JP2020082624A - Gas absorbing film - Google Patents

Abstract

To provide a gas absorbing film including a metal-based chemical absorbent and suppressing embrittlement in a high temperature environment.SOLUTION: The gas absorbing film 100a, 100b of the present invention includes a gas absorbing layer 10a, 10b containing polypropylene and a metal-based chemical absorbent 12. An oxygen absorbent 22 is further contained in the gas absorbing layer 10a and/or is contained in an oxygen absorbing layer 20 laminated on the gas absorbing layer 10b.SELECTED DRAWING: Figure 1

Description

The present invention relates to a gas absorption film.

BACKGROUND ART Conventionally, in the fields of foods, pharmaceuticals, electronic parts, precision machines, recording materials, etc., a method of enclosing a gas absorbent in order to prevent quality deterioration has been adopted. Further, in order to allow the packaging material itself to have a gas absorbing function without putting a separate gas absorbent in the package, the packaging material itself is made to contain the absorbent.

Specifically, as a packaging material that absorbs oxygen, in Patent Document 1, a polyolefin inner surface material, an oxygen absorbing layer made of a composition of polyolefin and an iron-based oxygen absorbent, a polyolefin buffer layer, an aluminum foil, a stretched film or an inorganic material. An oxygen-absorbing packaging material is disclosed in which vapor-deposited plastic films are sequentially laminated.

In addition, as a packaging material that absorbs a sulfide-based gas such as hydrogen sulfide and mercaptan, in Patent Document 2, a first skin layer including an olefin elastomer, and an inorganic adsorbent and a binder that adsorb sulfide are included. A sulfide-based gas adsorption laminate having an adsorption layer is disclosed.

As referred to in Patent Document 2, as an inorganic adsorbent for adsorbing sulfide, a metal-based chemical adsorbent such as copper, iron, zinc, manganese, cobalt, nickel, zirconium, and a lanthanoid element is used. It is known to use a compound or salt containing at least one selected metal.

JP-A-2000-343661 JP, 2016-112510, A

Depending on the application of the packaging material using the gas absorbing film, heat resistance capable of maintaining the shape for a long period of time in a high temperature environment may be required in addition to the gas absorbing property. In this case, it is preferable to use a polypropylene resin that is easy to form into a film and has excellent heat resistance. However, when a gas-absorbing film is produced using a polypropylene-based resin and a metal-based chemical absorbent and placed in a high temperature environment, the gas-absorbing film becomes brittle in a short period of time and the heat resistance of polypropylene cannot be fully utilized. The present inventors have found that

Therefore, there is a need to provide a gas-absorbing film that has a metal-based chemical absorbent and is suppressed from becoming brittle in a high temperature environment.

As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by the following means, and have completed the present invention. That is, the present invention is as follows:
<Aspect 1> Having a gas absorption layer containing polypropylene and a metal-based chemical absorbent,
An oxygen absorbent is further contained in the gas absorption layer, and/or contained in the oxygen absorption layer laminated on the gas absorption layer,
Gas absorption film.
<Aspect 2> Aspect 1, wherein the metal-based chemical absorber contains at least one selected from the group consisting of copper, cobalt, manganese, iron, nickel, zinc, silver, calcium, and titanium. Gas absorption film.
<Aspect 3> The gas absorbing film according to aspect 1 or 2, wherein the oxygen absorbent is contained in the gas absorbing layer.
<Aspect 4> The gas absorbing film according to any one of Aspects 1 to 3, wherein the oxygen absorbent is contained in an oxygen absorbing layer laminated on the gas absorbing layer.
<Aspect 5> A laminate for packaging, comprising the gas absorbing film according to any one of Aspects 1 to 4 and a base material layer laminated on the gas absorbing film.
<Aspect 6> The packaging laminate according to Aspect 5, wherein the base material layer comprises a barrier layer and a base resin layer.
<Aspect 7> A packaging bag enclosing the content,
The gas absorbing film according to any one of aspects 1 to 4 is further enclosed in the packaging bag, or the packaging laminate according to aspect 5 or 6 constitutes at least a part of the packaging bag. is doing,
Packaging bag.

According to the present invention, it is possible to provide a gas-absorbing film that has a metal-based chemical absorbent and is suppressed from becoming brittle in a high temperature environment.

FIG. 1 is a side sectional view of the gas absorbing film of the present invention. FIG. 2 is a side sectional view of the packaging laminate of the present invention.

<Gas absorption film>
As shown in FIG. 1, the gas absorbing films 100a and 100b of the present invention have gas absorbing layers 10a and 10b containing polypropylene and a metal-based chemical absorbent 12,
The oxygen absorbent 22 is contained in the gas absorption layer 10a (FIG. 1A) and/or contained in the oxygen absorption layer 20 laminated on the gas absorption layer 10b (FIG. 1B).

The present inventors have found that the embrittlement of the film is promoted by placing the polypropylene-based resin and the metal-based chemical absorbent in the presence of oxygen in a high temperature environment in a state of being in contact with each other. Without wishing to be bound by theory, it is believed that this is because the reaction between the oxidizable polypropylene resin and oxygen is promoted by the high temperature environment and the metal chemical absorber acting as a catalyst. Be done. With respect to this problem, the present inventors have found that the above-described configuration can suppress the embrittlement of the film by reducing the oxygen concentration that causes the embrittlement of the polypropylene resin.

Therefore, the gas absorbing film of the present invention has a high temperature, for example, 50°C or higher, 60°C or higher, 70°C or higher, 80°C or higher, or 90°C or higher, and 150°C or lower, 140°C or lower, 130°C or lower, 120°C or lower. Or, it can be used in an environment in which a temperature of 110° C. or lower can be reached. Therefore, the gas absorbing film of the present invention can be used, for example, for packaging all-solid-state lithium-ion batteries.

The gas-absorbing film of the present invention can be produced by melting and kneading the materials forming each layer of the gas-absorbing film, if necessary, forming a film, and laminating each layer as necessary.

The melt-kneading can be performed by using, for example, a kneader, a Henschel mixer, a batch-type kneader such as a mixing roll, or a continuous kneader such as a biaxial kneader.

The film formation can be performed by, for example, an inflation method, a T-die method, a calendar method, a casting method, a hot press molding, an extrusion molding or an injection molding.

The lamination can be performed by an extrusion laminating method such as a sand laminating method, a heat sealing method, a hot press molding, or the like.

Further, the film formation and the lamination may be simultaneously performed by a coextrusion method such as a coextrusion inflation method and a coextrusion T-die method.

Below, each component of this invention is demonstrated.

<Gas absorption layer>
The gas absorption layer contains a polypropylene resin and a metal chemical absorbent. Further, the gas absorption layer may further contain an oxygen absorbent. The metal-based chemical absorbent may be in contact with the polypropylene-based resin, and particularly may be dispersed in the polypropylene-based resin. The gas absorption layer may be a single layer or a laminated body. Further, in the case of a laminate, the gas absorbing layer may have a layer composed of a polypropylene resin on one or both sides of the layer containing the metal chemical absorbent, In this case, the layer containing the metal-based chemical absorbent may be a layer in which the metal-based chemical absorbent is dispersed in the polyethylene-based resin referred to below. Further, the layer containing the metal-based chemical absorbent may further contain an oxygen absorbent which is dispersed in the thermoplastic resin forming the layer.

The content rate of the metal-based chemical absorbent in the layer containing the metal-based chemical absorbent in the gas absorption layer is 1% by mass based on the mass of the above-mentioned entire layer from the viewpoint of ensuring good absorption capacity. It is preferably 3% by mass or more, 5% by mass or more, 7% by mass or more, or 10% by mass or more, and from the viewpoint of ensuring good film-forming properties, 70% by mass or less, 65% by mass or less, It is preferably 60% by mass or less, 55% by mass or less, or 50% by mass or less.

When the layer containing the metal-based chemical absorbent in the gas absorption layer further contains an oxygen absorbent, the content of the oxygen absorbent in the layer, from the viewpoint of ensuring a good absorption capacity, Based on the mass of the entire gas absorption layer, 1 mass% or more, 3 mass% or more, 5 mass% or more, 7 mass% or more, 10 mass% or more, 20 mass% or more, 30 mass% or more, 40 mass% or more, It is preferably 50% by mass or more, 60% by mass or more, or 70% by mass or more, and from the viewpoint of ensuring good film-forming properties, it is 90% by mass or less, 85% by mass or less, or 80% by mass or less. It is preferable.

The thickness of the gas absorption layer is preferably 1 μm or more, 2 μm or more, 3 μm or more, 5 μm or more, 10 μm or more, 20 μm or more, or 30 μm or more from the viewpoint of ensuring good absorption capacity, and 100 μm or less, 90 μm It is preferably not more than 80 μm, from the viewpoint of ensuring the flexibility of the film.

(Polypropylene resin)
In the present specification, a polypropylene-based resin is a resin that contains more than 50 mol%, 60 mol% or more, 70 mol% or more, or 80 mol% or more of propylene repeating units in the polymer main chain. Examples of the polypropylene resin include polypropylene (PP) homopolymer, random polypropylene (random PP), block polypropylene (block PP), chlorinated polypropylene, carboxylic acid-modified polypropylene, and derivatives thereof, and mixtures thereof.

(Metal chemical absorber)
The metal-based chemical absorbent may contain at least one selected from the group consisting of copper, cobalt, manganese, iron, nickel, zinc, silver, calcium, and titanium, and particularly these simple substances or compounds, particularly These salts may be, more particularly their silicates.

Particularly preferred metal-based chemical absorbents are metal silicates containing at least one metal selected from copper, zinc, manganese, cobalt and nickel, and more preferably the elemental composition (molar) ratio of metal to silicon is Metal/silicon=0.60 to 0.80. Such an inorganic adsorbent can be produced by reacting a metal salt with an alkali silicate salt. As the metal salt, an inorganic salt of at least one metal selected from copper, zinc, manganese, cobalt, nickel, such as sulfuric acid, hydrochloric acid, nitric acid, and/or an organic salt of formic acid, acetic acid, oxalic acid, etc. is used. be able to. Among these, copper (I), copper (II), and zinc (I) are preferable as the metal. As the above-mentioned silicate, the silicate of the formula of M ₂ O·nSiO ₂ ·xH ₂ O (wherein M represents a monovalent alkali metal, n is 1 or more, and x is 0 or more). Acid alkali salts can be mentioned. The most preferred metal silicate is copper(II) silicate which is a reaction product of copper(II) sulfate and sodium silicate, and is described in, for example, JP 2011-104274 A. For example, a copper (II) silicate-based adsorbent available from Toagosei Co., Ltd. under the name of Kesmon NS-20C can be used. In particular, when this metal-based chemical absorbent is used, hydrogen sulfide can be satisfactorily absorbed as mentioned in Patent Document 2.

(Oxygen absorber)
Examples of the oxygen absorber include metal oxides having oxygen deficiency, inorganic oxygen absorbers such as iron-based oxygen absorbers, and oxygen-absorbing metal-containing resin compositions containing metals and polyphenols. Be done.

Examples of the metal oxide having an oxygen deficiency include cerium oxide having an oxygen deficiency and titanium dioxide having a metal deficiency. Among them, cerium oxide having oxygen deficiency as an absorbent is preferable from the viewpoint of oxygen absorption.

The metal oxide having oxygen deficiency will be described more specifically. Oxygen deficiency of the metal oxide (MO ₂ ) is forcibly withdrawn from the crystal lattice of the metal oxide by the reduction treatment in a strong reducing atmosphere, as represented by the following formula (1). It is brought about by the oxygen deficiency state (MO _2-x , 0<x<2). The reduction treatment can be performed, for example, by heat treatment at a high temperature such as 1000° C. in a reducing atmosphere such as hydrogen gas.
MO ₂ +xH ₂ →MO _2-x +xH ₂ O (1)

Then, as shown in the following formula (2), the oxygen-deficient portion reacts with oxygen, so that the effect as an inorganic oxygen absorber is exhibited.
MO _2−x +(x/2)O ₂ →MO ₂ ...(2)

The value of x may be a positive number of 1.0 or less, and is preferably a positive number of 0.7 or less. As shown in equation (2) above, the metal oxide need not have water present in the atmosphere in the reaction with oxygen. Therefore, the use of a metal oxide having an oxygen deficiency as the inorganic oxygen absorber is particularly effective for contents that do not like water.

As the iron-based oxygen absorber, for example, iron powder (eg, reduced iron powder, atomized iron powder, activated iron powder, etc.), ferrous oxide, ferrous salt, etc. can be used.

<Oxygen absorption layer>
The oxygen absorption layer is a layer containing a thermoplastic resin and an oxygen absorbent. The oxygen absorber may be dispersed in the thermoplastic resin. As the oxygen absorbent, the oxygen absorbents mentioned for the gas absorption layer can be used.

The content of the oxygen absorbent in the oxygen absorbing layer is 1% by mass or more, 3% by mass or more, 5% by mass or more, 7% by mass based on the mass of the entire oxygen absorbing layer from the viewpoint of ensuring good absorption capacity. % Or more, 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, or 70% by mass or more, and good film-forming property From the viewpoint of ensuring the above, it is preferably 90% by mass or less, 85% by mass or less, or 80% by mass or less.

The thickness of the oxygen absorbing layer is preferably 1 μm or more, 2 μm or more, 3 μm or more, 5 μm or more, 10 μm or more, 20 μm or more, or 30 μm or more from the viewpoint of ensuring good absorption capacity, and 100 μm or less, 90 μm It is preferably not more than 80 μm, from the viewpoint of ensuring the flexibility of the film.

(Thermoplastic resin)
As the thermoplastic resin of the oxygen absorption layer, for example, polyolefin can be used. Examples of the polyolefin include polyethylene resin and polypropylene resin.

In the present specification, the polyethylene-based resin is a resin containing a repeating unit of an ethylene group in the main chain of the polymer in an amount of more than 50 mol%, 60 mol% or more, 70 mol% or more, or 80 mol% or more. As such polyethylene resin, polyethylene such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE) may be used. A copolymer with an ethylene-based monomer having a group or an ester group may be used.

As the polypropylene-based resin, the polypropylene-based resins mentioned for the gas absorption layer can be used.

<Skin layer>
The skin layer may be a layer existing on one side or both sides of the gas absorption layer and/or the oxygen absorption layer. Further, the skin layer may be fused to the gas absorption layer and/or the oxygen absorption layer.

The skin layer can prevent the metal-based chemical absorbent and/or the oxygen absorbent from coming off or coming into contact with the contents. Further, the skin layer may be a layer containing no metal-based chemical absorber and oxygen absorber.

The skin layer may be composed of polyolefin, for example. As the polyolefin, for example, the polyolefins mentioned for the oxygen absorbing layer can be used.

The thickness of the skin layer can be 1 μm or more, 3 μm or more, 5 μm or more, or 7 μm or more, and can be 50 μm or less, 40 μm or less, 30 μm or less, 20 μm or less, or 15 μm or less.

<<Laminate for packaging>>
As shown in FIG. 2, the packaging laminates 200a and 200b of the present invention include the gas absorbing films 100a and 100b, and the base material layer 30 laminated on the gas absorbing films 100a and 100b. There is.

More specifically, as shown in FIG. 2( a ), when the oxygen absorbent 22 is further dispersed in the gas absorbing layer 10 a, the packaging laminate 200 a has the above-mentioned gas absorbing film. 100a and the base material layer 30 laminated on the gas absorption layer 10a.

Further, as shown in FIG. 2( b ), when the oxygen absorbent 22 is contained in the oxygen absorbing layer 20 laminated on the gas absorbing layer 10 b, the packaging laminate 200 b has the above gas content. It has a base material layer 30 laminated on the absorption film 100b and the gas absorption layer 10b or the oxygen absorption layer 20.

In any of the embodiments, the base material layer 30 may include the barrier layer 32 and the base material resin layer 34.

The packaging laminate of the present invention can be used for various packaging applications, for example, as a laminated film for all solid state batteries.

<Base material layer>
The base material layer is a layer having a barrier property. Moreover, the base material layer may have a barrier layer and a base material resin layer.

Lamination of the base material layer and the gas absorption layer or oxygen absorption layer, and lamination of the following layers that can form the base material layer can be performed, for example, via an adhesive layer. As the adhesive layer, for example, a dry laminating adhesive, an anchor coat adhesive, a hot melt adhesive, a water-soluble adhesive, an emulsion adhesive, a non-solvent laminating adhesive, a thermoplastic resin for extrusion laminating and the like can be used. ..

(Barrier layer)
As the barrier layer, a material that can suppress permeation of moisture, organic gas, and inorganic gas such as oxygen from the outside into the functional layer can be used. Examples of the barrier layer include, but are not limited to, aluminum foil, metal foil such as aluminum alloy, aluminum vapor deposition film, silica vapor deposition film, alumina vapor deposition film, and inorganic vapor deposition film such as silica/alumina binary vapor deposition film. Alternatively, an organic coating film such as a polyvinylidene chloride coating film or a polyvinylidene fluoride coating film can be used. In particular, it is preferable to use an aluminum foil as the barrier layer from the viewpoint of facilitating compatibility between the barrier property and the handleability.

The thickness of the barrier layer is preferably 7 μm or more, 10 μm or more, or 15 μm or more from the viewpoint of ensuring strength and barrier properties, and is 45 μm or less, 40 μm or less, or 35 μm or less for easy handling. It is preferable from the viewpoint of improvement.

(Base resin layer)
As the base resin layer, a thermoplastic resin excellent in impact resistance, abrasion resistance, etc., such as polyolefin, vinyl polymer, polyester, polyamide, etc., may be used alone or in combination of two or more in a multi-layer structure. You can This base resin layer may be a stretched film or a non-stretched film. The base resin layer may be present on one side or both sides of the barrier layer. This base resin layer can protect the barrier layer.

As the polyolefin, for example, the polyolefins mentioned for the oxygen absorbing layer can be used.

Examples of the vinyl polymer include polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polychlorotrifluoroethylene, polytetrafluoroethylene, polyacrylonitrile (PAN) and the like.

Examples of polyesters include polyethylene terephthalate (PET) and polybutylene terephthalate.

Examples of the polyamide include nylon such as nylon (registered trademark) 6 and nylon MXD6.

The thickness of the base resin layer is preferably 7 μm or more, 10 μm or more, or 15 μm or more from the viewpoint of satisfactorily protecting the barrier layer, and is 55 μm or less, 50 μm or less, or 45 μm or less. It is preferable from the viewpoint of improving the property.

<< packaging bag >>
The packaging bag of the present invention is a packaging bag in which the contents are enclosed,
The above gas absorbing film is further enclosed in a packaging bag, or the above packaging laminate constitutes at least a part of the packaging bag.

<Contents>
The contents are not limited as long as they can be deteriorated by contact with the outside air, and include drugs, foods, cosmetics, medical instruments, medical devices, electronic members, precision machines, recording materials, etc. You can In addition to pharmaceutical preparations, the drugs include detergents, agricultural chemicals and the like.

Among them, when the content is an electronic member, particularly an all-solid-state lithium-ion battery using a sulfide-based solid electrolyte, heat resistance capable of withstanding heat generation during use, and hydrogen sulfide generated by the sulfide-based solid electrolyte Therefore, the packaging bag of the present invention becomes more useful.

The present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

<<Preparation of sample>>
<Comparative Example 1>
90 parts by mass of polypropylene (Novatech FL02A, Nippon Polypro Co., Ltd.) as a thermoplastic resin, and 10 parts by mass of a copper(II) silicate adsorbent (Kesmon NS-20C, Toagosei Co., Ltd.) as a metal chemical absorbent. Parts with a Banbury mixer at 190° C. for 10 minutes, cut into a predetermined mass, and hot press molded (press temperature 190° C., pressure 40 MPa, press time 2 minutes) to give a 100 μm thick layer. A film of Comparative Example 1 was produced.

<Comparative example 2>
A film of Comparative Example 2 having a thickness of 100 μm was produced in the same manner as Comparative Example 1 except that another polypropylene (Novatech FG3DC, Japan Polypro Co., Ltd.) was used as the thermoplastic resin.

<Example 1>
Using a Banbury mixer, 25 parts by mass of polypropylene (Novatech FG3DC, Nippon Polypro Co., Ltd.) as a thermoplastic resin and 75 parts by mass of cerium oxide CeO _2-x (x=0.5) having an oxygen deficiency as an oxygen absorbent are used. By kneading at 190°C for 10 minutes to prepare a masterbatch for oxygen absorption layer, cutting this into a predetermined mass, and hot press molding (pressing temperature 190°C, pressure 40 MPa, pressing time 2 minutes) An oxygen absorbing film having a thickness of 100 μm was produced.

The produced oxygen absorbing film and the film of Comparative Example 1 were superposed and subjected to hot press molding (press temperature 190° C., pressure 40 MPa, press time 2 minutes) to produce a film of Example 1 having a thickness of 200 μm. did.

<Example 2>
90 parts by mass of the above oxygen-absorbing masterbatch and 10 parts by mass of a copper(II) silicate-based adsorbent (Kesmon NS-20C, Toagosei Co., Ltd.) as a metal-based chemical absorbent were mixed with a Banbury mixer to obtain 190 parts. A film of Example 2 having a thickness of 100 μm was produced by kneading at 10° C. for 10 minutes, cutting this into a predetermined mass, and hot press molding (press temperature 190° C., pressure 40 MPa, press time 2 minutes). ..

<<Evaluation>>
<Evaluation as a film>
Each of the produced films was cut into a 5 cm square, and each film was sealed in a glass container having a volume of 22 ml. This was left for a time sufficient for the oxygen absorbing film to absorb oxygen in the container, and then the container was placed in an oven at 100° C. and stored for 5 days.

After storage, the film in the container was taken out, and cracks on the surface when the film was bent 180° were visually observed. The evaluation criteria are as follows.
A: No cracks and cracks were generated B: Cracks were generated C: Cracks were generated

<Evaluation as a laminate for packaging>
An aluminum foil with a thickness of 9 μm as a barrier layer is adhered to the gas absorption layer side of each produced film, and a polyethylene terephthalate (PET) with a thickness of 12 μm as a base resin layer is adhered thereto, and laminated for packaging. The body was made. Adhesion is performed by mixing Takelac A525S (Mitsui Chemicals, Inc.), Takenate A52 (Mitsui Chemicals, Inc.), and ethyl acetate in a predetermined composition, applying a coating amount of 3 g/m ² with a hand coater, and press-bonding. It was done by doing.

The produced packaging laminate was cut into a 5 mm square, and the same test as above was performed.

The configurations and evaluation results of the examples and comparative examples are shown in Table 1 below.

From Table 1, the films and packaging laminates of Comparative Examples 1 and 2 having no oxygen absorber had cracks or cracks, whereas the films and packaging of Examples 1 and 2 having an oxygen absorber. It can be seen that the laminate for use is free of cracks and cracks.

Although not shown in the table, a similar test was carried out by laminating a base material layer on the oxygen absorbing layer side of the film of Example 1, and the cracks and the cracks were used for packaging of Example 1 The same result as the laminate was obtained. From this, it can be understood that the packaging laminate of the present invention can suppress cracks and cracks regardless of which layer is in contact with oxygen.

10a, 10b Gas absorption layer 12 Metal-based chemical absorbent 20 Oxygen absorption layer 22 Oxygen absorption agent 30 Base material layer 32 Barrier layer 34 Base material resin layer 100a, 100b Gas absorption film 200a, 200b Packaging laminate

Claims (7)

Having a gas absorbing layer containing polypropylene and a metal-based chemical absorbent,
An oxygen absorbent is further contained in the gas absorption layer, and/or contained in the oxygen absorption layer laminated on the gas absorption layer,
Gas absorption film. The gas absorption according to claim 1, wherein the metal-based chemical absorbent contains at least one selected from the group consisting of copper, cobalt, manganese, iron, nickel, zinc, silver, calcium, and titanium. the film. The gas absorbent film according to claim 1, wherein the oxygen absorbent is further contained in the gas absorbent layer. The gas absorbing film according to claim 1, wherein the oxygen absorbing agent is contained in an oxygen absorbing layer laminated on the gas absorbing layer. A packaging laminate comprising the gas absorbing film according to any one of claims 1 to 4 and a base material layer laminated on the gas absorbing film. The packaging laminate according to claim 5, wherein the base layer comprises a barrier layer and a base resin layer. A packaging bag that encloses the contents,
The gas absorbing film according to any one of claims 1 to 4 is further enclosed in the packaging bag, or the packaging laminate according to claim 5 or 6 is at least a part of the packaging bag. Consists of,
Packaging bag.

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