JP6756148B2 - Laminated film and its manufacturing method - Google Patents

Description

The present invention relates to a laminated film used for packaging of foods and pharmaceuticals requiring high gas barrier properties and for electronic members such as solar cells, electronic papers, and organic electroluminescence (EL) displays, and a method for producing the same.

Physical vapor deposition (PVD method) such as vacuum deposition method, sputtering method, ion plating method, etc. using inorganic substances (including inorganic oxides) such as aluminum oxide, silicon oxide, magnesium oxide on the surface of the film substrate. ) Or, a vapor deposition layer of the inorganic substance is formed by using a chemical vapor deposition method (CVD method) such as a plasma chemical vapor deposition method, a thermochemical vapor deposition method, or a photochemical vapor deposition method. Gas barrier films are used as packaging materials for foods and pharmaceuticals that require blocking of various gases such as water vapor and oxygen, and as electronic device members such as electronic paper and solar cells. In these ^{members, 1.0 × 10 -4 g / m} 2 · 24hr · atm or less high gas barrier properties with water vapor permeability has been demanded.

As one of the methods for satisfying the high gas barrier property as described above, a gas barrier film in which defects are prevented from occurring due to a hole filling effect by alternately laminating organic layers and inorganic layers has been proposed (Patent Document 1). ). Further, for the purpose of reducing defects on the film substrate, a gas barrier film in which the surface of the substrate is flattened and an inorganic layer is formed has also been proposed (Patent Documents 2 and 3).

Further, a laminated sheet (Patent Document 4) in which a ZnO-SiO ₂ system film is formed on a film substrate by sputtering using a target containing ZnO and SiO ₂ as main components, or Si by the ion plating method. A gas barrier sheet (Patent Document 5) in which a Si—O—Zn film having an atomic number ratio of: O: Zn in the range of 100: 200 to 500: 2 to 100 is formed on a substrate has also been proposed.

However, simply forming an inorganic film on a film base material lacks flexibility, and when the film is bent, film cracking occurs, the refractive index of silicon nitride or the like is high, and the refractive index with the film base material is high. The reflectance may increase due to the difference.

JP-A-2005-324406 (Claims) Japanese Unexamined Patent Publication No. 2002-113826 (Claims) Japanese Unexamined Patent Publication No. 2008-246893 (Claims) Japanese Unexamined Patent Publication No. 2013-47363 (Claims) Japanese Unexamined Patent Publication No. 2009-24255 (Claims)

However, in the method in which the organic layer and the inorganic layer are alternately laminated, the polymer film base material is damaged by plasma radiant heat during the formation of the layer when several tens of layers are laminated, and the polymer film base material is warped due to heat loss. In some cases, the workability is deteriorated in the post-processing, the flexibility of the gas barrier film is poor, and the gas barrier property is deteriorated with respect to bending.

In addition, the method using a smoothing base material or a base material with an anchor coat for the purpose of surface smoothing as the base material forming the gas barrier layer improves the reproducibility of gas barrier properties by preventing the occurrence of pinholes and cracks. to although, since the nature of the gas barrier layer to be formed is not improved, achievement of ^{1.0 × 10 -4 g / m 2} · 24hr · atm or less high gas barrier properties has been difficult.

Further, if the inorganic film is simply formed on the film base material, the flexibility is poor, and when the film is bent, the film cracks or the refractive index of silicon nitride or the like is high, and the refractive index with the film base material is high. In some cases, the reflectance increased due to the difference.

In view of the background of the prior art, it is an object of the present invention to provide a laminated film having excellent transparency and exhibiting a high degree of gas barrier property, in which the gas barrier property is not easily lowered even with bending, and a method for producing the same. ..

The present invention adopts the following configuration in order to solve such a problem.
(1) A laminated film having an X layer containing a zinc compound and a compound of an element A other than zinc in groups 12 to 14 of the periodic table on at least one side of the film base material, and the X layer. When the content ratio of zinc Zn and element A (Zn / A) is divided by the content ratio of zinc Zn and element A in the X layer in the flat portion (Zn / A), it exceeds at least 1.15 and 3.00. A laminated film characterized in that there is a position having a value less than, and the position is present in a surface layer portion and / or an interface portion.
(2) When the content ratio (Zn / A) of zinc Zn and element A in the X layer is divided by the content ratio (Zn / A) of zinc Zn and element A in the X layer in the flat portion, 1.15. The laminated film according to (1), wherein the film thickness having a value of more than 3.00 and less than 3.00 is 5 to 50% of the total film thickness of the X layer.
(3) The laminated film according to (1) or (2), wherein the zinc compound is zinc oxide and / or zinc sulfide.
(4) The element A contains at least silicon, and the silicon is at least one silicon compound selected from the group consisting of silicon oxide, silicon nitride, silicon nitride and silicon carbide (1) to (1). The laminated film according to any one of 3).
(5) The X layer has a zinc (Zn) atomic concentration of 3 to 35 atm%, a silicon (Si) atomic concentration of 7 to 25 atm%, and an aluminum (Al) atomic concentration measured by X-ray photoelectron spectroscopy (XPS). The laminated film according to any one of (1) to (4), which has an oxygen (O) atom concentration of 50 to 70 atm% and 1 to 7 atm%.
(6) A method for producing a laminated film in which an X layer containing a zinc compound and a compound of an element A other than zinc in Groups 12 to 14 of the Periodic Table is formed on at least one side of a film base material. A method for producing a laminated film, characterized in that the maximum surface temperature of the film substrate at the time of forming the X layer is set to 40 to 200 ° C. by heating from the surface side of the film substrate.
(7) The method for producing a laminated film according to (6), wherein the surface of the film substrate is heated by a lamp heater.
(8) The method for producing a laminated film according to (7), wherein the lamp heater is a halogen lamp heater having a peak wavelength of 0.8 to 2.5 μm.
(9) The method for producing a laminated film according to any one of (6) to (8), wherein the method for forming the X layer is a sputtering method.
(10) The target material forming the X layer has a zinc (Zn) atomic concentration of 3 to 37 atm%, a silicon (Si) atomic concentration of 5 to 20 atm%, an aluminum (Al) atomic concentration of 1 to 7 atm%, and oxygen. (O) The method for producing a laminated film according to any one of (6) to (9), wherein the composition has an atomic concentration of 50 to 70 atm%.

According to the present invention, it is possible to provide a laminated film having excellent transparency and exhibiting a high degree of gas barrier property, in which the gas barrier property is not easily lowered even when bent, and a method for producing the same.

It is sectional drawing which showed an example of the laminated film of this invention. It is sectional drawing which showed an example of the laminated film of this invention. It is a schematic diagram which shows an example of the sputtering apparatus for manufacturing the laminated film of this invention. This is an example of an enlarged view of the vicinity of the magnetron sputtering cathode 18 in FIG. It is a schematic diagram which shows an example of the lamp heater provided with the parallel light type reflector. It is a schematic diagram which shows an example of the lamp heater provided with the condensing light type reflector. This is an example of an enlarged view of the vicinity of the magnetron sputtering cathode 18 in FIG. It is a schematic diagram which shows an example of the sputtering apparatus for manufacturing the laminated film of this invention. It is a depth profile of the composition ratio of the X layer in Example 1. It is a depth profile of the content ratio (Zn / A) of zinc Zn of the X layer and element A in Example 1. It is a depth profile of the composition ratio of the X layer in Example 2. It is a depth profile of the content ratio (Zn / A) of zinc Zn and element A of the X layer in Example 2. It is a depth profile of the composition ratio of the X layer in Example 3. 3 is a depth profile of the content ratio (Zn / A) of zinc Zn and element A in the X layer in Example 3. It is a depth profile of the composition ratio of the X layer in Example 4. It is a depth profile of the content ratio (Zn / A) of zinc Zn of the X layer and element A in Example 4. 5 is a depth profile of the composition ratio of the X layer in Example 5. 5 is a depth profile of the content ratio (Zn / A) of zinc Zn and element A in the X layer in Example 5. It is a depth profile of the composition ratio of the X layer in Comparative Example 1. It is a depth profile of the content ratio (Zn / A) of zinc Zn of the X layer and element A in Comparative Example 1. It is a depth profile of the composition ratio of the X layer in Comparative Example 2. It is a depth profile of the content ratio (Zn / A) of zinc Zn and element A of the X layer in Comparative Example 2. It is a depth profile of the composition ratio of the X layer in Comparative Example 3. It is a depth profile of the content ratio (Zn / A) of zinc Zn of the X layer and element A in Comparative Example 3. It is a depth profile of the composition ratio of the X layer in Comparative Example 4. It is a depth profile of the content ratio (Zn / A) of zinc Zn and element A of the X layer in Comparative Example 4. It is explanatory drawing about the content of this invention. It is an enlarged view in the range of the depth 5 to 35 nm of the graph of FIG. 27.

Hereinafter, embodiments of the present invention will be described with reference to the drawings, but the present invention is not limited to this figure as long as it is a laminated film satisfying the content of the claims and a method for producing the same.

[Laminated film]
The present inventors have conducted diligent studies for the purpose of obtaining a laminated film having excellent transparency and exhibiting a high degree of gas barrier property, in which the gas barrier property does not easily decrease even with bending, and on at least one surface of the film substrate. , A laminated film having an X layer containing a zinc compound and a compound of an element A other than zinc in groups 12 to 14 of the periodic table, and the content ratio of zinc Zn and the element A in the X layer ( When Zn / A) is divided by the content ratio (Zn / A) of zinc Zn and element A in the X layer in the flat portion, there is a position having a value of at least 1.15 and less than 3.00. , The present invention has been found to solve the above-mentioned problems when the position exists in the surface layer portion and / or the interface portion. In the following, the laminated film may be referred to as a gas barrier film. Further, the X layer may be referred to as a gas barrier layer.

As the zinc compound contained in the gas barrier layer, zinc oxide, zinc sulfide, zinc nitride, a mixture thereof and the like are preferably used, and zinc oxide and / or zinc sulfide is more preferable from the viewpoint of gas barrier properties. Zinc oxide is more preferred from the viewpoint of optical properties.

The gas barrier layer preferably contains a zinc compound and a compound of an element A other than zinc in Groups 12 to 14 of the Periodic Table. The element A contained in the gas barrier layer is not particularly limited as long as it is an element other than zinc belonging to groups 12 to 14 of the periodic table, and at least one element selected from the group consisting of silicon, aluminum, gallium, indium and tin. May be included. The form in which the element A is contained in the gas barrier layer is not limited to oxides, nitrides, oxide nitrides, carbides and the like, but exists as oxides, nitrides and oxide nitrides from the viewpoint of gas barrier properties and the like. Is preferable. From the viewpoint of forming an amorphous film and gas barrier property, the element A preferably contains at least silicon, and the silicon is at least one selected from the group consisting of silicon oxide, silicon nitride, silicon nitride and silicon carbide. It is more preferable that it is contained as a silicon compound.

As described above, the gas barrier layer may contain an inorganic compound other than the above as long as it contains a zinc compound and a compound of an element A other than zinc in Groups 12 to 14 of the periodic table. For example, the gas barrier layer may contain oxides of elements such as titanium, niobium, tantalum, and zirconium, nitrides, sulfides, and the like, or mixtures thereof.

In the present invention, the surface after etching the outermost surface of the gas barrier layer under the conditions described in the section of Examples is used as the surface reference surface. Next, when the composition was analyzed while etching from the surface reference surface toward the film substrate under the conditions described in the section of Examples, the surface where the Zn content ratio was 1.0 atm% or less for the first time was used as the interface reference. Make it a face. At this time, the film thickness from the surface reference surface to the interface reference surface is defined as the film thickness of the entire gas barrier layer.

In addition, when calculating the content ratio, the atomic number ratio evaluated by the method described in the section of Examples is used.

At this time, a portion having a film thickness of 0% or more and 20% or less of the film thickness of the entire gas barrier layer from the surface reference surface toward the film base material is defined as the surface layer portion ((A) in FIG. 27) of the gas barrier layer. Similarly, a portion having a film thickness of 0% or more and 40% or less of the film thickness of the entire gas barrier layer from the interface reference surface toward the surface of the gas barrier layer is defined as the interface portion of the gas barrier layer ((B) in FIG. 27). Here, as described above, the film thickness of the entire gas barrier layer is the film thickness from the surface reference surface to the interface reference surface.

The gas barrier film of the present invention is a gas barrier film having a gas barrier layer containing a zinc compound and a compound of an element A other than zinc in Groups 12 to 14 of the periodic table on at least one side of the film substrate. Therefore, the content ratio (Zn / A) of zinc Zn and element A in the gas barrier layer is changed to the content ratio (Zn / A) of zinc Zn and element A in the gas barrier layer in the flat portion (in FIG. 27 and FIG. 28 (D)). There is a position ((C) in FIG. 27) having a value of at least 1.15 and less than 3.00 when divided by A), and the position is present in the surface layer portion and / or the interface portion. Is preferable. The region when the position exists in the surface layer portion refers to (E) in FIG. 27, and the region when the position exists in the interface portion refers to (F) in FIG. 27. Here, when the content ratio (Zn / A) of zinc Zn and element A in the gas barrier layer is divided by the content ratio (Zn / A) of zinc Zn and element A in the gas barrier layer in the flat portion, it is at least 1.15. The existence of a position having a value of more than 3.00 and less than 3.00 means that the gas barrier layer is etched from the surface reference surface toward the film substrate according to the etching conditions described in the section of Examples to the interface reference surface. The analysis was carried out, and the content ratio (Zn / A) of zinc Zn and element A in the obtained gas barrier layer was determined by the content ratio (Zn / A) of zinc Zn and element A in the gas barrier layer in the flat portion described later. It means that there is a position having a value of more than 1.15 and less than 3.00 when divided. Further, the presence of a position having a value of more than 1.15 and less than 3.00 in the surface layer portion and / or the interface portion means that the position having a value of more than 1.15 and less than 3.00 is described above. It means that it exists in the surface layer part and / or the interface part.

Hereinafter, when there are a plurality of elements in the gas barrier layer that can be elements A other than zinc in groups 12 to 14 of the periodic table, the element having the highest content ratio is regarded as element A in the calculation.

At this time, the content ratio (Zn / A) of zinc Zn and element A in the gas barrier layer in the flat portion will be described below. First, the composition of the gas barrier layer is analyzed while being etched from the surface reference surface toward the film substrate under the conditions described in the section of Examples to the interface reference surface, and the zinc Zn and element A of the obtained gas barrier layer are analyzed. From each point of the content ratio (Zn / A) of and, select three consecutive points so that the average value of the content ratio (Zn / A) of two adjacent zinc Zn and element A is the smallest. The average value of these three points is taken as the content ratio (Zn / A) of zinc Zn and element A in the gas barrier layer in the flat portion (FIG. 27 and FIG. 28 (D)). Here, at the three points, the content ratio (Zn / A) of zinc Zn and element A at each point is ± 0.1, which is the average value of the content ratio (Zn / A) of zinc Zn and element A at three points. We will choose to meet the requirements.

When the content ratio of zinc Zn and element A (Zn / A) is divided by the content ratio of zinc Zn and element A in the gas barrier layer in the flat part (Zn / A) at all the measurement points of the surface layer and the interface. When the value of is 1.15 or less, the composition in the depth direction becomes close to uniform, so that the effect of improving flexibility or color may not be obtained. On the other hand, at all the measurement points of the surface layer portion and the interface portion, the content ratio of zinc Zn and element A (Zn / A) is divided by the content ratio of zinc Zn and element A in the gas barrier layer in the flat portion (Zn / A). When the value is 3.00 or more, the desired gas barrier property may not be obtained due to the large composition gradient in the depth direction.

When the content ratio of zinc Zn and element A (Zn / A) in the surface layer portion and / or the interface portion is divided by the content ratio of zinc Zn and element A in the flat portion (Zn / A), 1.15 is obtained. If there is a position having a value exceeding 3.00 and having a value less than 3.00, a value satisfying them may exist in a region other than the surface layer portion or the interface portion.

Further, when the content ratio (Zn / A) of zinc Zn and element A in the gas barrier layer is divided by the content ratio (Zn / A) of zinc Zn and element A in the gas barrier layer in the flat portion, it exceeds 1.15. The ratio of the film thickness having a value of less than 3.00 to the total film thickness of the gas barrier layer is preferably 5 to 50%.

Here, when the content ratio (Zn / A) of zinc Zn and element A in the gas barrier layer is divided by the content ratio (Zn / A) of zinc Zn and element A in the gas barrier layer in the flat portion, 1.15 is obtained. The ratio of the thickness having a value of more than 3.00 to less than 3.00 to the total thickness of the gas barrier layer is 5 to 50%, that is, zinc Zn and element A in the gas barrier layer obtained by the above method. The content ratio (Zn / A) divided by the content ratio (Zn / A) of zinc Zn and element A in the gas barrier layer in the flat portion is the content ratio (Zn / A) of two or more adjacent zinc Zn and element A. If all Zn / A) is more than 1.15 and less than 3.00, the gas barrier layer formed by a straight line connecting continuous points exceeding 1.15 and less than 3.00 in the thickness direction. The thickness is defined as a film having a value of more than 1.15 and less than 3.00, and the ratio of the film having a value of more than 1.15 and less than 3.00 to the thickness of the entire gas barrier layer is It means that it is 5 to 50%. When a plurality of film thicknesses having a value exceeding 1.15 and less than 3.00 are observed in the gas barrier layer, the total value of these multiple film thicknesses is more than 1.15 and less than 3.00. The film thickness is set to

If the film thickness having a value of more than 1.15 and less than 3.00 is smaller than 5% of the film thickness of the entire gas barrier layer, the composition in the depth direction becomes almost uniform, so that the effect of improving flexibility or color is improved. May not be obtained. Further, when the film thickness having a value exceeding 1.15 and less than 3.00 is larger than 50% of the film thickness of the entire gas barrier layer, the composition gradient in the depth direction becomes large, and the desired gas barrier property is obtained. It may not be possible.

The thickness of the gas barrier layer is preferably 10 to 500 nm, more preferably 30 to 300 nm. If the thickness of the gas barrier layer is thinner than 10 nm, there may be places where sufficient gas barrier properties cannot be ensured. Further, when the thickness is larger than 500 nm, the stress remaining in the layer becomes large, so that cracks are likely to occur in the gas barrier layer due to bending or an impact from the outside, and the gas barrier property may be deteriorated.

The composition ratio of the gas barrier layer is as follows: zinc (Zn) atomic concentration is 3 to 35 atm%, silicon (Si) atomic concentration is 7 to 25 atm%, aluminum (Al) atomic concentration is 1 to 7 atm%, and oxygen (O) atomic concentration is. It is preferably in the range of 50 to 70 atm%.

If the zinc atom concentration is less than 3 atm% or the silicon atom concentration is more than 25 atm%, the proportion of zinc atoms that make the gas barrier layer a highly flexible film is reduced, and the flexibility of the gas barrier film is impaired. In some cases. When the zinc atom concentration is higher than 35 atm% or the silicon atom concentration is lower than 7 atm%, the ratio of silicon atoms is reduced, so that the gas barrier layer tends to become a crystal film and cracks may easily occur. If the aluminum atom concentration is less than 1 atm%, the affinity between zinc oxide and silicon dioxide is impaired, so that voids and defects may easily occur in the gas barrier layer. Further, when the aluminum atom concentration is more than 7 atm%, the affinity between zinc oxide and silicon dioxide becomes excessively high, so that cracks may easily occur due to heat or external stress. If the oxygen atom concentration is less than 50 atm%, zinc, silicon, and aluminum may be insufficiently oxidized and the light transmittance may decrease. On the other hand, if the oxygen atom concentration is more than 70 atm%, oxygen is excessively taken in, so that voids and defects increase and the gas barrier property may decrease.

[Analysis of composition ratio in depth direction]
The composition ratio in the gas barrier layer in the present invention can be evaluated by a general composition analysis method such as X-ray spectroscopy (XPS) or Rutherford backscatter analysis (RBS). An example of depth direction analysis by XPS is shown below.

The composition ratio is calculated from the outermost surface of the gas barrier layer toward the film substrate by performing sputtering etching using argon ions under the conditions described in the section of Examples. The analysis is completed when the composition ratio of Zn becomes 1.0 atm% or less for the first time.

[Anchor coat layer]
It is preferable to form an anchor coat layer on the surface of the gas barrier film of the present invention and the film base material applied to the method for producing the same, as shown in FIG. 2, for the purpose of improving the adhesion to the gas barrier layer.

By having an anchor coat layer between the film base material of the obtained gas barrier film and the gas barrier layer, the flatness of the gas barrier layer is improved as compared with the case where the gas barrier layer is directly formed on the film base material, and the gas barrier property is improved. The flexibility of the gas barrier film is improved as compared with the case where the gas barrier layer is directly applied on the film substrate.

Materials of the anchor coat layer used for this anchor coat layer include polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicon resin, and alkyl titanate. Etc., and one or two or more of these can be used in combination. As the material of the anchor coat layer used in the present invention, a two-component curable resin composed of a main agent and a curing agent is preferable from the viewpoint of solvent resistance, and polyester resin, urethane resin, and acrylic resin are the main agents from the viewpoint of gas barrier property and water resistance. It is more preferable to use as. The curing agent is not particularly limited as long as it does not impair the properties such as gas barrier property and transparency, and general curing agents such as isocyanate-based and epoxy-based can be used. These anchor coat layers can also contain known additives.

The thickness of the anchor coat layer used in the present invention is preferably 0.3 to 10 μm. If the thickness of the layer is thinner than 0.3 μm, the surface roughness of the gas barrier layer may be increased due to the influence of the unevenness of the film base material, and the gas barrier property may be lowered. When the thickness of the layer is thicker than 10 μm, the stress remaining in the layer of the anchor coat layer increases, the film base material warps, and cracks occur in the gas barrier layer, so that the gas barrier property may decrease. Therefore, the thickness of the anchor coat layer is preferably 0.3 to 10 μm. Further, from the viewpoint of ensuring flexibility, 0.5 to 3 μm is more preferable.

As a method of forming the anchor coat layer on the surface of the film base material, a solvent, a diluent, etc. are added to the material of the anchor coat layer to prepare a coating agent, and then a roll coating, a gravure coating, a knife coating, a dip coating, and a spray are applied. An anchor coat layer can be formed by coating on a film substrate by a method such as coating to form a coating film, and drying and removing a solvent, a diluent and the like. As a method for drying the coating film, a heat roll contact method, a heat medium (air, oil, etc.) contact method, an infrared heating method, a microwave heating method, or the like can be used. Above all, the gravure coating method is preferable as a method suitable for coating a layer having a thickness of 0.3 to 10 μm, which is a preferable thickness of the anchor coating layer of the present invention.

[Film substrate]
The film substrate used in the present invention is not particularly limited as long as it is a film substrate containing an organic polymer compound, and for example, polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate and polyethylene naphthalate, and cycloolefin polymers. A film containing various polymers such as cycloolefin copolymer, polyamide, polycarbonate, polystyrene, polyvinyl alcohol, saponified product of ethylene vinyl acetate copolymer, polyacrylonitrile, and polyacetal can be used. The polymer constituting the film substrate may be a homopolymer or a copolymer, or may be a single polymer or a blend of a plurality of polymers.

The film substrate is preferably in the form of a roll from the viewpoint that the film substrate surface can be continuously and efficiently subjected to the film formation treatment by the winding type.

Further, as the film base material, a single-layer film, a film having two or more layers, for example, a film formed by a co-extrusion method, a film stretched in a uniaxial direction or a biaxial direction, or the like may be used. The surface on which the thin film is formed is treated with a corona treatment, an ion bombard treatment, a solvent treatment, a roughening treatment, and an anchor coat layer composed of an organic substance, an inorganic substance, or a mixture thereof in order to improve adhesion. Pretreatment such as may be applied. Further, on the surface opposite to the surface on which the thin film is formed, an organic substance or an organic substance is used for the purpose of improving the slipperiness when winding the film and reducing the friction with the thin film when winding the film after forming the thin film. A coating layer of an inorganic substance or a mixture thereof may be applied. The thickness of the film base material used is not particularly limited, but is preferably 10 to 200 μm from the viewpoint of heat loss and handling of the film base material during film formation.

[Manufacturing method of gas barrier film]
In the method for producing a gas barrier film in the present invention, a gas barrier is formed on at least one side of a film substrate by forming a gas barrier layer containing a zinc compound and a compound of an element A other than zinc in Groups 12 to 14 of the Periodic Table. It is a method for producing a sex film, which is preferably formed by heating from the surface side of the film base material so that the maximum surface temperature of the film base material at the time of forming the gas barrier layer is 40 to 200 ° C. ..

The gas barrier layer in the present invention can be formed by using a film forming mechanism such as a sputtering method, a vacuum vapor deposition method, an ion plating method, or a CVD method. Among these methods, the sputtering method is preferable as a method that is inexpensive, simple, and can obtain desired layer properties. The sputtering method may be performed by any method such as a single-wafer method or a winding method, but the winding method is preferable as a method for easily obtaining a desired gas barrier film. FIGS. 3 and 8 show an example of a roll-to-roll sputtering apparatus. The sputtering method will be described below as an example.

The gas barrier layer in the present invention is preferably obtained by heating the film base material from the surface side during sputtering to set the maximum surface temperature of the film base material to 40 to 200 ° C. By applying such conditions, the sputtered particles forming the gas barrier layer during sputtering can be uniformly diffused on the surface of the film substrate, so that the gas barrier layer can be densified. High gas barrier properties that could not be achieved can be obtained, and the composition in the gas barrier layer can be controlled. Here, the surface of the film base material refers to the surface of the film that forms the gas barrier layer. It should be noted that the fact that the sputtered particles forming the gas barrier layer diffuse uniformly on the surface of the film substrate during sputtering may be abbreviated as "surface diffusivity of the particles".

By heating from the surface side of the film substrate during sputtering, the maximum surface temperature of the film substrate is set to 40 to 200 ° C., so that the surface diffusivity of the particles is improved, thereby densifying the gas barrier layer. Is preferable because it enables. The maximum surface temperature of the film substrate is the highest temperature reached when the thermocouple is attached to the surface of the film substrate and the surface temperature of the film substrate is measured when the gas barrier layer is formed using a data logger. Say.

If the maximum surface temperature of the film substrate is lower than 40 ° C., the effect of improving the surface diffusivity of the particles cannot be sufficiently obtained, and the gas barrier property may be insufficient. On the other hand, if the maximum surface temperature of the film substrate is higher than 200 ° C., the film substrate may be melt-deformed and cannot be used as a gas barrier film. The maximum surface temperature of the film substrate is more preferably adjusted to 100 to 180 ° C., and even more preferably 100 to 150 ° C., from the viewpoint of gas barrier properties and suppressing heat loss of the film. From the viewpoint of effectively densifying the gas barrier layer, it is preferable that the maximum surface temperature appears when the interface portion of the gas barrier layer is formed.

Examples of the method of heating the surface of the film substrate include a method of heating with a lamp heater. The method for heating is not limited to the lamp heater as long as the film substrate can be heated from the film surface side, but the lamp heater is preferable from the viewpoint of effectively improving the surface diffusivity of the particles. Further, when the film base material is heated from the film front surface side, it is preferable to cool the back surface side of the film base material from the viewpoint of suppressing heat loss of the film.

The lamp heater used in the present invention is preferably an infrared (IR) heater having a peak wavelength of 0.8 to 2.5 μm. An infrared heater having a peak wavelength of 0.8 to 2.5 μm is a heater that uses light emitted from a heating element at about 900 to 2,800 ° C. in which 85% or more of the input power is converted to infrared rays. .. If the heater has a peak wavelength smaller than 0.8 μm, the irradiation energy is strong and the surface of the base material may be damaged. On the other hand, if the heater has a peak wavelength larger than 2.5 μm, the irradiation energy is small, and the film substrate may not be heated to the target temperature, or the film substrate may not be heated efficiently. From the viewpoint of heating efficiency and the like, a lamp heater having a peak wavelength of 0.8 to 1.8 μm is more preferable.

As the lamp heater used in the present invention, halogen lamp heaters, ceramic heaters, quartz tube heaters, carbon heaters and the like can be used among the infrared heaters. A halogen lamp heater is a light source having a peak wavelength in the near infrared region, and is a thermal radiation light source that converts electrical energy into thermal energy, raises the temperature of a solid, and uses radiation corresponding to that temperature. It is preferable to use a halogen lamp heater from the viewpoints that it can be used in a vacuum chamber, the irradiation energy rises and falls quickly, and the generation of particles is small. Further, it is more preferable that the halogen lamp heater has a peak wavelength of 0.8 to 2.5 μm.

The lamp heater used in the present invention is preferably arranged in the film forming chamber so as to satisfy any of the following.
(I) The lamp heater (A) is provided on the unwinding side of the film forming mechanism, and the lamp heater (A) has a reflector (C) having a variable irradiation angle. (Ii) On the winding side of the film forming mechanism. It has a lamp heater (B), and the lamp heater (B) has a reflector (D) with a variable irradiation angle (iii). The lamp heater (A) and the film forming mechanism are wound on the unwinding side of the film forming mechanism. The lamp heater (B) is provided on the taking side, and the lamp heater (A) has a reflector (C) having a variable irradiation angle (iv). The lamp heater (A) and the film forming are formed on the unwinding side of the film forming mechanism. The lamp heater (B) is provided on the winding side of the mechanism, and the lamp heater (B) has a reflector (D) having a variable irradiation angle. (V) The lamp heater (A) and the lamp heater (A) are provided on the winding side of the film forming mechanism. The lamp heater (B) is provided on the take-up side of the film forming mechanism, the lamp heater (A) has a reflector (C) having a variable irradiation angle, and the lamp heater (B) has a reflector having a variable irradiation angle (B). Has D).

Irradiation and the variable-angle reflector from a reference plane of the magnetron sputtering cathode 18 in FIG. 4, with respect to the lamp heater (A) 17 0 ° ≦ Θ A ≦ 90 °, 0 ° ≦ Θ with respect to the lamp heater (B) 19 _B It is preferable that the reflector has a variable irradiation angle at an angle of ≦ 90 °. Θ _A and Θ _B represent the irradiation angles of the lamp heater (A) and the lamp heater (B), respectively, and the outermost surface of the magnetron sputtering cathode 18 is set to 0 ° (reference plane), and the irradiation angles are respectively in the arrow directions in FIG. Is variable.

It is preferable to provide a lamp heater (A) having a reflector (C) with a variable irradiation angle on the unwinding side of the film forming mechanism because it is possible to control the film structure such as the film composition at the initial stage of thin film formation. From the viewpoint of effectively controlling the film structure such as the film composition at the initial stage of thin film formation, the irradiation angle of the reflector (C) of the lamp heater (A) on the unwinding side is 0 ° ≤ Θ _A ≤ 45 °. More preferred.

It is preferable to provide a lamp heater (B) having a reflector (D) with a variable irradiation angle on the take-up side of the film forming mechanism because it is possible to add an inclination to the film quality in the depth direction. From these viewpoints, it is more preferable that the reflector (D) of the lamp heater (B) on the take-up side is 0 ° ≤ Θ _B ≤ 60 °.

A lamp heater (A) is provided on the unwinding side of the film forming mechanism, a lamp heater (B) is provided on the winding side of the film forming mechanism, and the lamp heater (A) has a reflector (C) having a variable irradiation angle. Alternatively, since the lamp heater (B) has a reflector (D) with a variable irradiation angle, the lamp heater (A) can control the film structure at the initial stage of thin film formation, and the lamp heater (B) further reduces the thin film. This is preferable because it enables control of the film quality in the depth direction and control of the outermost layer of the thin film.

A lamp heater (A) is provided on the unwinding side of the film forming mechanism, a lamp heater (B) is provided on the winding side of the film forming mechanism, and the lamp heater (A) has a reflector (C) having a variable irradiation angle. Alternatively, since the lamp heater (B) has a reflector (D) with a variable irradiation angle, the lamp heater (A) can control the film structure at the initial stage of thin film formation, and the lamp heater (B) further reduces the thin film. It is preferable because it is possible to control the film quality in the depth direction and the outermost layer of the thin film, and it is possible to more easily control the film quality in the depth direction of the thin film.

The reflectors installed in the lamp heater are generally considered to be parallel light type reflectors, condensing type reflectors, parabola type reflectors, etc., but what if the film base material is resistant to heat loss and can be heated? It doesn't matter what type it is. The parallel light type reflector is a reflector capable of uniformly irradiating a fixed area as shown in FIG. It is preferable to arrange a plurality of lamp heaters equipped with parallel reflectors in parallel because it is possible to uniformly heat a wide area. However, in FIG. 5, for the sake of simplification of the figure, the light directly emitted from the lamp heater 21 to the base film is omitted. As shown in FIG. 6, the light-condensing reflector is a reflector capable of condensing light in a line shape, and is suitable when only a part of a film base material is to be quickly heated. However, in FIG. 6, for the sake of simplification of the figure, the light directly emitted from the lamp heater 26 to the film substrate is omitted. Further, the parabola type reflector is a reflector capable of uniformly irradiating a wide range, and since it is possible to irradiate a wider range than the parallel light type, it is necessary to uniformly irradiate a wide range. It is suitable when the space for installing the lamp heater is small and it is difficult to install multiple lamp heaters equipped with parallel light reflectors. In order to efficiently and uniformly heat the surface of the film substrate in a film forming chamber having a limited size, it is preferable to use a parallel light type reflector or a parabola type reflector having low directivity.

The composition ratio of the target material used in the present invention is as follows: zinc (Zn) atomic concentration is 3 to 37 atm%, silicon (Si) atomic concentration is 5 to 20 atm%, aluminum (Al) atomic concentration is 1 to 7 atm%, and oxygen ( O) The composition preferably has an atomic concentration of 50 to 70 atm%. When the zinc atom concentration is less than 3 atm% or the silicon atom concentration is more than 20 atm%, the proportion of zinc atoms that make the gas barrier layer a highly flexible film is small, so that the gas barrier property is obtained when the gas barrier layer is formed. The flexibility of the film may be impaired. From this point of view, the zinc atom concentration is more preferably 5 atm% or more. When the zinc atom concentration is higher than 37 atm% or the silicon atom concentration is lower than 5 atm%, the gas barrier layer formed by reducing the proportion of silicon atoms tends to become a crystal film and cracks may easily occur. is there. From this point of view, the zinc atom concentration is more preferably 36.5 atm% or less. From the same viewpoint, the silicon atom concentration is more preferably 7 atm% or more. If the aluminum atom concentration is less than 1 atm%, the conductivity of the target material is impaired, so that DC sputtering may not be possible. Further, when the aluminum atom concentration is more than 7 atm%, the affinity between zinc oxide and silicon dioxide becomes excessively high when the gas barrier layer is formed, so that cracks are likely to occur due to heat and external stress. In some cases. If the oxygen atom concentration is less than 50 atm%, the formed gas barrier layer tends to be insufficiently oxidized, and the light transmittance may decrease. When the oxygen atom concentration is more than 70 atm%, oxygen is easily taken in excessively when forming the gas barrier layer, so that voids and defects may increase and the gas barrier property may decrease.

[Use]
Since the gas barrier film of the present invention has a high gas barrier property, it can be suitably used as a packaging material for foods, electronic devices and the like. Further, due to its high gas barrier property, it can be suitably used for electronic member applications such as solar cells, electronic papers, and organic electroluminescent (EL) displays.

[Evaluation method]
(1) Depth direction analysis of composition ratio The composition analysis of the gas barrier layer was performed by X-ray photoelectron spectroscopy (XPS). By performing sputtering etching using argon ions, the composition ratio was analyzed for each etching from the outermost surface of the gas barrier layer toward the film substrate. After analyzing the composition ratio of the outermost surface, etching and analysis of the composition ratio were repeated, and the analysis was completed when the composition ratio of Zn became 1.0 atm% or less. When each Example / Comparative Example was etched under the following etching conditions, about 2 nm was etched per etching. The measurement conditions of the XPS method were as follows.
・ Equipment: ESCA 5800 (manufactured by ULVAC-PHI)
-Excited X-ray: monochromatic AlKα
・ X-ray output: 300W
・ X-ray diameter: 800 μm
・ Photoelectron escape angle: 45 °
-Ar ion etching: 2.0 kV, 10 mPa
・ One etching time: 3.0 min.

(2) Water vapor transmittance measurement Under the conditions of temperature 40 ° C., humidity 90% RH, and measurement area 50 cm ² , a water vapor transmittance measuring device (model name: DELTAPERM (registered trademark)) manufactured by Technolox, UK, is used. Used and measured. The number of samples was 2 samples per level. Averaged data obtained was measured in the two samples, rounded to the first decimal place, an average value in the levels were the values water vapor permeability and ^{(g / (m 2 · 24hr} · atm)).

(3) Color tone Based on the CIE standard (1976), the b ^* value of the transmitted color was measured using the spectrophotometric CM-2600d (manufactured by Konica Minolta Sensing Co., Ltd.). A D65 was used as the light source, and the measurement was performed under the condition of an angle of 2 °.

(4) Bending test A test piece having a length of 10 cm and a width of 10 cm was cut out, and bending was repeated 10,000 times with a bending radius of 3 mm and a bending angle of 180 ° with the gas barrier layer inside. The water vapor permeability of the test piece after the bending test was measured. The number of tests was two for each level.

(5) Measurement of maximum surface temperature of the film substrate The surface temperature of the film substrate was measured by a data logger by attaching a thermocouple to the surface of the film substrate with Capton tape to form a gas barrier layer. As the thermocouple, a K-type thermocouple (PA0210) manufactured by DATAPAQ was used. As the data logger, a data logger manufactured by DATAPAQ (DQ1863-S) was used. Since it is used in a vacuum, the data logger was used in a heat-resistant case for vacuum process (TB7400C) manufactured by DATAPAQ. The highest temperature reached during the measurement was taken as the maximum surface temperature measurement of the film substrate.

(Example 1)
[Synthesis of polyurethane compounds with aromatic ring structure]
300 parts by mass of bisphenol A diglycidyl ether acrylic acid adduct (manufactured by Kyoeisha Chemical Co., Ltd., trade name: epoxy ester 3000A) and 710 parts by mass of ethyl acetate are placed in a 5-liter four-necked flask, and the internal temperature reaches 60 ° C. I warmed it up. 0.2 parts by mass of di-n-butyltin dilaurate was added as a synthesis catalyst, and 200 parts by mass of dicyclohexylmethane 4,4'-diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 1 hour with stirring. The reaction was continued for 2 hours after the completion of the dropping, and then 25 parts by mass of diethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 1 hour. The reaction was continued for 5 hours after the dropping to obtain a polyurethane compound having an aromatic ring structure having a weight average molecular weight of 20,000.

[Formation of anchor coat layer]
As the film base material, a polyethylene terephthalate film having a thickness of 100 μm (“Lumirror” (registered trademark) U48 manufactured by Toray Industries, Inc.) was used.

As a coating liquid for forming the anchor coat layer, 150 parts by mass of the polyurethane compound, 20 parts by mass of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: light acrylate DPE-6A), 1-hydroxy-cyclohexylphenyl 5 parts by mass of ketone (BASF Japan, trade name: IRGACURE 184), 3 parts by mass of 3-methacryloxypropylmethyldiethoxysilane (Shinetsu Silicone, trade name: KBM-503), 170 parts by mass of ethyl acetate The coating liquid was adjusted by blending 350 parts by mass of toluene and 170 parts by mass of cyclohexanone. Next, the coating liquid was applied onto the film substrate with a microgravure coater (gravure wire number 150UR, gravure rotation ratio 100%), dried at 100 ° C. for 1 minute, dried, and then subjected to ultraviolet treatment under the following conditions to achieve a thickness of 1. An anchor coat layer of 000 nm was provided.

Ultraviolet processing device: LH10-10Q-G (manufactured by Fusion UV Systems Japan)
Introduced gas: N ₂ (Nitrogen Inert BOX)
Ultraviolet source: Microwave type electrodeless lamp Integrated light intensity: 400mJ / cm ²
Sample temperature control: room temperature.

[Formation of gas barrier layer]
Sputtering with argon gas and oxygen gas was performed using a sputtering target having a mass ratio of zinc oxide / silicon dioxide / aluminum oxide of 77/20/3 on the side where the anchor coat layer was formed on the film substrate, and the gas barrier layer was formed. (Thickness of gas barrier layer: 50 nm).

The specific operation is as follows. A gas barrier film was obtained using the take-up sputtering apparatus 4 having the structure shown in FIG. The arrangement of IR heaters was installed as shown in FIG.

First, a take-up type in which a sputtering target containing zinc oxide, silicon dioxide, and aluminum oxide and having a composition mass ratio of zinc oxide / silicon dioxide / aluminum oxide of 77/20/3 is installed on the magnetron sputtering cathode 18. In the winding chamber of the sputtering apparatus 4, the film base material 7 provided with the anchor coat layer is set on the unwinding roll 8, and after unwinding, the temperature is passed through the tension sensor rolls 9 and the guide rolls 10 and 11. It was passed through a temperature control roll 12 at 0 ° C. Next, evacuation was performed until the pressure reached 1.0 × 10 ^-3 Pa, and then argon gas and oxygen gas were introduced at a partial pressure of oxygen gas of 10% so as to have a decompression degree of 2.0 × 10 ^-1 Pa. While heating the film base material 7 with the lamp heaters 17 and 19, an input power of 3,000 W is applied to the magnetron sputtering cathode 18 by a DC power source to generate an argon / oxygen gas plasma, and the sputtering causes the film substrate 7. A gas barrier layer was formed on the surface of the film base material 7. As the lamp heater, Iwasaki Electric Co., Ltd. parallel light type irradiator IRE370-M was used, and the angle of the reflector in FIG. 4 was set to Θ _A = 12 ° and Θ _B = 12 °. The output of the lamp heater was adjusted so that the maximum surface temperature of the film substrate 7 was 150 ° C. Then, it was wound on the winding roll 16 via the guide rolls 13 and 14 and the tension sensor roll 15.

Subsequently, a test piece was cut out from the obtained gas barrier film, and composition analysis in the depth direction by XPS, water vapor transmittance, color tone, and bending resistance were evaluated. The results are shown in FIGS. 9, 10 and 1.

(Example 2)
_A gas barrier film was obtained in the same manner as in Example 1 except that the angle of the reflector was Θ _A = 45 ° and Θ _B = 45 °. The results are shown in FIGS. 11 and 12, Table 1.

(Example 3)
A gas barrier film was obtained in the same manner as in Example 1 except that the output of the lamp heater was adjusted so that the maximum surface temperature of the film substrate was 110 ° C. The results are shown in FIGS. 13 and 14, Table 1.

(Example 4)
_A gas barrier film was obtained in the same manner as in Example 1 except that the lamp heaters were arranged as shown in FIG. 7 and the angle of the reflector was set to Θ _A = 12 °. The results are shown in FIGS. 15 and 16, Table 1.

(Example 5)
A gas barrier film was obtained in the same manner as in Example 1 except that the retractable sputtering apparatus 30 having the structure shown in FIG. 8 was used and the lamp heaters were arranged as shown in FIG. The results are shown in FIGS. 17 and 18, Table 1.

(Comparative Example 1)
A gas barrier film was obtained in the same manner as in Example 1 except that the lamp heaters 17 and 19 of the retractable sputtering apparatus 4 having the structure shown in FIG. 3 were removed and used, and the temperature of the temperature control roll 15 was set to 0 ° C. It was. The results are shown in FIGS. 19 and 20 and Table 1.

(Comparative Example 2)
A gas barrier film was obtained in the same manner as in Comparative Example 1 except that the temperature of the temperature control roll was set to 100 ° C. The results are shown in FIGS. 21, 22 and Table 1.

(Comparative Example 3)
A gas barrier film was obtained in the same manner as in Comparative Example 1 except that a sputtering target having a mass ratio of zinc oxide / silicon dioxide / aluminum oxide of 58/39/4 was used. The results are shown in FIGS. 23 and 24, Table 1.

(Comparative Example 4)
A gas barrier film was obtained in the same manner as in Comparative Example 2 except that a sputtering target having a mass ratio of zinc oxide / silicon dioxide / aluminum oxide of 58/39/4 was used. The results are shown in FIGS. 25 and 26, Table 1.

In Examples 1 to 5, the gas barrier properties are the same and good before and after the bending test, and the color tone is also good. On the other hand, in Comparative Examples 1 and 2, although there is no change in the gas barrier property before and after the flexibility test, the color tone is high and a yellowish color is generated. In Comparative Examples 3 and 4, the color tone is good, but the gas barrier property after the bending test is poor. That is, by having the configuration of the present invention, it is possible to obtain a gas barrier film having excellent transparency and exhibiting a high degree of gas barrier property, in which the gas barrier property is less likely to decrease even with bending.

1, 7, 22, 27, 34 Film base material 2 Gas barrier layer 3 Anchor coat layer 4, 30 Take-up sputtering device 5, 31 Unwinding / winding chamber 6, 32, 33 Film formation chamber 8, 35 Unwinding roll 9, 15, 36, 43 Tension sensor rolls 10, 11, 13, 14, 37, 38, 41, 42 Guide rolls 12, 39, 40 Temperature control rolls 16, 44 Winding rolls 17, 45, 48 Variable irradiation angle Lamp heater (A) having a reflector (C)
18, 46, 49 Magnetron Sputtering Cathodes 19, 47, 50 Lamp heater (B) with variable irradiation angle reflector (D)
20 Parallel light type reflector 21, 26 Lamp heater 23, 28 Irradiation light of lamp heater 24, 29 Reflected light from reflector 25 Condensing type reflector

Claims (7)

A laminated film having an X layer containing a zinc compound and a compound of an element A other than zinc in groups 12 to 14 of the periodic table on at least one side of the film base material, wherein the element A contains at least silicon. Including, the silicon is at least one silicon compound selected from the group consisting of silicon oxide, silicon nitride, silicon oxide nitride and silicon carbide, and the content ratio (Zn / A) of zinc Zn and element A in the X layer is determined. When divided by the content ratio (Zn / A) of zinc Zn and element A in the X layer in the flat portion, there is a position having a value of at least 1.15 and less than 3.00, and this position is an interface. The content ratio (Zn / A) of zinc Zn and element A in the X layer, which is present in the portion or in the surface layer portion and the interface portion, is the content ratio of zinc Zn and element A in the X layer in the flat portion. Lamination characterized in that the ratio of the film thickness having a value of more than 1.15 and less than 3.00 to the thickness of the entire X layer when divided by (Zn / A) is 5 to 50%. the film. The laminated film according to claim 1, wherein the zinc compound is zinc oxide and / or zinc sulfide. The X layer has a zinc (Zn) atomic concentration of 3 to 35 atm%, a silicon (Si) atomic concentration of 7 to 25 atm%, and an aluminum (Al) atomic concentration of 1 to 7 atm as measured by X-ray photoelectron spectroscopy (XPS). The laminated film according to claim 1 or 2 , wherein the oxygen (O) atom concentration is 50 to 70 atm%. A method for producing a laminated film in which an X layer containing a zinc compound and a compound of an element A other than zinc in Groups 12 to 14 of the Periodic Table is formed on at least one side of the film base material by a lamp heater. By heating from the surface side of the film base material, the maximum surface temperature of the film base material at the time of forming the X layer is set to 40 to 200 ° C., and the lamp heater is placed in any of the following (i) to (v) in the film forming chamber. A method for producing a laminated film, which is characterized by being arranged in a form that satisfies the above conditions.
The unwinding side of the (i) film forming mechanism having a lamp heater (A), the lamp heater (A) has an irradiation angle variable Li Flector (C) at an angle of 0 ° ≦ ΘA ≦ 45 ° ( ii ) having a lamp heater (B) in the take-up side of the film formation mechanism, the lamp has a heater (B) irradiation angle variable re Flector at an angle of 0 ° ≦ ΘB ≦ 60 ° ( D) (iii) film It has a lamp heater (A) on the unwinding side of the forming mechanism and a lamp heater (B) on the winding side of the film forming mechanism, and the lamp heater (A ) has an irradiation angle of 0 ° ≤ ΘA ≤ 45 °. having a variable re Flector (C) (iv) having a lamp heater (B) to the take-out side of the film forming mechanism to a take-up side of the lamp heater (a) and said film forming mechanism, the lamp heater (B) lamp heater winding side of but 0 ° ≦ ΘB ≦ 60 ° angle in the irradiation angle variable Li having Flector (D) (v) film unwinding side lamp heater forming mechanism (a) and said film forming mechanism (B) has, the lamp has a heater (a) irradiation angle variable Li Flector (C) at an angle of 0 ° ≦ ΘA ≦ 45 °, the lamp heater (B) is 0 ° ≦ ΘB ≦ 60 having a ° angle in the irradiation angle variable Li Flector (D) The method for producing a laminated film according to claim 4 , wherein the lamp heater is a halogen lamp heater having a peak wavelength of 0.8 to 2.5 μm. The method for producing a laminated film according to claim 4 or 5 , wherein the method for forming the X layer is a sputtering method. The target material forming the X layer has a zinc (Zn) atomic concentration of 3 to 37 atm%, a silicon (Si) atomic concentration of 5 to 20 atm%, an aluminum (Al) atomic concentration of 1 to 7 atm%, and oxygen (O). The method for producing a laminated film according to any one of claims 4 to 6 , wherein the composition has an atomic concentration of 50 to 70 atm%.

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