JP2012193449A - Gas barrier film, and method and device for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier film having excellent adhesion as compared with conventional ones, with high production efficiency, through the formation of an adhesion layer and a gas barrier layer by means of an in-line deposition.SOLUTION: When an adhesion layer 2, which comprises silicon oxide and is formed by means of a plasma-chemical vapor-phase epitaxy system, and a gas barrier layer 3 are formed on a plastic film 1 serving as a base material, a metal roll electrode, on which the base material 1 runs, and a circular arc-like earthed electrode, which includes a magnet with one pair or more of S-N poles installed in a plane thereof, as a counter electrode, are provided; a high frequency wave of 10 kHz or higher and 30 MHz or lower is applied between the electrodes, while a pressure in a processing space is set at 0.5 Pa or higher and 20 Pa or lower by introducing, for example, hexamethyldisiloxane and oxygen, to form the adhesion layer 2 on a surface of the base material 1; and further the silicon oxide gas barrier layer 3 is formed on the adhesion layer.

Description

  TECHNICAL FIELD The present invention relates to a back barrier sheet for a solar cell, a gas barrier film used in the packaging field of foods, pharmaceuticals, and the like, a manufacturing method thereof, and a manufacturing apparatus thereof.

  The solar cell protection sheet is placed on the back side of the solar cell to prevent the deterioration of the patterned silicon thin film, which is the electromotive part of the solar cell module, due to humidity. Therefore, durability performance that does not deteriorate the gas barrier performance even when used under severe conditions such as the above is required.

  It is necessary to protect the contents of packaging materials used for packaging hard disks, semiconductor modules, foods and pharmaceuticals. Particularly in food packaging, it is necessary to suppress the oxidation and alteration of proteins, fats and oils, and to maintain the taste and freshness. In addition, pharmaceuticals that require handling in a sterile state are required to suppress the alteration of the active ingredient and maintain its efficacy. In order to protect the quality of these contents, there is a demand for a package having a gas barrier property that blocks oxygen, water vapor, and other gases that alter the contents.

Conventionally, as a package made of a plastic film, polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (EVOH), polyvinylidene chloride (PVDC), polyacrylonitrile (PAN), which are relatively excellent in gas barrier performance among polymers. Etc.) or plastic films laminated or coated with these resins have been used favorably. However, these films are highly temperature-dependent, and the gas barrier performance is deteriorated at high temperatures or high humidity. In food packaging applications, when the boil treatment or retort treatment under high temperature and high pressure conditions is performed, the gas barrier performance is reduced. Often the performance is significantly degraded. In addition, the gas barrier laminate using the PVDC polymer resin composition has low humidity dependency but temperature dependency, and also has high gas barrier performance (for example, 1 cc / m ² · day · atm or less). Can't get.

  In addition, since PVDC and PAN have a high risk of generation of harmful substances during disposal and incineration, a metal foil such as aluminum is used for packaging that has high moisture resistance and requires high gas barrier performance. As a result, the gas barrier performance had to be secured. However, since the metal foil is opaque, it is difficult to identify the contents through the packaging material, and the contents cannot be inspected by a metal detector and cannot be heat-treated in a microwave oven.

  In addition, when these packages are exposed to harsh conditions such as outdoors for a long time, there is a problem that delamination occurs between the plastic film and the ceramic layer, impairing the function of the package, and it can be used outdoors. In order to obtain a highly durable gas barrier package, intensive ingenuity is required.

  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. There are many cases where they 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

  The present invention has been made to solve the above-mentioned problems, and in order to improve the adhesion between the plastic film and the gas barrier film, which is insufficient with the conventional method, the adhesion layer and the gas barrier layer are formed in-line. By forming with, it is providing the gas barrier film excellent in adhesiveness compared with the past with high production efficiency.

According to the first aspect of the present invention, there is provided an adhesion layer made of silicon oxide (SiOx) and a gas barrier layer formed by plasma chemical vapor deposition (PECVD method) on one side or both sides of a plastic film as a substrate. In this method of manufacturing a gas barrier film formed in this order, a metal roll electrode that is a high-frequency application electrode on which the base material travels, and as a counter electrode, in a plane, a pair of magnets of S / N poles was installed. A ground electrode arranged in a shape along the metal roll electrode in an arc shape or a polyhedral shape, and tetraethylsiloxane, hexamethyldisiloxane, tetramethylcyclotetrasiloxane, hexamethyldisilazane, triethyl between the electrodes Silane, trimethylsilane, monosilane, disilane, octamethylcyclotetrasiloxane, tris One or more gases selected from methylaminosilane, tetrachlorosilane, tetraethoxysilane, and Vistatiarybutylaminosilane, and oxygen, ozone, water, hydrogen peroxide, ammonia, nitrogen, nitrous oxide, carbon dioxide, carbon monoxide Introducing one or more gases selected from hydrogen, argon and helium, setting the pressure in the processing space to 0.5 Pa to 20 Pa, and applying a high frequency of 10 kHz to 30 MHz between the electrodes, A step of generating a high-density plasma and forming the adhesion layer made of silicon oxide (SiOx) on the surface of the base material running on the metal roll electrode, and a dry coating method on the adhesion layer, Forming the gas barrier layer made of silicon oxide (SiOx). That is a method for producing a gas barrier film.
The invention according to claim 2 is the method for producing a gas barrier film according to claim 1, wherein the adhesion layer and the gas barrier layer are continuously processed in the same system under a reduced pressure environment. is there.
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.
According to a fourth aspect of the present invention, in the SiOx film in the adhesion layer, the value of x is 0.5 ≦ x ≦ 2.2. This is a method for producing a gas barrier film.
The invention according to claim 5 is the gas barrier according to any one of claims 1 to 4, wherein the SiOx film in the gas barrier layer has a value x of 1 ≦ x ≦ 2.2. It is a manufacturing method of an adhesive film.
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 as described in any one of 1 to 5.
The invention according to claim 7 is a gas barrier film in which an adhesion layer made of silicon oxide (SiOx) and a gas barrier layer formed in this order on one side or both sides of a plastic film as a base material, The SiOx film in the adhesion layer has an x value of 0.5 ≦ x ≦ 2.2, and the SiOx film in the gas barrier layer has an x value of 1 ≦ x ≦ 2.2, It is a gas barrier film.
The invention described in claim 8 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 as described in above.
The invention according to claim 9 is an apparatus for producing a gas barrier film in which an adhesion layer made of silicon oxide (SiOx) and a gas barrier layer formed on one side or both sides of a plastic film as a base material are formed in this order. A metal roll electrode that is a high-frequency application electrode on which the base material travels, and a counter electrode that has a pair of magnets with a pair of S / N poles installed in a plane, along the metal roll electrode in an arc shape or a multi-surface shape. Between the ground electrode and the electrode arranged in the form of tetraethylsiloxane, hexamethyldisiloxane, tetramethylcyclotetrasiloxane, hexamethyldisilazane, triethylsilane, trimethylsilane, monosilane, disilane, octamethylcyclotetrasiloxane , Trisdimethylaminosilane, tetrachlorosilane, tetraeth One or more gases selected from silane and bistia butylamino silane and selected from oxygen, ozone, water, hydrogen peroxide, ammonia, nitrogen, nitrous oxide, carbon dioxide, carbon monoxide, hydrogen, argon and helium A gas barrier film comprising: a gas introducing means for introducing one or more kinds of gases; and a forming means for forming the gas barrier layer made of silicon oxide (SiOx) by a dry coating method. It is a manufacturing apparatus.
The invention according to claim 10 is the apparatus for producing a gas barrier film according to claim 9, wherein the adhesion layer and the gas barrier layer are continuously processed in the same system under a reduced pressure environment. is there.
The invention according to claim 11 is the gas barrier film manufacturing apparatus according to claim 10 or 11, wherein the pair of magnets of the S and N poles are neodymium magnets.

  According to the said invention, the gas barrier film excellent in adhesiveness compared with the past can be provided with high production efficiency.

  As an effect of improving the adhesion, when the adhesion layer is formed by the plasma chemical vapor deposition method (PECVD method), the plastic film as the base material travels on the metal roll electrode which is the high frequency application electrode. The plastic film is exposed to a high density plasma nearby, and the bombardment effect and chemical reaction due to ions and electrons are increased, and the etching effect and plasma chemical vapor deposition (PECVD) due to the bombard effect due to ions and electrons. It is considered that the formation of a composite interface is caused by the simultaneous progress of film formation by the (method).

  In order to achieve high productivity, the conventional method for forming the underlayer and overcoat layer using the coating method under the atmospheric pressure environment requires changing the manufacturing equipment each time. This is considered to be possible by reducing the indirect time and generating loss due to contamination by performing a single device in a reduced pressure environment.

It is sectional drawing which shows an example of the gas barrier film of this invention. It is explanatory drawing of the manufacturing apparatus of the gas barrier film by 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. An adhesion layer 2 made of silicon oxide (SiOx) formed by plasma chemical vapor deposition (PECVD), a gas barrier layer 3 and, if necessary, a protective layer 4 are sequentially formed on the plastic film 1. ing. Each layer on the plastic film 1 may be formed on both surfaces thereof, or may be further multilayered on the protective layer 4.

  The plastic film 1 is not particularly limited and a known one can be used. For example, polyolefin (polyethylene, polypropylene, etc.), polyester (polyethylene naphthalate, polyethylene terephthalate, etc.), polyamide (nylon-6, nylon-66, etc.), polystyrene, ethylene vinyl alcohol, polyvinyl chloride, polyimide, polyvinyl alcohol , Polycarbonate, polyethersulfone, acrylic, cellulose-based (triacetylcellulose, diacetylcellulose, etc.), and the like. For example, when used as a packaging material, it is preferable to use a transparent film because the contents can be confirmed. Also, the thickness is not particularly limited, and in view of productivity and workability when forming a gas barrier film, a range of 6 to 100 μm is preferable for practical use.

In the present invention, the adhesion layer is formed by the following steps.
First, a metal roll electrode, which is a high-frequency application electrode, and a counter electrode are arranged in a shape along the metal roll electrode in an arc shape or a multi-faced shape with a pair of magnets of S / N poles installed in the plane. Prepare a ground electrode. Subsequently, a plastic film runs on the metal roll, where tetraethylsiloxane, hexamethyldisiloxane, tetramethylcyclotetrasiloxane, hexamethyldisilazane, triethylsilane, trimethylsilane, monosilane, disilane are interposed between the electrodes. One or more gases selected from, octamethylcyclotetrasiloxane, trisdimethylaminosilane, tetrachlorosilane, tetraethoxysilane, and Vistatiarybutylaminosilane, and oxygen, ozone, water, hydrogen peroxide, ammonia, nitrogen, and sub-oxidation One or more gases selected from nitrogen, carbon dioxide, carbon monoxide, hydrogen, argon and helium are introduced. The pressure in the processing space is set to 0.5 Pa or more and 20 Pa or less, a high frequency of 10 kHz or more and 30 MHz or less is applied, high density plasma is generated between both electrodes, and an adhesion layer is formed on the surface of the plastic film running on the metal roll electrode Form.

  When the adhesion layer 2 is formed on the plastic film 1, it is effective to use a plasma chemical vapor deposition method (PECVD method). By using the plasma chemical vapor deposition method (PECVD method), the etching effect by the bombard effect by ions and electrons and the film formation by the plasma chemical vapor deposition method (PECVD method) proceed at the same time. It is possible to form an adhesion layer that is excellent in adhesion to the substrate.

  When the adhesion layer 2 is formed by the plasma chemical vapor deposition method (PECVD method), the plastic film 1 runs on the side of the metal roll that is the high-frequency application electrode, and the permanent magnet is on the side of the ground electrode that is the counter electrode. By being installed, it is possible to strengthen the plasma, and it is possible to further promote the decomposition of the raw material gas to be used, thereby improving the production efficiency and efficiently colliding ions and electrons in the plasma with the plastic film 1. By demonstrating the bombard effect, it becomes possible to efficiently remove the layer that causes a decrease in adhesion strength, and the plastic film is exposed to high density plasma in the vicinity, and the bombard effect and chemicals caused by ions and electrons. As a result of the increased response, it is possible to produce excellent adhesion.

  As a method for improving the plasma density in the space, a high-frequency power source having a higher frequency than that of the metal roll side is connected to the counter electrode side, and a higher density plasma is generated on the counter electrode side, so that the self-bias on the metal roll side However, there is a method of attracting high-density ions, but there is a great possibility that the apparatus becomes complicated and widened.

  When forming the adhesion layer 2 by the plasma chemical vapor deposition method (PECVD method), by setting the deposition pressure to 20 Pa or less, the gas barrier performance and adhesion deterioration due to the undecomposition of the source gas used is reduced. It is possible to prevent inhibition of the gas barrier performance of the ceramic layer 3. Moreover, when the film-forming pressure becomes larger than 20 Pa, the plasma strengthening effect due to the permanent magnet installation may be difficult to be exhibited. On the other hand, when set to less than 0.5 Pa, stable discharge cannot be obtained.

  When the adhesion layer 2 is formed by the plasma chemical vapor deposition method (PECVD method), the high-frequency power source to be used is set to 10 kHz or more, so that the raw material gas decomposition performance by plasma is improved and a relatively low pressure such as 1 Pa. However, a stable discharge can be obtained. When the frequency exceeds 30 MHz, the source gas decomposition by plasma is further improved and the number of ions and electrons is increased, but the bombard effect is weakened because the voltage is lowered. In addition, it is very difficult to increase the size of the apparatus. Considering the number of ions and electrons, the bombardment momentum, the decomposition of the raw material gas by plasma, and the enlargement of the apparatus, 40 kHz to 400 kHz is more preferable.

  By setting the value of x in the SiOx film of the adhesion layer 2 to 0.5 ≦ x ≦ 2.2, an adhesion layer having excellent adhesion can be obtained. The value of x varies depending on the selection of gas and the flow rate during production. However, in consideration of simplification of equipment, safety, handling of the material itself, and adhesion between the adhesion layer 2 and the plastic film, hexa More preferably, helium or argon is combined with methyldisiloxane, and the value of x at that time is preferably 0.5 ≦ x ≦ 1.5.

  When the gas barrier layer 3 is formed, a dry coating method such as a sputtering method or a vacuum deposition method can be used. However, in the sputtering method, as the film thickness increases, the increase in gas barrier performance due to cracks due to internal stress of the film occurs, and the vacuum deposition method is the most productive, but the excellent gas barrier property It becomes difficult to demonstrate. In consideration of the production speed of the adhesion layer 2 by plasma chemical vapor deposition (PECVD) and flexibility, vacuum deposition is more preferable, but when higher level adhesion and gas barrier properties are required. The sputtering method is effective.

  By setting the value of x in the SiOx film of the gas barrier layer 3 to 1 ≦ x ≦ 2.2, it is possible to obtain a film having excellent transparency, durability, and gas barrier properties. In order to maximize the properties and gas barrier properties, it is more preferable to satisfy 1.5 ≦ x ≦ 1.8. By using the SiOx film, it is possible to make the film superior in durability as compared with the case of using aluminum oxide or titanium oxide. For example, even if a retort process at 121 ° C. for 30 minutes is performed, the adhesion and gas barrier properties are not easily deteriorated.

  By performing all processes in the same system (in-line) film formation under a reduced pressure environment, impurities are unlikely to cross each other, and it becomes easy to maintain a state suitable for the film formation environment. Moreover, it is thought that production efficiency improves compared with the offline film-forming when the adhesion layer 2 is formed by a coating method.

  In general, film formation by plasma chemical vapor deposition (PECVD) is slower than sputtering or vacuum deposition, and the rate of film formation is slow, and the rate is limited when performing in-line film formation. In order to improve the production speed of the adhesion layer 2 by the plasma chemical vapor deposition method (PECVD method), means for increasing the raw material gas flow rate is effective, but as the raw material gas increases, the combined gas flow rate is also increased. If there is a need to increase the film forming pressure, the gas barrier performance and adhesion deterioration due to the undecomposition of the source gas may occur, and the gas barrier performance of the gas barrier layer 3 may be inhibited. In order to maintain the performance, it is important to maintain the film formation pressure at 0.5 to 20 Pa.

  When it is difficult to maintain a film forming pressure of 0.5 to 20 Pa with increasing source gas, there is a method of increasing the number of adhesion layer film forming units and maintaining a dynamic rate defined by line speed × film forming film thickness. It is valid. For example, there are three adhesion film forming units and one gas barrier layer fine film forming unit, and selection of the number of units is important in consideration of a required film thickness and film forming speed for maintaining gas barrier performance.

  When the adhesion layer 2 is formed on the plastic film 1, the thickness of the adhesion layer 2 is desirably in the range of 1 to 1000 nm, and the value is appropriately selected. However, when the thickness is less than 1 nm, it may be difficult to obtain a uniform film thickness, or the required adhesion may not be obtained because the film thickness is insufficient. In addition, when the film thickness exceeds 1000 nm, the film thickness is too thick, so that the film formation time is prolonged and the substrate loses heat, resulting in poor appearance and adversely affecting gas barrier performance. There is a fear. More preferably, it is 1 nm to 50 nm.

  When a gas barrier layer is formed on the adhesion layer 2, the thickness of the gas barrier layer 3 is desirably within a range of 10 to 1000 nm, and the value is appropriately selected. However, when the thickness is less than 10 nm, it is difficult to obtain a uniform film thickness, or the required gas barrier property cannot be exhibited because the film thickness is insufficient. In addition, when the thickness exceeds 1000 nm, the film thickness is too thick, so that the film formation time is prolonged and the substrate loses heat, resulting in poor appearance and adverse effects on gas barrier performance and the like. There is a fear. In addition, the number of adhesion layer film forming units becomes enormous, and there is a risk that the apparatus configuration becomes complicated or large. More preferably, it is 10-60 nm.

FIG. 2 is an explanatory view of a gas barrier film manufacturing apparatus according to the present invention.
In the manufacturing apparatus 5, the plastic film travels on the metal roll electrode 7. A high frequency voltage is applied to the metal roll electrode 7 from the high frequency power source 6. As the counter electrode, a ground electrode 8 arranged in a shape along the metal roll electrode 7 in an arc shape or a multi-surface shape in which a pair of magnets of S and N poles are installed is installed in the plane. FIG. 2 shows an arc-shaped ground electrode 8 that is substantially parallel to the surface of the metal roll electrode 7. Apart from this, it is also possible to use a polyhedral ground electrode having a shape that substantially follows the surface of the metal roll electrode 7 and having a plurality of plate electrodes joined at the ends thereof. As an installation location of the S / N pole pair or more, for example, it is installed on the metal roll electrode 7 side of the ground electrode 8 along the flow direction of the plastic film. Further, the shape of the magnet 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.

  Further, between the metal roll electrode 7 and the ground electrode 8, tetraethylsiloxane, hexamethyldisiloxane, tetramethylcyclotetrasiloxane, hexamethyldisilazane, triethylsilane, trimethylsilane, monosilane, disilane, octane are introduced by gas introduction means. One or more gases selected from methylcyclotetrasiloxane, trisdimethylaminosilane, tetrachlorosilane, tetraethoxysilane, and binary butylaminosilane, oxygen, ozone, water, hydrogen peroxide, ammonia, nitrogen, nitrous oxide, A gas introduction means (not shown) for introducing one or more kinds of gases selected from carbon dioxide, carbon monoxide, hydrogen, argon and helium is installed. Then, the gas is introduced between the metal roll electrode 7 and the ground electrode 8 by the gas introduction means, and a high pressure voltage is applied to the metal roll electrode 7 with a constant pressure in the processing space. A dense plasma is generated to form an adhesion layer on the surface of the plastic film running on the metal roll electrode 7.

  A forming means for forming a gas barrier layer made of silicon oxide (SiOx) is provided on the adhesion layer. Specifically, the gas barrier layer film-forming roll 9 is installed, and the gas barrier layer is formed on the gas barrier layer film-forming roll 9 by a known dry coating method such as vacuum vapor deposition or sputtering. In order to combine the dynamic rate, the number of film forming units for forming the adhesion layer may be increased as necessary.

In the present invention, the protective layer 4 may be formed on the gas barrier layer 3. The protective layer 4 is preferably a layer formed by applying a mixed solution containing a metal alkoxide and a water-soluble polymer and heating and drying. Specifically, the metal alkoxide is represented by the general formula R ¹ (M-OR ² ) (where R ¹ and R ² are organic groups having 1 to 8 carbon atoms, and M is a metal atom). Examples of atoms include Si, Ti, Al, Zr and the like.

R ¹ (Si—OR ² ) in which the metal M is Si includes tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxy. A silane etc. can be mentioned.

Examples of R ¹ (Zr—OR ² ) in which the metal M is Zr include tetramethoxyzirconium, tetraethoxyzirconium, tetraisopropoxyzirconium, and tetrabutoxyzirconium.

Examples of R ¹ (Ti—OR ² ) in which the metal M is Ti include tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, and tetrabutoxytitanium.

Examples of R ¹ (Al—OR ² ) in which the metal M is Al include tetramethoxyaluminum, tetraethoxyaluminum, tetraisopropoxyaluminum, and tetrabutoxyaluminum.

  The metal alkoxide may be used alone or in combination of two or more. Acrylic acid, polyvinyl alcohol, urethane compound, polyester compound, and the like may be mixed, but it is desirable to mix a swellable water-soluble polymer material.

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

<Example 1>
An adhesion layer was formed on one surface of a polyethylene terephthalate film having a thickness of 12 μm by plasma chemical vapor deposition (PECVD), a gas barrier layer made of silicon oxide was formed thereon, and a protective layer was formed thereon.
Note that the adhesion layer and the gas barrier layer were formed by the manufacturing apparatus shown in FIG. At this time, two gases of hexamethyldisiloxane and helium were used when forming the adhesion layer.
The pressure in the treatment space was 5.0 Pa.
The applied power supply frequency was 400 kHz.
Two neodymium magnets were used as a pair of S and N poles.
The protective layer was formed using tetraethoxysilane as the metal alkoxide and polyvinyl alcohol as the water-soluble polymer.
At this time, the SiOx film in the adhesion layer had an x value of 1.0, and the SiOx film in the gas barrier layer had an x value of 1.7. In addition, the said value was measured with the photoelectron spectrometer (JPS-9010MX by JEOL).

<Comparative Example 1>
In Example 1, Example 1 was repeated except that the adhesion layer was not formed.

<Evaluation 1 Adhesion>
The adhesion of the gas barrier films obtained in Examples and Comparative Example 1 was measured using a Tensilon universal testing machine (RTC-1250 manufactured by ORIENTEC). The measurement was performed after a retort treatment at 130 ° C. for 60 minutes. The results are shown in Table 1.

<Evaluation 2 Gas barrier properties>
The gas barrier properties of the gas barrier films obtained in Examples and Comparative Example 1 were measured using a water vapor permeability measuring device (MOCON PERMATRAN 3/21 40 ° C. 90% RH atmosphere manufactured by Modern Control). In addition, the measurement was performed twice after the initial stage and the retort treatment at 130 ° C. for 60 minutes. The results are shown in Table 1.

  As the industrial applicability of the gas barrier film in the present invention, a gas barrier film used in the packaging field of solar cell backsheets, foods, pharmaceuticals, and the like can be considered.

DESCRIPTION OF SYMBOLS 1 ... Plastic film 2 ... Adhesion layer 3 ... Gas barrier layer 4 ... Protective layer 5 ... Manufacturing apparatus 6 ... High frequency power supply 7 ... Metal roll electrode 8 ... Ground electrode 9 ... Gas barrier layer deposition rolls

Claims (11)

Production of a gas barrier film in which an adhesion layer made of silicon oxide (SiOx) and a gas barrier layer are formed in this order on one or both sides of a plastic film as a base material by plasma chemical vapor deposition (PECVD method) A method,
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,
Between the electrodes, tetraethylsiloxane, hexamethyldisiloxane, tetramethylcyclotetrasiloxane, hexamethyldisilazane, triethylsilane, trimethylsilane, monosilane, disilane, octamethylcyclotetrasiloxane, trisdimethylaminosilane, tetrachlorosilane, tetraethoxysilane One or more gases selected from the group consisting of oxygen, ozone, water, hydrogen peroxide, ammonia, nitrogen, nitrous oxide, carbon dioxide, carbon monoxide, hydrogen, argon and helium One or more kinds of gases are introduced, the pressure in the processing space is set to 0.5 Pa or more and 20 Pa or less, and a high frequency of 10 kHz or more and 30 MHz or less is applied to generate high-density plasma between the electrodes, Above To the substrate surface that travels genus roll conductive electrode, and forming the adhesion layer made of such as silicon oxide (SiOx),
And a step of forming the gas barrier layer made of silicon oxide (SiOx) on the adhesion layer by a dry coating method.   The method for producing a gas barrier film according to claim 1, wherein the adhesion layer and the gas barrier layer are continuously treated in the same system under a reduced pressure environment.   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.   4. The method for producing a gas barrier film according to claim 1, wherein the SiOx film in the adhesion layer has a value x of 0.5 ≦ x ≦ 2.2. 5.   5. The method for producing a gas barrier film according to claim 1, wherein the SiOx film in the gas barrier layer has a value x of 1 ≦ x ≦ 2.2.   The 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. 6. The manufacturing method of the gas-barrier film of description. A gas barrier film in which an adhesive layer made of silicon oxide (SiOx) and a gas barrier layer formed in this order on one side or both sides of a plastic film as a substrate,
The SiOx film in the adhesion layer has an x value of 0.5 ≦ x ≦ 2.2, and the SiOx film in the gas barrier layer has an x value of 1 ≦ x ≦ 2.2. Gas barrier film.   The gas barrier film according to claim 7, 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. An apparatus for producing a gas barrier film in which an adhesive layer made of silicon oxide (SiOx) and a gas barrier layer formed in this order on one or both sides of a plastic film serving as a base material,
A metal roll electrode that is a high-frequency application electrode on which the substrate travels;
As a counter electrode, a ground electrode disposed 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,
Between the electrodes, tetraethylsiloxane, hexamethyldisiloxane, tetramethylcyclotetrasiloxane, hexamethyldisilazane, triethylsilane, trimethylsilane, monosilane, disilane, octamethylcyclotetrasiloxane, trisdimethylaminosilane, tetrachlorosilane, tetraethoxysilane One or more gases selected from the group consisting of oxygen, ozone, water, hydrogen peroxide, ammonia, nitrogen, nitrous oxide, carbon dioxide, carbon monoxide, hydrogen, argon and helium Gas introduction means for introducing one or more kinds of gases;
An apparatus for producing a gas barrier film, comprising: a forming means for forming the gas barrier layer made of silicon oxide (SiOx) by a dry coating method.   The apparatus for producing a gas barrier film according to claim 9, wherein the adhesion layer and the gas barrier layer are continuously processed in the same system under a reduced pressure environment.   The apparatus for producing a gas barrier film according to claim 10 or 11, wherein the pair of S · N pole pair magnets is a neodymium magnet.