. using an extrusion granulator with a diameter of 65 mm,
The pellets were granulated to obtain raw material pellets.

(Film Forming) Using the obtained polypropylene resin pellets, a film forming experiment of a biaxially stretched film was conducted by the following method. The polypropylene resin pellets were extruded at 280 ° C. using a sheet extruder having a screw diameter of 90 mmφ, and a sheet having a thickness of 1 mm was formed with a cooling roll at 30 ° C. Then, this sheet was roll-stretched by 4.5 times in the machine direction using a tenter type sequential biaxial stretching apparatus, and subsequently stretched by 10 times in the transverse direction in a tenter at 160 ° C. to obtain a film having a thickness of 20 μm. The biaxially stretched film was formed at a speed of 50 m / min.

During film formation, the roll heating temperature for longitudinal stretching is changed so that the film can be stably formed for 10 minutes without causing whitening of the film, unevenness in thickness, film breakage, longitudinal stretching and transverse stretching. Machine load (current value, unit ampere)
The film forming property (stretchability) was evaluated by. 8 hours more
Continuous operation was carried out to evaluate the number of film breakages. The thickness accuracy of the obtained film is determined by Yokogawa Denki's infrared thickness gauge WE installed between the tenter and the winder.
It was evaluated by the thickness pattern of the film measured using B GAGE. In addition, the film formed is 3 ° C at 35 ° C.
After aging for a day, the heat shrinkage was measured. Measurement of heat shrinkage is 15 mm in width and 300 mm in length and width
Was cut into strips and heated in an oven at 120 ° C. for 15 minutes to obtain the dimensional change. The results are shown in Table 1.

Comparative Example 1 Propylene homopolymerization was carried out in the same manner as in Example 1 except that 0.164 mol of cyclohexylmethyldimethoxysilane was used alone as the organosilicon compound, and the results are shown in Table 1.

Comparative Example 2 In Comparative Example 1, the ethylene component content was 0.5 mol%
A random copolymer of ethylene and propylene was polymerized, and the results are shown in Table 1.

Comparative Example 3 Ethyltriethoxysilane as an organosilicon compound
Homopolymerization of propylene was carried out in the same manner as in Example 1 except that 164 mol was used alone, and the results are shown in Table 1.

Examples 2 to 5 The amount of triethylaluminum used was 3.50 mol, and 0.013 mol of cyclohexylmethyldimethoxysilane and 0.262 mol of ethyltriethoxysilane were used as the organosilicon compound (Example 2). Aluminum is the same amount as described above, and cyclohexylmethyldimethoxysilane 0.0
66 mol and ethyltriethoxysilane 0.656mo
1 (Example 3), the amount of triethylaluminum used was 1.64 mol, and 0.0164 mol of diisopropyldimethoxysilane and 0.164 mol of pentyltriethoxysilane were used as the organosilicon compound (Example 4). Dimethoxysilane 0.0
164 mol and octyltriethoxysilane 0.164
Homopolymerization of propylene was carried out in the same manner as in Example 1 except that mol was used (Example 5), and the results are shown in Table 1.
It was shown to.

Comparative Examples 4 and 5 The use of 0.0033 mol of cyclohexylmethyldimethoxysilane and 0.099 mol of ethyltriethoxysilane as the organosilicon compound (Comparative Example 4), and 0.164 mo of cyclohexylmethyldimethoxysilane.
Homopolymerization of propylene was carried out in the same manner as in Example 2 except that 1 and 0.656 mol of ethyltriethoxysilane were used (Comparative Example 5), and the results are shown in Table 1.

Comparative Examples 6 and 7 0.164 mol of diisopropyldimethoxysilane was used alone as an organosilicon compound (Comparative Example 6).
Further, propylene homopolymerization was carried out in the same manner as in Example 4 except that 0.164 mol of pentyltriethoxysilane was used alone (Comparative Example 7), and the results are shown in Table 1.

Example 6 In the same manner as in Example 1, except that 0.0492 mol of cyclohexylmethyldimethoxysilane and 0.492 mol of tetraethoxysilane were used as the organosilicon compound, ethylene and propylene having an ethylene component content of 0.5 mol% were prepared. The random copolymer was polymerized and the results are shown in Table 1.

Example 7 In the same manner as in Example 1, except that 0.0492 mol of cyclohexylmethyldimethoxysilane and 0.492 mol of tetraethoxysilane were used as the organosilicon compound, butene-1 having a butene-1 component content of 0.5 mol% was obtained. A random copolymer of propylene and propylene was polymerized and the results are shown in Table 1.
It was shown to.

Example 8 In this polymerization, a propylene homopolymer obtained by polymerizing in the same manner as in Example 1 using 0.0492 mol of cyclohexylmethyldimethoxysilane and 0.492 mol of tetraethoxysilane as the organosilicon compound, Ethylene content obtained by polymerizing by the method of 1.0mo
5% each of 1% of random copolymerization powder
The raw material pellets were obtained by blending 0% by weight and granulating. The results are shown in Table 1.

Example 9 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. Purified hexane (6000 ml) and triethylaluminum (100 ml) were placed in a 10 L polymerization vessel which had been purged with nitrogen.
mmol, solid titanium catalyst component 1 in terms of titanium atom
After charging 0 mmol, 3-methyl-1-butene was continuously introduced into the reactor for 1 hour so that the total amount was 40 g with respect to 10 g of titanium component. During this period, the temperature was kept at 20 ° C. After 1 hour, 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-containing 3-methyl-1-butene polymer. 3 at this time
The weight of the -methyl-1-butene polymer was 36 g.

Polymerization of propylene was carried out in the same manner as the main polymerization of Example 1 except that the obtained titanium-containing 3-methyl-1-butene polymer was used. The content of 3-methyl-1-butene in all the polymers determined from the yield of the propylene polymer was about 330 ppm. The obtained polypropylene powder was granulated in the same manner as in Example 1 to obtain raw material pellets. The results are shown in Table 1.

[0058]

[Table 1]

[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 polypropylene resin 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 polypropylene resin of Example 1.

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Claims (2)

[Claims] 1. A melt flow rate of 0.1 to 10 g / 1.
A polypropylene resin characterized by having a peak temperature (Tp) of 105 to 125 ° C. and an elution peak width (σ) of 9.0 degrees or more in an elution curve by a temperature rising elution fractionation method at 0 minutes. 2. A stretched film made of the polypropylene resin according to claim 1.