JP2000185366A - Gas barrier film, its production and laminated material using gas barrier film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier film having extremely high barrier properties, a method for simply producing the gas barrier film, and a laminated material using this gas barrier film. SOLUTION: A gas barrier film is constituted by providing a metal film 3 and a metal oxide film 4 formed by anodically oxidizing the metal film 3 on at least one surface of a base material film 2. In this case, the oxygen gas permeability of the gas barrier film is set to 0.3 [cc/m2/day] or less and the steam permeability thereof is set to 0.3 [g/m2/day] or less. This gas barrier film is produced by forming the metal film 3 on at least one surface of the base material film 2 by either one of a vacuum vapor deposition method, an ion plating method, a sputtering method and a chemical vapor deposition method and forming the metal oxide film 4 due to anodic oxidation on the metal film by a method wherein the metal film 3 is dipped in an anodic oxidation soln. in a state connected to the anode of an external power supply to be opposed to a cathode and a current is applied across the anode and the cathode.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gas barrier film, and more particularly to a gas barrier film having a laminate of a metal film and a metal oxide film and having excellent gas barrier properties, a method for producing the same, and a laminate using the gas barrier film. .

[0002]

2. Description of the Related Art Conventionally, various materials have been developed and proposed as packaging materials having a barrier property against oxygen gas and water vapor and having good storage suitability for foods and pharmaceuticals. A barrier film composed of a laminate of polyvinylidene chloride or ethylene vinyl alcohol copolymer on a flexible plastic substrate, or an inorganic oxide such as silicon oxide or aluminum oxide on a flexible plastic substrate. A barrier film having a structure provided with the above thin film, and a packaging laminate and a packaging container using the same have been proposed.

[0003] These materials have a higher barrier property against water vapor, oxygen gas and the like, a higher fragrance retention property, etc. as compared with a conventional laminate material for packaging using aluminum foil or the like.
In addition, the demand is greatly expected.

[0004]

However, the barrier film laminated with the polyvinylidene chloride or ethylene vinyl alcohol copolymer described above does not have sufficient barrier properties against oxygen and water vapor, especially in sterilization treatment at high temperatures. There is a problem that remarkable reduction in barrier properties occurs. Furthermore, the barrier film laminated with polyvinylidene chloride generates toxic dioxin when incinerated, and there is a concern that it may have an adverse effect on the environment.

In general, a barrier film provided with a thin film of an inorganic oxide such as silicon oxide or aluminum oxide is formed by forming a thin film on a substrate film by a vapor deposition method, a chemical vapor deposition method or the like in a vacuum chamber. Manufactured. It is known that during this film formation, vapor-deposited substances (particles) having a large particle size are generated by peeling off from the vacuum chamber wall or by reacting in a gas phase. When such particles accumulate on the substrate film, the film does not deposit in the shadowed area, resulting in cavities, or after the film is formed, the particles peel off, resulting in defects such as voids in the thin film. Occurs. It is considered that such a defect is one of the causes for reducing the barrier property. It is also known that defects such as cavities occur in the deposited film even when the film is selectively grown, which is considered to be a cause of lowering the barrier property. Therefore, a conventional barrier film provided with a thin film of an inorganic oxide such as silicon oxide or aluminum oxide also has insufficient gas barrier properties.

[0006] In recent years, gas barrier films have also been used inside electronic members such as liquid crystal panels and solar cell panels. In these applications, higher gas barrier properties are required.

[0007] The present invention has been made in view of such circumstances, and a gas barrier film having an extremely high barrier property, a method for easily producing such a gas barrier film, and a gas barrier film having such a gas barrier property. An object is to provide a laminated material using a film.

[0008]

In order to achieve the above object, a gas barrier film of the present invention comprises: a base film; a metal film provided on at least one surface of the base film; A metal oxide film formed by anodizing the metal film, and having an oxygen gas permeability of 0.3 [cc / m ² /
day] or less, and the water vapor transmission rate is 0.3 [g / m ^2].
/ Day] or less.

Further, the gas barrier film of the present invention comprises:
The structure was such that the thickness of the metal oxide film was in the range of 5 to 300 nm.

Further, in the gas barrier film of the present invention, the metal film is formed of Al, Si, Ta, Nb, V, Bi,
The structure was made of at least one metal of Y, W, Mo, Zr and Hf.

The method for producing a gas barrier film of the present invention comprises forming a metal film on at least one surface of a substrate film by any one of a vacuum deposition method, an ion plating method, a sputtering method, and a chemical vapor deposition method. ,next,
The metal film was immersed in an anodic oxidation solution in a state where the metal film was connected to the anode of an external power supply, and the metal film was opposed to the cathode and energized to form a metal oxide film by anodic oxidation on the metal film.

The laminated material of the present invention has a structure in which a heat-sealing resin layer is provided on at least one surface of the gas barrier film.

Further, the laminated material of the present invention has a structure in which a heat-sealing resin layer is provided on the metal oxide film of the gas barrier film, and a base material on which the metal oxide film is not formed And a structure in which a heat-sealing resin layer is provided on a base material.

Further, the laminated material of the present invention has a structure having an anchor coat agent layer and / or an adhesive layer between the metal oxide film and the heat-sealing resin layer.

According to the present invention, by providing a metal oxide film on a metal film by anodic oxidation, even if a defect such as a pinhole exists in the metal film, the defect is filled by an increase in volume during anodic oxidation. Also, even if there is a defect in the metal oxide film in the process of formation, more current flows through the defective portion with relatively low resistance to form a metal oxide,
Defects are compensated.

[0016]

Next, an embodiment of the present invention will be described with reference to the drawings. Gas barrier film FIG. 1 is a schematic sectional view showing one embodiment of the gas barrier film of the present invention. In FIG. 1, a gas barrier film 1 includes a base film 2, a metal film 3 formed on one surface of the base film 2, and a metal oxide film 4 formed on the metal film 3. is there.

The substrate film 2 constituting the gas barrier film 1 of the present invention is not particularly limited as long as it can hold the metal film 3, and can be appropriately selected depending on the purpose of use of the gas barrier film. Specifically, as the base film 2, polyolefin resins such as polyethylene, polypropylene, and polybutene, (meth) acrylic resins, polyvinyl chloride resins, polystyrene resins, polyvinylidene chloride resins, and ethylene-vinyl acetate copolymers are used. Stretching (uniaxial or biaxial) of unified saponified product, polyvinyl alcohol, polycarbonate resin, fluorine resin, polyvinyl acetate resin, acetal resin, polyester resin such as polyethylene terephthalate or polyethylene naphthalate, polyamide resin, etc. or An unstretched flexible resin film can be used. The thickness of the base film 2 is 5 to 500 μm, preferably 10 to 10 μm.
It can be set appropriately within the range of 0 μm.

The base film 2 as described above may be, if necessary, coated on its surface with an anchor coat agent or the like and subjected to a surface smoothing treatment or the like.

The metal film 3 constituting the gas barrier film 1 of the present invention is made of a valve metal. here,
The valve metal is a metal that can be anodized, for example, Al, Si, Ta, Nb, V, Bi, Y, W, M
o, Zr, Hf and the like. The metal layer 3
It is made of at least one kind of the valve metal as described above, and the thickness varies depending on the type of the base film 2 and the valve metal to be used, the film forming conditions of the metal film 3, and the like. , About 5 to 300 nm, preferably 1
It can be set within a range of about 0 to 100 nm.

The metal oxide film 4 constituting the gas barrier film 1 of the present invention is a thin film formed by anodizing the metal layer 3. The thickness of the metal oxide film 4 is 5 to 300 nm,
Preferably, it can be set in the range of 10 to 100 nm. When the thickness of the metal oxide film 4 is less than 5 nm, the barrier properties of the metal oxide film 4 are insufficient, and
If it exceeds, cracks are likely to occur in the metal oxide film 4, and the barrier property is rather deteriorated.

The lamination of such a metal film 3 and a metal oxide film 4 has no defects such as pinholes, and the gas barrier film 1 has an oxygen gas permeability of 0.3 [cc / m ² /
day] or less, and the water vapor transmission rate is 0.3 [g / m ^2].
/ Day] or less, that is, extremely excellent gas barrier properties.

Method for Producing Gas Barrier Film Next, a method for producing the gas barrier film of the present invention will be described by taking the formation of the metal film 3 and the metal oxide film 4 on the base film 2 as an example.

The metal film 3 is formed of Al, Si, Ta, N
b, V, Bi, Y, W, Mo, Zr, Hf, or other one or more valve metals, using any one of a vacuum deposition method, an ion plating method, a sputtering method, and a chemical vapor deposition method Can be performed. Metal film 3
The thickness of the film is not limited, but may be 5 to 300 nm, preferably about 10 to 100 nm in consideration of the barrier property after anodic oxidation.

Next, a metal oxide film 4 is formed on the metal film 3. The metal oxide film 4 is formed by immersing the metal film 3 in an anodic oxidizing solution, facing the cathode, and energizing while the metal film 3 is connected to the anode of an external power supply.

FIG. 2 is a schematic diagram showing an example of the anodic oxidation step. In FIG. 2, a long base film 2 having a metal film 3 formed on one surface is sent out from a supply roll 11, and a metal roller 12 is brought into contact with the metal film 3.
After passing through the anodizing bath 13, the cleaning tank 15, and the drying device 17, it is taken up by a take-up roll 19.
The feed of the base film 2 may be continuous feed at a constant speed or intermittent feed.

The anodizing bath 13 holds the anodizing solution and includes a plurality of pass rollers 13a and 13b. The base film 2 is immersed in the anodizing solution by passing between the pass rollers 13a and 13b. A cathode 14 is arranged inside the anodic oxidation bath 13 so as to face the metal film 3. The cathode 14 is connected to the cathode of the constant voltage source 21, and the anode of the external power supply 21 is connected to the metal film 3 via the metal roller 12. The metal roller 12
The metal film 3 on the base film 2 conveyed while being immersed in the anodizing solution is always provided in a position not immersed in the anodizing solution in order to keep the metal film 3 electrically connected to the external power supply 21. The wall of the anodic oxidation bath 13 is insulated from the ground so that the current supplied from the external power supply 21 flows between the anode (metal film 3) and the cathode 14, and the metal oxide film 4 grows by anodic oxidation. State. Furthermore, a roll (pass roller 13b, a pass roller 15b in a washing tank 15 described later, a pass roller 17b in a drying device 17, and a roll that contacts the metal film 3 on the base film 2 other than the metal roller 12 described above)
b) is insulated from ground.

The above-mentioned cathode 14 is parallel to the surface of the metal layer 3 on the base film 2 conveyed in the anodizing solution, and is the same as the metal film 3 immersed in the anodizing solution. This is an electrode having a small area. Such a cathode 14
It is made of a material such as Pt having a lower ionization rate than hydrogen. Also, the anodizing solution is citric acid, ammonium borate,
It is an aqueous solution of ammonium tartrate, oxalic acid or the like. However, when the metal film 3 containing Al is anodized, in order to prevent the formed oxide film from dissolving and forming a porous film, ethylene glycol or the like is used as a solvent, or an alkali such as ammonia is used. It is necessary to adjust the pH of the anodic oxidation solution to around 7 by adding it.

The current during anodic oxidation in the anodic oxidation bath 13 can be set as appropriate. In addition, the thickness of the metal oxide film generated by anodic oxidation increases in proportion to the applied voltage. However, if the applied voltage is too high, the base film and the generated metal oxide film cause dielectric breakdown and are damaged. Therefore, care must be taken when the applied voltage is high or when the thickness of the base film or the thickness of the metal oxide film 4 to be formed is small.

The thickness of the metal oxide film 4 formed by anodic oxidation in the anodic oxidation bath 13 is 5 to 30 as described above.
It can be set in the range of 0 nm, preferably 10 to 100 nm. In such anodic oxidation, even if a defect such as a pinhole is present in the metal film 3 before the metal oxide film 4 is formed, the metal film 3 is increased due to an increase in volume caused by the metal being combined with oxygen in the anodic oxidation. Will be filled in. Even if a defect exists in the metal oxide film 4 during the formation, the resistance of the metal oxide film is 10 ⁶ to 10 ⁷ V / cm.
Since this is as high as possible, a large amount of current flows to a defect portion having a small thickness and a relatively low resistance in the metal oxide film. As a result, more metal oxide is formed at the defective portion, and a metal oxide film 4 having no defect can be obtained.

Base film 2 on which metal oxide film 4 is formed
Is sent to the cleaning tank 15, and the pass rollers 15a, 15b
It is washed with water by passing through the space to remove the anodizing solution. Then, pass roller 17 in drying device 17
a, 17b, and is dried and taken up by a winding roll 19
It is wound up.

According to the method for producing a gas barrier film of the present invention, a sheet-like base film 2 on which a metal film 3 is formed
Can be batch processed to produce the gas barrier film 1. In this case, in anodic oxidation, first, a constant current is applied between the anode (metal film 3) and the cathode to gradually form a metal oxide film. Since the applied voltage increases as a metal oxide film having a large resistance is formed, when the desired voltage is reached, the applied voltage value is fixed, and anodic oxidation is performed until the current value decreases to some extent.

Laminated Material Next, the laminated material of the present invention will be described with reference to an example using the above-described gas barrier film 1 of the present invention.

FIG. 3 is a schematic sectional view showing an embodiment of the laminated material of the present invention. In FIG. 3, a laminated material 31 includes a metal film 3 formed on one surface of a base film 2, a gas barrier film 1 including a metal oxide film 4 formed on the metal film 3, and a gas barrier film An anchor coating agent layer and / or an adhesive layer 3 on the metal oxide film 4 of the film 1
2 and a heat-sealable resin layer 33 formed therebetween.

The anchor coating agent layer 32 constituting the laminated material 31 uses, for example, an organic titanium anchor coating agent such as alkyl titanate, an isocyanate anchor coating agent, a polyethyleneimine anchor coating agent, a polybutadiene anchor coating agent, or the like. Can be formed. The anchor coating agent layer 32 is formed by coating the above anchor coating agent with a known coating method such as roll coating, gravure coating, knife coating, dip coating, spray coating, etc. Drying and removal can be performed. The coating amount of the above anchor coating agent is 0.1 to 5 g / m.
^{About 2} (dry state) is preferable.

The adhesive layer 32 constituting the laminated material 31
For example, polyurethane-based, polyester-based, polyamide-based, epoxy-based, poly (meth) acryl-based, polyvinyl acetate-based, polyolefin-based, casein, wax,
Using various types of laminating adhesives, such as solvent-based, aqueous-based, solvent-free, or hot-melt-based adhesives, whose main components are vehicles such as ethylene- (meth) acrylic acid copolymer and polybutadiene. Can be formed. The adhesive layer 32 is formed by coating the above-mentioned laminating adhesive by, for example, roll coating, gravure coating, knife coating, deb coating, spray coating, or other coating methods, and drying and removing a solvent, a diluent, and the like. You can do it. The amount of the laminating adhesive applied is preferably about 0.1 to 5 g / m ² (dry state).

Examples of the heat-sealing resin used for the heat-sealing resin layer 33 constituting the laminated material 31 include resins which can be melted by heat and fused to each other.
Specifically, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene Methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, polybutene polymer, polyolefin resin such as polyethylene or polypropylene, acrylic acid, methacrylic acid, maleic acid, maleic anhydride An acid-modified polyolefin resin modified with an unsaturated carboxylic acid such as an acid, fumaric acid, and itaconic acid, a polyvinyl acetate resin, a poly (meth) acrylic resin, a polyvinyl chloride resin, and the like can be used. The heat-sealable resin layer 33 may be formed by applying the heat-sealable resin as described above, or may be formed by laminating a film or sheet made of the heat-sealable resin as described above. . The thickness of the heat-sealing resin layer 33 is 5 to 300 μm, preferably 10 to 100 μm.
Can be set within the range.

FIG. 4 is a schematic sectional view showing another embodiment of the laminated material of the present invention. In FIG. 4, a laminated material 41 includes a metal film 3 formed on one surface of a base film 2, a gas barrier film 1 having a metal oxide film 4 formed on the metal film 3, and a gas barrier film 1. A heat-sealable resin layer 43 formed on the metal oxide film 4 of the film 1 via an anchor coat agent layer and / or an adhesive layer 42;
A substrate 44 provided on the other surface of the substrate film 2 of the gas barrier film 1.

The anchor coat agent layer, the adhesive layer 42 and the heat-sealing resin layer 43 constituting the laminated material 41
It can be the same as the anchor coat agent layer, the adhesive layer 32, and the heat-sealable resin layer 33 that constitute the laminated material 31 described above, and the description is omitted here.

As the base material 44 constituting the laminated material 41,
For example, when the laminated material 41 constitutes a packaging container, since the base material 44 is a basic material, it has excellent properties in mechanical, physical, chemical, etc., and particularly has strength. A resin film or sheet which is strong and tough and has heat resistance can be used. Specifically, stretching of strong resin such as polyester resin, polyamide resin, polyaramid resin, polyolefin resin, polycarbonate resin, polystyrene resin, polyacetal resin, fluorine resin, etc. (uniaxial or biaxial) Or an unstretched film or sheet can be mentioned. The thickness of the base material 44 is desirably about 5 to 100 μm, preferably about 10 to 50 μm.

In the present invention, a desired printed pattern such as a character, a figure, a symbol, a picture, a pattern, or the like, is printed on the base material 44 by a normal printing method. Is also good.

Further, in the present invention, for example, various paper substrates constituting a paper layer can be used as the substrate 44. Specifically, it is a paper substrate having shapeability, bending resistance, rigidity, etc., for example, a strong size bleached or unbleached paper substrate, or pure white roll paper, kraft paper, paperboard, processed Paper substrates such as paper can be used. Examples of such paper substrates, of the order of a basis weight of about 80~600g / m ^2, preferably, it is desirable to use of about a basis weight of about 100~450g / m ^2.

In the present invention, as the substrate 44, the above-mentioned resin film or sheet and the above-mentioned paper substrate can be used in combination.

FIG. 5 is a schematic sectional view showing another embodiment of the laminated material of the present invention. In FIG. 5, a laminated material 51 includes a metal film 3 formed on one surface of a base film 2, a gas barrier film 1 including a metal oxide film 4 formed on the metal film 3, and a gas barrier film 1. A heat-sealable resin layer 53 formed on the metal oxide film 4 of the film 1 via an anchor coat agent layer and / or an adhesive layer 52;
The gas barrier film 1 includes a substrate 54 provided on the other surface of the substrate film 2 of the gas barrier film 1, and a heat-sealing resin layer 55 formed on the substrate 54.

The anchor coat agent layer, the adhesive layer 52 and the heat-sealable resin layers 53 and 5 constituting the laminated material 51.
5 can be the same as the anchor coat agent layer, the adhesive layer 32 and the heat-sealable resin layer 33 constituting the laminated material 31 described above, and the base material 54 constituting the laminated material 51 is Since it can be the same as the base material 44 forming the laminated material 41, the description is omitted here.

The laminated material of the present invention further includes, for example, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, ethylene-propylene having a barrier property against water vapor, water and the like. Use of a resin film or sheet such as a copolymer, or a resin film or sheet such as polyvinylidene chloride, polyvinyl alcohol, or a saponified ethylene-vinyl acetate copolymer having a barrier property against oxygen, water vapor, and the like. Can be.

These materials can be used alone or in combination of two or more, and the thickness is optional.
Usually, it is about 5 to 300 μm, preferably about 10 to 100 μm.

Further, when the laminated material of the present invention is used for packaging, the packaging is usually subjected to severe physical and chemical conditions, so that the laminated material is also strict. Packaging suitability is required. Specifically, deformation prevention strength, drop impact strength, pinhole resistance, heat resistance, sealability,
Various conditions such as quality preservation, workability, hygiene, etc. are required. For this reason, the laminated material of the present invention is arbitrarily selected from materials satisfying the above-mentioned various conditions, It can be used as the film 1, the substrates 44, 54, or other components. Specifically, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ionomer resin, ethylene-ethyl acrylate Polymer, ethylene-acrylic acid or methacrylic acid copolymer, methylpentene polymer, polybutene resin, polyvinyl chloride resin, polyvinyl acetate resin, polyvinylidene chloride resin, vinyl chloride-vinylidene chloride copolymer, poly (Meth) acrylic resin, polyacrylonitrile resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyester resin, polyamide resin , Polycarbonate Resin,
Polyvinyl alcohol resin, saponified ethylene-vinyl acetate copolymer, fluorine resin, diene resin, polyacetal resin, polyurethane resin, nitrocellulose, etc. can do. In addition, for example, a film such as cellophane, synthetic paper, or the like can be used.
The above-mentioned film or sheet may be any of unstretched and uniaxially or biaxially stretched. The thickness is arbitrary, but is from several μm to 3 μm.
It can be used by selecting from a range of about 00 μm,
The lamination position is not particularly limited. In the present invention,
The film or sheet may be a film having any property such as extrusion film formation, inflation film formation, and coating film.

The laminated materials of the present invention, such as the laminated materials 31, 41 and 51 described above, can be formed by laminating ordinary packaging materials, for example, wet lamination, dry lamination, solventless dry lamination, extrusion lamination. It can be manufactured using a T-die extrusion molding method, a co-extrusion lamination method, an inflation method, a co-extrusion inflation method, or the like.

When performing the above lamination, if necessary,
For example, a film can be subjected to a pretreatment such as a corona treatment and an ozone treatment. For example, an anchor coating agent such as an isocyanate (urethane), polyethyleneimine, polybutadiene, and organic titanium, or a polyurethane, Known adhesives such as polyacrylic, polyester-based, epoxy-based, polyvinyl acetate-based, and cellulose-based adhesives for lamination can be used.

[0050]

Next, the present invention will be described in more detail with reference to examples.

Example 1 A base film having a thickness of 50
An Al film (film thickness 100 nm) was formed on one surface of a μm polyethylene terephthalate film (Toyobo Co., Ltd. E5100) using an EB vapor deposition apparatus under the following conditions. Conditions for forming an Al film in an EB vapor deposition apparatus : Vapor deposition raw material: Al Reaction pressure: 7.0 × 10 ⁻⁶ Torr

On the other hand, tartaric acid was dissolved in ethylene glycol, and the pH was adjusted to 7.0 with ammonia to prepare an anodized solution having a tartaric acid concentration of 0.3% by weight.

Next, the above-mentioned substrate film was immersed in this anodic oxidation solution, and the Al film was connected to the anode of an external power supply. Further, a Pt electrode having the same area as that of the base film was disposed in parallel with the anode at a distance between the electrodes of 20 mm, and this Pt electrode was disposed.
The electrodes were connected to the cathode of a constant voltage source.

Next, first, 0.1 mA / c was applied between the positive and negative electrodes.
A constant current of m ² was passed, and when the applied voltage became 11 V, a current was passed at a constant voltage. And the current density is 0.0
The anodic oxidation was terminated when the current decreased to 1 mA / cm ² .

Next, the substrate film was taken out of the anodizing solution, washed with pure water, and dried in an oven at 50 ° C. to obtain a gas barrier film (Example 1). The thickness of the anodic oxide film (AlO _x film) formed on the Al film of the gas barrier film (Example 1) was measured by an ellipsometer and is shown in Table 1 below.

(Example 2) In the same manner as in Example 1, an anodic oxidation solution having an ammonium citrate concentration of 0.3% by weight was used.
Was prepared. A gas barrier film (Example 2) was produced in the same manner as in Sample 1, except that this anodizing solution was used. The thickness of the anodic oxide film (AlO _x film) formed on the Al film of the gas barrier film was measured in the same manner as in Example 1 and is shown in Table 1 below.

(Comparative Example 1) A base film having a thickness of 50
A gas barrier film (Comparative Example 1) was formed by forming an AlO _x film (film thickness 280 nm) on one surface of a μm polyethylene terephthalate film (Toyobo Co., Ltd. E5100) under the following conditions using an EB vapor deposition apparatus. Was prepared. Conditions for forming an AlO _x film in an EB vapor deposition apparatus・ Evaporation raw material: Al · O ₂ flow rate: 30 sccm ・ Reaction pressure: 1.1 × 10 ⁻⁵ Torr

Comparative Example 2 An Al film (thickness: 100 nm) was formed in the same manner as in Example 1, and a gas barrier film (Comparative Example 2) was formed without performing anodic oxidation.

(Comparative Example 3) First, in the same manner as in Example 1,
An Al film (film thickness 100 nm) was formed. Then, the embodiment
Using the same anodic oxidation solution as in Example 1, 0.1 mA between positive and negative electrodes
/ Cm ^Two And the applied voltage became 3.3 V
By the way, a current was applied at a constant voltage. And the current density is
0.01 mA / cm^Two Where the anodization occurs
finished.

Next, the substrate film was taken out of the anodizing solution, washed with pure water, and dried in an oven at 50 ° C. to obtain a gas barrier film (Comparative Example 3). The thickness of the anodic oxide film (AlO _x film) formed on the Al film of the gas barrier film was measured in the same manner as in Example 1 and is shown in Table 1 below.

(Comparative Example 4) First, an Al film (film thickness 5) was formed in the same manner as in Example 1 except that the film forming conditions were set as follows.
00 nm). Conditions for forming an Al film in an EB vapor deposition apparatus : Vapor deposition raw material: Al Reaction pressure: 7.0 × 10 ⁻⁶ Torr

Next, using the same anodic oxidation solution as in Example 1, a constant current of 0.1 mA / cm ² was passed between the positive and negative electrodes. When the applied voltage reached 385 V, a current was passed at a constant voltage. . When the current density decreased to 0.01 mA / cm ² , the anodic oxidation was terminated.

Next, the substrate film was taken out of the anodizing solution, washed with pure water, and then dried in an oven at 50 ° C. to obtain a gas barrier film (Comparative Example 4. On the Al film of this gas barrier film, Anodic oxide film (A
The thickness of (IO _x film) was measured in the same manner as in Example 1, and
It was shown to.

(Evaluation) Each gas barrier film produced as described above (Examples 1 and 2 and Comparative Examples 1 to 4)
Was measured under the following conditions, and the results are shown in Table 1 below. Oxygen gas permeability measurement conditions / measurement equipment: MOCON O manufactured by Modern Control
XTRAN ・ Measurement atmosphere: 23 ° C, 0% RH water vapor transmission rate Measurement conditions・ Measuring equipment: MOCON P manufactured by Modern Control
ERMATRAN ・ Measurement atmosphere: 38 ° C, 100% RH

[0065]

[Table 1] As shown in Table 1, the gas barrier films of the present invention (Examples 1 and 2) have extremely high gas barrier properties (oxygen gas permeability is 0.3 [cc / m ² / day] or less, and The water vapor transmission rate is 0.3 [g / m ² / da
y] below).

However, in Comparative Example 1 in which the barrier layer was composed of only an AlO _x film, the gas barrier properties were significantly lower than in Examples 1 and 2. In addition, an anodic oxide film (AlO
Comparative Example 2 in which no _x- film) was formed, and Comparative Example 3 in which the thickness of the anodic oxide film (AlO _x film) was small,
The gas barrier properties were inferior to those of No. 2. further,
Comparative Example 4, in which the thickness of the anodic oxide film (AlO _x film) is large,
Cracks occurred in the anodic oxide film, and gas barrier properties were inferior to those of Examples 1 and 2.

[0067]

As described above in detail, according to the present invention, even if a defect such as a pinhole is present in the metal film before the metal oxide film is formed, the metal is combined with oxygen in the anodic oxidation. Defects existing in the metal film are filled by the increase in volume, and even if defects exist in the metal oxide film during formation,
Since a large amount of current flows through a relatively low-resistance defect portion in a high-resistance metal oxide film, a metal oxide is formed.
A metal oxide film having no defect is formed, and the lamination of such a metal film and a metal oxide film formed on the metal film by anodic oxidation exhibits extremely high gas barrier properties. Also,
A laminated material using this gas barrier film has, in addition to the gas barrier properties described above, a post-processing suitability with a heat-sealing resin layer, and a packaging container made or bagged using such a laminated material. Has excellent suitability for filling and packaging the contents.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view showing one embodiment of a gas barrier film of the present invention.

FIG. 2 is a schematic diagram illustrating an example of an anodizing step in the method for producing a gas barrier film of the present invention.

FIG. 3 is a schematic cross-sectional view showing one embodiment of a laminated material using the gas barrier film of the present invention.

FIG. 4 is a schematic sectional view showing another embodiment of a laminated material using the gas barrier film of the present invention.

FIG. 5 is a schematic cross-sectional view showing another embodiment of a laminated material using the gas barrier film of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Gas barrier film 2 ... Base film 3 ... Metal film 4 ... Metal oxide film 12 ... Metal roller 13 ... Anodizing bath 14 ... Cathode 15 ... Cleaning tank 17 ... Drying device 21 ... External power supply 31, 41, 51 ... Lamination Materials 32, 42, 52: Anchor coating agent layer, adhesive layer 33, 43, 53: Heat sealing resin layer 44, 54: Base material 55: Heat sealing resin layer

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F100 AA17C AB01B AB10B AB11B AB19B AB20B AB40B AK01D AK42A AT00A BA04 BA07 BA10A BA10C BA10D EH66B EH661 EJ122 EJ612 GB15 GB41 JA20C JD03 JD04 JL12Y JC02Y

Claims (9)

[Claims] A substrate film, a metal film provided on at least one surface of the substrate film, and a metal oxide film formed by anodizing the metal film; 0.3 [cc / m ² / day] or less and a water vapor permeability of 0.3 [g / m ² / day] or less. 2. The method according to claim 1, wherein said metal oxide film has a thickness of 5 to 300 nm.
The gas barrier film according to claim 1, wherein the gas barrier film falls within the range. 3. The metal film is made of Al, Si, Ta, N
3. The gas barrier film according to claim 1, wherein the gas barrier film is made of at least one metal selected from the group consisting of b, V, Bi, Y, W, Mo, Zr, and Hf. 4. 4. A vacuum deposition method, an ion plating method,
A metal film is formed on at least one surface of the base film by any one of a sputtering method and a chemical vapor deposition method, and then the metal film is immersed in an anodic oxidation solution while being connected to an anode of an external power supply. Forming a metal oxide film on the metal film by anodic oxidation by energizing the gas barrier film so as to face the cathode. 5. A laminated material, wherein a heat-sealing resin layer is provided on at least one surface of the gas barrier film according to claim 1. 6. A laminated material, wherein a heat-sealing resin layer is provided on a metal oxide film of the gas barrier film according to any one of claims 1 to 3. 7. The laminated material according to claim 6, wherein a substrate is laminated on a substrate film on which no metal oxide film is formed. 8. The laminated material according to claim 7, wherein a heat-sealing resin layer is provided on the base material. 9. The laminate according to claim 5, wherein an anchor coat agent layer and / or an adhesive layer are provided between the metal oxide film and the heat-sealing resin layer. .