JP2000006297A - Gas barrier film and its manufacture, and laminated material in which gas barrier film is used - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier film having excellent gas barrier properties and causing no problem in view of food safety, a simple manufacturing method of such gas barrier film and a laminated material using the gas barrier film. SOLUTION: A gas barrier film 1 is provided with an aluminum layer 3 on at least one side of a base film 2 and an inorganic oxide thin film layer 4 on the aluminum layer 3. The aluminum layer 3 is formed on the base film 2 in a vacuum chamber by a method selected from vacuum metallizing, ion plating and spattering. Thereafter, the inorganic oxide thin film layer 4 is formed on the aluminum layer 3 by a method selected from spattering and an oxygen ion plasma method before the aluminum layer 3 contacts with other members in the vacuum chamber.

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 an aluminum layer and 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 Heretofore, gas barrier films having an aluminum layer have been used as packaging materials having good storage suitability for foods, pharmaceuticals and the like. Such a gas barrier film is obtained by forming an aluminum thin film on a base film, and the aluminum thin film can be formed by a winding type vacuum evaporation apparatus, a sputtering apparatus, an ion plating apparatus, or the like, but the apparatus configuration is simple. The vacuum deposition method is most often used in view of the fact that the film forming speed is high.

In general, a metal material such as aluminum has a high surface energy. However, usually, a metal oxide layer having a low surface energy is formed at a thickness of several tens of the outermost surface by contact with air. Therefore, even if a metal thin film is formed, a metal layer having high surface energy does not exist on the surface. However, in the gas barrier film having the aluminum layer, the aluminum thin film is formed on the substrate film in a vacuum chamber, and the aluminum thin film comes into contact with air until the batch film is opened to the atmosphere. Nothing. Therefore, no aluminum oxide layer is formed on the surface of the aluminum layer, and the aluminum layer has a high surface energy. When the surface of the aluminum thin film having a high surface energy comes into contact with the surface of another substance, for example, when it comes into contact with various rolls constituting a winding mechanism, or when it comes into contact with the back surface of the base film on the winding roll, it is extremely difficult. In some cases, the aluminum thin film formed on the base film may be peeled finely. When the aluminum thin film is peeled in this manner, the gas barrier property at that location is lost, which causes a reduction in the gas barrier property of the entire gas barrier film.

[0004]

In order to solve the above-mentioned problem, a polyfunctional acrylic monomer is applied in a vacuum chamber to the surface of an aluminum thin film formed on a base film, and is irradiated with an electron beam or ultraviolet rays. A method of protecting the surface of an aluminum thin film having high surface energy by irradiating and curing to form a resin thin film has been developed.

[0005] However, the above method requires a complicated mechanism for applying the polyfunctional acrylic monomer in a vacuum, and the polyfunctional acrylic monomer is expensive and
It is an unfavorable material in terms of food safety and has practical problems.

There is also a method in which an aluminum oxide thin film having a low surface energy is formed instead of an aluminum thin film. However, aluminum oxide which is a ceramic has poor flexibility, and when a gas barrier film is used as a soft packaging material, There is a problem that cracks occur and the barrier properties are reduced.

[0007] The present invention has been made in view of such circumstances, and a gas barrier film having excellent barrier properties and having no problem in food safety, and a gas barrier film having such a simple property. It is an object of the present invention to provide a manufacturing method and a laminated material using such a gas barrier film.

[0008]

In order to achieve the above object, a gas barrier film of the present invention comprises: a base film; an aluminum layer provided on at least one surface of the base film; And an inorganic oxide thin film layer provided on the aluminum layer.

Further, the gas barrier film of the present invention comprises:
The structure was such that the thickness of the inorganic oxide thin film layer was in the range of 10 to 500 °.

Further, the gas barrier film of the present invention comprises:
The aluminum layer was formed by vacuum evaporation, ion plating, or sputtering.

Further, the gas barrier film of the present invention has a structure in which the inorganic oxide thin film layer is an aluminum oxide thin film layer formed by subjecting the aluminum layer to oxygen ion plasma treatment.

The method for producing a gas barrier film of the present invention comprises forming an aluminum layer on at least one surface of a substrate film in a vacuum chamber by any one of a vacuum deposition method, an ion plating method, and a sputtering method. Before the aluminum layer comes into contact with other members in the vacuum chamber, an inorganic oxide thin film layer is formed on the aluminum layer by either a sputtering method or an oxygen plasma method.

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 constitution in which a heat-sealing resin layer is provided on the inorganic oxide thin film layer of the gas barrier film, and a base film on which the inorganic oxide thin film layer is not formed. The structure was such that a base material was laminated on the base material, and further the heat sealable resin layer was provided on the 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 inorganic oxide thin film layer and the heat sealing resin layer.

According to the present invention, the inorganic oxide thin film layer provided on the aluminum layer prevents the aluminum layer having a high surface energy from coming into direct contact with the surface of another substance and peeling off the gas. A high gas barrier property is imparted to the film, and a laminated material using the gas barrier film is imparted with post-processing suitability by the heat-sealing resin layer in addition to the above-described properties.

[0017]

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, an aluminum layer 3 formed on one surface of the base film 2, and an inorganic oxide thin film layer 4 formed on the aluminum layer 3. still,
The gas barrier film of the present invention may have an aluminum layer 3 and an inorganic oxide thin film layer 4 on both sides of the base film 2.

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 aluminum layer 3, and can be appropriately selected depending on the intended 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. Stretched (uniaxial or biaxial) or unstretched flexible resin film of unified saponified product, polyvinyl alcohol, polycarbonate resin, fluorine resin, polyvinyl acetate resin, acetal resin, polyester resin, polyamide resin, etc. Can be used. The thickness of the base film 2 is 5 to 500 μm, preferably 10 to 500 μm.
It can be set appropriately within the range of 100 μm.

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

The aluminum layer 3 constituting the gas barrier film 1 of the present invention functions as a barrier layer, and
Flexible, for example, gas barrier film 1
Is a layer for exhibiting stable gas barrier properties without cracking even when used as a soft packaging material. The thickness of the aluminum layer 3 varies depending on the type of the base film 2 to be used, the conditions for forming the aluminum layer 3, and the like, but is, for example, about 50 to 3000 °, preferably about 100 to 1000 °. Can be selected and set. In addition, this aluminum layer 3
Metals such as magnesium, calcium, potassium, sodium, titanium, zirconium, yttrium, carbon,
Nonmetallic elements such as boron, nitrogen and fluorine may be contained.

The inorganic oxide thin film layer 4 constituting the gas barrier film 1 of the present invention is a thin film of aluminum oxide, zinc oxide, titanium oxide, zirconium oxide, magnesium oxide, silicon oxide, or the like. 50
0 °, preferably in the range of 10 to 300 °. When the thickness of the inorganic oxide thin film layer 4 is less than 10 °, the strength of the inorganic oxide thin film layer 4 is insufficient, and when it exceeds 500 °, cracks are easily generated in the inorganic oxide thin film layer 4, which is not preferable. . Such an inorganic oxide thin film layer 4 has a high surface energy without deteriorating the flexibility of the aluminum layer 3.
It protects the surface. Method for Producing Gas Barrier Film Next, a method for producing a gas barrier film of the present invention will be described with reference to the formation of the aluminum layer 3 and the inorganic oxide thin film layer 4 on the base film 2 described above as an example.

The aluminum layer 3 is formed by a vacuum evaporation method,
It can be performed by any of an ion plating method and a sputtering method.

The formation of the aluminum layer 3 on the base film 2 by the vacuum deposition method uses aluminum as a raw material.
This can be heated and evaporated in a vacuum chamber to form a thin film on the base film 2 to form the aluminum layer 3.

The aluminum layer 3 is formed on the base film 2 by the ion plating method by using aluminum as a raw material, evaporating it in a vacuum chamber, ionizing it, and colliding with the base film 2 so as to collide with the aluminum layer 3. It can be.

In forming the aluminum layer 3 on the base film 2 by the sputtering method, a conventionally known sputtering method such as a high frequency sputtering method or a magnetron sputtering method can be used. The formation of the aluminum layer 3 on the base film 2 by the high-frequency sputtering method is performed by setting aluminum on the electrode surface using aluminum as a target material, introducing an inert gas such as an argon gas into the chamber, and reducing the pressure in the chamber to 0. 1-5
Pa, and a frequency of, for example, 13.5
By applying a voltage of several hundred volts at a high frequency of 6 MHz, a discharge is generated in the chamber to perform sputtering of the target material, thereby forming a thin film on the base film 2 to form the aluminum layer 3. it can. In addition, the formation of the aluminum layer 3 on the base film 2 by the magnetron sputtering method is the same as the above-described high-frequency sputtering method, except that a permanent magnet or an electromagnet is installed near an electrode on which a target material is installed to form a magnetic field. This is to form an aluminum thin film on the base film 2 by increasing the electron density of discharge and improving the efficiency of sputtering.

In the chamber in which the aluminum layer 3 is formed, the inorganic oxide thin film layer 4 is formed on the aluminum layer 3 such that the aluminum layer 3 is formed of another member, for example, a back surface of a base film on a transport roll or a take-up roll. Can be formed by any one of a sputtering method and an oxygen plasma method before contacting the substrate.

The inorganic oxide thin film layer 4 is formed by a sputtering method by using aluminum oxide as a target material,
Using a desired inorganic oxide such as zinc oxide, titanium oxide, zirconium oxide, magnesium oxide, or silicon oxide, high-frequency sputtering, magnetron sputtering, or the like can be used. In this case, a predetermined sputtering device is disposed downstream from the position where the aluminum layer 3 is formed.

In the formation of the inorganic oxide thin film layer 4 by the oxygen plasma method, a flat plate electrode is provided so as to face the aluminum layer 3, and the surroundings are surrounded by a shielding plate to confine oxygen gas, and the high frequency There are a method of generating plasma by applying electric power or DC power, a method of using a hollow cathode type plasma gun, and the like. Also in this case, the oxygen plasma processing apparatus is disposed downstream from the deposition position of the aluminum layer 3 in the chamber.

FIG. 2 is a schematic diagram showing an example of a roll-up type vacuum evaporation apparatus that can be used in the method for producing a gas barrier film of the present invention. In FIG. 2, a vacuum deposition apparatus 1
Reference numeral 1 denotes a vacuum chamber 12, a supply roll 13a, a take-up roll 13b, a coating drum 14 disposed in the chamber 12, a vapor deposition chamber 15 partitioned from the vacuum chamber 12 by partition plates 19, 19, and a vapor deposition chamber. 15, a crucible 16, an evaporation source 17,
Masks 18 and 18 are provided. Further, the inorganic oxide thin film forming means 2 is provided between the take-up roll 13b and the downstream side of the coating drum 14 in the chamber 12.
1 is provided. In the vacuum evaporation apparatus 11, the base film 2 fed from the supply roll 13 a in the vacuum chamber 12 passes through the coating drum 14 and enters the evaporation chamber 15. This deposition chamber 15
In the inside, aluminum evaporates from the evaporation source 17 heated by the crucible 16, and the evaporated aluminum adheres to the base film 2 located between the masks 18 and 18 on the cooled coating drum 14 and becomes aluminum. The layer 3 is formed. Next, the aluminum layer 3
The substrate film 2 on which the aluminum oxide film is formed is fed into the vacuum chamber 12, and the inorganic oxide thin film layer 4 is formed on the aluminum layer 3 by the inorganic oxide thin film forming means 21 composed of a sputtering device or a plasma oxygen ion gun as described above.
Is formed and then wound up on a winding roll 13b, whereby the gas barrier film 1 of the present invention can be manufactured. 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 an aluminum layer 3 formed on one surface of the base film 2,
A gas barrier film 1 having an inorganic oxide thin film layer 4 formed on the aluminum layer 3 and an anchor coat agent layer and / or an adhesive layer 32 on the inorganic oxide thin film layer 4 of the gas barrier film 1 And a heat-sealable resin layer 33 formed therebetween.

The anchor coating agent layer 32 constituting the laminated material 31 is made of, 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 that 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, the laminated material 41 includes an aluminum layer 3 formed on one surface of the base film 2.
And a gas barrier film 1 having an inorganic oxide thin film layer 4 formed on the aluminum layer 3, and an anchor coat agent layer and / or an adhesive layer on the inorganic oxide thin film layer 4 of the gas barrier film 1. And a heat-sealing resin layer 43 formed through the gas barrier film 1
And a substrate 44 provided on the other surface (the surface on which the inorganic oxide thin film layer is not formed) of the substrate film 2.

The anchor coat agent layer, the adhesive layer 42 and the heat-sealable 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 print pattern such as, for example, a character, a figure, a symbol, a picture, or a pattern is printed on the base material 44 by front printing or back printing by a normal printing method. Is also good.

Further, in the present invention, as the base material 44, for example, various paper base materials constituting a paper layer can be used. 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, the laminated material 51 includes an aluminum layer 3 formed on one surface of the base film 2.
And a gas barrier film 1 having an inorganic oxide thin film layer 4 formed on the aluminum layer 3, and an anchor coat agent layer and / or an adhesive layer on the inorganic oxide thin film layer 4 of the gas barrier film 1. 52, a heat-sealing resin layer 53 formed through
And a heat-sealing resin layer 55 formed on the other surface (the surface on which the inorganic oxide thin film layer is not formed) of the base film 2.

The anchor coating 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 the purpose of a packaging container, usually, the packaging container is 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 film or sheet is unstretched,
Any of those uniaxially or biaxially stretched can be used. The thickness is arbitrary,
It can be used by selecting from a range of about several μm to 300 μm, and the lamination position is not particularly limited. In the present invention, the film or sheet is formed by extrusion film formation,
Any film such as an inflation film or a coating film may be used.

The laminated material of the present invention, such as the laminated materials 31, 41, 51 described above, can be formed by laminating a usual packaging material, for example, a wet lamination method, a dry lamination method, a solventless dry lamination method, an 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-mentioned 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.

[0048]

Next, the present invention will be described in more detail with reference to examples. Example 1 A roll-shaped biaxially stretched polyethylene terephthalate film (Lumirror P-60 manufactured by Toray Industries, Inc., thickness 12 μm, width 660 mm, length 50) as a base film
00m) was prepared and mounted in a vacuum chamber of a roll-up type vacuum evaporation apparatus as shown in FIG. This vacuum deposition apparatus is provided with an oxygen plasma processing apparatus as a means for forming an inorganic oxide thin film between the film forming section of the coating drum and the take-up roll, at a position where surface treatment can be performed before coming into contact with other members. is there. Next, the ultimate vacuum degree of 1.0 × 10 ⁻⁵ Torr (1.3 × 10 ⁵ Torr) was applied to the inside of the chamber of the vacuum evaporation apparatus by an oil rotary pump and an oil diffusion pump.
^-3 Pa). In addition, aluminum fine particles (manufactured by Kojundo Chemical Laboratory Co., Ltd.) were prepared as a raw material (evaporation source) and placed in a copper crucible.

Next, the aluminum fine particles in the copper crucible are heated and evaporated by an electron beam heating device to form an aluminum thin film on the base film running on the coating drum, and then disposed downstream of the coating drum. Before the aluminum layer came into contact with other members in the chamber, the surface of the aluminum layer was subjected to oxygen plasma treatment to form an aluminum oxide layer (thickness: 100 °) by the provided oxygen plasma processing apparatus. Thus, a gas barrier film (Sample 1) of the present invention was obtained.

The output of the above electron beam heating device is 10 k
W, and the running speed of the base film was set to 300 m / min so that the aluminum layer thickness was 500 °. The oxygen plasma processing apparatus has a flat plate electrode (length: 100 mm, width: 660 mm) facing the drum and a shield plate for confining oxygen gas. The plate electrode has a high frequency of 13.56 MHz and 2.5 kW. Power was applied. The flow rate of the oxygen gas was set to 200 sccm, and the pressure of the plasma processing unit was set to 10 mTorr. Further, the thickness of the aluminum layer and the aluminum oxide layer were determined by a fluorescent X-ray analyzer (RIX-310, manufactured by Rigaku Corporation).
0) and the cross section was measured by electron microscope observation. Example 2 A roll-shaped biaxially stretched polyethylene terephthalate film (Lumirror P-60 manufactured by Toray Industries, Inc., thickness 12 μm, width 660 mm, length 50) as a base film
00m) was prepared and mounted in a vacuum chamber of a roll-up type vacuum evaporation apparatus as shown in FIG. In this vacuum evaporation apparatus, as a means for forming an inorganic oxide thin film, a high-frequency sputtering apparatus is provided between a film forming section of a coating drum and a take-up roll at a position where surface treatment can be performed before coming into contact with other members. . Next, the ultimate vacuum degree of 1.0 × 10 ⁻⁵ Torr (1.3 × 1) was set in the chamber of the vacuum evaporation apparatus by an oil rotary pump and an oil diffusion pump.
0 ^-3 Pa) pressure was reduced to. In addition, aluminum fine particles (manufactured by Kojundo Chemical Laboratory Co., Ltd.) were prepared as a raw material (evaporation source) and placed in a copper crucible. Further, a silicon dioxide sintered body (length: 100 mm, width: 660 mm, manufactured by Omiya Kasei Co., Ltd.) was placed on the electrode surface of the high-frequency sputtering device.

Next, the aluminum fine particles in the copper crucible were heated and evaporated by an electron beam heating device to form a thin film of aluminum on the base film running on the coating drum. At the same time, in a high-frequency sputtering device disposed downstream of the coating drum, a high-frequency power of 13.56 MHz and a power of 5 kW is applied to the electrode to generate a discharge in the chamber to sputter the target material (silicon dioxide). Then, a silicon oxide thin film layer (thickness: 20) is formed on the surface of the aluminum layer.
0 °). The running speed of the base film was set at 300 m / min so that the thickness of the aluminum layer was 500 °. Thus, a gas barrier film (Sample 2) of the present invention was obtained.

Incidentally, the thickness of the aluminum layer and the aluminum oxide layer were measured using a fluorescent X-ray analyzer (RIX manufactured by Rigaku Corporation).
-3100) and an electron microscope observation of the cross section. Comparative Example 1 A gas barrier film (Comparative Sample 1) was obtained in the same manner as in Example 1 except that the aluminum oxide layer was not formed by the oxygen plasma treatment. (Evaluation) The oxygen permeability of each gas barrier film (Sample 1, 2 and Comparative Sample 1) prepared as described above was determined by
Oxygen gas permeability measuring device (OX manufactured by Modern Control)
TRAN 2/20), temperature 23 ° C, humidity 50%
Measured at RH. As a result, as shown below, each of the gas barrier films of the present invention (samples 1 and 2) showed high oxygen barrier properties. However, in the comparative gas barrier film (Comparative Sample 1), a decrease in the oxygen barrier property, which is considered to be caused by peeling-off of the aluminum layer during the manufacturing process, was observed.

Measurement result of oxygen permeability Sample 1: 0.5 (cc / cm ² · day · atm) Sample 2: 0.7 (cc / cm ² · day · atm) Comparative sample 1: 2.5 (cc / Cm ²・ day ・ atm)

[0054]

As described above in detail, according to the present invention, an aluminum layer and an inorganic oxide thin film layer are laminated on at least one surface of a substrate film to form a gas barrier film,
The above aluminum layer is formed by a vacuum deposition method, an ion plating method, and a sputtering method.
An inorganic oxide thin film layer is formed on the aluminum layer by either a sputtering method or an oxygen plasma method before the aluminum layer is formed on the base film in the vacuum chamber and then comes into contact with other members in the vacuum chamber. Is formed, the inorganic oxide thin film layer prevents the aluminum layer having a high surface energy from directly contacting and adhering to the surface of another substance, preventing the aluminum layer from peeling off and having an excellent gas barrier property. Gas barrier film, since the conductive film is possible, and the inorganic oxide thin film layer has no problem in food safety, and the lamination of the aluminum layer and the inorganic oxide thin film layer is flexible and does not crack. Is also suitable for use as a soft packaging material, and is also suitable for forming an inorganic oxide thin film layer on an aluminum layer. Does not require a complicated mechanism such as a coating mechanism in vacuum, the effect of the manufacturing facilities of the gas barrier film having a conventional aluminum layer can be used are achieved. In addition, the laminated material using the gas barrier film has, in addition to the above-described properties, post-processing suitability with a heat-sealing resin layer, and was formed into a bag or a box using such a laminated material. The packaging container 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 configuration diagram illustrating an example of a vacuum evaporation apparatus used 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 ... Aluminum layer 4 ... Inorganic oxide thin film layer 11 ... Vacuum evaporation device 12 ... Vacuum chamber 14 ... Coating drum 15 ... Vapor deposition chamber 17 ... Raw material 21 ... Inorganic oxide thin film layer forming means 31, 41, 51 ... laminated material 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

Continued on the front page F-term (reference) 4F100 AA00D AA00E AA19D AA19E AB10B AB10C AK41 AR00E AT00A BA05 CB00 CB03 EH66B EH66C EH662 EJ38 EJ58D EJ58E EJ582 EJ61D EJ61E EJ613 J15JD12J03 J15JD12J03

Claims (10)

[Claims] 1. A gas barrier property comprising: a base film; an aluminum layer provided on at least one surface of the base film; and an inorganic oxide thin film layer provided on the aluminum layer. the film. 2. The inorganic oxide thin film layer has a thickness of 10 to 5
The gas barrier film according to claim 1, wherein the thickness is in the range of 00 °. 3. The gas barrier film according to claim 1, wherein the aluminum layer is formed by any one of vacuum deposition, ion plating, and sputtering. 4. The method according to claim 1, wherein the inorganic oxide thin film layer is an aluminum oxide thin film layer formed by subjecting the aluminum layer to oxygen ion plasma treatment. Gas barrier film. 5. A vacuum deposition method, an ion plating method,
And, by any of the sputtering methods, an aluminum layer is formed on at least one surface of the base film in the vacuum chamber, and before the aluminum layer contacts another member in the vacuum chamber, the aluminum layer is formed on the aluminum layer. A method for producing a gas barrier film, comprising forming an inorganic oxide thin film layer by one of a sputtering method and an oxygen plasma method. 6. A laminated material, wherein a heat-sealing resin layer is provided on at least one surface of the gas barrier film according to any one of claims 1 to 4. 7. A laminated material, wherein a heat-sealing resin layer is provided on the inorganic oxide thin film layer of the gas barrier film according to any one of claims 1 to 4. 8. The laminate according to claim 7, wherein a substrate is laminated on a substrate film on which no inorganic oxide thin film layer is formed. 9. The laminated material according to claim 8, further comprising a heat-sealing resin layer on the base material. 10. The method according to claim 6, further comprising an anchor coating agent layer and / or an adhesive layer between the inorganic oxide thin film layer and the heat-sealing resin layer. Laminated material.