JPH07278377A - Propylene polymer film - Google Patents

Abstract

PURPOSE:To obtain a polypropylene film which is produced from a resin composition comprising a propylene polymer and a specific copolymer and is useful in food packaging because it has excellent clarity, heat-sealing properties at low temperature, high strength, and good processability. CONSTITUTION:The object propylene film is produced from a resin composition comprising (A) 50-99wt.% of a propylene polymer such as propylene-ethylene random copolymer or propylene homopolymer of 0.1-50g/10min. MFR, (B) 1-50% of a copolymer from ethylene and an alpha-olefin of 4-40 carbon atoms using a metallocene catalyst, having the following properties: (i) 0.86-0.935g/cm<3> density; (ii) 0.1-20g/10min. MFR; (iii) the temperature rise elution fractionation (TREF) gives one or more peaks in its elution curve where all of the peaks are in the range lower than 100 deg.C and the peak may include substances which elute at other temperature than the peak one in the elution curve; (iv) the integrated elution according to the TREF exceeds 90% at 90 deg.C elution temperature.

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION

FIELD OF THE INVENTION The present invention relates to a film made of a propylene resin composition. More specifically, the present invention relates to the component resin (A
The present invention relates to a propylene-based film which is free from uneven mixing of B and B), is excellent in film strength such as transparency, low temperature heat sealability, impact strength and tear strength, has a good workability balance, and has good workability.

[0002]

[Outline of Invention]

[0003]

SUMMARY OF THE INVENTION The object of the present invention is to provide a resin having uniform mixing, excellent film strength such as transparency, low temperature heat sealability, impact strength and tear strength, and good workability balance. To obtain a propylene-based film having good properties.

[0004]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that the present invention achieves the above objects. <Summary> That is, the propylene-based film according to the present invention is characterized by being obtained from a resin composition containing the following components A and B. Component A: Propylene polymer 50 to 99% by weight Component B: Ethylene and carbon number 4 to 4 having the following properties (a) to (d) produced using a metallocene catalyst.
Copolymer with 40 α-olefins 1 to 50% by weight (a) Density 0.86 to 0.935 g / cm ³ (b) MFR 0.1 to 20 g / 10 min (c) Temperature rising elution fractionation There is at least one peak in the elution curve of (TREF), and all the peaks are 10
It is 0 ° C or lower. Further, the peak may be one that elutes at a temperature other than the peak temperature, which is substantially present in the elution curve. (D) The integrated elution amount by temperature rising elution fractionation (TREF) is 90% or more when the elution temperature is 90 ° C. <Effect> The propylene-based film according to the present invention is excellent in film strength such as transparency, low-temperature heat-sealing property, impact strength and tear strength, excellent in processability, and good in workability of the film. Fields, for example, various food packaging fields such as fresh foods such as vegetables and fish, dried foods such as snacks and noodles, aqua foods such as soups and pickles, medical products in various forms such as tablets, powders and liquids, and medical treatment. The field of packaging medical-related products used for peripheral materials etc., the field of various electrical equipment such as electrical parts and cassette tapes, and the field of packaging various electrical equipment,
It can be applied to a wide range of fields, such as the field for packing miscellaneous goods, and is industrially useful.

[Detailed Description of the Invention] <Resin Composition> The propylene-based film according to the present invention comprises:
It is obtained from a resin composition containing the following components A and B. Here, "comprising" means not only the components shown above, that is, the components A and B, but also the components containing other purposeful components. (I) Component A / Propylene-based Polymer (1) Basic Content The propylene-based polymer of component A of the present invention is a homopolymer of propylene or a small amount of propylene (up to 40% by weight as a content in the copolymer). A) Random or block copolymer with α-olefin. The production method thereof is not particularly limited, and generally, a Ziegler-Natta catalyst which is used in combination with a so-called titanium-containing solid transition metal component and an organic component, in particular, the transition metal component contains titanium, magnesium and halogen as essential components. And a solid component containing an electron-donating compound as an optional component or titanium trichloride, and an organometallic component as an organoaluminum compound using a catalyst, slurry polymerization, gas phase polymerization, bulk polymerization, solution polymerization, or a combination thereof. Propylene homopolymer obtained by homopolymerizing propylene in a single stage or multiple stages, or propylene and ethylene or (and) α having 4 to 12 carbon atoms.
Can be obtained by copolymerizing with olefins, preferably ethylene, in one or more stages. Also,
These propylene-based polymers may be random polymers or block polymers, but preferred are random copolymers. Two or more kinds of these propylene-based polymers may be used.

(2) Supplementary Requirements In addition to the above, the component A of the present invention preferably has the following conditions with respect to MFR, activation energy, characteristics by pulsed NMR and α-olefin content. It is preferable that they are satisfied. MFR The MFR of the propylene-based polymer of the present invention is preferably 0.1 to 50 g / 10 minutes, more preferably 1 to 30 g.
/ 10 minutes, particularly preferably 3 to 15 g / 10 minutes. If the MFR is higher than the above value, the strength tends to decrease, which is not preferable. When the MFR is lower than the above value, the film appearance is deteriorated, which is not preferable. Activation energy (Ea) The activation energy when the shear rate obtained from the viscosity of the propylene-based polymer of the present invention is 24 sec-1 is preferably 4 to 20 KJ / mol, more preferably 6 to 17 KJ / mol, and particularly preferably It is preferably 7 to 15 KJ / mol. If the activation energy is out of the above range, the workability tends to become impractical, which is not preferable.

The activation energy referred to here is "rheology" (published by Misuzu Shobo, Tsurutaro Nakagawa, and Hirotaro Kobe 6
04p), "Kodansha Modern Chemistry Series 18 Rheology" (Kodansha, Shizuo Hayashi, 160-161p) and other documents that describe the relationship between viscosity and temperature Arr.
It can be obtained by a method of calculating the activation energy from the Henius equation or the Andrade equation. Specifically, the measurement temperature is 190 ° C. (463 ° K), 230 ° C. (503 ° K), and 2 with a capillograph type viscosity measuring device.
The shear viscosity at a shear rate of 24 sec -1 is determined from the viscosity curve (viscosity dependence curve for shear rate) measured at each temperature of 60 ° C (533 ° K). Next, 1 / T
The intercept: logA is obtained from a graph with (T = measured temperature: ° K) on the horizontal axis and log η on the vertical axis. The activation energy (Ea) is calculated by substituting each obtained value into the following equation. η = Ae ^{−Ea / RT} → log η = log A−Ea / RT (η: shear viscosity (poise), A: frequency factor, Ea: activation energy (KJ / mol), R: gas constant (= 8.3145J / K)
.Mol), T: absolute temperature (° K)) Characteristics by pulsed NMR The propylene-based polymer of the present invention is a "Multiple-Pulse Mag".
netic Resonance onSome Crystalline Polymers (Polym
er Journal, Vol 3, No.4, p448-462 (1972); K. Fujimot
o, T. Nishi and R. Kado), the respective ratios of the crystalline component (I), the constrained amorphous component (II) and the unconstrained amorphous component (III) determined by the pulse method NMR described in
The weight ratio of (I) / (II) is preferably 1.5 to 4, more preferably 2 to 3.5, and (III) is preferably 3 to 30% by weight, more preferably 5 to 20. % By weight.

If (I) / (II) is smaller than the above range, the heat resistance tends to be inferior, which is not preferable. If it exceeds the above range, the strength is deteriorated, which is not preferable. When (III) is smaller than the above range, the impact strength tends to be poor, which is not preferable. If the amount exceeds the above range, the workability of the film tends to deteriorate, which is not preferable. α-olefin content The propylene-based polymer of the component A of the present invention is propylene
The α-olefin content in the case of an α-olefin copolymer is preferably 1 to 40% by weight, more preferably 1 to 25% by weight, particularly preferably 2 to 20% by weight in the case of a block copolymer. is there. In the case of a random copolymer, it is preferably 10% by weight or less, more preferably 0.
5 to 7% by weight.

(II) Component B / ethylene / α-olefin copolymer (1) Basic content Component B has the following properties (a) to (d) produced using a metallocene catalyst. Ethylene and 4 to 4 carbon atoms
It is a copolymer with 40 α-olefins. (A) Density The density of the ethylene / α-olefin copolymer of the component B of the present invention is 0.86 to 0.935 g / cm ³ , preferably 0.88 to 0.91 g / cm ³ , and particularly preferably 0. .8
9 to 0.91 g / cm ³ . If the density is higher than the above value, the transparency of the produced film deteriorates, which is not preferable. If the density is lower than the above value, the film tends to become sticky, which is not preferable. (B) MFR The MFR of the ethylene / α-olefin copolymer of the component B of the present invention is 0.1 to 20 g / 10 minutes, preferably 0.5.
-10 g / 10 minutes, particularly preferably 1-7 g / 10 minutes,
Is. If the MFR is lower than the above value, extrusion becomes difficult, which is not preferable. When the MFR is higher than the above value, the miscibility with the component A deteriorates, which is not preferable. (C) Peak in elution curve The ethylene / α-olefin copolymer of the component B of the present invention has a temperature rising elution fractionation (TREF: Temperature Rising).
All peaks of the elution curve obtained by Elution Fractionation are 100 ° C. or lower, preferably one peak, and the peak temperature of the peak is 100 ° C. or lower,
Preferably 0 to 85 ° C, more preferably 10 to 70 ° C,
Particularly preferably, it is 20 to 60 ° C.,
Moreover, what is eluted at a temperature other than the elution temperature of the peak may be substantially present in the elution curve. (D) Integrated elution amount The ethylene / α-olefin copolymer of the component B of the present invention has an integrated elution amount of 90% or more, preferably 9% at an elution temperature of 90 ° C., obtained from an elution curve by temperature rising elution fractionation.
95% or more at 0 ° C, particularly preferably 97% at 90 ° C
That is all.

Here, the measurement of the elution curve by the temperature rising elution fractionation (TREF) is a well-known technique.
Is, for example, Journal of Applied Polymer Science.
Vol.126, 4217-4231 (1981), Proceedings of Macromolecular Discussion Group 2P1C09
It is carried out based on the principle described in documents such as (1988). That is, first, the target polyethylene is completely dissolved once in a solvent (for example, o-dichlorobenzene). It is then cooled and left in the solution to form a thin polymer layer on the surface of the inert carrier. Next, the temperature is raised in a continuous or stepwise manner, and first at a low temperature, an amorphous component in the target polyethylene composition, that is, one having a large degree of branching of short-chain branches of polyethylene
Elute from. As the elution temperature rises, the one with less degree of branching gradually elutes, and finally the unbranched linear part elutes, and the measurement ends. The compositional distribution of the polymer can be seen from the graph drawn by detecting the concentration of the elution portion at each temperature and drawing the elution amount and the elution temperature.

(2) Production of Component B The ethylene / α-olefin copolymer of the component B of the present invention is produced using a metallocene catalyst.
Therefore, in the present invention, for example, JP-A-58-193 is used.
09, 59-95292, 60-35005.
No. 60, No. 60-35006, No. 60-35007, No. 60-35008, No. 60-35009, No. 61-
130314, Japanese Patent Laid-Open No. 163088/1993,
European Patent Application Publication No. 420436, US Pat. No. 5,055,438 and International Publication WO
Ethylene / α-olefin copolymers according to the method described in 91/04257 are targeted for component A. A metallocene catalyst, particularly a metallocene alumoxane catalyst, or a catalyst composed of a metallocene compound and a compound that reacts with the metallocene compound described below to form a stable ion, as disclosed in International Publication WO 92/01723, etc. A copolymer produced by copolymerizing ethylene as a main component and α-olefin as a subcomponent is preferable because it has excellent film strength, transparency and low temperature heat sealability.

Here, the compound which reacts with the metallocene compound to form a stable ion is an ionic compound or an electrophilic compound formed from an ion pair of a cation and an anion, which is stable upon reaction with the metallocene compound. It becomes an ion and forms a polymerization active species. Among these, one group of ionic compounds is represented by the following formula (I). [Q] ^{m +} [Y] ^m- (I) Q is a cation component of an ionic compound, and is a carbonium cation, tropylium cation, ammonium cation, oxonium cation, sulfonium cation,
Examples thereof include phosphonium cations and the like, and metal cations and organometallic cations which are themselves easily reduced.

These cations are listed in Table 1-5019.
Not only cations that can give a proton as disclosed in Japanese Patent Publication No. 50, but also cations that do not give a proton may be used. Specific examples of these cations include triphenylcarbonium, diphenylcarbonium, cycloheptatrienium, indenium, triethylammonium, tripropylammonium, tributylammonium, N, N-dimethylanilinium, dipropylammonium, dicyclohexylammonium, Triphenylphosphonium, trimethylphosphonium, tri (dimethylphenyl) phosphonium, tri (methylphenyl) phosphonium, triphenylsulfonium, triphenyloxonium, triethyloxonium, pyrylium, silver ion, gold ion, platinum ion, palladium ion, Examples include mercury ions and ferrocenium ions. Of these, triphenylcarbonium and N, N-dimethylanilinium are particularly preferable.

On the other hand, Y is an anion component of an ionic compound and is a component which reacts with a metallocene compound to form a stable ion, and is an organic boron compound anion, an organic aluminum compound anion, an organic gallium compound anion, an organic phosphorus compound. Anions, organic arsenic compound anions, organic antimony compound anions and the like, particularly organic boron compound anions are mentioned. Specifically, tetraphenylboron, tetrakis (3,4,5-trifluorophenyl) boron, tetrakis (3,5-di (trifluoromethyl) phenyl) boron, tetrakis (pentafluorophenyl) boron, tetraphenylaluminum , Tetrakis (3,4,5-trifluorophenyl)
Aluminum, tetrakis (3,5-di (trifluoromethyl) phenyl) aluminum, tetrakis (pentafluorophenyl) aluminum, tetraphenylgallium, tetrakis (3,4,5-trifluorophenyl) gallium, tetrakis (3,5- Di (trifluoromethyl) phenyl) gallium, tetrakis (3,5-di (t-butyl) phenyl) gallium, tetrakis (pentafluorophenyl) gallium, tetraphenylphosphorus,
Tetrakis (pentafluorophenyl) phosphorus, tetraphenylarsenic, tetrakis (pentafluorophenyl) arsenic, tetraphenylantimony, tetrakis (pentafluorophenyl) antimony, decaborate, undecaborate, carbadodecaborate, decachlorodecaborate, etc. . Of these, tetrakis (pentafluorophenyl) boron is particularly preferable.

The electrophilic compound is a compound known as a Lewis acid compound, which is a compound which reacts with a metallocene compound to form a stable ion to form a polymerization active species. Examples thereof include metal halides and metal oxides known as solid acids. Specific examples include magnesium halides and Lewis acidic inorganic compounds. (3) α-Olefin The α-olefin constituting the component B has 4 to 4 carbon atoms.
40 α-olefins, preferably for example 1-butene, 1-pentene, 1-hexene, 1-octene, 1-
Heptene, 4-methylpentene-1,4-methylhexene-1,4,4-dimethylpentene-1, octadecane and the like can be mentioned. Among these α-olefins, preferably 4 to 12 carbon atoms, particularly preferably 6 to 10 carbon atoms,
belongs to. In the present invention, one type or two or more types of α-
2 to 60% by weight of olefin, preferably 5 to 50% by weight, particularly preferably 10 to 30% by weight, and ethylene 40
The component B is preferably a copolymer obtained by copolymerizing with -98% by weight, preferably 50-95% by weight, particularly preferably 70-90% by weight. (4) Copolymerization As the polymerization method adopted when the component B is produced by copolymerizing ethylene with the above-mentioned α-olefin, there are a gas phase method, a slurry method, a solution method, a high pressure ionic polymerization method and the like. Can be mentioned. Among these, the solution method and the high-pressure ionic polymerization method are preferable, and the high-pressure ionic polymerization method is particularly preferable. The high pressure ionic polymerization method means that the pressure is 100 kg / cm ² or more, preferably 200 to 2000 kg /
cm ² , temperature is 125 ° C. or higher, preferably 130 to 250
It is a continuous process for producing an ethylene polymer, which is carried out under reaction conditions of 150 ° C., particularly preferably 150 to 200 ° C. (for example, JP-A-56-18607 and JP-A-58-2251).
No. 06, etc.).

(III) Composition (1) Blending ratio The blending ratio of component A and component B is as follows: component A: component B = 9
9: 1 to 50: 50% by weight, preferably 98: 2 to 6
0: 40% by weight, particularly preferably 95: 5 to 70:30
% By weight. If the compounding amount of the component B is more than the above value, the workability of the film is deteriorated, which is not preferable. If the blending amount of the component B is less than the above value, the effect of improving the film strength and heat sealability is small, which is not preferable. (2) Other Additive Components In the propylene-based film of the present invention, generally used resin additive components, for example, antioxidants, antiblocking agents, slip agents, antistatic agents, nucleating agents, heat stabilizers,
A light stabilizer, an ultraviolet absorber, a neutralizing agent, an antifogging agent, a coloring agent and the like can be added. Also, other resin components, for example,
An ethylene polymer other than the component A and the component B can be added within a range that does not impair the effects of the present invention. (3) Physical Properties MFR (melt flow rat) of the propylene-based film of the present invention
e) is 1 to 50 g / 10 minutes, preferably 3 to 30 g / 10 minutes,
Particularly preferably, it is 4 to 20 g / 10 minutes. (4) Production of Composition The propylene-based film according to the present invention is
Specifically, by a method involving at least softening, preferably melting, of components A and B, for example, a propylene-based polymer of component A and an ethylene / α-olefin copolymer of component B are uniaxially or biaxially mixed. Extruder, Brabender blast graph, Banval-mixer, kneader blender, etc. to melt and knead into pellets by a commonly used method, or dry blend with a V blender etc. to obtain You can Preferably, L / D = 24 or more is preferably melt-kneaded and pelletized by a single-screw extruder or a twin-screw extruder.

<Production of Film> The film can be produced using the above-mentioned composition by any known method such as T-die molding method, water-cooled inflation molding method and air-cooled inflation molding method.

Further, by a dry laminating method, an extrusion laminating method, a sandwich laminating method, a coextrusion method or the like,
It can also be carried out by extrusion coating on various substrates or by coextrusion with the substrates.

The ethylene-based resin film thus obtained can be made into a composite film by laminating another film or the like on at least a part thereof. That is,
For example, it can be used as a sandwich laminate base material of various base materials and a sealant base material.

Examples of the above-mentioned various base materials include high molecular weight polymers such as paper, aluminum foil, cellophane, woven cloth, non-woven cloth and film, for example, high density polyethylene, medium to low density polyethylene, and ethylene / vinyl acetate. Polymers, ethylene / acrylic acid ester copolymers, ionomers, propylene-based polymers, poly-1-butene, poly-
Olefinic polymers such as 4-methylpentene-1, vinyl copolymers such as polyvinyl chloride, polyvinylidene chloride, polystyrene, polyacrylate and polyacrylonitrile, nylon 6, nylon 66, nylon 7, nylon 10, nylon 11, Nylon 12, Nylon 610,
Examples thereof include polyamides such as polymethaxylene adipamide, polyesters such as polyethylene terephthalate, polyethylene terephthalate / isophthalate and polybutylene terephthalate, polyvinyl alcohols, ethylene / vinyl alcohol copolymers, polycarbonates and polyurethanes.

[0021]

The following examples serve to explain the present invention more specifically. [1] Measurement and Evaluation of Physical Properties Measurement and evaluation of physical properties in Examples and Comparative Examples were carried out by the methods described below. (1) Measurement of physical properties (a) MFR: According to JIS K7210 (Propylene polymer: 230 ° C., 2.16 kg load, ethylene / α
-Olefin copolymer: 190 ° C, 2.16 kg load) (b) Density: According to JIS 7112 (c) Elution curve measurement: Temperature rising elution fractionation (TR) in the present invention
The elution curve is measured by EF) by once completely dissolving the polymer at a high temperature and then cooling it to form a thin polymer layer on the surface of the inert carrier that was present in the solution, and then continuously heating the temperature. Alternatively, it is possible to collect the eluted components by gradually raising the temperature, detect the concentration continuously, and see the polymer composition distribution at the peak of the graph (elution curve) drawn by the amount and the elution temperature. it can.

The elution curve was measured as follows. Cross sorter as a measuring device (Mitsubishi Yuka Co., Ltd.)
Manufactured by CFC T150A) according to the measurement method in the attached operation manual.

This cross fractionation device comprises a temperature rise elution fractionation (TREF) mechanism for fractionating samples by utilizing the difference in melting temperature, and a size exclusion chromatograph for further fractionating the fractions by molecular size.
y: SEC) is a device connected online.

First, a sample to be measured is dissolved at 140 ° C. using a solvent (o-dichlorobenzene) so that the concentration becomes 4 mg / ml, and this is injected into a sample loop in the measuring device. The following measurements are automatically performed according to the set conditions.

The sample solution held in the sample loop is separated by utilizing the difference in melting temperature. TREF column (inner diameter 4 m filled with glass beads as an inert carrier)
m, 150 mm long stainless steel column attached to the device)
0.4 ml is injected into. The sample is then cooled from 140 ° C. to 0 ° C. at a rate of 1 ° C./min and coated on the inert carrier. At this time, the polymer layers are formed on the surface of the inert carrier in the order of the highly crystalline component (those that are easily crystallized) to the low crystalline component (that is difficult to crystallize). TRE
After the F column was kept at 0 ° C for an additional 30 minutes, 2 ml of the dissolved component at 0 ° C was added to the T column at a flow rate of 1 ml / min.
REF column to SEC column (Showa Denko AD80M
/ S 3).

While the molecular size is fractionated by SEC, the temperature is raised to the next elution temperature (5 ° C.) in the TREF column and the temperature is maintained for about 30 minutes. The measurement of each elution section by SEC was performed at 39 minute intervals. The elution temperature is raised stepwise at the following temperatures.

0, 5, 10, 15, 20, 25, 30,
35, 40, 45, 49, 52, 55, 58, 61, 6
4, 67, 70, 73, 76, 79, 82, 85, 8
8, 91, 94, 97, 100, 102, 120, 14
The absorbance of the solution separated by the molecular size by the SEC column was measured by an infrared spectrophotometer attached to the device, which was proportional to the concentration of the polymer (wavelength: 3.42 μ, detected by stretching vibration of methylene), and each elution temperature was measured. A chromatogram of the partition is obtained.

Using the built-in data processing software, the baseline of the chromatogram of each elution temperature section obtained in the above measurement is drawn and the calculation processing is performed. The area of each chromatogram is integrated and an integrated elution curve is calculated. Further, this integrated elution curve is differentiated by temperature to calculate the differential elution curve. The plot of the calculation result is output to the printer. The output of the differential elution curve is plotted with the elution temperature of 100 ° C on the horizontal axis.
89.3 mm per axis, the amount of differentiation on the vertical axis (total integrated elution amount was standardized to 1.0, and the amount of change at 1 ° C was used as the amount of differentiation) 0.1
Per 76.5 mm. (D) Activation energy (Ea) "Capirograph 1B / PMD-C" manufactured by Toyo Seiki Seisakusho Ltd.
Using a capillary with a diameter of 1 mm and a length of 10 mm, the extrusion speed is 2.5, 5, 10, 20, 50, 10
The autospeed was set at 0,200 m / min, the viscosity at each temperature was measured, and the viscosity was calculated by the activation energy (Ea) calculation method described above. (E) Using pulse method NMR JEOL-GSX270 (manufactured by JEOL Ltd.),
The solid echo is measured with a 90 ° pulse width of 1.8 μs for a sample at 30 ° C. The obtained magnetization decay curve is logarithmically plotted, and the reference is made by K. Fujimoto, T. Nishi and R. Kad.
o, Polym.J., Vol.3, 448-462 (1972), separate the components and obtain the fraction of each component.

(2) Evaluation (a) HAZE: According to JIS K7105 (b) GLOSS: According to JIS K7105 (c) 300 g Heat sealing temperature: 80 ° C. to 5 ° C. intervals with a hot plate heat sealer manufactured by Toyo Seiki Seal pressure at:
Heat seal at ² kg / cm ² and seal time: 1 second, and measure the heat seal strength with a tensile tester. The temperature at which this heat seal strength is 300 g / 15 mm is 300
g Load heat seal temperature. (D) DDI: In accordance with JIS Z1707 (e) Elemendorff tear strength: In accordance with JIS K7128 (f) Tensile strength / elongation: In accordance with JIS K6781 (g) Tensile modulus: In accordance with ISO R1184 (h) Neck-in: Measure the film width before the winder,
Calculate from the following formula. Neck-in (mm) = (die width (30 cm) -film width before winding machine) / 2

[Example 1] <Resin used as component A> Propylene resin: propylene / ethylene random copolymer MFR = 8 g / 10 min, ethylene content = 4.4 wt%, pulse method NMR: (I) /(II)=2.6, (III) = 9
% Activation energy = 11 KJ / mol, propylene resin: propylene / ethylene random copolymer MFR = 1.8 g / 10 min, ethylene content = 3.2 wt%, pulse method NMR: (I) / (II) = 2.4 (III) = 8
% Activation energy = 4 KJ / mol, propylene resin: propylene homopolymer MFR = 9 g / 10 min, pulse method NMR: (I) / (II) = 2.5, (III) = 4
% Activation energy = 9 KJ / mol, Propylene resin: Propylene homopolymer MFR = 1 g / 10 min, Pulse method NMR: (I) / (II) = 2.3, (III) = 3
% Activation energy = 4 KJ / mol,

<Component B Production of ethylene / α-olefin copolymer> Complex ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride 2.
Methylalumoxane (manufactured by Toyo Stoufer Co., Ltd.) was added to 0 mmol in an amount of 1000 times the molar amount of the above complex, and diluted with toluene to 10 liters to prepare a catalyst solution, which was polymerized by the following method.

A mixture of ethylene and 1-hexene was fed to a continuous autoclave type reactor having an internal volume of 1.5 liters so that the composition of 1-hexene was 80% by weight, and the pressure in the reactor was adjusted. 1200kg / cm ² to keep, 150
The reaction was carried out at a temperature of ° C.

After the reaction, the MFR was 2.3 g / 10 minutes, the density was 0.891 g / cm ³ , the Q value was 2, the TREF elution curve had one peak, and the peak temperature was 43 ° C. Some elute at an elution temperature other than the peak, and
An ethylene / 1-hexene copolymer (1-hexene content 23% by weight) having an integrated elution amount at 0 ° C of 100% was obtained.

<Preparation and molding of composition> 85% by weight of the above-mentioned propylene polymer as component A and 15% by weight of ethylene / α-olefin copolymer as component B were charged in a single screw 40 mmφ extruder. The mixture was melt-kneaded at a temperature of 200 ° C. to obtain a pellet-shaped resin composition. Using this pellet, T-die molding was performed under the following conditions. The obtained film was evaluated. The evaluation results are shown in the table.

Model: Placo Co., Ltd. 35 mm φT die forming machine Die: Width 30 cm Chill roll temperature: 40 ° C., single side air cooling Molding temperature: 250 ° C. Film thickness: 30 μm

[Examples 2 to 7] Ingredient A and ingredient B shown in the table
And the composition ratios were used respectively, and the film thickness was set to 30 μm. Therefore, the same experiment as in Example 1 was carried out except that the take-up speed at the time of molding was adjusted. As shown in the table.

[Example 8] Molding and evaluation were carried out in the same manner as in Example 1 except that a propylene-based polymer was used as the component A and an ethylene / α-olefin copolymer produced by the following method was used as the component B. did. The evaluation results are shown in the table.

<Component B Production of ethylene / α-olefin copolymer> Complex ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride
Methylalumoxane (manufactured by Toyo Stoufer Co., Ltd.) was added to 0 mmol in an amount of 1000 times the molar amount of the above complex, and diluted with toluene to 10 liters to prepare a catalyst solution, which was polymerized by the following method. A mixture of ethylene and 1-hexene was fed to a stirring autoclave type continuous reactor having an internal volume of 1.5 liters so that the composition of 1-hexene was 78% by weight, and the pressure in the reactor was 1600 kg / cm. Keep ² and 1
The reaction was carried out at 65 ° C.

After completion of the reaction, MFR was 13 g / 10 min, density was 0.898 g / cm ³ , one peak of the elution curve by TREF, the peak temperature was 55 ° C., and the elution was performed at a temperature other than the elution temperature of the peak. To obtain an ethylene / 1-hexene copolymer having a 90 ° C. integrated elution amount of 100% and a Q value of 2 (1-hexene content 20% by weight).

Comparative Examples 1 to 4 Films of component A alone were molded and evaluated in the same manner as in Example 1. The evaluation results are shown in the table.

[0041]

[Table 1]

[0042]

[Table 2]

[0043]

The propylene film according to the present invention is
Excellent film strength such as transparency, low temperature heat sealability, impact strength and tear strength, excellent processability, and good workability of the film, therefore, various packaging fields, for example, fresh foods such as vegetables and fish meat. , Dried foods such as snacks and noodles,
Various food packaging fields such as aquatic foods such as soups and pickles, medical products in various forms such as tablets, powders and liquids, medical related product packaging used for medical peripheral materials, electrical components and cassette tapes It is possible to apply to a wide range of fields such as electric equipment peripheral products and various electric equipment packaging fields, miscellaneous goods packaging fields, etc., and is industrially useful as described above in the section of [Summary of the Invention]. .

Claims (4)

[Claims] 1. A propylene-based film, which is obtained from a resin composition containing the following components A and B. Component A: Propylene polymer 50 to 99% by weight Component B: Ethylene and carbon number 4 to 4 having the following properties (a) to (d) produced using a metallocene catalyst.
Copolymer with 40 α-olefins 1 to 50% by weight (a) Density 0.86 to 0.935 g / cm ³ (b) MFR 0.1 to 20 g / 10 min (c) Temperature rising elution fractionation There is at least one peak in the elution curve of (TREF), and all the peaks are 10
It is 0 ° C or lower. Further, the peak may be one that elutes at a temperature other than the peak temperature, which is substantially present in the elution curve. (D) The integrated elution amount by temperature rising elution fractionation (TREF) is 90% or more when the elution temperature is 90 ° C. 2. The propylene-based film according to claim 1, wherein the propylene-based polymer as the component A has an MFR of 0.1 to 50 g / 10 minutes. 3. The propylene-based film according to claim 1, wherein the propylene-based polymer as the component A is a propylene / ethylene random copolymer. 4. The propylene-based film according to claim 1, wherein the propylene-based polymer of the component A is polypropylene.