WO2003095533A1

WO2003095533A1 - Cast film, process for production thereof, and bags made of the film

Info

Publication number: WO2003095533A1
Application number: PCT/JP2003/005837
Authority: WO
Inventors: Tetsuya Fudaba; Nobuyuki Mitarai; Katsuharu Tagashira; Kazuyuki Watanabe
Original assignee: Showa Denko Plastic Products Co., Ltd.
Priority date: 2002-05-10
Filing date: 2003-05-09
Publication date: 2003-11-20
Also published as: KR20040107517A; JP2004027212A; TW200400224A; CN1653113A

Abstract

The cast film of the invention is made from a composition which comprises (A) a polypropylene component and (B) a copolymer elastomer component and has an MFR of 0.1 to 15.0g/10min and a propylene unit content of the component (B) of 50 to 85 % and the xylene solubles Xs of which satisfy the following requirements (I) to (V), and is excellent in the balance between impact resistance and rigidity at low temperature, transparency and heat-sealing strength; and the bags of the invention are made of the cast film, little suffer from orange peel, and are excellent in breakage resistance in falling and blocking resistance: (I) the fraction of propylene (Fp) is 50 to 80 %, (II) the limiting viscosity [η]Xs of the xylene solubles Xs is 1.4 to 5 dL/g, (III) the ratio of [η]Xs/[η]Xi (limiting viscosity of xylene insolubles Xi) is 0.7 to 1.5, (IV) the propylene content (Pp) of high-propylene-content component is 60 to 95 % and the propylene content (P’p) of low-propylene-content component is 20 to 60 %, and (V) Pp, P’p, Pf1 (the proportion of Fp which the high-propylene-content component accounts for), and (1-Pf1) (the proportion of Fp which the low-propylene-content component accounts for) satisfy a specific relationship.

Description

Description Cast film, method for producing the same, and container made of cast film

The present invention relates to a cast film made of a polypropylene resin composition. More specifically, the present invention relates to a cast film comprising a polypropylene resin composition containing a xylene-soluble component having a specific composition distribution. More specifically, the present invention relates to a cast film which is excellent in transparency, and has excellent impact resistance, heat resistance and rigidity at low temperatures. Further, the present invention relates to a container having excellent fuse skin, dropping strength, and blocking resistance.

This application is based on Japanese Patent Application No. 2002-135752 and Japanese Patent Application No. 2003-125360, the contents of which are incorporated herein by reference. Background art

Molded articles made of polypropylene are economical and are used in a wide variety of fields.

However, in general, a molded article using a propylene homopolymer has high rigidity, but has a drawback that it is inferior in impact resistance, particularly at low temperatures.

Therefore, many proposals have been made to improve the impact resistance. For example, a propylene block copolymer obtained by first producing a propylene homopolymer and then producing an ethylene-propylene copolymer elastomer is exemplified. Molded articles using this propylene block copolymer are widely used in various industrial fields such as automobiles and home appliances because of their excellent impact resistance.

However, this propylene block copolymer is excellent in low-temperature impact resistance and rigidity, but has poor transparency, and is not applicable to applications requiring transparency, and has a drawback that the application is restricted.

Therefore, various studies have been made to solve the disadvantage. For example, JP-A-6-93061, JP-A-6-313048, JP-A-7-286 Japanese Patent Publication No. 0200 and Japanese Patent Application Laid-Open No. Hei 8-27238 disclose a propylene block copolymer in which the respective viscosities of crystalline polypropylene and propylene copolymer elastomer, their viscosity ratio and their content are controlled. Is disclosed.

However, even in these, the balance of impact resistance and rigidity and transparency are not sufficient; furthermore, when they are used in the field of film, there is a problem that the heat sealing strength is not sufficient. Further, the container made of such a film has problems that the skin is inferior, the dropping strength is low, and the blocking resistance is poor. The present invention has been made in order to solve the above-mentioned problems, and an object of the present invention is to provide a cast film which is excellent in balance between impact resistance and rigidity at low temperature, excellent in transparency, and excellent in heat seal strength. is there.

Further, another object of the present invention is to provide a method for producing a cast film, and a container using the cast film, which is capable of suppressing fuse skin and having excellent bag dropping strength and blocking resistance. Disclosure of the invention

The present inventors have focused on the composition distribution of the xylene-soluble component of the polypropylene resin composition in order to solve the above-described problems of the prior art, and as a result, have found that propylene blocks having a specific composition distribution have a xylene-soluble component. The inventors have found that the polymer is excellent not only in balance of impact resistance and rigidity at low temperature and transparency, but also in heat sealing strength when formed into a film, and have completed the present invention.

That cast film of the present invention, (A) and the polypropylene component 5 0-8 0 weight ^_0/0, (B) propylene with ethylene and / or copolymer elastomer of flight one Orefu in carbon number 4 to 1 2 A cast film comprising a composition containing 50 to 20% by mass of one component, wherein the composition comprises:

Menoleto flow rate from 0.1 to: I 5.0 g O min range,

50-85% by mass of units derived from propylene in the component (B) of the copolymer elastomer, and

The xylene-soluble component Xs satisfies the following requirements (I) to (V). (I) Propylene content Fp is 50 to 80% by mass.

(II) Intrinsic viscosity of xylene-soluble component Xs [77] Xs is 1.4 to 5 dL / g.

(III) Intrinsic viscosity [7]] The ratio of the intrinsic viscosity [η] Χί of Xs to the xylene-insoluble component Xi is 0.7 to 1.5.

(IV) The propylene content (P _p ) of the high propylene content component defined by the two-site model is 60% by mass or more and less than 95% by mass, and the propylene content (P ' _P ) of the low propylene content component is 20% by mass or more. Less than 60% by mass.

(V) The propylene content (P _p ) of the high propylene content component, the propylene content (P ' _p ) of the low propylene content component, and the ratio of the high propylene content component to the F p defined by the two-site model (P _fl ) and the proportion of the low propylene content component to the F p (1—P _fl ) satisfies the following formulas (1) and (2).

2.00 <P _fl / (1 P _fl ) <6.00… (2)

Such cast films are particularly excellent in the balance between impact resistance and rigidity at low temperatures and in transparency, and are also excellent in heat seal strength. Therefore, it can be used for a wider range of applications, including the automobile and home appliance fields.

Here, propylene content F p of the xylene-soluble portion X s is preferably more than 60 mass ^_0/0. By setting the propylene content Fp of the xylene-soluble component Xs to be more than 60% by mass, the transparency and heat seal strength of the cast film can be further increased.

Further, the refractive index of the xylene-insoluble component Xi is desirably 1.490 to 1.510, and the refractive index of the xylene-soluble component Xs is desirably in the range of 1.470 to 1.490. By setting the refractive index of the xylene-insoluble component Xi and the refractive index of the xylene-soluble component Xs within a specific range, the transparency, impact resistance, rigidity, and heat resistance of the cast film can be further improved. Can be balanced.

The method for producing a cast film according to the present invention is characterized in that the composition is filtered in a molten state using a metal filter and then molded.

Here, it is desirable to use a metal fiber filter having a filtration accuracy of 5 to 150 im according to JISB 8356. In addition, the laminate of the present invention includes an aluminum foil, a metal-deposited film layer, a silicon oxide-deposited film layer, a vinylidene chloride resin layer, an ethylene monoacetate copolymer resin nitride resin layer, a polyamide resin layer, and a polyester resin layer. And at least one layer selected from a polycarbonate resin layer and an oxygen absorbent layer, and a layer made of the cast film of the present invention.

The container of the present invention is characterized by using the cast film of the present invention. Further, the container of the present invention is characterized by using the laminate of the present invention. Such a container suppresses the fuse skin, and is excellent in dropping strength and blocking resistance. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is an example of a ¹³ C-NMR spectrum of a propylene-ethylene copolymer elastomer.

FIG. 2 is a diagram showing names of carbons derived from a linkage distribution. BEST MODE FOR CARRYING OUT THE INVENTION

The polypropylene resin composition of the present invention is a composition containing (A) a polypropylene component and (B) a copolymer elastomer component.

The (A) polypropylene component in the present invention is selected from propylene homopolymer, or a copolymer of propylene with ethylene and Z or α-olefin having 4 to 12 carbon atoms, and a mixture thereof. Here, as the α-olefin having 4 to 12 carbon atoms, any one of 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 4-methyl-1-pentene and the like can be used. Can be used. These polymers may be used alone or in combination of two or more.

However, the (II) polypropylene component in the present invention refers to a component having 95% by mass or more of units derived from propylene, and the content of these copolymer components is 5.0% by mass or less. More preferably, the copolymer component is 0.1-3.5% by mass. If the content of E styrene and Ζ or number 4-1 2 carbon α- Orebuin is more than 5 mass ⁰ I It is not preferable because the rigidity and heat resistance of the molded product are significantly reduced.

These polymers are produced, for example, by a known polymerization method using a known Ziegler-Natta catalyst or a metallocene catalyst.

(A) The polypropylene component is preferably a propylene homopolymer when rigidity and heat resistance are particularly required, and propylene and ethylene when impact resistance and transparency are particularly required. It is preferably a copolymer of Z or α-olefin.

(Ii) The polypropylene component desirably has an intrinsic viscosity [7] of force S, 2.0 to 4.8 dL / g. More preferably, it is in the range of 2.5-4.5 dL / g, and even more preferably in the range of 2.8-4.0 dL / g. If the intrinsic viscosity [η] exceeds 4.8 dL / g, poor extrusion may occur during molding and transparency of the molded product may decrease. If the intrinsic viscosity [η] is less than 2.0 dLZg, extrusion rigidity during molding and lowering of transparency are less likely to occur, but the rigidity and impact resistance of the product may be reduced.

The (B) copolymer elastomer component of the present invention is a copolymer elastomer component of propylene and ethylene and / or α-olefin having 4 to 12 carbon atoms. Any ct-olefin having 4 to 12 carbon atoms that constitutes one component of the copolymer elastomer can be used. Specifically, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene , 1-decene, 4-methyl-1-pentene, etc. In the present invention, the component (B) of the copolymer elastomer is 50 to 85 mass units derived from propylene. / ₀ means things. Preferably it is 55 to 85% by mass, more preferably 55 to 80% by mass. If it exceeds 85% by mass, the impact resistance at low temperatures becomes insufficient, and if it is less than 50% by mass, the transparency or the heat seal strength may decrease.

The polypropylene resin composition of the present invention contains (A) 50 to 80% by mass of the polypropylene component and (B) 50 to 20% by mass of one component of the copolymer elastomer. In the composition of the present invention, if the content of the copolymer elastomer (B) is less than 20% by mass, the impact resistance is poor, and if it exceeds 50% by mass, the rigidity and heat resistance are increased. It is inferior in sex. (B) The content of one component of the copolymer elastomer is preferably in the range of 45 to 20% by mass, and more preferably in the range of 40 to 23% by mass. The melt flow rate (hereinafter sometimes referred to as MFR) of the polypropylene resin composition of the present invention is in the range of 0.1 to 15.0 gZlO, and the viewpoint of transparency, rigidity and impact resistance of the molded product is high. The range is preferably from 0.5 to 10.0 gZlO, more preferably from 0.7 to 7.0 gZlO. If the MFR is less than 0.1 g / 10 minutes, poor dispersion and discharge of each component may occur during kneading or molding by an extruder, resulting in impact resistance and rigidity of the molded product. May reduce the transparency. If the MFR exceeds 15.0 g / 10 minutes, impact resistance and transparency may be reduced. The MFR is a value measured at 230 ° C and a load of 2.16 kg in accordance with JIS K7210.

The polypropylene resin composition of the present invention has a mass of 20 to 50 mass / ⁰ . Containing xylene solubles Xs. The xylene-soluble content Xs is preferably in the range of 20 to 45% by mass, and more preferably in the range of 23 to 40% by mass.

The propylene content Fp of the xylene-soluble portion is 50 to 80% by mass, preferably 60 to 80% by mass. In particular, it is more than 60% by mass. Further more preferred details, 65-80 mass%, further, the range of 70 to 80 wt%, and even more favorable Mashiku is 70-78 mass ^_0/0. If the propylene content of the xylene-soluble component is less than 50% by mass, the transparency is reduced, and the heat sealing strength when formed into a film may be reduced. If the propylene content Fp exceeds 80% by mass, the impact resistance at low temperatures decreases.

The intrinsic viscosity of the xylene-soluble component in the polypropylene resin composition of the present invention [ii] Xs is in the range of l to 5.0 d LZg, preferably in the range of 2.0 to 4.5 d LZg, more preferably 2.5 to 4.0 d LZg. It is in the range of L / g. When the intrinsic viscosity [77] Xs exceeds 5.0 dL / g, the impact resistance is improved but the transparency is reduced. When the intrinsic viscosity [77] Xs is less than 1.4 dLZg, the impact resistance is undesirably reduced.

In the polypropylene resin composition of the present invention, the ratio of the intrinsic viscosity [η] Xs of the xylene-soluble component to the intrinsic viscosity [η] Xi of the xylene-insoluble component of the polypropylene resin composition ([7?] Xs / [77] Xi) is in the range of 0.7 to 1.5. It is preferably in the range of 0.7 to: I.3, and more preferably in the range of 0.8 to 1.2. If the ratio is less than 0.7, the transparency is improved, but the impact resistance at low temperatures is reduced, and if it exceeds 1.5, the transparency is reduced.

It is desirable that the refractive index of the xylene-soluble component is 1.470 to 1.490. It is preferably from 1.470 to 1.485, more preferably from 1.473 to 1.485. If the refractive index of the xylene-soluble component is greater than 1.490, the transparency may be improved, but the impact resistance may be reduced. If it is less than 1.470, the impact resistance is improved, but the transparency is apt to be reduced.

Further, the refractive index of the xylene-insoluble component is desirably 1.490 to 1.510. It is preferably in the range of 1.493 to: 1.505, more preferably 1.495 to: 1.503. If the refractive index of the xylene-insoluble component is less than 1.490, transparency and impact resistance are improved, but rigidity and heat resistance may be reduced. On the other hand, if it is larger than 1.510, the stiffness and heat resistance are improved, but the impact resistance is reduced. In the xylene-soluble component Xs, the high propylene content component defined by the two-site model The propylene content P _p , the propylene content P ' _{p of} the low propylene content component, the proportion P _{fI of} the high propylene content component in the F p, and the proportion (1 P _fl ) of the low propylene content component in the F p are represented by the following formulas. Meet (1) and (2).

2.00 <P _fl / (1-P _fl ) <6.00… (2)

If P _p / P, _p is less than _1.90 , or if P _fl Z (1-P _fl ) is less than 2.00, the interface strength between xylene-soluble and xylene-insoluble components will decrease. However, this results in a decrease in heat seal strength. When P _fl Z (1 -P _fl ) is 6.00 or more, the interface strength is improved, but the rigidity ゃ impact resistance is reduced. These formulas are indices indicating the composition distribution of the xylene-soluble component. The formula (1) is a measure of the composition difference between components generated from the two active points, and the formula (2) is a measure of the two activities. It is a measure for the amount of components generated from points.

The propylene content (P.) of the high propylene content component is 60 mass% or more and 95 %. Preferably 65 to 90 wt%, more preferably from 70-9 0 mass ^_0/0. Propylene content of low propylene content component (P _'p) is less than 60 mass% 20 mass ^_0/0 above. Preferably 25 to 55 wt%, more preferably 30 to 50 weight ⁰ /. It is.

The definition of the two-site model is described in HNCHENG, Jounal of Applied Polymer Sience, Vol. 35 pl639_1650 (1988). That is, assuming two active sites (P) that polymerize propylene preferentially and an active site (Ρ ′) that polymerizes ethylene preferentially, the reaction probability at these two active sites, that is, propylene content Ρ _ρ Using the stochastic equations in Table 1 as parameters, Pfl and the ratio P _fl occupying the entire active site of the active site (P) where propylene polymerizes preferentially, and the actual ¹³ C-NMR spectrum It is obtained by optimizing the above three parameters so that the relative strength of the vector and this probability equation match. Thus, the obtained P _p , P'p and P _fl and the propylene content Fp satisfy the relationship of the following equation (3).

F p = P _p XP _fl + P, _p X (1— P _fl )… (3)

P _p and P ′ _p preferably satisfy the following expression (4), more preferably the following expression (5).

1.95≤P _P / P ' _P ≤2.40… (4)

1.95≤P _p / P ' _p ≤2.35… (5)

P _fl / (1−P _fl ) preferably satisfies the following expression (6), more preferably the following expression (7).

2.50≤P _fl / (1-P _fl ) <5.50… (6)

3.00 <P _fl / (1— P _fl ) <5.00… (7)

Note that P _p , P ' _p , F p and P _fl can be obtained by statistical analysis of ¹³ C-NMR spectrum. table 1

Signal Probability equation for the two-site model.

(1) Sa P _P ² xPfi + P'p ² x (1—Pfi)

(2) Sa γ (-2Pp ³ + 2P _p ² ) x P _f i + (-2P'p ³ + 2P'p ² ) x (1-P _f1 )

(3) Sa 6 (2Pp ³ -4P _p ² + 2Pp) x P _f1 + (2P ' _p ³ -4P'p ² + 2P'p) (1 -P _f1 )

(4) Τδ δ (Pp ³ -2Pp ² + P _p ) x P _f1 + (P'p ³ -2P'p ² + P ' _p ) x (1 -Pfi)

(5) Sr r + τβ δ (Pp ⁴ -4Pp ³ + 3P _p ² ) x P _f i + (P'p ⁴ -4Pp ³ + 3P ' _p ² ) (1P)

D

(6) Srd (-2Pp ⁴ + 6Pp ³ -6Pp ² + 2P _p ) x P _f1 + (-2P'p ⁴ + 6P'p ³ -6P ^, p ² + 2P'p) x (1 -Pfi)

(7) S (5 δ (Pp ⁴ -5Pp ³ + 9Pp ² -7P _p +2) xP _f1 -l- (P'p -5P'p ³ + 9P ^, p ² -7P ^, p + 2) x ( 1 -P)

(8) Τβ β Pp ³ xP _f1 + P ' _p ³ x (1-Pfi)

_{(9) S δ (2P p} 3 -4Pp 2 + 2Pp) x P f1 - (2P, p 3 -4P'p 2 + 2P'p) x (1 one Pfi)

(10) Sj8 β (-Pp ³ + 2P _P ² ) x Pfi + (-P ' _p ³ + P'p ² ) ^x (1 -Pn)

Hereinafter, this method will be described by taking the case where the component (B) is a propylene-ethylene copolymer elastomer as an example.

Figure 1 shows a ¹³ C-NMR spectrum of a typical propylene-ethylene copolymer elastomer, which has 10 different peaks due to differences in the chain distribution (the order of ethylene and propylene). . The name of this chain is described in Macromolecules, Vol. 10, p536-544 (1977), and is named as shown in FIG. Such a chain can be expressed as a product of the reaction probabilities, assuming a copolymerization reaction mechanism. Therefore, when the overall peak intensity is set to 1, the relative intensities of the peaks (1) to (10) are calculated using the Bernoulli statistics using the reaction probability and the abundance ratio of each site as parameters. It can be expressed as an equation. (L) In the case of S Act, if the propylene unit is symbol P and the ethylene unit is symbol E, there are three possible chains: [PPPP], [P PEE], and [EPPE]. Are represented by the reaction probabilities, and are added together. Formulas are set for the remaining peaks (2) to (10) in the same manner, and parameters are set so that these ten formulas and the actually measured peak intensities are closest, ie, the above-mentioned P _p , P ′ _p And by optimizing P _fl . In optimization, perform regression calculation until the residual of measured and theoretical values obtained from the equations are shown in Table 1 of the peak intensity becomes 1 X 10- ⁵ or less by the method of least squares. An algorithm for performing such regression calculation and the like are described in, for example, HNCHENG, Jounal of Applied Polymer Sience, Vol. 35 pl 639-1650 (1988).

Next, a method for producing the polypropylene resin composition of the present invention will be described. The method for producing the polypropylene resin composition in the present invention is not particularly limited, and a known method can be employed. For example, after mixing the components (A) and (B) using a ribbon blender, tumbler, Henschel mixer or the like, the components are mixed at a temperature of 170 to 280 ° C, preferably 190 to 260 ° C. It can be obtained by melt-kneading using an Eder, Mixing-Gall, Bumpari mixer, single-screw or twin-screw extruder.

Further, the polypropylene resin composition of the present invention may be one in which the component (A) and the component (B) are produced in one polymerization system by a multistage polymerization method. Furthermore, component (A) and component (B) were produced in one polymerization system by a multistage polymerization method. That is, the composition may further contain the component (A) and Z or (B). The polypropylene component (A) and the copolymer elastomer component (B) can be produced by a known method. Specifically, it can be produced by polymerizing propylene or copolymerizing propylene and other olefins using a Ziegler catalyst or a meta-mouth catalyst. Examples of the Ziegler catalyst include a titanium trichloride-based catalyst and a magnesium-supported titanium catalyst. As a magnesium-supported catalyst system,

A catalyst system comprising (a) a solid catalyst component containing titanium, magnesium, and halogen as essential components, (b) an organoaluminum compound, and (c) an electron-donating compound. These are JP-A-57-63310, JP-A-57-63311, JP-A-58-83006, JP-A-58-138708, JP-A-62-20507, and JP-A-61-296006. And JP-A-2-229806, JP-A-2-33103, and JP-A-2-70708. These may be used as a prepolymerized catalyst in which a small amount of olefin is polymerized prior to the production of each component.

In the production of the component (B) in the present invention, there is no particular limitation as long as the production conditions satisfy the requirements for the composition in the present invention, and the following method is specifically exemplified.

1. A method for producing the component (B) using a catalyst that gives a polymer having a relatively wide composition distribution, stereoregular distribution, or molecular weight distribution among the above catalysts.

2. A method for preparing the above catalyst under conditions where the composition distribution, stereoregularity distribution, or molecular weight distribution is relatively wide, that is, by changing the amount of the electron donating compound or the organoaluminum compound used or by using a plurality of electron donating compounds. A method for producing the component (B) using a catalyst prepared using the above method.

3. A method of manufacturing under polymerization conditions where the composition distribution, stereoregularity distribution, or molecular weight distribution is relatively wide, ie, (a) by changing the polymerization conditions such as the temperature of each stage and the monomer composition ratio by multistage polymerization. (B) The method for producing the component, (Mouth) Since the composition distribution varies depending on the composition of the generally obtained polymer, the composition of the copolymer elastomer is adjusted so that the desired composition distribution is obtained. (B) A method for producing the component.

4. While having a uniform composition distribution obtained with a metallocene catalyst, etc., A method of using a plurality of components having different amounts.

By using the component (B) produced by these methods, a polypropylene resin composition in which the composition distribution of the xylene-soluble component is adjusted can be easily obtained. In producing each of the components, hexane, heptane Polymerization methods such as slurry polymerization, bulk polymerization, solution polymerization and gas phase polymerization performed in the presence of an inert hydrocarbon such as kerosene or a liquefied α-olefin solvent such as propylene are employed. C, preferably in the temperature range of 30 to 150 ° C., in the range of 0.2 to 5. OMPa pressure range. As the reactor in the polymerization step, those usually used in the technical field can be appropriately used.For example, a continuous system, a semi-batch system, a batch system using a stirred bed reactor, a fluidized bed reactor, and a circulation reactor can be used. Any of these methods may be used. In addition, at the time of polymerization, for example, the molecular weight of the obtained polymer can be adjusted by adding hydrogen or the like. The polypropylene resin composition of the present invention may contain other resins, additives and the like within a range that does not impair the purpose of the present invention. Examples of these other additives include antioxidants, weathering stabilizers, antistatic agents, lubricants, antiblocking agents, antifogging agents, dyes, pigments, oils, waxes, and the like.

The film of the present invention is a cast film obtained by molding the polypropylene resin composition of the present invention by a T-die method or the like. This cast film can be used alone or can be laminated with other materials.

As a method for producing the film of the present invention, a method in which the above polypropylene resin composition is filtered in a molten state using a metal fiber filter and formed by various film forming methods is preferable.

Examples of the metal fiber filter used in the present invention include a wire mesh filter, a sintered wire mesh filter, a hollow metal filter, a sintered metal fiber filter, and a combination of these filters as appropriate. As the metal fiber filter, those having a filtration accuracy of 5 to 150 / ini according to JISB 8356 are preferable, those having a filtration accuracy of 20 to L20 m are more preferable, and those having a filter accuracy of 40 to 1: 1 are particularly preferable. Those with a diameter of 0 m are preferred. If the filtration accuracy is less than 5 μm, the pressure during extrusion molding tends to increase, which may impair the moldability.In some cases, the shear heat of the molten resin will not be excessive. Gas may be generated. On the other hand, when it exceeds 150 // m, the effect of improving the fluff skin tends to be hardly exhibited, and gel is easily generated in the cast film. Examples of the shape of the metal fiber filter include a tube type filter, a pleated type cylindrical filter, a leaf disk filter, and a flat type cylindrical filter. Among them, a leaf disc filter is preferred in view of the effect of improving the fuse skin, pressure resistance and filtration area. The metal fiber filter is commercially available from Nippon Seisen Co., Ltd. as "Trade name: Nathlon filter" and from Fuji Filter Industries, Ltd. as "Trade name: Fujimetal fiber", and these can be suitably used. The above metal fiber filter is preferably installed between an extruder of a film forming machine such as a T die forming machine and a die, and is installed so that the molten resin passes through the die immediately after passing through the metal filter portion. Preferably, it is more preferably installed immediately before the die. The temperature of a part of the metal fiber filter installed in the extruder is preferably from 200 to 280 ° C, more preferably from 220 to 260 ° C. If the temperature is lower than 200 ° C, the effect of improving the skin of the fuse is poor and the extrusion pressure tends to increase. On the other hand, when the temperature exceeds 280 ° C, the resin is degraded and the effect of improving the skin of the fuse is reduced.

In particular, the use of a T-die molding machine among these film molding machines is excellent. The obtained cast film has excellent film thickness accuracy, has low anisotropy in physical properties such as shrinkage and strength, and has a low film impact strength. It is preferable from the point of being high.

The laminate of the present invention comprises, on the film of the present invention, an aluminum foil, a metal-deposited film, a silicon oxide-deposited film, a vinylidene chloride resin layer, an ethylene-vinyl acetate copolymer resin, a nitride resin layer, a polyamide resin layer, It is obtained by laminating at least one layer selected from a polyester resin layer, a polycarbonate resin layer and an oxygen absorbent layer. Among these layers, vinylidene chloride resin and ethylene monoacetate copolymer copolymer are effective as a gas barrier layer. Examples of the oxygen absorbent layer include a layer containing iron oxide.

The laminate of the present invention can be obtained by a co-extrusion method, a dry lamination method and an extrusion lamination method using a known dry laminating machine or the like with or without an adhesive on the film of the present invention. Can be obtained by stacking layers Wear. .

The container of the present invention uses the film or the laminate of the present invention. Examples of the container include a bag-like container in which two films or a laminate are sealed on four sides, and a free-standing bag-like container such as a standing bouch. The packaging container is, for example, two films or a laminate of four sides at a temperature of 180 to 250. It can be manufactured by heat sealing with C for 0.2 to 10 seconds.

INDUSTRIAL APPLICABILITY The container of the present invention can be suitably used for a packaging container of food or the like which is sterilized by heating. In particular, the resin composition of the present invention, a film and a packaging container comprising the same contain oil-based foods such as cutlet curry, gome rice, beef, pork, and chicken, which are apt to cause cracks in conventional packaging containers. It is a container with excellent appearance without the occurrence of blemishes even after retort sterilization.

The heat sterilization in the present invention is a method for killing microorganisms, which are the main cause of food deterioration, and is usually performed in a temperature range of 60 to 135 ° C, depending on the target bacteria. I have. Of these heat sterilization methods, which use heat mainly consisting of heated steam at a temperature of 100 ° C or higher and hot water, are called retort sterilization, and are treated at high temperature and for a short time so as not to impair the taste and flavor of the contents. How to Example

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

In addition, the measuring method of various physical properties is as follows.

Melt flow rate (MFR) measurement:

It was measured under the conditions of a temperature of 230 ° C and a load of 2160 g according to JIS-K7210.

¹³ C-NMR measurement (calculation of P _p , P ' _p and P _fl ):

Measured by JNM-GSX400 manufactured by JEOL (measurement mode: proton decoupling method, pulse width: 8.05, pulse repetition time: 3.0 s, number of integrations: 10,000 times, measurement temperature: 120 ° C, internal standard: to Xamethyldisiloxane, solvent: 1,2,4-trichlorobenzene benzene / benzene-d6 (volume ratio 31), test The sample concentration was 0.1 g / ml), and P _p , P ′ _p and P _fi were determined as described above by the statistical analysis.

Measurement of xylene solubles Xs:

Add 2.5 g of sample to 250 ml of ortho-xylene, stir while heating, raise the temperature to the boiling temperature, and dissolve completely over 30 minutes. After confirming complete dissolution, the mixture is allowed to cool to 100 ° C. or less while stirring, and further kept in a thermostat kept at 25 ° C. for 2 hours. Then, the precipitated component (xylene-insoluble content Xi) was separated by filter paper. Then, while heating the filtrate, xylene was distilled off under a nitrogen stream and dried to obtain a xylene-soluble component Xs.

Determination of propylene content:

It was calculated based on the results of the ¹³ C-NMR.

Measurement of intrinsic viscosity:

Measured in decalin at 135 ° C.

Refractive index measurement:

Press molding a film with a thickness of 50-80 μπι for xylene solubles X s and xylene insolubles X i (preheating at 230 ° C for 5 minutes, degassing for 30 seconds, pressurizing at 6MPa for 1 minute, 30 ° C for 3 minutes in a press). After conditioning the obtained film at normal temperature for 24 hours, measurement was carried out with an Abbe refractometer manufactured by Patago Co., Ltd. using ethyl salicylate as an intermediate solution.

Production of component (A) and component (B)

The component (A) was produced in the first stage of the multistage polymerization in the following manner, and the component (B) of the copolymer elastomer was produced in the second stage following the bow I. Tables 2 and 3 show the physical properties of these components.

[Manufacture of PP 1]

Preparation of solid catalyst

56.8 g of anhydrous magnesium chloride, 100 g of absolute ethanol, 500 ml of Serine oil "CP 15N" manufactured by Idemitsu Kosan Co., Ltd. and 500 ml of silicone oil "KF96" manufactured by Shin-Etsu Silicone Co., Ltd. It was completely dissolved. This mixture was mixed with a TK homomixer manufactured by Tokushu Kika Kogyo Co., Ltd. The mixture was stirred at 5,000 rpm for 20 minutes at Z rotation for 2 minutes. While maintaining agitation, the solution was transferred into 2 liters of anhydrous heptane not to exceed 0 ° C. The obtained white solid was thoroughly washed with anhydrous heptane, dried in a vacuum at room temperature, and partially deethanolated under a nitrogen stream. The resulting _{_{Mg C 1 2 · 1.2C 2 H}} 5 OH spherical solid 30 g was suspended in anhydrous heptane 20 Om 1. While stirring at 0 ° C., titanium tetrachloride 5 O Oml was added dropwise over 1 hour. Next, when the temperature reached 40 ° C after the start of heating, 4.96 g of disobutynole phthalate was added, and the temperature was raised to 100 ° C in about 1 hour. After reacting at 100 ° C. for 2 hours, a solid portion was collected by filtration under heating. Thereafter, 5 O Oml of titanium tetrachloride was added to the reaction mixture, and the mixture was stirred, and reacted at 120 ° C for 1 hour. After completion of the reaction, a solid portion was collected again by hot filtration, and washed 7 times with 1.0 liter of hexane at 60 ° C. and 3 times with 1.0 liter of hexane at room temperature to obtain a solid catalyst. The titanium content in the obtained solid catalyst component was measured and found to be 2.36% by mass.

1) Prepolymerization

In a 3 liter autoclave under a nitrogen atmosphere, n-heptane 5 O Oml, triethylaluminum 6.0 g, cyclohexylmethyldimethoxysilane 0.99 g, and the polymerization catalyst 10 g obtained above were charged, and 0 to 5 ° C. The mixture was stirred for 5 minutes in the temperature range. Then, pyrene was supplied into the autoclave so that 10 g of propylene was polymerized per 1 g of the polymerization catalyst, and prepolymerization was performed for 1 hour in a temperature range of 0 to 5 ° C. The obtained prepolymerized catalyst was washed three times with 500 ml of n-heptane and used for the following polymerization.

2) Main polymerization

Stage 1: (A) Production of polypropylene component

In a nitrogen atmosphere, 2.0 g of the prepolymerized solid catalyst prepared in the manner described above, 11.4 g of triethylaluminum, 1.88 g of cyclohexylmethyldimethoxysilane, and 1.88 g of cyclohexylmethyldimethoxysilane were placed in an autoclave having an internal volume of 60 liters with a stirrer. Was charged to 500 Omo at 1 ppm, and the temperature was raised to 70 ° C. to perform polymerization for 1 hour. One hour later, unreacted propylene was removed to terminate the polymerization. Second stage: (B) Production of propylene-ethylene copolymer elastomer As described above, after the completion of the first stage polymerization, liquid propylene is removed, and ethylene / propylene = 26 74 at a temperature of 75 ° C. Hydrogen was supplied at a mixing ratio of 2.2 Nm ³ Z (mass ratio) for a total amount of ethylene, propylene and hydrogen of 40,00 Omo 1 ppm for polymerization for 60 minutes. After 40 minutes, the unreacted gas was removed, and the polymerization was terminated. As a result, 6.6 kg of a polymer was obtained.

[Manufacture of PP-2]

Stage 2: (B) The polymerization was carried out in the same manner as in the production of PP-1, except that the amount of hydrogen used in the production of the propylene-ethylene copolymer elastomer was 50,00 Omo 1 ppm. went. As a result, 6.3 kg of a polymer was obtained.

[Manufacture of PP-3]

Second stage: (B) The polymerization was carried out in the same manner as in the production of PP-1, except that the amount of hydrogen used in the production of the propylene-ethylene copolymer elastomer was adjusted to 20,00 Omo 1 ppm. went. As a result, 5.8 kg of a polymer was obtained.

[Manufacture of P P-4]

Stage 1: (A) Production of polypropylene component

Under a nitrogen atmosphere, in a 60-liter autoclave equipped with a stirrer, 2.0 g of the prepolymerized solid catalyst prepared by the method of PP-1, 11.4 g of triethylaluminum, 1.88 g of cyclohexylmethyldimethoxysilane, and 18.88 g of propylene were then added. Hydrogen was charged so as to be 650 Omo 1 ppm with respect to 120 L of ethylene and propylene, and the temperature was raised to 70 ° C to perform polymerization for 1 hour. One hour later, unreacted propylene was removed.

Stage 2: (B) Production of propylene-ethylene copolymer elastomer Hydrogen was supplied to 40,00 Omo at 1 ppm, and polymerization was carried out in the same manner as PP-1 except that polymerization was carried out for 40 minutes. went. As a result, 5.7 kg of a polymer was obtained.

[Manufacture of PP-5]

In the second-stage polymerization, the mass ratio of the mixed gas of ethylene and propylene was set at 26/74, and hydrogen was supplied for 30 minutes while supplying hydrogen at 30,00 Omo at 1 ppm. Polymerization was carried out in the same manner as in the production of PP-1, except that the polymerization was carried out. As a result, 6.1 kg of a polymer was obtained.

[Manufacture of PP-6]

Polymerization was carried out in the same manner as in the production of PP-1, except that the mass ratio of the ethylene / propylene mixed gas was changed to 50/50.

[Manufacture of PP-7]

Polymerization was carried out in the same manner as in the production of PP-1, except that the mass ratio of the ethylene / propylene mixed gas was 38/62.

[PP-8 and PP-9]

The polypropylene resin compositions of Comparative Examples 3 and 4 shown in Table 3 were produced using a solid catalyst in which titanium tetrachloride was supported on magnesium chloride, a catalyst comprising an organic aluminum conjugate and an electron-donating compound.

[Production of P P-10]

Preparation of _{_{T i C 1 4 [C 6}} H 4 (COO i C 4 H 9) 2]

To a solution of hexane 1.0 liters to include titanium tetrachloride 1 9 g, phthalate Jiiso _{_{heptyl: C 6 H 4 (COO i}} C 4 H 9) a ₂ 27.8 g, about 30 minutes while maintaining the temperature 0 ° C It was dropped. After completion of the dropwise addition, the temperature was raised to 40 ° C. and the reaction was carried out for 30 minutes. After the completion of the reaction, a solid portion was collected and washed five times with 500 ml of hexane to obtain a desired product.

Preparation of solid catalyst

PP- 1 of the solid catalyst 20 g obtained in the production method was suspended in toluene 300 meters 1, at a temperature 25 ° C, T i C 1 4 in which the obtained _{_{[C 6 H 4 (COO i}} C 4 H 9 ) ₂ ], and the mixture was stirred for 1 hour, and a solid portion was collected by hot filtration. The reaction is then 90. C was washed three times with 500 ml of toluene and three times with 500 ml of hexane at room temperature. The titanium content in the obtained solid catalyst component was 1.78% by mass.

Prepolymerization

In a 3 liter autoclave under a nitrogen atmosphere, 500 ml of n-heptane, 6.0 g of triethylaluminum, 3.98 g of dicyclopentyldimethoxysilane and 3.98 g of the solid catalyst obtained above g was added and the mixture was stirred for 5 minutes in a temperature range of 0 to 5 ° C. Next, 10 g of propylene was polymerized per 1 g of polymerization catalyst. Feed propylene into the autoclave to 0-5. Prepolymerization was performed for 1 hour in the temperature range of C. The obtained prepolymerized solid catalyst was washed three times with 50 mL of n-heptane and used for the following polymerization. Stage 1: Production of homopolypropylene

Under a nitrogen atmosphere, 2.0 g of the prepolymerized solid catalyst prepared in the above manner, 11.4 g of triethylaluminum, 6.84 g of disc-opened pentyl dimethoxysilane were placed in a 60-liter autoclave with a stirrer, and then 18 kg of propylene. Then, hydrogen was charged so as to be 1.4 mol% with respect to propylene, and the temperature was raised to 70 ° C. to carry out polymerization for 1 hour. One hour later, unreacted propylene was removed.

Second stage: Production of propylene-ethylene copolymer elastomer

After the first-stage polymerization, copolymerization was performed at a temperature of 75 ° C for 40 minutes at a feed rate of a mixed gas of ethylene / propylene = 40/60 (mass ratio) 2.2 Nm ³ / hour and hydrogen 2 ONL / hour. . After 40 minutes, unreacted gas was removed and the polymerization was terminated.

Manufacture of polypropylene resins, compositions and films

[Example 1]

To 100 parts by mass of the PP-1 obtained above, 0.30 parts by mass of a phenolic antioxidant and 0.1 parts by mass of calcium stearate were added, and mixed with a Henschel mixer at room temperature for 3 minutes. The mixture was kneaded with an extruder having a screw diameter of 4 Omm (Nakaya VSK type 40 mm extruder) at a cylinder set temperature of 210 ° C to obtain a pellet of the composition.

An extruder equipped with a T-die using this pellet (extruder manufactured by Toshiba Machine Co., double flute screw, screw diameter 65 mm, L / Ό 26.2, die temperature 260 ° C, cylinder temperature 260 ° C) The film was formed under the conditions of a screw rotation speed of 80 rpm, a take-up speed of 12 msec, and a chill port temperature of 50 ° C, to form a finolem having a thickness of about 70 m.

[Examples 2 to 5, Comparative Examples 1 to 5]

A resin composition and a film were produced in the same manner as in Example 1, except that PP-1 was replaced with those described in Tables 2 and 3, respectively. For each of the films obtained in Examples 1 to 5 and Comparative Examples 1 to 5, the heat seal strength, film impact (low-temperature impact strength), tensile modulus (Young's modulus), and transparency were measured. Tables 2 and 3 show the measurement results. The measuring method is as follows. Heat sealing strength:

A PET film having a thickness of 60 μm on which an adhesive resin is laminated and a film made of the above-mentioned polypropylene resin yarn are laminated in two sets so that the polypropylene resin composition film is on the inner side. Heat-sealed using a heat sealer (Heat seal bar width: 5 mm, seal temperature: 160 ° C and 170 ° C, 0.2 MPa-C l ¾Pj ±, Direction perpendicular to the resin flow direction (MD).

After conditioning for 48 hours at room temperature, the heat-sealed film was sampled to a width of 15 mm, and the heat-sealed part was moved at a speed of 50 mm between chucks and a pulling speed of 300 mm / min. Tensile load was applied in the direction of opening at 0 ° until the heat-sealed part was broken, and the average strength during this period was determined. The average value of the seven points of the average strength was defined as the heat seal strength.

Measurement of film impact (low-temperature impact strength):

The film was sampled in a size of 10 cm × 1 m and left in a constant temperature room at 15 ° C. for 2 hours. After that, in this constant temperature chamber, a striker with a radius of 1 to 2 inches was attached to a film impact tester manufactured by Toyo Seiki Seisaku-sho, Ltd., and the test was performed 10 times for each sample to measure the impact energy. The value of these impact energies was divided by the film thickness, and the average value of the 10 points was taken as the film impact and used as a measure of impact resistance.

Tensile modulus (Young's modulus):

The flow direction (MD) of the resin at the time of molding was measured according to the method of JIS K 712, under the conditions of a sample width of 2 O mm, a gap between chucks of 25 O mm, and a pulling speed of 5 mm.

transparency:

The total haze was measured according to the method of JISK7105. Table 2

Beauty jsuy i real JSU ri 2 real 5S example 3 example 4 example 5 example ¾1 example D

1st stage of PP1 1st stage of PP2 1st stage of PP3 1st stage of PP4 1st stage of PP5 1st stage of PP11

(A) Ethylene content mass% 0 0 0 2.3 0 0

Composition amount% 70 70 70 78 75 70

Second stage of PP1 Second stage of ΡΡ2 Second stage of ΡΡ3 Second stage of ΡΡ4 Second stage of ΡΡ5 Second stage of PP11

(B) Propylene content mass% 70.0 70.0 70.0 65.0 65.0 70.0

Composition amount% by mass 30 30 30 22 25 30

Melt flow rate g / 10min 1.2 1.2 0.8 1.3 1.0 0.8

Xs content 29.6 27.2 26.2 24.6 23 26

[3.6 3.6 2.9 3.5 3.6

Xi

Refractive index I.OU l.oU Ι.οϋ ι.οϋϋ Ί.Οϋ Ί .DUO t

["] Xs dL / g. (. E

.D 4

Pp mass% o .o Ol .Ί C5U.0

Pp mass% D. ί 0.4 6f

Xs (P p P'p) ゥ on

Pf1 / (1-Pf1) 4.72 3.60 3.97 3.09 3.22 4.01

Refractive index 1.479 1.479 1.479 1.479 1.479 1.479

73.9 72.9 73.4 71.5 71.5 73.0

[7?] XsZ [r?] Xi 0.92 0.79 1.19 1.10 1.03 1.17

Heat seal strength 160 ° C N / 15mm 58.8 63.7 58.8 53.0 48.0 58.0

Heat seal strength 170 ° C N / 15mm 58.8 61.8 57.9 55.9 55.0 57.0

Low temperature impact strength J / mm 12.2 10.7 11.9 12.0 9.8 12.3

Young's modulus MD MPa 640 630 750 580 800 740

Total haze% 20 31 38 22 32 37

Table 3

[Manufacture of PP-11]

1) Prepolymerization

In a 3 liter autoclave under a nitrogen atmosphere, n-heptane 50 Om1, triethylaluminum 6.0 g, cycle-mouth hexylmethyldimethoxysilane 0.99 g and the polymerization catalyst obtained above (= described in [Production of PP_1]) 10 g of the solid catalyst), and stirred for 5 minutes in a temperature range of 0 to 5 ° C. Next, propylene was supplied into the autoclave so that 10 g of propylene was polymerized per 1 g of the polymerization catalyst, and prepolymerization was performed for 1 hour in a temperature range of 0 to 5 ° C. The obtained prepolymerized catalyst was washed three times with 500 ml of n-heptane and used for the following polymerization.

2) Main polymerization

In a first loop polymerization reactor set at 70 ° C, the prepolymerized solid catalyst prepared according to the above method was added for 10 gZ hours, triethyl aluminum for 57 gZ hours, and cyclohexylmethyldimethoxysilane for 9.4 gZ hours. The polymerization was carried out while supplying propylene at a rate of 90 kg hours and hydrogen at a rate of 21.6 gZ hours to produce (A) a polypropylene component. After liquid propylene was removed from the mixture discharged from the first polymerization reactor, the mixture was supplied to a second polymerization reactor set at 0.75 ° C. At the same time, gas-phase polymerization was performed for 50 hours while supplying a mixed gas of ethylene propylene = 2674 (mass ratio) to the second polymerization reactor at a rate of 2.2 Nm ³ / hour and hydrogen at a rate of 4 g / hour. (B) Propylene-ethylene copolymer elastomer was produced. Unreacted propylene gas and the like were removed from the composition discharged from the second polymerization reactor to obtain a target composition.

[Example 6]

Using a Henschel mixer, add a mixture of 0.10 parts by mass of a phenolic antioxidant and 0.05 parts by mass of calcium stearate at room temperature to 100 parts by mass of the PP-11 obtained above at a screw diameter of 65 mm. The pellets of the composition were obtained by continuous feeding at a set temperature of 230 ° C by a cylinder extruder and kneading.The film forming machine was equipped with an extruder with a diameter of 115ιηπιφ and a diameter of 65ιηπιψ. 3,400mm width, 0.8mm lip width, feed block type Using a T-die molding machine manufactured by Toshiba Machine Co., Ltd., a metal with 80 sheets of Nippon Seisen Co., Ltd. product name: Naslon Filter NF 12D (filtration accuracy of 40 im according to JISB 8356) set between the extruder and the die. A fiber filter was placed.

The above pellet is melted by an extruder, and the melted resin is fed through a metal fiber filter to a T die at a die temperature of 230 ° C, and a film with a thickness of 70 μm is formed at a cooling temperature of 50 ° C. Was molded.

The film obtained in Example 6 was measured for heat seal strength, film impact (low-temperature impact strength), tensile modulus (Young's modulus), and transparency. The measurement results are shown in Fuku 2. In addition, the following items were evaluated. The results are shown in Table 4. Measurement of blocking strength:

The film was cut into a size of 10 cm × 10 cm, the films were overlaid, a load of 10 kg was applied, and the film was allowed to stand in an atmosphere at a temperature of 50 ° C. for 24 hours. Next, using a tensile tester (Tensilon UCT-500 manufactured by ORI ENTEC), the strength of peeling the entire surface of the blocking film at a peeling speed of 50 OmmZ was measured. The average value was taken as the blocking strength (g / 100 cm ² ). The higher the blocking strength, the more severe the blocking. Letnolet processing:

A polyester film with a thickness of 12 tm, an aluminum foil with a thickness of 9 m, and the above film in this order, and a dry lamination method so that the thickness of the polyurethane adhesive layer between each film and the aluminum foil is 2 // m. They were laminated to produce a laminate. Two layers of this laminated body (15 cm x 18 cm) are stacked so that the above films are in contact with each other, and the three edges are heat-sealed with a width of 8 mm, a temperature of 230 ° C, a pressure of 0.3 MPa, and a sealing time of 2 seconds. A heat-sealed packaging bag was prepared, and the heat-sealing strength of the heat-sealed portion was measured (heat-sealing strength before retort). The packaging bag is filled with 50 grams of “trade name: green pepper meat thread” manufactured by Ajinomoto Co., Inc., which is a commercially available retort food, and the other one is heat-sealed in the same manner as the other three. A container consisting of a packaging bag was prepared. This container was retorted at a temperature of 121 ° C. for 30 minutes using RCS-40T manufactured by Nissan Seisakusho Co., Ltd. Heat sealing part of container after retort treatment Was measured for heat seal strength. In addition, the evaluation of the skin was visually performed.

In addition, a container in which only salad oil was similarly enclosed in a packaging bag, and a container in which a mixed solution of water and salad oil (volume ratio) of 9: 1 was similarly enclosed in a packaging bag were prepared. These containers were retorted under the same conditions, and the heat seal strength of the heat seal portion of the containers after the retort was measured.

Evaluation of the skin:

With respect to the fluffy skin, the state of occurrence of unevenness on the surface layer of the packaging bag after the retort treatment (blizzard) was visually determined by a five-step method based on the following criteria.

1: No occurrence of crack skin is observed.

2: Although some fuzzy skin with unclear unevenness is observed, it can be used.

3: Although the generation of fuzzy skin with unclear unevenness is considerably observed, it can be used.

4: The surface of the fuse has a distinctly uneven shape, and is seen on the entire surface of the packaging bag and cannot be used.

5: Severe irregularities on the skin of the fuse.

Dropping strength test:

180 g of water was sealed in a 15 cm × 18 cm packing bag prepared by the above method to prepare a bouch. Next, retort treatment was performed under the same method and conditions as described above. Thirty obtained bouches were repeatedly dropped in an atmosphere at a temperature of 0 ° C in a state where the height was set to 1.2 m and horizontal, and the number of times until half of 30 bouches, fifteen, were broken (F50) I asked.

[Example 7]

Example 6 was carried out in the same manner as in Example 6, except that as a metal fiber filter, a filter in which 80 sheets of a NASLON filter NF 14D (filtration accuracy: 80 μπι) manufactured by Nippon Seisen Co., Ltd. was used was used.

[Example 8]

Aperture instead of metal fiber filter

The procedure was performed in the same manner as in Example 6, except that a mesh screen mesh was used.

[Comparative Example 6]

Except that the resin of Comparative Example 1 was used, the same procedure as in Example 6 was performed. Table 4 shows the measurement results of Examples 7 to 8 and Comparative Example 6 above.

As is clear from Tables 2 and 3, in the film made of the polypropylene resin composition of this example, the heat seal strength, film impact (low temperature impact strength), tensile modulus (Young's modulus), and transparency were all Well enhanced.

However, in Comparative Example 1 where the unit derived from propylene in the component (B) of the copolymer elastomer is small, the transparency is low. In addition, the heat seal strength was low in V, which did not satisfy the lower limit of the expression (2), in Comparative Example 2, and in Comparative Example 3, which did not satisfy the expression (1). Further, in Comparative Example 4 in which the propylene content Fp of Xs is large and does not satisfy the upper limit of the expression (2), the heat seal strength and the impact resistance are low. (2) The lower limit of the formula is not satisfied. In Comparative Example 5, the heat seal strength was low.

As is evident from Table 4, the container according to the present example suppresses the occurrence of fuzzy skin, has an excellent appearance, has little change in heat seal strength before and after retort, has excellent bag dropping strength, and has excellent blocking resistance. . Industrial applicability

As described above, the cast film of the present invention is particularly excellent in the balance between impact resistance and rigidity at low temperatures and transparency, and is also excellent in heat seal strength. Therefore, it can be used for a wider range of applications, such as in the field of automobiles and home appliances.

In particular, it is assumed that the propylene content Fp of the xylene-soluble component Xs exceeds 60% by mass. By doing so, the transparency and the heat sealing strength can be further increased. In addition, by setting the refractive index of the xylene-insoluble component Xi and the refractive index of the xylene-soluble component Xs within a specific range, transparency, impact resistance, rigidity, and heat resistance are more highly balanced. be able to.

Further, the container of the present invention suppresses the skin of the fuse, and is excellent in bag dropping strength and blocking resistance.

Claims

The scope of the claims

1. (A) Polypropylene component 50-80 mass ⁰ /. And (B) a copolymer film comprising propylene and ethylene and / or 50 to 20% by mass of a copolymer elastomer component of α-olefin having 4 to 12 carbon atoms, the cast film comprising: The adult is

Melt flow rate is 0.:! ~ 15.0 gZlO min range,

A cast finolem wherein the xylene-soluble component Xs satisfies the following requirements (I) to (V).

(I) a propylene content F p is 50 to 80 mass ^_0/0.

(II) Intrinsic viscosity of xylene-soluble component Xs [7)] Xs is 1.4 to 5 dL / g.

(III) Intrinsic viscosity [7)] The intrinsic viscosity of Xs and the xylene-insoluble content Xi [7)] The ratio of Xi is 0.7 to 1.5.

(IV) The propylene content (P _p ) of the high propylene content component defined by the two-site model is 60 mass ⁰ /. Or more and less than 95 wt%, propylene emissions content of the low propylene content component (P _'p) is less than 20 wt% to 60 wt%.

2.00 <P _fl / (1-P _fl ) <6.00… (2)

2. The cast film according to claim 1, wherein the propylene content Fp of the xylene-soluble component Xs exceeds 60% by mass.

3. Xylene insoluble content Xi has a refractive index of 1.490 to 1.510, and xylene is acceptable 3. The cast finolem according to claim 1, wherein the refractive index of the dissolved component Xs is in the range of 1.470 to 1.490.

4. (A) and the polypropylene component 50 to 80 mass ^_0/0, (B) a copolymer elastomer monocomponent 50 to 20 wt% of propylene and E Ji Ren and / or a C 4 to 12 α- Orefuin Containing

Melt flow rate in the range of 0.1 to 15.0 g / 10 minutes,

A method for producing a cast film, comprising: filtering a composition having a xylene-soluble content X s satisfying the following requirements (I) to (V) in a molten state using a metal filter, followed by molding.

(I) Propylene content Fp is 50 to 80% by mass.

(III) The intrinsic viscosity [rj] Xs and the intrinsic viscosity [r]] Xi of the xylene-insoluble component Xi are 0.7 to 1.5.

(IV) 2 propylene containing amount of the high propylene content component as defined by cyclic interface model (P _p) is less than 60 wt% to 95 wt%, propylene emissions content of the low propylene content component (P'p) is more than 20 wt% Less than 60% by mass.

(V) The propylene content (P _p ) of the high propylene content component, the propylene content (P'p) of the low propylene content component, and the ratio of the high propylene content component to the F p defined by the two-site model (P _fl ) and the proportion of the low propylene content component to the F p (1 P _fl ) satisfies the following formulas (1) and (2).

Ρ _Ρ ΖΡ ' _Ρ ≥ 1 · 90… (1)

2.00 <P _fl / (1-P _fl ) <6.00… (2)

5. The method for producing a cast film according to claim 4, wherein a filter having a filtration accuracy according to JISB 8356 of 5 to 150 μηι is used as the metal fiber filter.

6. Aluminum foil, metal deposited film layer, silicon oxide deposited film layer, polyvinyl chloride resin layer, ethylene vinyl acetate copolymer resin sample resin layer, polyamide resin layer, polyester resin layer, polycarbonate resin layer and At least one layer selected from the oxygen absorbent layer,

A laminate comprising: a layer comprising the cast film according to any one of claims 1 to 3.

7. A container using the cast film according to any one of claims 1 to 3.

8. A container using the laminate according to claim 6.