JP2002321320A - Multilayered film having oxygen gas barrier property and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a multilayered film having an oxygen gas barrier property which has an excellent oxygen gas barrier property, especially exerts the excellent oxygen gas barrier property even under a high humidity, and can be manufactured from an easily available material at low cost. SOLUTION: In this multilayered film, an oxygen gas barrier layer which comprises a mixture of a polyvinyl alcohol resin layer of 100 pts.wt. and a polyalkyleneglycol surfactant of 0.01-5 pts.wt. is formed at least on one side face of a base material film layer, an oxygen permeability under an atmosphere at 23 deg.C and relative humidity of 85% is 1000 mL/m<2> .day.MPa or less.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an oxygen gas barrier multilayer film and a method for producing the same, and more particularly to an oxygen gas barrier multilayer film having excellent oxygen gas barrier properties under high humidity and a method for producing the same. The oxygen barrier multilayer film of the present invention has excellent oxygen gas barrier properties even under high humidity and can be applied to various fields,
It can be suitably used mainly in the field of packaging, for example, a film for food packaging.

[0002]

2. Description of the Related Art Conventionally, food and drink, pharmaceuticals, chemicals,
Various organic polymer films are used as a packaging material for filling and packaging various goods such as daily necessities, and as an important characteristic, a high oxygen gas barrier property for protecting and preserving the quality of a packaged object ( Oxygen barrier properties), but at present, a single film does not have sufficient gas barrier properties.

Therefore, as a means for imparting oxygen gas barrier properties, coating a film with a material having oxygen gas barrier properties has been performed. As one of them,
Polyvinylidene chloride resin (hereinafter, “PVDC resin”)
May be abbreviated. ) Is coated on a film, has little hygroscopicity, and has a good oxygen gas barrier property even under high humidity. However, since the PVDC-based resin-coated film contains chlorine, it has a problem in that toxic hydrogen chloride gas and dioxin are generated by combustion. In particular, in recent years, there has been a strong demand for an oxygen gas barrier film made of a material that does not contain chlorine as part of measures against dioxin, and development studies are underway.

[0004] Such materials having high oxygen gas barrier properties include polyvinyl alcohol-based resin (hereinafter sometimes abbreviated as "PVA-based resin"), ethylene-vinyl alcohol copolymer resin (hereinafter referred to as "EVOH-based resin"). (May be abbreviated). Films coated with such a resin show excellent oxygen gas barrier properties under low humidity, but because of their high hygroscopicity, the oxygen gas barrier properties decrease as the relative humidity increases, which is considered to be poor in practicality. Had been.

Japanese Patent Application Laid-Open No. Hei 3-30944 discloses "P
Patent Document 2 discloses a method of adding a swellable colloidal hydrated layered silicate compound to a VA resin coating solution.
JP-A-789705 discloses a "method of forming a layer composed of a PVA-based resin modified with at least one of a swellable colloidal hydrated layered silicate compound and a compound having a silyl group in the molecule". I have. However, any of these coated films obtained by coating these on a base film layer made of an organic polymer has a high production cost, and is not sufficient as a substitute for a PVDC-based resin coat film having a low production cost. Thus, at present,
At present, practical films that can be substituted for PVDC-based resin-coated films have not yet been obtained because of insufficient oxygen gas barrier properties under high humidity and high cost.

[0006]

The oxygen gas barrier multilayer film having a conventional organic polymer film as a base film layer has the above-mentioned problems. The present invention solves the problems of the multilayer resin film having an oxygen gas barrier property having the conventional organic polymer film as a base film layer, and has a high oxygen gas barrier property,
In particular, it demonstrates excellent oxygen gas barrier properties even under high humidity,
Moreover, it is an object of the present invention to provide an oxygen gas barrier multilayer film that can be manufactured at low cost from easily available materials.

[0007]

In order to achieve the above object, the oxygen gas barrier multilayer film of the present invention comprises a base film layer having at least one surface provided with 100 parts by weight of a polyvinyl alcohol-based resin and a polyalkylene glycol-based interface. A multilayer film formed by forming an oxygen gas barrier layer comprising a mixture of 0.01 to 5 parts by weight of an activator,
Oxygen permeability in an atmosphere at 85 ° C and a relative humidity of 85% is 100
It is not more than 0 mL / m ² · day · MPa.

[0008] The oxygen gas barrier multilayer film of the present invention having the above structure has a high oxygen gas barrier property, and in particular, exhibits excellent oxygen gas barrier properties even under high humidity, and has a low oxygen gas barrier property. It is an oxygen gas barrier multilayer film that can be manufactured at low cost.

In this case, the crystallinity parameter (CP (M //) ⊥) of the oxygen gas barrier layer can be set to 0.8 or more.

Here, the crystallinity degree parameter is a crystallinity degree parameter (CP (M / M) obtained by a polarization ATR spectrum in an infrared polarization ATR method (total reflection measurement method).
/) ⊥), and specifically, this crystallinity parameter utilizes the absorption band of a polyvinyl alcohol-based resin, and is 1140 with respect to the absorption intensity near 1095 cm ^−1.
It means the ratio of the absorption intensity around cm ^-1 .

In this case, the substrate film layer and the oxygen gas barrier layer may be laminated via an adhesive layer.

In this case, the base film layer may be a polypropylene resin film.

In this case, the adhesive layer can be a layer made of an adhesive containing an acid-modified polyolefin.

In this case, the thickness of the polyvinyl alcohol-based resin layer can be 1 μm or less.

Further, in the method for producing an oxygen gas barrier multilayer film according to the present invention, after stretching an unstretched base film layer in one direction, at least one surface of the base film layer is coated with 100 wt. And an aqueous solution comprising a mixture of 0.01 parts by weight and 0.01 to 5 parts by weight of a polyalkylene glycol-based surfactant, and then stretching in a direction perpendicular to the stretching direction.

In this case, the unstretched base film having the adhesive layer formed on at least one surface is stretched in one direction, and then the surface of the adhesive layer is coated with 100 parts by weight of polyvinyl alcohol resin and polyalkylene. An aqueous solution comprising a mixture of 0.01 to 5 parts by weight of a glycol-based surfactant can be applied, and then stretched in a direction perpendicular to the stretching direction.

The method for producing an oxygen gas barrier multi-layer film of the present invention having the above-mentioned constitution provides high oxygen gas barrier properties, particularly excellent oxygen gas barrier properties even under high humidity, and reduces the amount of easily available materials. An oxygen gas barrier multilayer film can be manufactured at low cost.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the oxygen gas barrier multilayer film of the present invention and a method for producing the same will be described.

As shown in FIG. 1 (a), the oxygen gas barrier multi-layer film of the present invention comprises a multi-layer resin having a basic structure in which an oxygen gas barrier layer 2 is formed on at least one surface of a base film layer 1. Film. In the example having an adhesive layer, as shown in FIG. 1B, the substrate film layer 1 has an oxygen gas barrier layer 2 laminated via an adhesive layer 3. FIG. 1C shows an example in which the oxygen gas barrier layer 2 is provided on any surface of the base film layer.

1 (a), 1 (b) and 1 (c) are schematic views illustrating the oxygen gas barrier multilayer film of the present invention, and the present invention is not limited to this. It is also possible to laminate an arbitrary resin film such as a heat-sealing resin or a material other than the resin on the oxygen gas barrier multilayer film to obtain a configuration suitable for the purpose. Further, lamination processing on the oxygen gas barrier multilayer film of the present invention,
Various processing may be performed according to the purpose such as printing.
Further, another layer other than the adhesive layer may be provided between the organic polymer film constituting the base film layer and the oxygen gas barrier layer as long as the oxygen gas barrier property is not impaired.

The organic polymer film constituting the base film layer used in the present invention is, for example, melt-extruded from an organic polymer, and if necessary, stretched in the longitudinal direction and / or the width direction, cooled, and heat-set. The organic polymer is nylon 4.6, nylon 6, nylon 6.
6, polyamides represented by nylon 12, etc., polyethylene terephthalate, polybutylene terephthalate,
In addition to polyesters represented by polyethylene-2,6-naphthalate and the like, polyolefins represented by polyethylene, polypropylene, polybutene, etc., polyvinyl alcohol, wholly aromatic polyamide, polyamideimide,
Examples include polyimide, polyetherimide, and polysulfone.

Among them, the substrate film layer used in the present invention is preferably a polypropylene resin film, particularly a biaxially stretched polypropylene resin film, from the viewpoint of effectively improving the oxygen gas barrier property. In the polypropylene-based resin film, its raw material, mixing ratio and the like are not particularly limited. For example, polypropylene homopolymer (propylene homopolymer), α-
It may be a random copolymer or a block copolymer with one or more selected from olefins, or a mixture of two or more of these polymers. Known additives such as an antioxidant, an antistatic agent, and a plasticizer may be added for the purpose of improving physical properties, and for example, a petroleum resin or a terpene resin may be added.

On the other hand, the material of the adhesive layer is not particularly limited, but it is preferable that the adhesive layer contains an acid-modified polyolefin. For example, those containing an acid-modified polyolein obtained by modifying a polyolefin-based polymer with an unsaturated carboxylic acid such as (meth) acrylic acid, maleic acid, maleic anhydride, and fumaric acid are recommended.
An adhesive layer containing a graft copolymer obtained by graft copolymerizing 5 mol% of maleic acid or maleic anhydride with an olefin polymer is suitably used. Although the thickness of the adhesive layer is not particularly limited, it is desirable that the thickness of the adhesive layer be 0.5 to 5 μm from the viewpoint of adhesiveness and cost. Further, an additive such as an antistatic agent may be added to the adhesive layer according to the purpose.

The substrate film layer used in the present invention comprises:
Any thickness can be used according to the desired purpose such as mechanical strength and transparency. Although not particularly limited,
Usually, it is recommended that the thickness be 5 to 250 μm, and when it is used as a packaging material, it is desirable that the thickness be 10 to 60 μm.

The base film layer used in the present invention may be a single-layer film or a laminated film in which a plurality of resin films are laminated. The type, number of layers, lamination method, and the like of the laminate in the case of a laminated film are not particularly limited, and can be arbitrarily selected from known methods according to the purpose.

An oxygen gas barrier layer is laminated on at least one surface of such a substrate film layer.

The degree of polymerization and the degree of saponification of the polyvinyl alcohol-based resin forming the oxygen gas barrier layer are determined by the properties of the target oxygen gas barrier multilayer film, particularly the viscosity and coating of the PVA resin aqueous solution during the production of the oxygen gas barrier multilayer film. It is determined from the stretchability of the later coat layer. Regarding the stretchability, the higher the degree of polymerization, the slower the crystallization rate and the better the stretchability. However, if the degree of polymerization is too high, the coating becomes difficult because the aqueous solution has a high viscosity and gels easily. Accordingly, the degree of polymerization is 200 or more from the viewpoint of the stretchability of the coat layer, and 26 or more from the workability of the coating.
It is preferably at most 00. More preferably 50
0 to 2000. If the saponification degree is less than 90%, the necessary oxygen gas barrier property under high humidity cannot be obtained.
If it exceeds 9.7%, it is difficult to adjust the aqueous solution, it is easy to gel, and it is not suitable for industrial production. Therefore, the degree of saponification is 90-
99.7% is preferable, and 93 to 99% is more preferable.
It is. Further, the polyvinyl alcohol-based resin is a polymer having a monomer unit of vinyl alcohol as a main component, and is obtained by saponifying a vinyl acetate polymer, a trifluorovinyl acetate polymer, a vinyl formate polymer, a trimethylsilyl vinyl ether polymer, or the like. And the like.

The oxygen gas barrier layer in the present invention must be composed of a mixture of 100 parts by weight of a polyvinyl alcohol-based resin and 0.01 to 5 parts by weight of a polyalkylene glycol-based surfactant. By using a polyalkylene glycol-based surfactant as a component,
A coat film with few coat defects is obtained, and the oxygen gas barrier property under high humidity is improved. When the content of the polyalkylene glycol-based surfactant is less than 0.01 part by weight, the wettability to the substrate film layer surface is insufficient,
It becomes a film with many coat defects. On the other hand, when the content of the polyalkylene glycol-based surfactant exceeds 5 parts by weight, the oxygen barrier property under high humidity is deteriorated because the polyvinyl alcohol resin portion is reduced.

The polyalkylene glycol-based surfactant used in the present invention includes higher alcohol ethylene oxide adducts, alkylphenol ethylene oxide adducts, fatty acid ethylene oxide adducts, polyhydric alcohol fatty acid ester ethylene oxide adducts, higher alkylamine ethylenes. Oxide adducts, fatty acid amide ethylene oxide adducts, ethylene oxide adducts of fats and oils, polypropylene glycol ethylene oxide adducts and the like can be mentioned. Of these, higher alcohol ethylene oxide adducts, alkylphenol ethylene oxide adducts, and polypropylene glycol ethylene oxide adducts are preferred from the viewpoint of not lowering the oxygen gas barrier properties. Often, HLB (Hydrophile-Lypophile Balance) is used as an index indicating the hydrophilicity. HLB is preferably 10 to 17 in view of compatibility with a polyvinyl alcohol-based resin and film-thickness.

In the oxygen gas barrier layer used in the present invention, the crystallinity parameter (CP (M //) ⊥) obtained from the deflection ATR spectrum is preferably 0.8 or more. Crystallinity parameter (CP (M //) ⊥)
Is 0.8 or more, excellent oxygen gas barrier properties can be exhibited even under high humidity.

In the present invention, the crystallinity parameter is a value obtained by measuring the oxygen gas barrier layer of the oxygen gas barrier multilayer film by the infrared polarization ATR method (total reflection measurement method). The crystallinity parameter (CP (M
//) ⊥). Incidentally, PVA is determined by IR spectrum.
When evaluating the crystallinity of the oxygen gas barrier layer composed of a system resin, it is usually evaluated at an absorption intensity around 1140 cm ^-1 . Because of the strong influence, the evaluation is preferably made based on the relative intensity with other absorption intensities. Therefore, the crystallinity parameter in the present invention is 1140c for the absorption intensity around 1095 cm ^-1.
The ratio of the absorption intensities around m ^-1 was determined. Crystallinity parameter C
The higher the value of P (M //) ⊥, the more excellent the oxygen gas barrier property is obtained. Therefore, it is preferably 1.0 or more, more preferably 1.2 or more, and most preferably 1.9 or more.

As a method for laminating a mixture of a polyvinyl alcohol-based resin and a polyalkylene glycol-based surfactant constituting the oxygen gas barrier layer, coating is generally preferred. Specifically, a method of coating a base film layer with an aqueous solution of a mixture of a polyvinyl alcohol-based resin and a polyalkylene glycol-based surfactant is employed. The coating method is not limited, but an optimum method may be selected depending on the amount and viscosity of the coating solution to be used. Reverse roll coating method,
A roll knife coating method, a die coating method, or the like may be employed.

The conditions of drying and heat treatment at the time of coating depend on the thickness of the coating and the conditions of the apparatus. Preferably. In such a case, it is usually performed at about 80 to 170 ° C. In addition,
Before forming the coating layer, the base film layer may be subjected to a corona discharge treatment, another surface activation treatment, or an anchor treatment using a known anchor treatment agent. The addition of various known inorganic and organic additives such as an antistatic agent, a slip agent and an antiblocking agent to the coating layer is optional as long as the object of the present invention is not hindered.

The thickness of the oxygen gas barrier layer varies depending on the base film layer and the required oxygen gas barrier property.
The minimum thickness for exhibiting the oxygen gas barrier property is good, and it is usually preferable that the dry thickness is 1 μm or less in terms of transparency, handleability, and economy.

In the oxygen gas barrier multilayer film of the present invention, a heat sealable resin layer called a sealant is usually formed on the oxygen gas barrier layer. The formation of the heat-sealable resin layer is usually performed by an extrusion lamination method or a dry lamination method.

The thermoplastic polymer used to form the heat-sealable resin layer used in the present invention may be any one capable of sufficiently exhibiting sealant adhesiveness.
A polyethylene resin such as PE or LLDPE, a polypropylene resin, an ethylene-vinyl acetate copolymer, an ethylene-α-olefin random copolymer, an ionomer resin, and the like can be used. Usually, a heat-sealing resin that is not a chlorine-containing resin is preferable from the viewpoint of environmental problems during incineration.

According to the present invention, it is inexpensive, has excellent oxygen gas barrier properties under high humidity, does not contain dioxin and hydrogen chloride gas in incineration exhaust gas, and is effective for environmental protection, which has recently been a problem. Some films can be provided.

[0038]

Next, the present invention will be described specifically with reference to the following examples and comparative examples, but the present invention is not limited to these examples. The indication of the concentration in the liquid is based on weight unless otherwise specified, and the evaluation of characteristic values was performed by the following method.

1) Oxygen permeability The oxygen permeability was measured by MOCON OX-TRA manufactured by Modern Control.
The measurement time was 30 minutes under an atmosphere controlled at 23 ° C. and a relative humidity of 85% using “N 2/20”. The unit of the oxygen permeability was mL / m ² · day · MPa.

2) Crystallinity Parameters An ATR measuring accessory (Perkin-Elmer), a polarizer, and an Internal Reflection Element having a symmetrical edge are provided on an FT-IR (FTS-60A / 896) manufactured by Bio Rad. (Ge, incident angle 4
The crystallinity of each test piece (length 45 mm x width 17 mm) was measured by an infrared polarization ATR method using an ATR apparatus equipped with 5 degrees and a thickness of 2 mm x a length of 50 mm x a width of 20 mm.

The infrared light at the end was blocked so that the infrared light was incident only on the central part (width 12 mm) of the internal reflection element.

The length of the test piece was taken in the width direction of the film (perpendicular to the flow direction), and the PVA-based resin layer was
The measurement was performed by irradiating the reflective surface of the test piece with vertically polarized light in close contact with the internal reflection element. The obtained spectrum is designated as Spectrum (M //) ⊥.

In the obtained polarized ATR spectrum,
1140cm^-1Near absorption and 1095cm^-1Nearby absorption
The absorbance is determined. At this time, the polarization ATR spectrum
1140cm^-1The valley on the high wavenumber side of the nearby peak and 109
5cm^-1Connected two points in the valley on the low wavenumber side of the nearby peak
Line as the baseline and the peak of the absorption band from the baseline.
The height up to the peak is defined as the absorbance of the PVA-based resin layer absorption band.
1140cm^-1A1140, 1
095cm^-1The absorbance of the nearby peak is defined as A1095.
You. 1140 cm if no clear peak is observed
^-1, 1095cm ^-1Absorbance at the position of A1140, A
1095.

For the spectrum of Spectrum (M //) ⊥,
The ratio of A1140 to A1095 (A1140 / A1
095). This value is used as the crystallinity parameter,
CP (M //)}.

(Example 1) Preparation of coating solution 900 g of an aqueous solution containing 7% of isopropyl alcohol
While stirring, 97 g of a powder of a polyvinyl alcohol-based resin (a saponification degree of 98.5 mol% and a polymerization degree of 1000) was gradually added to the aqueous solution. After heating to about 80 ° C to completely dissolve, it was cooled to 40 ° C. Thereafter, 0.0097 g (0.01 parts by weight to 100 parts by weight of the polyvinyl alcohol-based resin) of the polyalkylene glycol-based surfactant Neugen EA110 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., HLB: 11) was added to the polyvinyl alcohol resin solution. did.

Film Coating and Evaluation Petroleum resin (ESCOLETZ E5300: 97% by weight of a polypropylene resin as a base layer) substantially free of polar groups
A resin mixed with 3% by weight (made by Tonex Corporation) and an acid-modified polyolefin were used for the adhesive layer. These were applied at a ratio of base layer / adhesive layer = 19/1 (weight ratio) at a resin temperature of 26.
Co-extruded from a T-die in a two-layer state to reach 0 ° C,
After casting with a casting roll at a temperature of 25 ° C., the film was stretched four times in the machine direction to obtain a film having a thickness of 180 μm. Next, the coating solution was applied on the adhesive layer surface of the obtained laminated film by a reverse roll coating method, and then stretched 9 times in the horizontal direction. The oxygen permeability and the crystallinity parameter of this coated film were measured.

(Examples 2 to 6, Comparative Examples 2 and 3) Samples were produced and evaluated in the same manner as in Example 1 except that the amount of the polyalkylene glycol-based surfactant Neugen EA110 was changed. Was.

Example 7 Neugen EA140 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., HLB: 14) was used as a polyalkylene glycol-based surfactant, and the addition amount was 0.97 g (1%).
A sample was manufactured and evaluated in the same manner as in Example 1 except that the weight ratio was changed to 100 parts by weight of the polyvinyl alcohol resin.

(Comparative Example 1) As a coat layer, a polyvinyl alcohol-based resin (a saponification degree of 98.5 mol%, a polymerization degree of 10
A sample was manufactured and evaluated in the same manner as in Example 1 except that only Example 00) was used.

Comparative Example 4 An isocyanate-based adhesive as an anchoring agent was dried and gravure-coated on a surface of a biaxially stretched polypropylene-based resin film having a thickness of 20 μm so as to have a coating amount of 3 g / m ² after drying. . The same coating solution as in Example 1 was gravure coated on the anchor layer and dried at 140 ° C. to obtain a laminated film.

Table 1 shows the coating compositions and the evaluation results in the above Examples and Comparative Examples.

[0052]

[Table 1]

[0053]

According to the oxygen gas barrier multilayer film of the present invention, it has a high oxygen gas barrier property, exhibits particularly excellent oxygen gas barrier properties even under high humidity, and has a low cost from easily available materials. Can be manufactured.

[Brief description of the drawings]

FIGS. 1A, 1B, and 1C are examples of cross-sectional views of an oxygen gas barrier multilayer film of the present invention.

[Description of Signs] 1 Base film layer 2 Oxygen gas barrier layer 3 Adhesive layer

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor: Yutaka Matsumura, 344 Maebata, Mazuhata, Kizu, Inuyama, Aichi Prefecture Inside the Inuyama Plant of Toyobo Co., Ltd. In the Inuyama Plant of Toyobo Co., Ltd. (72) Inventor Ishi Nakatani 344, Maebata, Inayama, Inuyama, Aichi Prefecture In the Inuyama Plant of Toyobo Co., Ltd. F term in the Inuyama factory of Yossei Co., Ltd. (reference) 4F006 AA12 AB20 AB32 BA05 CA07 DA04 4F100 AK01A AK03G AK07A AK21B AK54B AL07G AT00A BA02 CA18B CA18H CC01B EH46 EJ38 GB15 JA11B JD03 JD03B YY00B

Claims (8)

[Claims] An oxygen gas barrier layer comprising a mixture of 100 parts by weight of a polyvinyl alcohol-based resin and 0.01 to 5 parts by weight of a polyalkylene glycol-based surfactant is formed on at least one surface of a substrate film layer. A multilayer film having an oxygen permeability of 1000 mL / m ² · day · MPa under an atmosphere of 23 ° C. and a relative humidity of 85%.
An oxygen gas barrier multilayer film characterized by the following. 2. The oxygen gas barrier multilayer film according to claim 1, wherein a crystallinity parameter (CP (M //) ⊥) of the oxygen gas barrier layer is 0.8 or more. 3. The oxygen gas barrier multilayer film according to claim 1, wherein the base film layer and the oxygen gas barrier layer are laminated via an adhesive layer. 4. The substrate film layer is a polypropylene-based resin film.
The oxygen gas barrier multilayer film according to the above. 5. The oxygen gas barrier multilayer film according to claim 3, wherein the adhesive layer comprises an adhesive containing an acid-modified polyolefin. 6. The oxygen gas barrier multilayer film according to claim 1, wherein the thickness of the oxygen gas barrier layer is 1 μm or less. 7. The method for producing an oxygen gas barrier multilayer film according to claim 1, 2, 3, 4, 5, or 6, wherein the unstretched base film layer is stretched in one direction and then the base material is stretched. An aqueous solution comprising a mixture of 100 parts by weight of a polyvinyl alcohol-based resin and 0.01 to 5 parts by weight of a polyalkylene glycol-based surfactant is applied to at least one surface of the film layer, and then in a direction perpendicular to the stretching direction. A method for producing an oxygen gas barrier multilayer film, comprising stretching. 8. An unstretched substrate film having an adhesive layer formed on at least one surface is stretched in one direction, and then the surface of the adhesive layer is coated with 100 parts by weight of a polyvinyl alcohol-based resin and a polyalkylene glycol-based interface. Activator 0.01-5
8. The method for producing an oxygen gas barrier multilayer film according to claim 7, wherein an aqueous solution comprising a mixture of parts by weight is applied.