JP2012172101A - Gas-barrier film, and method of manufacturing the same - Google Patents

Abstract

Provided is a gas barrier film that realizes high-speed inline processing of a gas barrier layer on a web-like substrate, has high production efficiency, and can improve adhesion durability between the substrate and the gas barrier layer, and a method for producing the same. To do.
In a reactive ion etching (RIE) processing apparatus configuration in which a metal roll electrode as a high-frequency application electrode and a ground electrode are arranged, an inert gas is introduced between the electrodes at a pressure of 0.5 Pa or more and less than 50 Pa. A high-frequency voltage having a specific value is applied between electrodes at a specific interval to generate a high-density plasma, and the surface of the plastic film 100 is subjected to plasma treatment between the gas barrier layer 102 made of a base material and silicon oxide (SiOx). A gas-barrier film and a method for producing the same, characterized by providing sufficient adhesion performance.
[Selection] Figure 1

Description

  The present invention relates to a gas barrier film and a method for producing the same, and relates to, for example, a functional film having a gas barrier property used in the packaging field of foods and pharmaceuticals, a protective sheet for solar cells, and the like, and a method for producing the functional film.

  The gas barrier performance of water vapor and oxygen has recently attracted much attention as a protective sheet application for organic EL displays and thin-film solar cells, in addition to conventional applications in the packaging field of foods and pharmaceuticals. Among them, the protective sheet for the solar cell is disposed on the back side of the solar cell in order to prevent deterioration due to the humidity of the silicon thin film that is the electromotive part of the solar cell module, and shuts off oxygen and water vapor from the outside air. At the same time, even when used in harsh outdoor environments, there is a demand for durability performance with little appearance deterioration.

  Conventionally, foods, pharmaceuticals, and packaging materials used for packaging hard disks and semiconductor modules have been required for the purpose of protecting contents. For example, in food packaging, it is necessary to suppress oxidation and alteration and maintain taste and freshness. In addition, in pharmaceuticals that require handling in a sterile state, it is required to suppress the alteration of the active ingredient and maintain its efficacy. When protecting the quality of these contents, there is a need for a packaging material that has a gas barrier property that blocks oxygen, water vapor, and other gases that alter the contents, and durability that does not deteriorate in each environment of use. .

  As the gas barrier film, a large number of highly transparent gas barrier films in which a metal oxide film made of silicon oxide, aluminum oxide or the like is formed on the surface of a plastic film substrate are generally put into practical use. Patent Document 1 discloses a gas barrier film having silicon carbide oxide on a polymer resin film. Patent Document 2 discloses a gas barrier film in which an amorphous aluminum oxide thin film is provided on a transparent plastic substrate. However, even if these vapor-deposited films are simply laminated on a plastic substrate, the adhesion between the substrate and the vapor-deposited layer is not sufficient, and retort treatment, boil treatment, environmental resistance test, etc. It is often easy to peel off.

  Therefore, in order to improve the adhesion between the base material and the vapor deposition layer, a general surface treatment such as plasma treatment, flame treatment or corona treatment is applied to the base material surface (Patent Document 3), anchor coating Many methods for coating a layer by a wet method have been proposed (Patent Documents 4, 5, and 6). In particular, the surface treatment method using the low-pressure plasma treatment can realize simplification of the process by the treatment in the same system (in-line) as the vapor deposition layer forming process. However, since the in-line contact process requires a processing speed equivalent to that of a high-speed vapor deposition process, sufficient contact processing cannot often be obtained. There is a demand for an in-line adhesion method that has a high production efficiency and can provide a strong adhesion.

JP 2008-179104 A JP 62-179935 A JP 2001-322200 A JP 2006-116703 A JP 2006-205533 A JP 2006-321194 A

  In the present invention, in order to solve the above problems, a high-speed in-line treatment of the gas barrier layer on the web-like substrate is realized, the production efficiency is high, and the adhesion durability between the substrate and the gas barrier layer is also improved. An object of the present invention is to provide a gas barrier film and a method for producing the same.

The invention according to claim 1 is a method for producing a gas barrier film in which a surface treatment by glow plasma and a gas barrier layer are formed in this order on a web-like substrate,
A metal roll electrode that is a high-frequency application electrode on which the substrate travels;
As a counter electrode, it is provided with a ground electrode arranged in a shape along the metal roll electrode in an arc shape or a multi-surface shape in which a pair of magnets of S / N poles are installed in a plane,
Using a reactive ion etching (RIE) processing apparatus installed at dmin ≦ 50 mm, where dmin is the shortest distance between the two electrodes,
One or more kinds of gases selected from nitrogen, helium and argon are introduced between the electrodes, the pressure in the processing space is set to 0.5 Pa or more and less than 50 Pa, and a high frequency of 30 kHz or more and 4 MHz or less is applied. The value obtained from the product of the power density (W / m ² ) calculated from the ratio of the power (W) input to the metal roll electrode and the area (m ² ) of the plasma irradiation portion and the processing time (sec) is the Epd value. When defined, the base material that travels on the metal roll electrode by generating a high-density plasma between the electrodes by applying a high-frequency voltage so that the Epd value is 350 W · sec / m ² or more. Forming a surface treatment layer on the surface;
And a step of forming a gas barrier layer made of silicon oxide (SiOx) on the surface treatment layer by a dry coating method.
Invention of Claim 2 is a manufacturing method of the gas barrier film of Claim 1 which processes the said surface treatment layer and the said gas barrier layer continuously in-line.
A third aspect of the present invention is the method for producing a gas barrier film according to the first or second aspect, wherein the pair of S · N pole pair magnets is a neodymium magnet.
Invention of Claim 4 is a manufacturing method of the gas-barrier film in any one of Claims 1-3 using a polyethylene terephthalate (PET) as said base material.
The gas barrier film according to any one of claims 1 to 4, wherein the silicon oxide (SiOx) has a value x of 1 ≦ x ≦ 2.2. It is a manufacturing method.
The invention described in claim 6 is characterized in that a protective layer formed by applying a mixed solution containing a metal alkoxide and a water-soluble polymer on the gas barrier layer and drying by heating is formed. It is a manufacturing method of the gas-barrier film in any one of -5.
The invention according to claim 7 is a method for producing a gas barrier film in which a surface treatment by glow plasma and a gas barrier layer are formed in this order on a web-like substrate,
A metal roll electrode that is a high-frequency application electrode on which the substrate travels;
As a counter electrode, it is provided with a ground electrode arranged in a shape along the metal roll electrode in an arc shape or a multi-surface shape in which a pair of magnets of S / N poles are installed in a plane,
Using a reactive ion etching (RIE) processing apparatus installed at dmin ≦ 50 mm, where dmin is the shortest distance between the two electrodes,
One or more kinds of gases selected from nitrogen, helium and argon are introduced between the electrodes, the pressure in the processing space is set to 0.5 Pa or more and less than 50 Pa, and a high frequency of 30 kHz or more and 4 MHz or less is applied. The value obtained from the product of the power density (W / m ² ) calculated from the ratio of the power (W) input to the metal roll electrode and the area (m ² ) of the plasma irradiation portion and the processing time (sec) is the Epd value. When defined, the base material that travels on the metal roll electrode by generating a high-density plasma between the electrodes by applying a high-frequency voltage so that the Epd value is 350 W · sec / m ² or more. Forming a surface treatment layer on the surface;
A gas barrier film produced by a production method comprising a step of forming a gas barrier layer made of silicon oxide (SiOx) on the plasma surface treatment layer by a dry coating method.
The invention according to claim 8 is the gas barrier film according to claim 7, wherein the plasma surface treatment layer and the gas barrier layer are continuously treated in-line.
A ninth aspect of the present invention is the gas barrier film according to the seventh or eighth aspect, wherein the magnet of the pair of S and N poles is a neodymium magnet.
The invention according to claim 10 is the gas barrier film according to any one of claims 7 to 9, wherein polyethylene terephthalate (PET) is used as the substrate.
The gas barrier film according to any one of claims 7 to 10, wherein the silicon oxide (SiOx) has an x value of 1 ≦ x ≦ 2.2. It is.
The invention described in claim 12 is characterized in that a protective layer formed by applying a mixed solution containing a metal alkoxide and a water-soluble polymer on the gas barrier layer and drying by heating is formed. It is a gas barrier film in any one of -11.

  According to the present invention, a gas barrier film capable of realizing high-speed in-line treatment of a gas barrier layer on a web-like substrate, having high production efficiency, and improving adhesion durability between the substrate and the gas barrier layer, and production thereof A method can be provided.

  The effect of increasing the adhesion is brought about by forming a treatment layer by plasma treatment as defined in the present invention between the substrate and the gas barrier layer. This makes it possible to maintain strong adhesion even after retort sterilization treatment, boil treatment, pressure cooker test (PCT), various environmental durability tests, and the like.

  In addition, since the vapor deposition and adhesion treatment capable of high-speed film formation can be processed in-line, productivity is greatly improved.

It is sectional drawing which shows an example of the gas barrier film of this invention. It is explanatory drawing of the apparatus which performs the surface treatment by a glow plasma on a web-like base material. It is explanatory drawing of the apparatus which performs the surface treatment by a glow plasma on a web-like base material. It is explanatory drawing of the manufacturing apparatus of the gas barrier film of this invention.

  Embodiments of the present invention will be described below.

  FIG. 1 is a cross-sectional view showing an example of the gas barrier film of the present invention. A gas barrier layer 102 made of silicon oxide formed by vapor deposition on one surface of a base material 100 made of a plastic film material via a surface treatment (adhesion treatment layer) 101 by plasma treatment according to the present invention, if necessary The protective layer 103 is formed.

  The base plastic film 100 is not particularly limited, and a known one can be used. Polyethylene terephthalate (PET) is particularly suitable, but other polyester films such as polyethylene naphthalate (PEN), polyolefin films such as polyethylene (PE) and polypropylene (PP), nylon-6, nylon-66. And polyamide films such as polystyrene film, polyamide film, polycarbonate film, polyacrylonitrile film, polyimide film, and cellulose film. Further, surface treatment such as corona treatment, and various known additives and stabilizers such as antistatic agents, ultraviolet ray preventing agents, plasticizers and lubricants may be used on the surface of the base material.

  The thickness of the substrate is not particularly limited, and is in the range of 6 to 100 μm in consideration of workability when forming the adhesion treatment layer and the gas barrier layer, and further, post-workability. Is preferred.

  Plasma treatment consisting of ion etching treatment is performed on the plastic film 100. One or more inert gases selected from nitrogen, helium and argon are introduced into the plasma processing space. Preferably, argon gas, which is extremely low in reactivity and is a relatively heavy gas, is preferable.

  In this case, when plasma treatment is performed by introducing a highly reactive gas such as oxygen, bonds resulting from the treatment gas are often formed on the surface of the plastic film. Since the bond by the plasma processing gas bonds with the plastic film with a weak force, sufficient adhesion cannot be obtained. Therefore, even if the bond by the plasma treatment shows sufficient adhesion to the gas barrier layer, sufficient adhesion cannot be obtained between the plastic film and adhesion strength cannot be obtained.

  In the treatment chamber of the adhesion treatment layer 101, the above gas is appropriately selected and the pressure is adjusted to be 0.5 Pa or more and less than 50 Pa. If the pressure is less than 0.5 Pa, the discharge is difficult to stabilize and a stable sample cannot be obtained. When the pressure is 50 Pa or more, the self-bias voltage decreases, and a sufficient ion etching effect cannot be obtained. Further, in the region of 40 Pa or more, the magnetic induction effect by the magnet installed on the ground electrode 2 is rapidly weakened. Therefore, it is preferable to carry out the treatment in a pressure band of 1 to 25 Pa.

As the plasma generating power source, a power source having a frequency of MF to RF frequency band of 30 kHz to 4 MHz is used. The power output is 350 W · the product of the power density (W / m ² ) calculated from the ratio of the electric power (W) input to the metal roll electrode and the area (m ² ) of the plasma irradiation portion and the processing time (sec). It is necessary to apply electric power that is at least sec / m ² . If it is weaker than this, sufficient processing cannot be performed on the plastic film.

  The gas barrier layer 102 formed on the adhesion treatment layer 101 will be described. As the gas barrier layer, silicon oxide is formed by a dry coating method. The gas barrier layer is a layer having transparency and gas barrier performance such as oxygen and water vapor. Preferably, when the chemical formula of silicon oxide is SiOx, the range of x is 1.0 ≦ x ≦ 2.2, whereby transparency and gas barrier properties can be obtained.

  The optimum thickness of the gas barrier layer 102 varies depending on the application and configuration and is not particularly limited, but generally a thickness in the range of 5 to 300 nm is preferably used. If the film thickness is less than 5 nm, the film thickness is not sufficient, and the function as a gas barrier layer cannot be sufficiently achieved. On the other hand, if the film thickness exceeds 300 nm, the flexibility cannot be maintained, and the thin film tends to crack. Moreover, productivity also deteriorates. In consideration of performance and productivity, a film thickness of 10-200 nm is more preferable.

  As a dry coating method for forming the gas barrier layer 102, a vacuum deposition method, a sputtering method, an ion plating method, a chemical vapor deposition method (CVD), or the like can be used. However, in consideration of productivity, the vacuum evaporation method is the optimum production method. As a heating method of the vacuum vapor deposition method, it is preferable to use any one of an electron beam heating method, a resistance heating method, and an induction overheating method. In order to improve the denseness of the deposited film, an assist method using plasma, an ion beam, or the like can be employed. By providing an adhesion treatment chamber in the preceding stage of such a coating treatment chamber, a gas barrier film having extremely good productivity and good adhesion can be produced continuously in-line.

  Further, a protective layer or an overcoat layer for improving post-processing suitability such as a laminate may be laminated on the gas barrier layer 102 made of an inorganic oxide. In this case, for example, a water-soluble polymer melted with water or a water / alcohol mixed solvent is mixed with a metal alkoxide that has been treated directly or previously hydrolyzed, and this mixed solution is mixed with an inorganic oxide. It can be formed by coating and drying. A silane coupling agent or the like may be added to the mixed solution.

  2 and 3 are explanatory views of an apparatus for performing surface treatment with glow plasma on a web-like substrate. However, the shape of the apparatus is not limited to the apparatus shown in FIGS.

  The metal roll electrode 1 is applied with a high frequency voltage of MF to RF band from a high frequency power source 3. The temperature of the metal roll electrode 1 is preferably adjusted from 20 ° C to 80 ° C. As the counter electrode, a ground electrode 2 arranged in a shape along the metal roll 1 in an arc shape or a multi-surface shape in which a pair of magnets 5 and 6 of S / N poles are installed in the plane is installed. FIG. 2 shows an arc-shaped ground electrode 2 that is substantially parallel to the surface of the metal roll electrode 1. FIG. 3 shows a polyhedral ground electrode 2 having a shape that substantially follows the surface of the metal roll electrode 1 and having a plurality of plate electrodes joined at the ends thereof. Reference numeral 4 denotes a gas introduction pipe. For example, as shown in FIGS. 2 and 3, the S / N pole pair of magnets 5 and 6 are installed on the metal roll electrode 1 side of the ground electrode 2 along the flow direction of the plastic film. . The installation location of the magnets 5 and 6 having a pair of S / N poles is not limited to the installation location shown in FIGS. 2 and 3, and can be installed in any plane of the ground electrode 2 as long as the plasma density can be increased. May be. Further, the shape of the magnets 5 and 6 and the number of S / N pole pairs are appropriately selected depending on the size of the apparatus, the degree of plasma density, and the like. In the present invention, it is preferable to use a neodymium magnet in view of the effect. At this time, dmin ≦ 50 mm is set, where dmin is the shortest distance connecting both electrodes. A plastic film which is a metal roll electrode processing substrate is formed with an adhesion processing layer 101 while running on the cathode side, that is, on the metal roll electrode 1. By installing the plastic film on the cathode side, the ions can efficiently collide with the base material, so that strong adhesion can be obtained. The positional relationship between the base material and the electrode arrangement is the same as in the reactive ion etching (RIE) process, and the RIE processing apparatus can be applied and developed as it is.

  FIG. 4 is an example of a gas barrier film manufacturing apparatus according to the present invention. According to the present invention, as shown in FIG. 4, the process of the adhesion processing layer and the gas barrier layer can be processed in-line in the same (vacuum chamber 7) system. That is, in the vacuum chamber 7, the web-shaped substrate is unwound from the unwinding roll 7, an adhesion treatment layer is formed in the plasma treatment chamber 10, and then a gas barrier layer is formed in the vapor deposition treatment chamber 11. It is wound up by a winding roll 9.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.

<Example 1>
An adhesion treatment layer was formed on the untreated surface of a polyethylene terephthalate (PET) film having a thickness of 12 μm under the following conditions. For the adhesion treatment layer, the apparatus shown in FIG. 2 was used.

Process gas: Argon pressure: 5Pa
Power supply frequency: 300 kHz
Input power: 350 W · sec / m ²
Line speed: 90m / min
Ground electrode magnet: Yes dmin: 45mm

  After the adhesion treatment was performed under the above conditions, a silicon oxide film having a thickness of 40 nm was laminated by vacuum vapor deposition using an electron beam heating method to prepare a gas barrier film.

<Example 2>
An adhesion treatment layer was formed on the untreated surface of a polyethylene terephthalate (PET) film having a thickness of 12 μm under the following conditions. For the adhesion treatment layer, the apparatus shown in FIG. 2 was used.

Process gas: Argon pressure: 20 Pa
Power supply frequency: 300 kHz
Input power: 1000 W · sec / m ²
Line speed: 90m / min
Ground electrode magnet: Yes dmin: 45mm

  After the adhesion treatment was performed under the above conditions, a silicon oxide film having a thickness of 40 nm was laminated by vacuum vapor deposition using an electron beam heating method to prepare a gas barrier film.

<Comparative Example 1>
An adhesion treatment layer was formed on the untreated surface of a polyethylene terephthalate (PET) film having a thickness of 12 μm under the following conditions.

Process gas: Argon pressure: 5Pa
Power supply frequency: 300 kHz
Input power: 350 W · sec / m ²
Line speed: 90m / min
Ground electrode magnet: None dmin: 45 mm

  After the adhesion treatment was performed under the above conditions, a silicon oxide film having a thickness of 40 nm was laminated by vacuum vapor deposition using an electron beam heating method to prepare a gas barrier film.

<Comparative example 2>
An adhesion treatment layer was formed on the untreated surface of a polyethylene terephthalate (PET) film having a thickness of 12 μm under the following conditions.

Process gas: Argon pressure: 5Pa
Power supply frequency: 300 kHz
Input power: 150 W · sec / m ²
Line speed: 90m / min
Ground electrode magnet: Yes dmin: 45mm

  After the adhesion treatment was performed under the above conditions, a silicon oxide film having a thickness of 40 nm was laminated by vacuum vapor deposition using an electron beam heating method to prepare a gas barrier film.

<Comparative Example 3>
An adhesion treatment layer was formed on the untreated surface of a polyethylene terephthalate (PET) film having a thickness of 12 μm under the following conditions.

Process gas: Oxygen pressure: 5Pa
Power supply frequency: 300 kHz
Input power: 500 W · sec / m ²
Line speed: 90m / min
Ground electrode magnet: Yes dmin: 45mm

  After the adhesion treatment was performed under the above conditions, a silicon oxide film having a thickness of 40 nm was laminated by vacuum vapor deposition using an electron beam heating method to prepare a gas barrier film.

<Comparative example 4>
A gas barrier film is formed by laminating a silicon oxide film having a thickness of 40 nm directly on an untreated surface of a polyethylene terephthalate (PET) film having a thickness of 12 μm by vacuum evaporation using an electron beam heating method without performing an adhesion treatment. Created.

On the films prepared in the above Examples and Comparative Examples, a solution in which A liquid and B liquid shown below were mixed to 6/4 at a blending ratio (wt%) was prepared, applied and dried by a gravure coating method, A protective layer having a thickness of 0.4 μm was formed.
Solution A: 89.6 g of hydrochloric acid (0.1N) was added to 10.4 g of tetraethoxysilane and stirred for 30 minutes to obtain a hydrolyzed solution having a solid content of 3 wt% (in terms of SiO ₂ ).
Liquid B: Polyvinyl alcohol 3 wt% water / isopropyl alcohol solution (water: isopropyl alcohol weight ratio 90:10).

  Furthermore, a laminate sample of the above gas barrier film / stretched nylon (15 μm) / unstretched polypropylene (70 μm) was prepared by dry lamination using a two-component curable polyurethane adhesive.

<Evaluation 1 Gas barrier properties>
The laminated sample was cut into A4 size, put 200 cc of tap water, sealed in a bag shape, and retort sterilized at 121 ° C. for 30 minutes. After the retort treatment, the gas barrier property after 24 hours and when the retort treatment was not performed (before the retort treatment) was measured using a water vapor permeability measuring device (Modern Control, MOCON PERMATRAN 3/33 40 ° C. 90% RH atmosphere). ,It was measured. The results are shown in Table 1.

<Evaluation 2 Adhesion>
The laminated sample was cut into A4 size, put 200 cc of tap water, sealed in a bag shape, and retort sterilized at 121 ° C. for 30 minutes. Within 2 hours after the retort treatment, the laminate strength of 180 degree peeling between the gas barrier film of the sample cut to a width of 15 mm and nylon was measured. A Tensilon universal testing machine RTC-1250 manufactured by Orientec was used for the test. The peeling rate was 300 mm / min, and the measurement was performed while the measurement site was wetted with water.

[Table 1]

  The gas barrier films prepared in Examples 1 and 2 showed good barrier performance and sufficient adhesion performance compared to the comparative example.

  Industrial applicability of the gas barrier film according to the present invention is considered to be a gas barrier film used in the packaging field of foods, pharmaceuticals, etc., and a back sheet of a solar cell.

DESCRIPTION OF SYMBOLS 100 ... Plastic film 101 ... Adhesion process layer 102 ... Gas barrier layer 103 ... Protective layer 1 ... Metal roll electrode 2 ... Ground electrode 3 ... High frequency power supply 4 ... Gas introduction Tube 5 ... Magnet N pole 6 ... Magnet S pole 7 ... Vacuum chamber 8 ... Unwinding roll 9 ... Winding roll 10 ... Plasma treatment chamber 11 ... Deposition treatment chamber

Claims (12)

A method for producing a gas barrier film in which a surface treatment with a glow plasma and a gas barrier layer are formed in this order on a web-like substrate,
A metal roll electrode that is a high-frequency application electrode on which the substrate travels;
As a counter electrode, it is provided with a ground electrode arranged in a shape along the metal roll electrode in an arc shape or a multi-surface shape in which a pair of magnets of S / N poles are installed in a plane,
Using a reactive ion etching (RIE) processing apparatus installed at dmin ≦ 50 mm, where dmin is the shortest distance between the two electrodes,
One or more kinds of gases selected from nitrogen, helium and argon are introduced between the electrodes, the pressure in the processing space is set to 0.5 Pa or more and less than 50 Pa, and a high frequency of 30 kHz or more and 4 MHz or less is applied. The value obtained from the product of the power density (W / m ² ) calculated from the ratio of the power (W) input to the metal roll electrode and the area (m ² ) of the plasma irradiation portion and the processing time (sec) is the Epd value. When defined, the base material that travels on the metal roll electrode by generating a high-density plasma between the electrodes by applying a high-frequency voltage so that the Epd value is 350 W · sec / m ² or more. Forming a surface treatment layer on the surface;
And a step of forming a gas barrier layer made of silicon oxide (SiOx) on the surface treatment layer by a dry coating method.   The method for producing a gas barrier film according to claim 1, wherein the surface treatment layer and the gas barrier layer are continuously treated in-line.   3. The method for producing a gas barrier film according to claim 1, wherein the pair of S · N pole pair magnets is a neodymium magnet. 4.   The method for producing a gas barrier film according to claim 1, wherein polyethylene terephthalate (PET) is used as the substrate.   5. The method for producing a gas barrier film according to claim 1, wherein the silicon oxide (SiOx) has a value x of 1 ≦ x ≦ 2.2.   6. The gas barrier according to claim 1, wherein a protective layer is formed by applying a mixed solution containing a metal alkoxide and a water-soluble polymer on the gas barrier layer and drying by heating. For producing a conductive film. A method for producing a gas barrier film in which a surface treatment with a glow plasma and a gas barrier layer are formed in this order on a web-like substrate,
A metal roll electrode that is a high-frequency application electrode on which the substrate travels;
As a counter electrode, it is provided with a ground electrode arranged in a shape along the metal roll electrode in an arc shape or a multi-surface shape in which a pair of magnets of S / N poles are installed in a plane,
Using a reactive ion etching (RIE) processing apparatus installed at dmin ≦ 50 mm, where dmin is the shortest distance between the two electrodes,
One or more kinds of gases selected from nitrogen, helium and argon are introduced between the electrodes, the pressure in the processing space is set to 0.5 Pa or more and less than 50 Pa, and a high frequency of 30 kHz or more and 4 MHz or less is applied. The value obtained from the product of the power density (W / m ² ) calculated from the ratio of the power (W) input to the metal roll electrode and the area (m ² ) of the plasma irradiation portion and the processing time (sec) is the Epd value. When defined, the base material that travels on the metal roll electrode by generating a high-density plasma between the electrodes by applying a high-frequency voltage so that the Epd value is 350 W · sec / m ² or more. Forming a surface treatment layer on the surface;
A gas barrier film produced by a production method comprising a step of forming a gas barrier layer made of silicon oxide (SiOx) on the plasma surface treatment layer by a dry coating method.   The gas barrier film according to claim 7, wherein the plasma surface treatment layer and the gas barrier layer are continuously treated in-line.   The gas barrier film according to claim 7 or 8, wherein the pair of S · N pole pairs or more are neodymium magnets.   The gas barrier film according to any one of claims 7 to 9, wherein polyethylene terephthalate (PET) is used as the base material.   11. The gas barrier film according to claim 7, wherein the silicon oxide (SiOx) has a value x of 1 ≦ x ≦ 2.2.   The gas barrier according to any one of claims 7 to 11, wherein a protective layer is formed by applying a mixed solution containing a metal alkoxide and a water-soluble polymer on the gas barrier layer and drying by heating. Sex film.

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