JP2016193526A - Gas barrier film, and electronic device using the gas barrier film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier film having gas barrier properties excellent in adhesiveness and bending resistance.SOLUTION: There is provided a gas barrier film 111 which has a first inorganic barrier layer 120a formed by applying a coating film obtained by applying a coating liquid containing polysilazane onto a resin substrate 110 with vacuum ultraviolet rays and a second inorganic barrier layer 120b which is arranged in contact with the first gas barrier layer 120a and is formed by a CVD method, where the second inorganic barrier layer 120b contains at least one or more metal selected from Al, Ti, Zr, Ta, Nb, Hf, Ru or Y, a content of the metal of the second inorganic barrier layer 120b is 25-50 at% based on the total of elements of the whole layer, and a content of carbon of the second inorganic barrier layer 120b is 0.1-10 at% based on the total of the elements of the whole layer. A content of nitrogen of the first inorganic gas barrier layer 120a is 10-40 at% based on the total of silicone, oxygen and nitrogen.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a gas barrier film and an electronic device using the gas barrier film.

  Conventionally, a gas barrier film in which a thin film (gas barrier layer) containing a metal oxide such as aluminum oxide, magnesium oxide, or silicon oxide is formed on the surface of a plastic substrate or film is used for packaging articles in the fields of food, medicine, etc. It is used for. By using the gas barrier film, it is possible to prevent alteration of the article due to gas such as water vapor or oxygen.

  By the way, in recent years, gas barrier films that prevent permeation of water vapor, oxygen, and the like as described above are also used in the field of electronic devices such as liquid crystal display elements (LCD), solar cells (PV), and organic electroluminescence (EL). It's getting on. In order to apply a gas barrier film to an electronic device, a particularly high gas barrier property is required.

  In general, a gas barrier film is produced by forming an inorganic barrier layer on a base film by a vapor deposition method such as vapor deposition, sputtering, or CVD. In recent years, a manufacturing method for forming a gas barrier layer by applying energy to a precursor layer formed by applying a solution on a substrate has been studied. In particular, studies using a polysilazane compound as a precursor have been widely conducted, and studies are being conducted as a technique for achieving both high productivity and barrier properties by coating. In particular, the modification of the polysilazane layer using excimer light having a wavelength of 172 nm has attracted attention.

  For example, Patent Document 1 discloses an optical thin film device in which a SiOx (0 ≦ x ≦ 2) layer and a high refractive index layer are sequentially formed on a substrate. In the optical thin film device, when the distance of moisture passing therethrough is increased, the passage resistance is increased and the amount of moisture can be remarkably suppressed. Patent Document 2 discloses a gas barrier film in which a buffer layer containing polysilazane and a gas barrier layer containing a silicon-metal composite oxide are sequentially laminated on a base material. According to the film, it is said that flexibility can be secured while having high gas barrier properties.

  Further, Patent Document 3 has at least one barrier layer made of a ceramic material, and the barrier layer is coated with a solution of perhydropolysilazane (PHPS) and then modified to form silicon oxide (SiOx). A gas barrier film in which a layer of) is formed is disclosed. In Patent Document 4, an energy ray (for example, a vacuum) is applied to a coating film formed by applying a polysilazane solution to which a transition metal compound is added on a substrate and drying the coating film in an atmosphere substantially free of oxygen or moisture. A gas barrier film formed by performing (ultraviolet) irradiation is disclosed. According to this method, the reforming proceeds in a short time to form a high nitrogen concentration film, and high gas barrier properties are exhibited. In Patent Document 5, for example, one extreme value is included in a carbon distribution curve that includes silicon, oxygen, and carbon with a specific composition, the carbon amount changes in the film thickness direction, and indicates the ratio of the carbon atom weight to the film thickness direction. A gas barrier film having the above-described thin film layer is disclosed. According to the gas barrier film having such a configuration, it is said that a decrease in gas barrier characteristics when the film is bent is suppressed.

JP 2000-211053 A JP 2009-220342 A Special table 2008-536711 gazette JP 2012-148416 A JP 2011-73430 A

  In the gas barrier films of Patent Documents 1 and 2, polysilazane has not been subjected to modification treatment, and such a gas barrier film has a low gas barrier function, and has insufficient adhesion and flex resistance. .

In the techniques described in Patent Documents 3 to 5, the surface is modified to show a high gas barrier property, and under a general condition, a high gas barrier property is exhibited. As a result, there has been a problem that the gas barrier property is rapidly lowered. In addition, since the adhesiveness is low and the flexibility is low, it is not sufficient from the viewpoint of bending resistance. As described above, the gas barrier film described in Patent Documents 1 to 5 has sufficient gas barrier properties. It did not have adhesion and bending resistance.

  Then, an object of this invention is to provide the gas barrier film which has the gas barrier property which has the outstanding gas barrier property, and is excellent in adhesiveness and bending resistance.

  The present inventor has intensively studied to solve the above problems. As a result, a resin base material, a first inorganic barrier layer, and a second inorganic barrier layer containing a specific metal formed in contact with the first inorganic barrier layer, the metal and carbon in the second inorganic barrier layer The present invention has been completed by finding that the above-mentioned problems can be solved by a gas barrier film in which the content of is within a predetermined range.

  That is, the present invention provides a first inorganic barrier layer formed by applying vacuum ultraviolet light to a coating obtained by applying and drying a coating liquid containing polysilazane on a resin substrate, and the first inorganic barrier. A second inorganic barrier layer formed by plasma enhanced chemical vapor deposition, which is disposed in contact with the layer, wherein the second inorganic barrier layer is made of Al, Ti, Zr, Ta, Nb, Hf, Ru And at least one metal selected from the group consisting of Y, and the content of the metal in the second inorganic barrier layer is 25 to 50 at% with respect to 100 at% of the total amount of elements in the entire layer. The carbon content of the second gas barrier layer is a gas barrier film that is 0.1 to 10 at% with respect to 100 at% of the total amount of elements in the entire layer.

  ADVANTAGE OF THE INVENTION According to this invention, it has the gas barrier property which has the outstanding gas barrier property, and is excellent in adhesiveness and bending resistance.

FIG. 1 is a schematic cross-sectional view showing a gas barrier film according to an embodiment of the present invention. FIG. 2 is a schematic view showing an example of a manufacturing apparatus used for forming a gas barrier layer by plasma enhanced chemical vapor deposition.

  The present invention provides a first inorganic barrier layer formed by applying vacuum ultraviolet light to a coating obtained by applying and drying a coating liquid containing polysilazane on a resin substrate, and the first inorganic barrier layer. And a second inorganic barrier layer formed by plasma enhanced chemical vapor deposition, wherein the second inorganic barrier layer comprises Al, Ti, Zr, Ta, Nb, Hf, Ru and Y. One or more metals selected from the group consisting of: the metal content of the second inorganic barrier layer is 25 to 50 at% with respect to the total amount of elements of 100 at% of the entire layer; The carbon content of the two gas barrier layer is a gas barrier film that is 0.1 to 10 at% with respect to 100 at% of the total amount of elements in the entire layer. The gas barrier film of the present invention having such a configuration is excellent in gas barrier properties, adhesion and flex resistance. The reason why the above effect can be obtained by the gas barrier film of the present invention is unknown, but the following mechanism is conceivable. Note that the following mechanism is based on speculation, and the present invention is not limited to the following mechanism.

  In the gas barrier film of the present invention, the first inorganic barrier layer and the second inorganic barrier layer are referred to as a gas barrier layer (hereinafter, the two layers of the first inorganic barrier layer and the second inorganic barrier layer are collectively referred to as “gas barrier layer”). Function as). That is, a first inorganic barrier layer formed by subjecting a coating film containing polysilazane to a modification treatment (hereinafter sometimes simply referred to as “first inorganic barrier layer containing a polysilazane modified product”) and a specific metal. The second inorganic barrier layer containing each has gas barrier properties. The first inorganic barrier layer is a layer containing silicon oxide or silicon oxynitride obtained by modifying polysilazane, the second inorganic barrier layer contains a specific metal, and the content of metal and carbon is within a predetermined range. Therefore, the two layers have resistance to moist heat and can protect the resin base material satisfactorily.

  In the gas barrier film of the present invention, the first inorganic barrier layer and the second inorganic barrier layer are formed in contact with each other. Under the present circumstances, the specific metal atom contained in a 2nd inorganic barrier layer has a low electronegativity compared with the silicon atom contained in a 1st inorganic barrier layer. Thereby, the second inorganic barrier layer is likely to be oxidized earlier than the first inorganic barrier layer, and it is considered that higher gas barrier performance is exhibited by the presence of such a second inorganic barrier layer.

  The second inorganic barrier layer of the present invention is formed by plasma enhanced chemical vapor deposition. Thereby, a 1st inorganic barrier layer and a 2nd inorganic barrier layer can be closely_contact | adhered and formed, and also the 2nd inorganic barrier layer with high flexibility is formed. Therefore, the adhesion and bending resistance of the gas barrier film are improved.

  As described above, as a result of intensive studies, the present inventors have achieved excellent gas barrier properties by forming the first inorganic barrier layer containing the modified polysilazane and the second inorganic barrier layer containing the specific metal in contact with each other. In addition, by specifying the formation method of each inorganic barrier layer and the composition of the second inorganic barrier layer, adhesion and flex resistance are improved, and more excellent gas barrier properties are achieved. Was found.

  In the gas barrier film of the present invention, the nitrogen content of the first gas barrier layer is preferably 10 to 40 at% with respect to the total amount of silicon, oxygen and nitrogen of 100 at%. If the nitrogen content of the first inorganic barrier layer is within the above range, the elements constituting the first inorganic barrier layer are electrically stabilized by the interaction with the metal atoms of the second inorganic barrier layer, and the oxidation rate is increased. Is significantly suppressed, it is possible to maintain a high water vapor barrier property over a long period of time.

  Hereinafter, preferred modes of the gas barrier film of the present invention will be described. In addition, this invention is not limited only to the following embodiment. In addition, the dimensional ratios in the drawings are exaggerated for convenience of explanation, and may be different from the actual ratios.

  In this specification, unless otherwise specified, measurement of operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50% RH.

  FIG. 1 is a schematic cross-sectional view showing a gas barrier film according to an embodiment of the present invention. In the gas barrier film 111 of FIG. 1, a resin base material 110 and a gas barrier layer 120 are disposed. The gas barrier layer 120 includes a first inorganic barrier layer 120a and a second inorganic barrier layer 120b. The gas barrier film 111 may include other layers in addition to the first inorganic barrier layer 120a and the second inorganic barrier layer 120b. Here, the other layer may be formed between the resin base 110 and the first inorganic barrier layer 120a, or may be formed on the second inorganic barrier layer 120b. May be formed on the opposite side (the side opposite to the side on which the gas barrier layer 120 is formed). Further, the number of units of the first inorganic barrier layer 120a and the second inorganic barrier layer 120b is not limited to one, and a plurality of units may exist. In FIG. 1, the second inorganic barrier layer 120b is formed on the first inorganic barrier layer 120a. However, the first inorganic barrier layer 120a and the second inorganic barrier layer 120b are formed in contact with each other on the resin base material. However, the order is not particularly limited, but preferably, the resin base 110, the first inorganic barrier layer 120a, and the second inorganic barrier layer 120b are laminated in this order.

  Hereinafter, each structure of the gas barrier film will be described.

[First inorganic barrier layer]
The first inorganic barrier layer is disposed on at least one surface side of the resin base material. The said 1st inorganic barrier layer is formed by applying a vacuum ultraviolet-ray to the coating film obtained by apply | coating and drying the coating liquid containing polysilazane. The 1st inorganic barrier layer may contain additives, such as inorganic particles, an amine catalyst, and a metal catalyst, as needed.

  The first inorganic barrier layer exhibits gas barrier properties by irradiation with vacuum ultraviolet rays. Further, unlike the case where the film is formed by the vapor deposition method, foreign substances such as particles are not mixed at the time of film formation, so that the gas barrier layer has very few defects.

  In addition, as described above, the nitrogen content of the first gas barrier layer is preferably 10 to 40 at%, more preferably 20 to 50 at%, with respect to 100 at% of the total amount of silicon, oxygen and nitrogen. More preferably, it is 30 to 40 at%. . A method for analyzing the composition of these first inorganic barrier layers will be described in the column of the second inorganic barrier layer described later.

  The first inorganic barrier layer may be a single layer or a laminated structure of two or more layers. When the first inorganic barrier layer has a laminated structure of two or more layers, other compounds may be mixed as long as the polysilazane modified product is contained in each layer. When the first inorganic barrier layer has a laminated structure of two or more layers, the total thickness of the first inorganic barrier layer is the thickness of the first inorganic barrier layer.

  From the viewpoint of gas barrier performance, the thickness of the first inorganic barrier layer (the total thickness in the case of a laminated structure of two or more layers) is the thickness of the second gas barrier layer (in the case of a laminated structure of two or more layers). The total thickness) is preferably 10 to 1000 nm, more preferably 50 to 600 nm, and still more preferably 50 to 300 μm. If it is this range, the balance of gas barrier property and durability becomes favorable and is preferable. The thickness of the first inorganic barrier layer can be measured by TEM observation.

The first inorganic barrier layer is formed by irradiating a coating film obtained by applying and drying a coating liquid containing polysilazane with vacuum ultraviolet rays. Polysilazane is a polymer having a silicon-nitrogen bond, and ceramics such as SiO ₂ , Si ₃ N ₄ , and both intermediate solid solutions SiO _x N _y having bonds such as Si—N, Si—H, and N—H. It is a precursor inorganic polymer.

  Specifically, the polysilazane preferably has the following structure.

In the general formula (I), R ₁ , R ₂ and R ₃ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group. . At this time, R ₁ , R ₂ and R ₃ may be the same or different.

  In the general formula (I), n is an integer, and the polysilazane having the structure represented by the general formula (I) is determined to have a number average molecular weight of 150 to 150,000 g / mol. Is preferred.

In the compound having the structure represented by the general formula (I), one of preferred embodiments is perhydropolysilazane in which all of R ₁ , R ₂ and R ₃ are hydrogen atoms.

  Alternatively, polysilazane has a structure represented by the following general formula (II).

In the general formula (II), R _{1 ′} , R _{2 ′} , R _{3 ′} , R _{4 ′} , R _{5 ′} and R _{6 ′} are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, An aryl group, a vinyl group or a (trialkoxysilyl) alkyl group. In this case, R _{1 ′} , R _{2 ′} , R _{3 ′} , R _{4 ′} , R _{5 ′} and R _{6 ′} may be the same or different. In the general formula (II), n ′ and p are integers, and the polysilazane having the structure represented by the general formula (II) is determined to have a number average molecular weight of 150 to 150,000 g / mol. It is preferred that Note that n ′ and p may be the same or different.

Among the polysilazanes of the above general formula (II), R _{1 ′} , R _{3 ′} and R _{6 ′} each represent a hydrogen atom, and R _{2 ′} , R _{4 ′} and R _{5 ′} each represent a methyl group; R _{1 '} , R _3' and R _{6 '} each represents a hydrogen atom, R _2' , R _{4 '} each represents a methyl group, and R _5' represents a vinyl group; R _{1 '} , R _3' , R ₄ A compound in which _' and R _6' each represent a hydrogen atom and R _{2 '} and R _5' each represents a methyl group is preferred.

  Alternatively, polysilazane has a structure represented by the following general formula (III).

In the general formula (III), R _{1 ″} , R _{2 ″} , R _{3 ″} , R _{4 ″} , R _{5 ″} , R _{6 ″} , R _{7 ″} , R _{8 ″} and R _{9 ″} are each independently A hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, vinyl group or (trialkoxysilyl) alkyl group, wherein R _{1 ″} , R _{2 ″} , R _{3 ″} , R _{4 ″} , R _{5 ″} , R _{6 ″} , R _{7 ″} , R _{8 ″} and R _{9 ″} may be the same or different.

In the general formula (III), n ″, p ″ and q are integers, and the polysilazane having the structure represented by the general formula (III) has a number average molecular weight of 150 to 150,000 g / mol. It is preferable to be determined as follows. Note that n ″, p ^″ and q may be the same or different.

Of the polysilazanes of the above general formula (III), R _{1 ″} , R _{3 ″} and R _{6 ″} each represent a hydrogen atom, and R _{2 ″} , R _{4 ″} , R _{5 ″} and R _{8 ″} each represent a methyl group. , R _{9 ″} represents a (triethoxysilyl) propyl group, and R _{7 ″} represents an alkyl group or a hydrogen atom.

  On the other hand, the organopolysilazane in which a part of the hydrogen atom portion bonded to Si is substituted with an alkyl group or the like has improved adhesion to the base material as a base by having an alkyl group such as a methyl group and is hard. The brittle polysilazane ceramic film can be toughened, and there is an advantage that the occurrence of cracks can be suppressed even when the (average) film thickness is increased. For this reason, these perhydropolysilazane and organopolysilazane may be appropriately selected according to the application, and may be used in combination.

  Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on 6- and 8-membered rings. Its molecular weight is about 600 to 2000 (polystyrene conversion) in terms of number average molecular weight (Mn), and there are liquid or solid substances, and the state varies depending on the molecular weight.

  Polysilazane is commercially available in the form of a solution dissolved in an organic solvent, and the commercially available product can be used as it is as the first inorganic barrier layer forming coating solution. As a commercially available product of polysilazane solution, NN120-10, NN120-20, NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL120-20, NL150A, NP110, NP140, SP140, etc. manufactured by AZ Electronic Materials Co., Ltd. Is mentioned. These polysilazane solutions can be used alone or in combination of two or more.

  Another example of the polysilazane that can be used in the present invention is not limited to the following. For example, a silicon alkoxide-added polysilazane obtained by reacting the above polysilazane with a silicon alkoxide (Japanese Patent Laid-Open No. 5-238827) or glycidol is reacted. Glycidol-added polysilazane (Japanese Patent Laid-Open No. 6-122852) obtained by reaction, alcohol-added polysilazane obtained by reacting alcohol (Japanese Patent Laid-Open No. 6-240208), metal carboxylate obtained by reacting metal carboxylate Addition polysilazane (JP-A-6-299118), acetylacetonate complex-added polysilazane (JP-A-6-306329) obtained by reacting a metal-containing acetylacetonate complex, metal obtained by adding metal fine particles Fine particle added polysila Emissions, such as (JP-A-7-196986), and a polysilazane ceramic at low temperatures.

  When polysilazane is used, the content of polysilazane in the first inorganic barrier layer before application of vacuum ultraviolet light can be 100% by mass when the total mass of the first inorganic barrier layer is 100% by mass. When the first inorganic barrier layer before application of vacuum ultraviolet rays contains a material other than polysilazane, the content of polysilazane in the layer is preferably 10% by mass or more and 99% by mass or less, and 40% by mass or more. More preferably, it is 95 mass% or less, Most preferably, it is 70 mass% or more and 95 mass% or less.

(Coating liquid for forming the first inorganic barrier layer)
The solvent for preparing the coating solution for forming the first inorganic barrier layer is not particularly limited as long as it can dissolve polysilazane, but water and reactive groups (for example, hydroxyl group, easily reacting with polysilazane). Alternatively, an organic solvent which does not contain an amine group and is inert to polysilazane is preferable, and an aprotic organic solvent is more preferable. Specifically, the solvent is an aprotic solvent; for example, carbon such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso, terpenes, etc. Hydrogen solvents; Halogen hydrocarbon solvents such as methylene chloride and trichloroethane; Esters such as ethyl acetate and butyl acetate; Ketones such as acetone and methyl ethyl ketone; Aliphatic ethers such as dibutyl ether, dioxane and tetrahydrofuran; Alicyclic ethers and the like Ethers: Examples include tetrahydrofuran, dibutyl ether, mono- and polyalkylene glycol dialkyl ethers (diglymes), and the like. The solvent is selected according to purposes such as the solubility of polysilazane and the evaporation rate of the solvent, and may be used alone or in the form of a mixture of two or more.

  The concentration of polysilazane in the first inorganic barrier layer-forming coating solution is not particularly limited, and varies depending on the film thickness of the layer and the pot life of the coating solution, but is preferably 1 to 80% by mass, more preferably 5 to 50% by mass. %, More preferably 10 to 40% by mass.

  The first inorganic barrier layer forming coating solution preferably contains a catalyst in order to promote reforming. As the catalyst applicable to the present invention, a basic catalyst is preferable, and in particular, N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine, N, N, N ', N'-tetramethyl-1,3-diaminopropane, amine catalysts such as N, N, N', N'-tetramethyl-1,6-diaminohexane, Pt compounds such as Pt acetylacetonate, propion Examples thereof include metal catalysts such as Pd compounds such as acid Pd, Rh compounds such as Rh acetylacetonate, and N-heterocyclic compounds. Of these, it is preferable to use an amine catalyst. The concentration of the catalyst added at this time is preferably in the range of 0.1 to 10% by mass, more preferably 0.5 to 7% by mass, based on the silicon compound. By setting the amount of the catalyst to be in this range, it is possible to avoid excessive silanol formation due to rapid progress of the reaction, reduction in film density, increase in film defects, and the like.

  The following additives can be used in the first inorganic barrier layer forming coating solution as necessary. For example, cellulose ethers, cellulose esters; for example, ethyl cellulose, nitrocellulose, cellulose acetate, cellulose acetobutyrate, etc., natural resins; for example, rubber, rosin resin, etc., synthetic resins; Aminoplasts, particularly urea resins, melamine formaldehyde resins, alkyd resins, acrylic resins, polyester resins or modified polyester resins, epoxy resins, polyisocyanates or blocked polyisocyanates, polysiloxanes, and the like.

(Method of applying the first inorganic barrier layer forming coating solution)
As a method of applying the first inorganic barrier layer forming coating solution, a conventionally known appropriate wet coating method may be employed. Specific examples include spin coating method, roll coating method, flow coating method, ink jet method, spray coating method, printing method, dip coating method, casting film forming method, bar coating method, die coating method, gravure printing method and the like. It is done.

  The coating thickness can be appropriately set according to the preferred thickness and purpose.

  After applying the coating solution, it is preferable to dry the coating film. By drying the coating film, the organic solvent contained in the coating film can be removed. At this time, all of the organic solvent contained in the coating film may be dried or may be partially left. Even when a part of the organic solvent is left, a suitable first inorganic barrier layer can be obtained. The remaining solvent can be removed later.

  Although the drying temperature of a coating film changes also with the base material to apply, it is preferable that it is 50-200 degreeC. For example, when a polyethylene terephthalate base material having a glass transition temperature (Tg) of 70 ° C. is used as the base material, the drying temperature is preferably set to 150 ° C. or lower in consideration of deformation of the base material due to heat. The temperature can be set by using a hot plate, oven, furnace or the like. The drying time is preferably set to a short time. For example, when the drying temperature is 150 ° C., the drying time is preferably set within 30 minutes. The drying atmosphere may be any condition such as an air atmosphere, a nitrogen atmosphere, an argon atmosphere, a vacuum atmosphere, or a reduced pressure atmosphere with a controlled oxygen concentration.

  The coating film obtained by applying the coating liquid for forming the first inorganic barrier layer may include a step of removing moisture before irradiation with vacuum ultraviolet rays or during irradiation with vacuum ultraviolet rays. As a method for removing moisture, a form of dehumidification while maintaining a low humidity environment is preferable. Since humidity in a low-humidity environment varies depending on temperature, a preferable form is shown for the relationship between temperature and humidity by defining the dew point temperature. A preferable dew point temperature is 4 ° C. or lower (temperature 25 ° C./humidity 25%), a more preferable dew point temperature is −5 ° C. or lower (temperature 25 ° C./humidity 10%), and the time to be maintained is that of the first inorganic barrier layer. It is preferable to set appropriately depending on the film thickness. Specifically, it is preferable that the dew point temperature is −5 ° C. or lower and the maintained time is 1 minute or longer. The lower limit of the dew point temperature is not particularly limited, but is usually −50 ° C. or higher and preferably −40 ° C. or higher. This is a preferred form from the viewpoint of promoting the dehydration reaction of the first inorganic barrier layer converted to silanol by removing water before or during the modification treatment.

<Vacuum UV irradiation>
Subsequently, the coating film formed as described above is irradiated with vacuum ultraviolet rays to perform a conversion reaction of polysilazane to silicon oxynitride or the like, and the inorganic thin film in which the first inorganic barrier layer can exhibit gas barrier properties. To reform.

  The ultraviolet irradiation can be adapted to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate to be used. For example, in the case of batch processing, it can be processed in an ultraviolet baking furnace equipped with an ultraviolet ray generation source. The ultraviolet baking furnace itself is generally known. For example, an ultraviolet baking furnace manufactured by I-Graphics Co., Ltd. can be used. Further, when the object is a long film, it can be converted to ceramics by continuously irradiating ultraviolet rays in a drying zone equipped with the ultraviolet ray generation source as described above while being conveyed. The time required for ultraviolet irradiation is generally 0.1 seconds to 10 minutes, preferably 0.5 seconds to 3 minutes, although it depends on the composition and concentration of the substrate used and the first inorganic barrier layer.

(Vacuum ultraviolet irradiation treatment: excimer irradiation treatment)
Modification by vacuum ultraviolet irradiation uses light energy of 100 to 200 nm, preferably light energy of a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in the polysilazane compound, and only bonds photons called photon processes to bond atoms. In this method, a film containing silicon oxynitride is formed at a relatively low temperature (about 200 ° C. or lower) by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly. In addition, when performing an excimer irradiation process, it is preferable to use heat processing (for example, 50-80 degreeC) together.

  The vacuum ultraviolet ray source in the present invention may be any source that generates light having a wavelength of 100 to 180 nm, but is preferably an excimer radiator (for example, Xe excimer lamp) having a maximum emission at about 172 nm, and an emission line at about 185 nm. Low pressure mercury vapor lamps with medium pressure and medium and high pressure mercury vapor lamps with wavelength components of 230 nm or less, and excimer lamps with maximum emission at about 222 nm.

  Among these, the Xe excimer lamp emits ultraviolet light having a short wavelength of 172 nm at a single wavelength, and thus has excellent luminous efficiency. Since this light has a large oxygen absorption coefficient, it can generate radical oxygen atom species and ozone at a high concentration with a very small amount of oxygen.

  Moreover, it is known that the energy of light having a short wavelength of 172 nm has a high ability to dissociate organic bonds. Due to the high energy possessed by the active oxygen, ozone and ultraviolet radiation, the polysilazane coating can be modified in a short time.

  Since the excimer lamp has high light generation efficiency, it can be turned on with low power. In addition, light having a long wavelength that causes a temperature increase due to light is not emitted, and energy is irradiated in the ultraviolet region, that is, in a short wavelength, so that the increase in the surface temperature of the irradiation object is suppressed. For this reason, it is suitable for flexible film materials such as PET that are easily affected by heat.

  Oxygen is required for the reaction at the time of vacuum ultraviolet irradiation, but since vacuum ultraviolet rays are absorbed by oxygen, the efficiency in the ultraviolet irradiation process tends to decrease. In addition, it is preferably performed in a state where the water vapor concentration is low. That is, the oxygen concentration at the time of vacuum ultraviolet irradiation is preferably 10 to 20,000 volume ppm (0.001 to 2 volume%), and preferably 50 to 10,000 volume ppm (0.005 to 1 volume%). More preferably. Also, the water vapor concentration during the conversion process is preferably in the range of 1000 to 4000 ppm by volume.

  As a gas that satisfies the irradiation atmosphere used at the time of irradiation with vacuum ultraviolet rays, a dry inert gas is preferable, and a dry nitrogen gas is particularly preferable from the viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.

In vacuum ultraviolet irradiation step, more that illuminance of the vacuum ultraviolet rays in the coated surface of the polysilazane coating film is subjected is preferable to be ^{1mW / cm 2 ~10W / cm 2} , a 30mW / cm ² ~200mW / cm 2 ^preferably, further preferably at ^{50mW / cm 2 ~160mW / cm 2} . If it is 1 mW / cm ² or more, the reforming efficiency is improved, and if it is 10 W / cm ² or less, ablation that can occur in the coating film and damage to the substrate can be reduced.

In the present invention, the amount of irradiation energy (irradiation amount) of vacuum ultraviolet rays on the surface of the coating film is preferably 1 J / cm ² or more. When the irradiation energy amount is 1 J / cm ² or more, the gas barrier property of the first inorganic barrier layer is improved, and the resistance under high temperature and high humidity conditions is remarkably improved. The irradiation energy amount is preferably 1.5 J / cm ² or more from the viewpoint of production stability (a property in which the gas barrier performance does not decrease or is low even in a storage environment after forming the modified layer), 2.0 J / cm ² or more is more preferable, and 2.5 J / cm ² or more is more preferable. On the other hand, the upper limit value of the irradiation energy amount is not particularly limited, but is preferably 10 J / cm ² or less. If it is this range, generation | occurrence | production of the crack by excessive reforming and the thermal deformation of a base material can be suppressed, and productivity will improve.

The vacuum ultraviolet ray used may be generated by plasma formed of a gas containing at least one of CO, CO ₂ and CH ₄ . Further, as the gas containing at least one of CO, CO ₂ and CH ₄ (hereinafter also referred to as carbon-containing gas), the carbon-containing gas may be used alone, but carbon containing rare gas or H ₂ as the main gas. It is preferable to add a small amount of the contained gas. Examples of plasma generation methods include capacitively coupled plasma.

[Second inorganic barrier layer]
The second inorganic barrier layer is formed on the first inorganic barrier layer disposed on one surface side of the resin base material in contact with the first inorganic barrier layer by a plasma chemical vapor deposition method. The second inorganic barrier layer contains carbon, oxygen, and metal. The metal contained in the second inorganic barrier layer is at least one selected from the group consisting of Al, Ti, Zr, Ta, Nb, Hf, Ru, and Y. Hereinafter, Al, Ti, Zr, Ta, Nb, Hf, Ru, and Y contained in the second inorganic barrier layer may be referred to as a metal M. In the second inorganic barrier layer, the metal content is 25 to 50 at% with respect to the total amount of elements of 100 at% of the entire layer, and the carbon content is 100 at% of total element of the entire layer. Is 0.1 to 10 at%. In addition, even if the metal is 1 type individual, 2 or more types may be mixed and contained. When two or more kinds of metals are contained, the metal content is the total amount. In addition, a form containing at least one metal selected from the group consisting of Al, Ti, Zr, Ta, Nb, Hf, Ru, and Y and Si is also preferable from the viewpoint of a gas barrier film. When the second inorganic barrier layer contains Si, the metal content is also calculated by adding the silicon content.

  That is, the second gas barrier layer of the present invention is formed by plasma enhanced chemical vapor deposition, includes a specific metal, and has a metal and carbon content within a predetermined range.

  The modified polysilazane contained in the first inorganic barrier layer contains silicon oxynitride and thereby exhibits excellent gas barrier properties. However, the modified polysilazane is not completely stable against oxidation, and may be gradually oxidized in a high-temperature and high-humidity environment to lower the gas barrier property. That is, the modified polysilazane has a SiOxNy composition, which is not stable against oxidation, and is gradually oxidized in a high-temperature and high-humidity environment to an approximately SiOz composition, resulting in a reduction in barrier properties. As a result of intensive studies, on the first inorganic barrier layer containing the polysilazane modified product, a layer containing a specific metal is formed as a second inorganic barrier layer in contact with the first inorganic barrier layer. It has been found that oxidation (change from the SiOxNy composition to the SiOz composition) is suppressed and high barrier properties can be maintained.

  That is, by forming the second inorganic barrier layer containing a specific metal in contact with the first inorganic barrier layer containing the polysilazane modified product by the plasma chemical vapor deposition method, the oxidation of the polysilazane modified product is suppressed and more excellent. A gas barrier film can be obtained. Although the mechanism by which oxidation of the polysilazane modified product is suppressed is not clear, specific metal atoms (M), carbon atoms (C), and nitrogen atoms contained in the first inorganic barrier layer contained in the second inorganic barrier layer (N) is presumed to be due to the formation of a “M—C—N” bond at the interface between the first inorganic barrier layer and the second inorganic barrier layer. For example, when the second inorganic barrier layer does not contain carbon, an “MN” bond is formed at the interface between the first inorganic barrier layer and the second inorganic barrier layer.

  In these two bonding forms, it is presumed that the degree of polarization is different between the metal atom and the nitrogen atom. That is, in the “MN” bond, “N” is highly negatively polarized, and therefore “M” tends to be largely positively polarized. On the other hand, in the “M—C—N” bond, “M” tends to be positively polarized and “N” tends to be negatively polarized. A relatively weak positive polarization is formed as “C”. The positively polarized side is believed to be more susceptible to oxidation by oxygen, so, for example, in the “MN” and “MCN” bond forms, the “MN” bond form “M” is easily oxidized. From the viewpoint that the metal in the second inorganic barrier layer is likely to be oxidized, either form of bonding may be used. However, a slow oxidation reaction at the interface is preferable from the viewpoint of oxidative deterioration of the first inorganic barrier layer.

  Therefore, the second inorganic barrier layer of the present invention contains a specific metal and carbon in a predetermined range, thereby suppressing oxidation of the first inorganic barrier layer and maintaining high barrier properties. Presumed to be. In addition, said mechanism is based on estimation and this invention is not restrict | limited to the said mechanism at all.

  For example, there is a water vapor that leaks in a spot manner from the base material side, and the polysilazane modified product is spot-oxidized by this water vapor to form a portion having a reduced gas barrier property. In the gas barrier film applied to the solar cell, if there is a portion where the gas barrier property is lowered, water vapor enters from the portion, and as a result, a dark spot is considered to be formed. On the other hand, in the gas barrier film of the present invention, since the second inorganic barrier layer is present adjacent to the first inorganic barrier layer, the second inorganic barrier layer is oxidized before the first inorganic barrier layer, Oxidation of the first inorganic barrier layer is suppressed, and as a result, excellent gas barrier properties are maintained.

  The second inorganic barrier layer may be a single layer or a laminated structure of two or more layers. When the second inorganic barrier layer has a laminated structure of two or more layers, the metals contained in each second inorganic barrier layer may be the same or different. When the second inorganic barrier layer has a laminated structure of two or more layers, the total thickness of the second inorganic barrier layer is the thickness of the second inorganic barrier layer.

  From the viewpoint of gas barrier performance, the thickness of the second inorganic barrier layer (the total thickness in the case of a laminated structure of two or more layers) is the thickness of the second gas barrier layer (in the case of a laminated structure of two or more layers). The total thickness) is preferably 10 to 1000 nm, more preferably 50 to 600 nm, and still more preferably 50 to 300 μm. If it is this range, the balance of gas barrier property and durability becomes favorable and is preferable. The thickness of the second inorganic barrier layer can be measured by TEM observation.

  The second inorganic barrier layer formed by plasma enhanced chemical vapor deposition is preferably in a form having particles on the film surface, and the size of the particles is preferably 2 to 100 nm, and preferably 5 to 50 nm. Is more preferable. If it is this range, the balance of gas barrier property and durability becomes favorable and is preferable. The particle size of the second inorganic barrier layer can be measured by TEM observation.

  As described above, the metal contained in the second inorganic barrier layer is at least one selected from the group consisting of Al, Ti, Zr, Ta, Nb, Hf, Ru, and Y. It is considered that the degree of polarization of the “MCN” bond formed at the interface between the first inorganic barrier layer and the second inorganic barrier layer depends on the electronegativity of the metal (M). That is, a desired polarization can be set according to the electronegativity of the metal (M) contained in the second inorganic barrier layer. In the present invention, from the viewpoint of the effect of suppressing oxidation of the second inorganic barrier layer, the difference in electronegativity between carbon and metal is preferably 0.3 to 1.4, and is preferably 0.5 to 1.3. Is more preferable. From the above, as the metal contained in the second inorganic barrier layer, Ti, Ta, and Nb are preferable, and Nb is more preferable.

  Table 1 below shows the electronegativity of metals used in the second inorganic barrier layer of the present invention.

  The metal content in the second inorganic barrier layer is preferably 25 to 50 at%, more preferably 30 to 40 at%, with respect to 100 at% of the total amount of elements in the entire layer. The carbon content in the second inorganic barrier layer is preferably 0.1 to 10 at%, more preferably 0.1 to 5 at%, with respect to 100 at% of the total amount of elements in the entire layer. If the amount of the metal and carbon in the second inorganic barrier layer is within the above range, the oxidation suppressing effect of the first inorganic barrier layer is more exhibited. Further, the oxygen content in the second inorganic barrier layer is preferably 40 to 75 at%, more preferably 55 to 65 at%, with respect to 100 at% of the total amount of elements in the entire layer. When the amount of oxygen in the second inorganic film barrier layer is in the above range, oxidation deterioration is unlikely to occur, which is preferable.

  In the present invention, composition analysis of the first inorganic barrier layer and the second inorganic barrier layer is performed in the depth direction of the film by performing a depth profile using X-ray photoelectron spectroscopy (XPS). The composition can be analyzed. That is, while etching the surface of the gas barrier layer of the gas barrier film, the composition in the depth (thickness) direction from the surface is measured.

  The composition analysis of the first inorganic barrier layer and the second inorganic barrier layer is a metal distribution curve (metal M: group consisting of aluminum, titanium, zirconia, tantalum, niobium, hafnium, ruthenium, and yttrium obtained by XPS depth profile measurement. 1 or more selected distribution curves), a silicon distribution curve, an oxygen distribution curve, a carbon distribution curve, and a nitrogen distribution curve. The obtained distribution curve can be created with the vertical axis as the atomic ratio of each element (unit: at%) and the horizontal axis as the etching time (sputtering time). In the element distribution curve with the horizontal axis as the etching time in this way, the etching time is generally correlated with the distance (L) from the surface of the gas barrier layer in the film thickness direction of the gas barrier layer in the film thickness direction. As the “distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer”, use the distance from the surface of the gas barrier layer calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement. Can do.

  In the present invention, a metal distribution curve, an oxygen distribution curve, a carbon distribution curve, and an oxygen carbon distribution curve were created under the following XPS measurement conditions.

<< XPS analysis conditions >>
・ Device: QUANTERASXM (manufactured by ULVAC-PHI Co., Ltd.)
・ X-ray source: Monochromatic Al-Kα
Measurement area: Si2p, Al2p, Nb3d, Ta4d, Hf4d, Ti2p, Zr3d, Ru3d, Y3p, C1s, N1s, O1s
・ Irradiated X-ray: Single crystal spectroscopy AlKα
・ X-ray spot and its size: 800 × 400 μm oval shape ・ Sputtering ion: Ar (2 keV)
Depth profile: Repeat measurement after sputtering for 1 minute.

Sputtering conditions;
Etching rate (converted to SiO ₂ thermal oxide film): 0.05 nm / sec;
Etching interval (SiO ₂ equivalent value): 10 nm;
・ Data processing: MultiPak (manufactured by ULVAC-PHI)
Quantification: The background was determined by the Shirley method, and quantified using the relative sensitivity coefficient method from the obtained peak area.

  Under the above measurement conditions, XPS measurement and rare gas ion sputtering such as argon are used in combination, and the surface composition analysis is sequentially performed while exposing the inside of the sample (XPS depth profile measurement), and a metal distribution curve (metal M: The metal distribution curves of aluminum, titanium, zirconia, tantalum, niobium, hafnium, ruthenium and yttrium), silicon distribution curve, oxygen distribution curve, carbon distribution curve, and nitrogen distribution curve are obtained. As a distribution curve obtained by XPS depth profile measurement, the vertical axis represents the atomic ratio (unit: at%) of each element, and the horizontal axis represents the etching time (sputtering time). In each such distribution curve, the total amount of elements (unit :) shown in the distribution curve (for example, carbon distribution curve, oxygen distribution curve, and metal distribution curve) of elements detected in the region corresponding to the second inorganic barrier layer. (at%) is 100, the metal amount indicated by the metal distribution curve of the region corresponding to the second inorganic barrier layer is defined as the “metal content” of the second inorganic barrier layer, and the region corresponding to the second inorganic barrier layer The carbon content indicated by the carbon distribution curve was defined as the “carbon content” of the second inorganic barrier layer. Similarly, the first inorganic barrier when the total amount of elements (unit: at%) shown in the “silicon distribution curve, oxygen distribution curve, and nitrogen distribution curve” in the region corresponding to the first inorganic barrier layer is 100 is used. The nitrogen amount indicated by the nitrogen distribution curve in the region corresponding to the layer is defined as the “nitrogen content” of the first inorganic barrier layer.

  In the distribution curve thus created, the portion where the metal M was 0 at% was determined as the interface between the first inorganic barrier layer and the second inorganic barrier layer.

  The second inorganic barrier layer is formed by plasma enhanced chemical vapor deposition. By forming the second inorganic barrier layer by a plasma chemical vapor deposition method, the second inorganic barrier layer is formed in close contact with the surface on which the second inorganic barrier layer is formed, and can be a gas barrier film having adhesion and bending resistance. .

  When the second inorganic barrier layer of the present invention is formed on the first inorganic barrier layer, the component forming the second inorganic barrier layer is the surface of the first inorganic barrier layer (polysilazane modified product) during the formation of the second inorganic barrier layer. In particular, the nitrogen atom contained in the modified polysilazane). Thereby, since a bond is formed between the first inorganic barrier layer and the second inorganic barrier layer, the bending resistance and adhesion of the gas barrier film are further improved. Therefore, as the gas barrier film of the present invention, it is preferable to form the second inorganic barrier layer on the first inorganic barrier layer after forming the first inorganic barrier layer.

  A plasma-enhanced chemical vapor deposition (hereinafter, also simply referred to as “plasma CVD method”), which is a method for forming the second inorganic barrier layer, is not particularly limited. Examples thereof include a plasma CVD method at or near atmospheric pressure described in No. 033333, and a plasma CVD method using a plasma CVD apparatus having a counter roll electrode.

  Especially, since productivity is high, it is preferable to form a 2nd inorganic barrier layer by the plasma CVD method using the plasma CVD apparatus which has a counter roll electrode. That is, the plasma chemical vapor deposition method is preferably performed by a plasma CVD apparatus having a counter roll electrode. The plasma CVD method may be a Penning discharge plasma type plasma CVD method.

  Hereinafter, a method for forming the second barrier layer by a plasma CVD method using a plasma CVD apparatus having a counter roll electrode will be described.

  When generating plasma in the plasma CVD method, it is preferable to generate a plasma discharge in a space between a plurality of film forming rollers. A pair of film forming rollers is used, and a film is applied to each of the pair of film forming rollers. More preferably, the plasma is generated by discharging between the pair of film forming rollers. Thus, by using a pair of film forming rollers, placing a film on the pair of film forming rollers, and discharging between the pair of film forming rollers, one film forming roller is placed on the film forming roller. While forming an existing film, it is possible to form a film on the surface of the substrate on the other film forming roller at the same time, so that a thin film can be produced efficiently and a normal roller is not used. Compared with the plasma CVD method, the film formation rate can be doubled, and a film having a substantially identical structure can be formed.

  Further, when discharging between the pair of film forming rollers in this way, it is preferable to reverse the polarities of the pair of film forming rollers alternately. Further, as a film forming gas used in such a plasma CVD method, an organic metal complex (CVD precursor) including a group consisting of Al, Ti, Zr, Ta, Nb, Hf, Ru, and Y, and oxygen is included. The oxygen content in the film forming gas is preferably less than the theoretical oxygen amount necessary to completely oxidize the entire amount of the organometallic complex in the film forming gas. As a preferred embodiment of the present invention, the second inorganic barrier layer comprises one or more metals selected from the group consisting of Al, Ti, Zr, Ta, Nb, Hf, Ru and Y, and Si. Therefore, it is preferable to use the above-described organometallic complex (CVD precursor) and an organosilicon compound as a film forming gas. In that case, the content of oxygen in the film forming gas is preferably less than the theoretical oxygen amount necessary to completely oxidize the entire amount of the organometallic complex and the organosilicon compound in the film forming gas.

  Hereinafter, with reference to FIG. 2, when a base material is used, a gas barrier layer formed by a plasma CVD method in which the base material is disposed on a pair of film forming rollers and plasma is generated by discharging between the pair of film forming rollers. The forming method will be described in more detail. FIG. 2 is a schematic view showing an example of a manufacturing apparatus that can be suitably used for forming a gas barrier layer by this method. In the following description and drawings, the same or corresponding elements are denoted by the same reference numerals, and redundant description is omitted.

  The manufacturing apparatus 31 shown in FIG. 2 includes a delivery roller 32, transport rollers 33, 34, 35, and 36, film formation rollers 39 and 40, a gas supply pipe 41, a plasma generation power source 42, and a film formation roller 39. And magnetic field generators 43 and 44 installed inside 40 and a winding roller 45. In such a manufacturing apparatus, at least the film forming rollers 39 and 40, the gas supply pipe 41, the plasma generating power source 42, and the magnetic field generating apparatuses 43 and 44 are arranged in a vacuum chamber (not shown). ing. Further, in such a manufacturing apparatus 31, the vacuum chamber is connected to a vacuum pump (not shown), and the pressure in the vacuum chamber can be appropriately adjusted by the vacuum pump.

  In such a manufacturing apparatus, each film-forming roller has a power source for plasma generation so that the pair of film-forming rollers (the film-forming roller 39 and the film-forming roller 40) can function as a pair of counter electrodes. 42. Therefore, in such a manufacturing apparatus 31, it is possible to discharge the space between the film formation roller 39 and the film formation roller 40 by supplying electric power from the plasma generation power source 42. Plasma can be generated in the space between the film roller 39 and the film formation roller 40. In this way, when the film forming roller 39 and the film forming roller 40 are also used as electrodes, the material and design thereof may be appropriately changed so that they can also be used as electrodes. Moreover, in such a manufacturing apparatus, it is preferable to arrange | position a pair of film-forming roller (film-forming rollers 39 and 40) so that the central axis may become substantially parallel on the same plane. Thus, by arranging a pair of film forming rollers (film forming rollers 39 and 40), the film forming rate can be doubled and a film having the same structure can be formed. According to such a manufacturing apparatus, it is possible to form a gas barrier layer by a CVD method. While depositing the gas barrier layer component on the film forming roller 39, the gas barrier layer component is also formed on the film forming roller 40. Therefore, the gas barrier layer can be formed efficiently.

  Inside the film forming roller 39 and the film forming roller 40, magnetic field generators 43 and 44 fixed so as not to rotate even when the film forming roller rotates are provided, respectively.

  The magnetic field generators 43 and 44 provided on the film forming roller 39 and the film forming roller 40 are respectively a magnetic field generating device 43 provided on one film forming roller 39 and a magnetic field generating device provided on the other film forming roller 40. It is preferable to arrange the magnetic poles so that the magnetic field lines do not cross between them and the magnetic field generators 43 and 44 form a substantially closed magnetic circuit. By providing such magnetic field generators 43 and 44, it is possible to promote the formation of a magnetic field in which magnetic lines of force swell near the opposing surface of each film forming roller 39 and 40, and the plasma is converged on the bulging portion. Since it becomes easy, it is excellent at the point which can improve the film-forming efficiency.

  The magnetic field generators 43 and 44 provided in the film forming roller 39 and the film forming roller 40 respectively have racetrack-shaped magnetic poles that are long in the roller axis direction, and one magnetic field generator 43 and the other magnetic field generator. It is preferable to arrange the magnetic poles so that the magnetic poles facing to 44 have the same polarity. By providing such magnetic field generators 43 and 44, the opposing space along the length direction of the roller shaft without straddling the magnetic field generator on the roller side where the magnetic lines of force of each of the magnetic field generators 43 and 44 are opposed. A racetrack-like magnetic field can be easily formed in the vicinity of the roller surface facing the (discharge region), and the plasma can be focused on the magnetic field, so that a wide base wound around the roller width direction can be obtained. It is excellent in that another gas barrier layer which is a vapor deposition film can be efficiently formed on a material or the like.

  As the film forming roller 39 and the film forming roller 40, known rollers can be appropriately used. As such film forming rollers 39 and 40, those having the same diameter are preferably used from the viewpoint of forming a thin film more efficiently. Further, the diameters of the film forming rollers 39 and 40 are preferably in the range of 300 to 1000 mmφ, particularly in the range of 300 to 700 mmφ, from the viewpoint of discharge conditions, chamber space, and the like. If the diameter of the film forming roller is 300 mmφ or more, the plasma discharge space will not be reduced, so that the productivity will not be deteriorated, and it is possible to avoid applying the total amount of heat of the plasma discharge to the substrate in a short time. It is preferable because damage to materials and the like can be reduced. On the other hand, if the diameter of the film forming roller is 1000 mmφ or less, it is preferable because practicality can be maintained in terms of apparatus design including uniformity of plasma discharge space.

  In such a manufacturing apparatus 31, the base material etc. are arrange | positioned on a pair of film-forming roller (The film-forming roller 39 and the film-forming roller 40) so that the surfaces, such as a base material, may each oppose. By disposing the substrate and the like in this way, when the plasma is generated by performing discharge in the facing space between the film forming roller 39 and the film forming roller 40, the base existing between the pair of film forming rollers is present. It becomes possible to form films on the surfaces of the materials and the like simultaneously. That is, according to such a manufacturing apparatus, the gas barrier layer component is deposited on the surface of the substrate or the like on the film forming roller 39 by the plasma CVD method, and the gas barrier layer component is further deposited on the film forming roller 40. Therefore, the gas barrier layer can be efficiently formed on the surface of the substrate or the like.

  As the feed roller 32 and the transport rollers 33, 34, 35, and 36 used in such a manufacturing apparatus, known rollers can be appropriately used. Further, the take-up roller 45 is not particularly limited as long as it can take up a film having a gas barrier layer formed on a substrate or the like, and a known roller can be used as appropriate.

  Further, as the gas supply pipe 41 and the vacuum pump, those capable of supplying or discharging the source gas or the like at a predetermined speed can be appropriately used.

  The gas supply pipe 41 as a gas supply means is preferably provided in one of the facing spaces (discharge region; film formation zone) between the film formation roller 39 and the film formation roller 40, and is a vacuum as a vacuum exhaust means. A pump (not shown) is preferably provided on the other side of the facing space. As described above, by providing the gas supply pipe 41 as the gas supply means and the vacuum pump as the vacuum exhaust means, the film formation gas is efficiently supplied to the facing space between the film formation roller 39 and the film formation roller 40. It is excellent in that the film formation efficiency can be improved.

  Furthermore, as the plasma generating power source 42, a known power source of a plasma generating apparatus can be used as appropriate. Such a plasma generating power supply 42 supplies power to the film forming roller 39 and the film forming roller 40 connected thereto, and makes it possible to use these as counter electrodes for discharge. Such a plasma generating power source 42 can perform plasma CVD more efficiently, and can alternately reverse the polarity of the pair of film forming rollers (AC power source or the like). Is preferably used. Moreover, as such a plasma generating power source 42, it becomes possible to perform plasma CVD more efficiently, so that the applied power can be set to 100 W to 10 kW, and the AC frequency is set to 50 Hz to 500 kHz. More preferably, it is possible to do this. As the magnetic field generators 43 and 44, known magnetic field generators can be used as appropriate.

  Using such a manufacturing apparatus 31 shown in FIG. 2, for example, the type of source gas, the power of the electrode drum of the plasma generator, the pressure in the vacuum chamber, the diameter of the film forming roller, and the film (base material, etc.) The gas barrier layer can be formed by appropriately adjusting the transport speed. That is, using the manufacturing apparatus 31 shown in FIG. 2, a discharge is generated between the pair of film forming rollers (film forming rollers 39 and 40) while supplying a film forming gas (raw material gas, etc.) into the vacuum chamber. As a result, the film forming gas (raw material gas or the like) is decomposed by plasma, and the gas barrier layer is formed on the surface of the base material on the film forming roller 39 and the surface of the base material on the film forming roller 40 by plasma CVD. It is formed by. At this time, a racetrack-shaped magnetic field is formed in the vicinity of the roller surface facing the facing space (discharge region) along the length direction of the roller axes of the film forming rollers 39 and 40, and the plasma is converged on the magnetic field. For this reason, when a base material etc. pass the A point of the film-forming roller 39 in FIG. 2, and the B point of the film-forming roller 40, the maximum value of a carbon distribution curve is formed in a gas barrier layer. On the other hand, when the substrate or the like passes through the points C1 and C2 of the film forming roller 39 and the points C3 and C4 of the film forming roller 40 in FIG. It is formed. For this reason, five extreme values are usually generated for two film forming rollers. Further, the distance between the extreme values of the gas barrier layer (the difference between the distance (L) from the surface of the gas barrier layer in the thickness direction of the gas barrier layer at one extreme value of the carbon distribution curve and the extreme value adjacent to the extreme value) (Absolute value) can be adjusted by the rotation speed of the film forming rollers 39 and 40 (conveying speed of the substrate or the like). In such film formation, the substrate and the like are conveyed by the delivery roller 32 and the film formation roller 39, respectively, so that they are formed on the surface of the substrate and the like by a roll-to-roll continuous film formation process. Then, the gas barrier layer 3 is formed.

  As the film forming gas (such as source gas) supplied from the gas supply pipe 41 to the facing space, source gas, reaction gas, carrier gas, and discharge gas can be used alone or in combination of two or more. The source gas in the film forming gas used for forming the second inorganic barrier layer can be appropriately selected and used according to the material of the second inorganic barrier layer to be formed. As such a source gas, for example, an organic compound gas containing carbon can be used. When the second inorganic barrier layer contains Si, an organosilicon compound containing silicon can be used.

  Examples of silicon-containing organosilicon compounds include hexamethyldisiloxane (HMDSO), hexamethyldisilane (HMDS), 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, and hexamethyl. Disilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, propylsilane, phenylsilane, vinyltriethoxysilane, vinyltrimethoxysilane, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), phenyltrimethoxysilane, methyltri Examples include ethoxysilane and octamethylcyclotetrasiloxane. Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of handling properties of the compound and gas barrier properties of the other gas barrier layers obtained. These organosilicon compounds can be used alone or in combination of two or more.

  Examples of the organic compound gas containing carbon include methane, ethane, ethylene, and acetylene. As these organosilicon compound gas and organic compound gas, an appropriate source gas is selected according to the type of the gas barrier layer.

  The second inorganic barrier layer of the present invention is preferably formed from a compound (organometallic complex) containing a metal as a CVD precursor (precursor). The CVD precursor for forming the second inorganic barrier layer is at least selected from the group consisting of metal alkoxides, metal amino compounds, metal chlorides, metal cyclopentadienyl compounds, metal alkoxy β-diketone complexes, and metal alkoxyimide complexes. One type is preferably used.

  Specific organometallic complexes are shown below. In the following examples, Me represents a methyl group, Et represents an ethyl group, iPr represents an isopropyl group, nBu represents an n-butyl group, and t-Bu (tBu) represents a tert-butyl group. .

As the metal alkoxide compound, M (OR) x (wherein M represents a metal, R represents an alkyl group having 1 to 6 carbon atoms, and x is 1 to 6) (x depends on the valence of the metal). For example, pentaethoxyniobium (Nb (OEt) ₅ ), pentaethoxy tantalum (Ta (OEt) ₅ ), pentaboxyhafnium (Hf (OBu) ₅ ), tetraisopropoxy Titanium (Ti (O—iPr) ₄ ) and the like can be mentioned.

As the metal amino compound, M (NRz) x (wherein M represents a metal, R represents an alkyl group having 1 to 6 carbon atoms, x is 1 to 6, and z is 2) (x Is determined by the valence of the metal), for example, Nb (N (tBu) ₂ ) (NMe ₂ ) ₃ , Ta (N (tBu) ₂ ) (NEt ₂ ) ₃ , Hf ( NMe ₂ ) ₄ , Zr [NMeEt] _{4 and the} like.

The metal chloride is a compound represented by M (Cl) x (where M represents a metal and x is 1 to 6) (x is determined by the valence of the metal), for example, , HfCl ₄ , TiCl ₄ , Al ₂ Cl ₃ , ZrCl _{4 and the} like.

As the metal cyclopentadienyl compound, M (RCp) x (wherein M represents a metal, Cp represents a cyclopentadienyl group, R represents an alkyl group having 1 to 6 carbon atoms, and x represents 1 (X is determined by the valence of the metal), and examples thereof include Ru (EtCp) ₂ , Y (MeCp) ₃ , Y (nBuCp) ₃ , and the like.

As the metal alkoxy β-diketone complex, M (OR) x (βdiketone) y (where M is a metal, R is an alkyl group having 1 to 6 carbon atoms, x is 1 to 6, and y is 1 to 6) (Wherein x and y are determined by the valence of the metal), for example, Y (OiPr) (DPM: dipivaloylmethane) ₂ , Y (OEt) (TMOD: 2, 2,6,6-tetramethyl-3,5-octadione) _{2 and the} like.

  As the metal alkoxyimide complex, M (OR) x (= NR) y (where M represents a metal, R represents an alkyl group having 1 to 6 carbon atoms, y represents 1 to 6, x represents 1 to 6), for example, Nb (tri (tert-butoxy) tert-butylimidium), Ta (tri (tert-butoxy) tert-butylimidium), and the like. Can be mentioned.

  These CVD precursors can be used as a film forming gas or a raw material gas.

  In the present invention, the second inorganic barrier layer contains carbon and metal in a predetermined amount. In order to form such a second inorganic barrier layer, for example, the metal content controls the amount of the CVD precursor put into the CVD system, and the carbon content controls the amount of oxygen put into the CVD system. By doing so, a second inorganic barrier layer having a desired composition can be formed. Specifically, in order for the carbon content to be 0.1 to 10 at% with respect to 100 at% of the total amount of elements in the entire layer, the gas flow rate of the CVD precursor and the oxygen gas flow rate as the reaction gas are The ratio is preferably set to a gas flow ratio of 1: 1 to 20, more preferably 1: 1 to 10. Moreover, in order for the metal content to be 25 to 50 at% with respect to 100 at% of the total amount of elements in the entire layer, the ratio of the gas flow rate of the CVD precursor and the oxygen gas flow rate as the reaction gas is preferably 1 : 1 to 20, more preferably 1: 1 to 10 gas flow ratio.

  In addition to the source gas, a reactive gas may be used as the film forming gas. As such a reactive gas, a gas that reacts with the raw material gas to become an inorganic compound such as an oxide or a nitride can be appropriately selected and used. As a reaction gas for forming an oxide, for example, oxygen or ozone can be used. Moreover, as a reactive gas for forming nitride, nitrogen and ammonia can be used, for example. These reaction gases can be used alone or in combination of two or more. For example, when forming an oxynitride, a reaction gas for forming an oxide and a reaction gas for forming a nitride can be used in combination.

  As the film forming gas, a carrier gas may be used as necessary to supply the source gas into the vacuum chamber. Further, as a film forming gas, a discharge gas may be used as necessary in order to generate plasma discharge. As such carrier gas and discharge gas, known ones can be used as appropriate, for example, rare gases such as helium, argon, neon, xenon; hydrogen can be used.

  When such a film forming gas contains a raw material gas and a reactive gas, the ratio of the raw material gas and the reactive gas is the reaction gas that is theoretically necessary to completely react the raw material gas and the reactive gas. It is preferable that the ratio of the reaction gas is not excessively increased rather than the ratio of the amount. By not making the ratio of the reaction gas excessive, it is excellent in that excellent barrier properties and bending resistance can be obtained by the other gas barrier layers to be formed. Moreover, when the film-forming gas contains an organosilicon compound and oxygen, the amount is preferably less than or equal to the theoretical oxygen amount necessary for complete oxidation of the entire amount of the organosilicon compound in the film-forming gas.

  In addition, the pressure (degree of vacuum) in the vacuum chamber can be appropriately adjusted according to the type of the raw material gas, but is preferably in the range of 0.5 to 50 Pa.

  In such a plasma CVD method, in order to discharge between the film forming roller 39 and the film forming roller 40, an electrode drum connected to the plasma generating power source 42 (in this embodiment, the film forming roller 39) is used. The electric power to be applied to the power source can be adjusted as appropriate according to the type of the raw material gas, the pressure in the vacuum chamber, etc. It is preferable to be in the range. If such an applied power is 0.1 kW or more, the generation of particles can be sufficiently suppressed. On the other hand, if the applied power is 10 kW or less, the amount of heat generated during film formation can be suppressed. It can suppress that the temperature of the film surface rises. Therefore, it is excellent in that wrinkles can be prevented during film formation without losing heat to the film.

  The film conveyance speed (line speed) can be appropriately adjusted according to the type of source gas, the pressure in the vacuum chamber, and the like, but is preferably in the range of 0.25 to 100 m / min. More preferably, it is set to a range of ˜20 m / min. If the line speed is 0.5 m / min or more, generation of wrinkles due to heat of the film can be effectively suppressed. On the other hand, if it is 20 m / min or less, it is excellent at the point which can ensure sufficient film thickness as another gas barrier layer, without impairing productivity.

  As described above, as a more preferable aspect of the present embodiment, the second inorganic barrier layer is formed by a plasma CVD method using the plasma CVD apparatus (roll-to-roll method) having the counter roll electrode shown in FIG. It is a film. This is excellent in flexibility (flexibility) and mechanical strength, especially in roll-to-roll, when mass-produced using a plasma CVD apparatus (roll-to-roll method) having a counter roll electrode. This is because the second inorganic barrier layer having both durability and barrier performance can be efficiently produced. Such a manufacturing apparatus is also excellent in that it can inexpensively and easily mass-produce gas barrier films that are required for durability against temperature changes used in solar cells and electronic components.

[Resin substrate]
Specifically, as the resin base material according to the present invention, polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene resin, transparent fluororesin, polyimide, fluorinated polyimide resin, polyamide resin, polyamideimide resin , Polyetherimide resin, cellulose acylate resin, polyurethane resin, polyether ether ketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyether sulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring modified polycarbonate resin , A base material containing a thermoplastic resin such as an alicyclic modified polycarbonate resin, a fluorene ring modified polyester resin, or an acryloyl compound. These resin substrates can be used alone or in combination of two or more.

  Since the gas barrier film according to the present invention is used as an electronic device such as a solar cell or an organic EL, the resin substrate is preferably transparent. That is, the light transmittance is usually 80% or more, preferably 85% or more, and more preferably 90% or more. The light transmittance is calculated by measuring the total light transmittance and the amount of scattered light using the method described in JIS K7105: 1981, that is, using an integrating sphere light transmittance measuring device, and subtracting the diffuse transmittance from the total light transmittance. can do.

  However, even when the gas barrier film according to the present invention is used for display applications, transparency is not necessarily required when it is not installed on the observation side. Therefore, in such a case, an opaque material can be used as the plastic film. Examples of the opaque material include polyimide, polyacrylonitrile, and known liquid crystal polymers.

  Moreover, the unstretched film may be sufficient as the resin base material quoted above, and a stretched film may be sufficient as it. The resin substrate can be produced by a conventionally known general method. About the manufacturing method of these base materials, the matter described in paragraphs “0051” to “0055” of International Publication No. 2013/002026 can be appropriately employed.

  The surface of the resin substrate may be subjected to various known treatments for improving adhesion, such as corona discharge treatment, flame treatment, oxidation treatment, or plasma treatment, and the above treatments may be combined as necessary. May go.

  The resin substrate may be a single layer or a laminated structure of two or more layers. When the resin base material has a laminated structure of two or more layers, the resin base materials may be the same type or different types.

  The thickness of the resin substrate according to the present invention (the total thickness in the case of a laminated structure of two or more layers) is preferably 10 to 200 μm, and more preferably 20 to 150 μm.

[Layers with various functions]
In the gas barrier film of the present invention, layers having various functions can be provided.

  In addition, when providing a functional layer in the gas barrier film of this invention, since it utilizes as electronic devices, such as a solar cell and an organic EL element, it is preferable that a functional layer is also transparent. That is, the light transmittance is usually 80% or more, preferably 85% or more, and more preferably 90% or more.

(Anchor coat layer)
An anchor coat layer may be formed on the surface of the resin substrate on the side where the first inorganic barrier layer according to the present invention is formed for the purpose of improving the adhesion between the resin substrate and the first inorganic barrier layer. .

  As anchor coating agents used for the anchor coat layer, polyester resins, isocyanate resins, urethane resins, acrylic resins, ethylene vinyl alcohol resins, vinyl modified resins, epoxy resins, modified styrene resins, modified silicon resins, alkyl titanates, etc. are used alone Or in combination of two or more.

Conventionally known additives can be added to these anchor coating agents. The above-mentioned anchor coating agent is coated on the support by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, etc., and anchor coating is performed by drying and removing the solvent, diluent, etc. be able to. The application amount of the anchor coating agent is preferably about 0.1 to 5.0 g / m ² (dry state).

  The anchor coat layer can also be formed by a vapor phase method such as physical vapor deposition or chemical vapor deposition. For example, as described in JP-A-2008-142941, an inorganic film mainly composed of silicon oxide can be formed for the purpose of improving adhesion and the like. Alternatively, by forming an anchor coat layer as described in Japanese Patent Application Laid-Open No. 2004-314626, when an inorganic thin film is formed thereon by a vapor phase method, the gas generated from the substrate side is blocked to some extent. Thus, an anchor coat layer can be formed for the purpose of controlling the composition of the inorganic thin film.

  The thickness of the anchor coat layer is not particularly limited, but is preferably about 0.5 to 10 μm.

(Hard coat layer)
A hard coat layer may be provided on the surface (one side or both sides) of the resin substrate. Examples of the material contained in the hard coat layer include a thermosetting resin and an active energy ray curable resin, but an active energy ray curable resin is preferable because it is easy to mold. Such curable resins can be used singly or in combination of two or more.

  The active energy ray-curable resin refers to a resin that is cured through a crosslinking reaction or the like by irradiation with active energy rays such as ultraviolet rays and electron beams. As the active energy ray curable resin, a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and cured by irradiating an active energy ray such as an ultraviolet ray or an electron beam to cure the active energy ray. A layer containing a cured product of the functional resin, that is, a hard coat layer is formed. Typical examples of the active energy ray curable resin include an ultraviolet curable resin and an electron beam curable resin, and an ultraviolet curable resin that is cured by irradiation with ultraviolet rays is preferable. You may use the commercially available resin base material in which the hard-coat layer is formed previously. As the ultraviolet curable resin, for example, Z-731L (manufactured by Aika Industry Co., Ltd.), Opstar Z7527 (manufactured by JSR Corporation) and the like are preferably used.

  The method for forming the hard coat layer is not particularly limited, but is preferably formed by a wet coating method such as a spin coating method, a spray method, a blade coating method, or a dip method, or a dry coating method such as an evaporation method.

  The thickness of the hard coat layer is not particularly limited, but is preferably about 0.5 to 10 μm.

(Smooth layer)
In the gas barrier film of the present invention, a smooth layer may be provided between the resin substrate 110 and the gas barrier layer 120. The smooth layer used in the present invention flattens the rough surface of the resin base material where protrusions and the like exist, or flattens the unevenness and pinholes generated in the transparent inorganic compound layer by the protrusions existing on the resin base material. To be provided. Such a smooth layer is basically produced by curing a photosensitive material or a thermosetting material.

  As the photosensitive material of the smooth layer, for example, a resin composition containing an acrylate compound having a radical reactive unsaturated compound, a resin composition containing an acrylate compound and a mercapto compound having a thiol group, epoxy acrylate, urethane acrylate, Examples thereof include a resin composition in which a polyfunctional acrylate monomer such as polyester acrylate, polyether acrylate, polyethylene glycol acrylate, or glycerol methacrylate is dissolved. Specifically, a UV curable organic / inorganic hybrid hard coating material OPSTAR (registered trademark) series manufactured by JSR Corporation can be used. It is also possible to use an arbitrary mixture of the above resin compositions, and any photosensitive resin containing a reactive monomer having one or more photopolymerizable unsaturated bonds in the molecule can be used. There are no particular restrictions.

  Specific examples of thermosetting materials include TutProm Series (Organic Polysilazane) manufactured by Clariant, SP COAT heat-resistant clear paint manufactured by Ceramic Co., Ltd., Nanohybrid Silicone manufactured by Adeka, and Unidic manufactured by DIC. (Registered trademark) V-8000 series, EPICLON (registered trademark) EXA-4710 (ultra-high heat resistant epoxy resin), various silicon resins manufactured by Shin-Etsu Chemical Co., Ltd., inorganic / organic nanocomposite material SSG manufactured by Nittobo Co., Ltd. Examples include coats, thermosetting urethane resins composed of acrylic polyols and isocyanate prepolymers, phenol resins, urea melamine resins, epoxy resins, unsaturated polyester resins, and silicon resins. Among these, an epoxy resin-based material having heat resistance is particularly preferable.

  The method for forming the smooth layer is not particularly limited, but is preferably formed by a wet coating method such as a spin coating method, a spray method, a blade coating method, or a dip method, or a dry coating method such as an evaporation method.

  In the formation of the smooth layer, additives such as an antioxidant, an ultraviolet absorber, and a plasticizer can be added to the above-described photosensitive resin as necessary. In addition, regardless of the position where the smooth layer is laminated, in any smooth layer, an appropriate resin or additive may be used for improving the film formability and preventing the generation of pinholes in the film.

  The thickness of the smooth layer is preferably in the range of 1 to 10 μm, more preferably in the range of 2 to 7 μm from the viewpoint of improving the heat resistance of the film and facilitating the balance adjustment of the optical properties of the film. Is preferred.

  The smoothness of the smooth layer is a value expressed by the surface roughness specified by JIS B 0601: 2001, and the ten-point average roughness Rz is preferably 10 nm or more and 30 nm or less. If it is this range, even if it is a case where a barrier layer is apply | coated with an application | coating form, even if it is a case where a coating means contacts the smooth layer surface by application methods, such as a wire bar and a wireless bar, applicability | paintability is impaired. In addition, it is easy to smooth the unevenness after coating.

[Characteristics of gas barrier film]
The water vapor permeability of the gas barrier film of the present invention is preferably less than 1 × 10 ⁻³ g / (m ² · day), and preferably 5 × 10 ⁻⁴ g / (m ² · day) or less. More preferably, it is 1 × 10 ⁻⁴ g / (m ² · day) or less. In addition, in this specification, the value measured by the method based on JISK7129-1992 shall be employ | adopted for the value of "water vapor permeability". The measurement conditions are temperature: 60 ± 0.5 ° C. and relative humidity (RH): 90 ± 2%.

[Electronic device]
The gas barrier film of the present invention can be preferably applied to a device whose performance is deteriorated by chemical components (oxygen, water, nitrogen oxide, sulfur oxide, ozone, etc.) in the air. That is, the present invention provides an electronic device using the gas barrier film of the present invention.

  Examples of the electronic device body used in the electronic device of the present invention include, for example, an organic electroluminescence element (organic EL element), a liquid crystal display element (LCD), a thin film transistor, a touch panel, electronic paper, a solar cell (PV), and the like. be able to. From the viewpoint that the effect of the present invention is more efficiently exhibited, the electronic device body is preferably an organic EL element or a solar cell, and more preferably an organic EL element.

  The effects of the present invention will be described using the following examples and comparative examples. In the following examples, “parts” and “%” mean “parts by mass” and “mass%”, respectively, unless otherwise specified, and each operation is performed at room temperature (25 ° C.). In addition, this invention is not limited to a following example.

Example 1: Production of gas barrier film 1 (base material)
A transparent PET film resin substrate with a clear hard coat (thickness: 125 μm, width: 350 mm, manufactured by Kimoto Co., Ltd., trade name “KB film GSAB”, clear hard coat layer: 4 μm) was used as the substrate. The arithmetic average roughness (Ra) of the clear hard coat surface of the resin substrate was 0.4 to 0.5 nm, and the film thickness of the clear hard coat layer was 4 μm.

(Formation of the first inorganic barrier layer)
Next, according to the following excimer method, a first inorganic barrier layer having a thickness of 80 nm was formed on the clear hard coat layer of the resin base material.

<Preparation of coating solution for forming first inorganic barrier layer>
A 10% by mass dibutyl ether solution of perhydropolysilazane (Aquamica NN120-10, non-catalytic type, manufactured by AZ Electronic Materials Co., Ltd.) was used as a coating solution for forming a polysilazane layer.

<Formation of polysilazane layer>
The prepared polysilazane layer-forming coating solution is applied with a wireless bar so that the (average) layer thickness after drying is 80 nm, and treated for 1 minute in an atmosphere at a temperature of 85 ° C. and a relative humidity of 55%. The polysilazane layer was formed by drying and further holding in an atmosphere of a temperature of 25 ° C. and a relative humidity of 10% (dew point temperature −8 ° C.) for 10 minutes to perform dehumidification.

<Formation of first inorganic barrier layer: Modification treatment of polysilazane layer by vacuum ultraviolet light>
Next, after the ultraviolet device described below was installed in the vacuum chamber, the inside of the vacuum chamber was replaced with oxygen and nitrogen so that the volume concentration of oxygen became the value described below. Then, after adjusting the pressure in the apparatus, the base material on which the polysilazane layer fixed on the operation stage was formed was modified under the following conditions to form a first inorganic barrier layer.

・ Ultraviolet irradiation device Device: M.D.COM Excimer irradiation device MODEL: MECL-M-1-200
Irradiation wavelength: 172 nm
Lamp filled gas: Xe
-Modification | reformation process conditions The shrinkage process was performed on the following conditions with respect to the resin base material in which the polysilazane layer fixed on the movable stage was formed, and the inorganic polymer layer was formed.

Excimer lamp light intensity: 130 mW / cm ² (172 nm)
Distance between sample and light source: 1mm
Stage heating temperature: 70 ° C
Oxygen concentration in the irradiation device: 1.0% by volume
Excimer lamp irradiation time: 5 seconds.

(Formation of second layer: roller CVD method)
Using the inter-roller discharge plasma CVD apparatus (roller CVD method) to which the magnetic field described in FIG. 2 is applied, the surface on which the first inorganic barrier layer is formed is used as the CVD film-forming surface, and the resin substrate is attached to the apparatus. The first layer, which is an NbOC film, was formed under the condition that the thickness was 20 nm. As a power source for applying a voltage to the cathode electrode, a high frequency power source of 27.12 MHz was used, and the distance between the electrodes was 20 mm. As a source gas, pentaethoxyniobium (Nb (OEt) ₅ ) having a flow rate of 50 sccm (Standard Cubic Centimeter per Minute) was introduced into the vacuum chamber together with oxygen gas having a flow rate of 1200 sccm. The conveyance speed of the resin base material was 10 m / min.

<Film formation conditions by CVD>
Internal pressure during film formation: 2 Pa
Power applied to electrode drum: 1kW
Roll temperature: 30 ° C
Power supply frequency: 84 kHz
The average particle diameter of the film surface of the formed second inorganic barrier layer was 38 nm and the film thickness was 50 nm.

Example 2: Production of gas barrier film 2 In Example 1, except that the conditions of plasma CVD were changed as follows so that the metal and carbon of the second inorganic barrier layer had the contents shown in Table 2. In the same manner as in Example 1, a gas barrier film 2 was produced.

Source gas: pentaethoxyniobium (Nb (OEt) ₅ )
Source gas flow rate: 150 sccm
Reaction gas: oxygen gas, flow rate: 600 sccm
Transport speed of resin base material: 10 m / min.

Example 3 Production of Gas Barrier Film 3 In Example 1, in forming the second inorganic barrier layer, the raw material gas used was changed, and the metal and carbon in the second inorganic barrier layer had the contents shown in Table 2. A gas barrier film 3 was produced in the same manner as in Example 1 except that the plasma CVD conditions were changed as follows.

Source gas: pentaethoxytantalum (Ta (OEt) ₅ )
Source gas flow rate: 150 sccm
Reaction gas: oxygen gas, flow rate: 600 sccm
Transport speed of resin base material: 10 m / min.

Example 4: Production of gas barrier film 4 In forming the second inorganic barrier layer of Example 1, the raw material gas used was changed so that the metal and carbon in the second inorganic barrier layer had the contents shown in Table 2. A gas barrier film 4 was produced in the same manner as in Example 1 except that the plasma CVD conditions were changed as follows.

Source gas: Tetraisopropoxy titanium (Ti (OiPr) ₄ )
Source gas flow rate: 150 sccm
Reaction gas: oxygen gas, flow rate: 600 sccm
Transport speed of resin base material: 10 m / min.

Example 5 Production of Gas Barrier Film 5 In the first inorganic barrier layer of Example 1, the stage heating temperature was set to 80 ° C. and the oxygen concentration in the irradiation apparatus was set to 3. so that the nitrogen content was as shown in Table 2. In the formation of the second inorganic barrier layer, the plasma CVD conditions are changed so that the metal and carbon in the second inorganic barrier layer have the contents shown in Table 2 in the following manner. A gas barrier film 5 was produced in the same manner as in Example 1 except that the conditions were changed as follows.

Source gas: pentaethoxyniobium (Nb (OEt) ₅ )
Source gas flow rate: 150 sccm
Reaction gas: oxygen gas, flow rate: 600 sccm
Transport speed of resin base material: 10 m / min.

Example 6: Production of gas barrier film 6 In the formation of the first inorganic barrier layer of Example 1, the stage heating temperature was set to 75 ° C. and the oxygen concentration in the irradiation apparatus was adjusted so that the nitrogen content was as shown in Table 2. The volume was changed to 1.5% by volume, and in the formation of the second inorganic barrier layer, the plasma CVD conditions were changed as follows so that the metal and carbon in the second inorganic barrier layer had the contents shown in Table 2. Produced a gas barrier film 6 in the same manner as in Example 1.

Source gas: pentaethoxyniobium (Nb (OEt) ₅ )
Source gas flow rate: 150 sccm
Reaction gas: oxygen gas, flow rate: 600 sccm
Transport speed of resin base material: 10 m / min.

Example 7: Production of gas barrier film 7 In the formation of the first inorganic barrier layer of Example 1, the stage heating temperature was set to 60 ° C and the oxygen concentration in the irradiation apparatus was adjusted so that the nitrogen content was as shown in Table 2. Other than changing the conditions of plasma CVD as follows so that the content of the metal and carbon of the second inorganic barrier layer was changed to 0.5% by volume and the contents of the metal and carbon of the second inorganic barrier layer were as shown in Table 2 Produced a gas barrier film 7 in the same manner as in Example 1.

Source gas: pentaethoxyniobium (Nb (OEt) ₅ )
Source gas flow rate: 150 sccm
Reaction gas: oxygen gas, flow rate: 600 sccm
Transport speed of resin base material: 10 m / min.

Example 8: Production of gas barrier film 8 In the formation of the first inorganic barrier layer of Example 1, the stage heating temperature was 65 ° C. and the oxygen concentration in the irradiation apparatus was adjusted so that the nitrogen content was as shown in Table 2. The amount of vacuum ultraviolet irradiation energy was changed as shown in Table 2, and the contents of the metal and carbon of the second inorganic barrier layer in the formation of the second inorganic barrier layer are shown in Table 2. A gas barrier film 8 was produced in the same manner as in Example 1 except that the plasma CVD conditions were changed as follows.

Source gas: pentaethoxyniobium (Nb (OEt) ₅ )
Source gas flow rate: 150 sccm
Reaction gas: oxygen gas, flow rate: 600 sccm
Transport speed of resin base material: 10 m / min.

Example 9 Production of Gas Barrier Film 9 After forming the second inorganic barrier layer on the substrate, the first inorganic barrier layer was formed on the second inorganic barrier layer.

  The formation conditions of the inorganic barrier layer are as follows: In the formation of the second inorganic barrier layer of Example 1, the conditions of plasma CVD are as follows so that the metal and carbon of the second inorganic barrier layer have the contents shown in Table 2. A gas barrier film 9 was produced in the same manner as in Example 1 except for the change.

Source gas: pentaethoxyniobium (Nb (OEt) ₅ )
Source gas flow rate: 150 sccm
Reaction gas: oxygen gas, flow rate: 1200 sccm
Transport speed of resin base material: 10 m / min.

Example 10 Production of Gas Barrier Film 10 After forming the second inorganic barrier layer on the substrate, the first inorganic barrier layer was formed on the second inorganic barrier layer.

  The formation conditions of the inorganic barrier layer are as follows: In the formation of the second inorganic barrier layer of Example 1, the conditions of plasma CVD are as follows so that the metal and carbon of the second inorganic barrier layer have the contents shown in Table 2. A gas barrier film 10 was produced in the same manner as in Example 1 except for the change.

Source gas: pentaethoxyniobium (Nb (OEt) ₅ )
Source gas flow rate: 150 sccm
Reaction gas: oxygen gas, flow rate: 600 sccm
Transport speed of resin base material: 10 m / min.

Example 11: Production of gas barrier film 11 In the formation of the second inorganic barrier layer of Example 1, the source gas used was co-evaporated using pentaethoxyniobium as the Nb source and tetramethoxysilane (TMOS) as the Si source. A gas barrier film 11 was produced in the same manner as in Example 1 except that the plasma CVD conditions were changed as follows so that the metal and carbon in the inorganic barrier layer had the contents shown in Table 2.

Nb source gas flow rate: 75 sccm
Si source gas flow rate: 75 sccm
Reaction gas: oxygen gas, flow rate: 600 sccm
Transport speed of resin base material: 10 m / min.

Comparative Example 1: Production of Gas Barrier Film 12 In the formation of the second inorganic barrier layer of Example 1, the oxygen gas flow rate used was set to a large flow rate, and the metal and carbon in the second inorganic barrier layer had the contents shown in Table 2. A gas barrier film 12 was produced in the same manner as in Example 1 except that the plasma CVD conditions were changed as follows.

Source gas: pentaethoxyniobium (Nb (OEt) ₅ )
Source gas flow rate: 150 sccm
Reaction gas: oxygen gas, flow rate: 1700 sccm
Transport speed of resin base material: 10 m / min.

Comparative Example 2: Production of Gas Barrier Film 13 In the formation of the second inorganic barrier layer of Example 1, the source gas used was changed so that the metal and carbon in the second inorganic barrier layer had the contents shown in Table 2. A gas barrier film 13 was produced in the same manner as in Example 1 except that the plasma CVD conditions were changed as follows.

Source gas: Tetramethoxysilane Source gas flow rate: 300 sccm
Reaction gas: oxygen gas, flow rate: 450 sccm
Transport speed of resin base material: 10 m / min.

Comparative Example 3: Production of Gas Barrier Film 14 In the formation of the first inorganic barrier layer of Example 1, the stage heating temperature was set to 90 ° C. and the oxygen concentration was adjusted to be within the irradiation apparatus so that the nitrogen content was as shown in Table 2. The oxygen concentration is changed to 4.5% by volume, the vacuum ultraviolet irradiation energy is changed as shown in Table 2, and the metal and carbon of the second inorganic barrier layer are listed in Table 2 in forming the second inorganic barrier layer. A gas barrier film 14 was produced in the same manner as in Example 1 except that the conditions of plasma CVD were changed as follows so as to obtain the content of.

Source gas: pentaethoxyniobium (Nb (OEt) ₅ )
Source gas flow rate: 150 sccm
Reaction gas: oxygen gas, flow rate: 600 sccm
Transport speed of resin base material: 10 m / min.

Comparative Example 4: Production of Gas Barrier Film 15 In forming the first inorganic barrier layer of Example 1, the vacuum ultraviolet irradiation energy was changed as shown in Table 2, the stage heating temperature was 80 ° C., and the oxygen in the irradiation apparatus The concentration was changed to 2.5% by volume, and in the formation of the second inorganic barrier layer, the conditions of plasma CVD were changed as follows so that the metal and carbon of the second inorganic barrier layer had the contents shown in Table 2. A gas barrier film 15 was produced in the same manner as in Example 1 except that.

Source gas: pentaethoxyniobium (Nb (OEt) ₅ )
Source gas flow rate: 150 sccm
Reaction gas: oxygen gas, flow rate: 600 sccm
Transport speed of resin base material: 10 m / min.

Comparative Example 5 Production of Gas Barrier Film 16 A gas barrier film 16 was produced in the same manner as in Example 1 except that the second inorganic barrier layer was not formed.

  The obtained gas barrier films 1 to 16 were subjected to the following measurements and performance evaluations.

[XPS measurement]
<Measurement of element distribution profile>
The composition of the obtained gas barrier film of the present invention was measured in the depth (thickness) direction from the surface of the gas barrier layer using X-ray photoelectron spectroscopy (XPS). In other words, the composition analysis of the film in the depth direction was performed while etching the sample by performing the XPS depth profile. The XPS analysis conditions are shown below.

・ Device: QUANTERASXM (manufactured by ULVAC-PHI Co., Ltd.)
・ X-ray source: Monochromatic Al-Kα
Measurement area: Si2p, Al2p, Nb3d, Ta4d, Hf4d, Ti2p, Zr3d, Ru3d, Y3p, C1s, N1s, O1s
・ Irradiated X-ray: Single crystal spectroscopy AlKα
・ X-ray spot and its size: 800 × 400 μm oval shape ・ Sputtering ion: Ar (2 keV)
Depth profile: Repeat measurement after sputtering for 1 minute.

Sputtering conditions;
Etching rate (converted to SiO ₂ thermal oxide film): 0.05 nm / sec;
Etching interval (SiO ₂ equivalent value): 10 nm;
・ Data processing: MultiPak (manufactured by ULVAC-PHI)
Quantification: The background was determined by the Shirley method, and quantified using the relative sensitivity coefficient method from the obtained peak area.

  The composition analysis of the first inorganic barrier layer and the second inorganic barrier layer includes metal distribution curves (metal M: respective metal distribution curves of aluminum, titanium, zirconia, tantalum, niobium, hafnium, ruthenium and yttrium), silicon distribution curves, Surface composition analysis was performed on the oxygen distribution curve, carbon distribution curve, and nitrogen distribution curve in combination with XPS measurement and rare gas ion sputtering such as argon, while exposing the inside of the sample (XPS depth profile measurement). ). As a distribution curve obtained by XPS depth profile measurement, the vertical axis represents the atomic ratio (unit: at%) of each element, and the horizontal axis represents the etching time (sputtering time).

  In the distribution curve thus created, the portion where the metal M was 0 at% was determined as the interface between the first inorganic barrier layer and the second inorganic barrier layer.

  In each of the distribution curves obtained as described above, the total of the elements shown in the distribution curves (for example, the carbon distribution curve, the oxygen distribution curve, and the metal distribution curve) of the detected elements in the region corresponding to the second inorganic barrier layer. When the amount (unit: at%) is 100, the metal amount indicated by the metal distribution curve in the region corresponding to the second inorganic barrier layer is defined as the “metal content” of the second inorganic barrier layer, and the second inorganic barrier layer The carbon content indicated by the carbon distribution curve in the region corresponding to is defined as the “carbon content” of the second inorganic barrier layer. When silicon was contained in the second inorganic barrier layer, the amount of silicon was also added as the metal content. Similarly, the first inorganic barrier when the total amount of elements (unit: at%) shown in the “silicon distribution curve, oxygen distribution curve, and nitrogen distribution curve” in the region corresponding to the first inorganic barrier layer is 100 is used. The nitrogen content indicated by the nitrogen distribution curve in the region corresponding to the layer was defined as the “nitrogen content” of the first inorganic barrier layer.

<Adhesion evaluation>
Adhesion evaluation was evaluated according to the following criteria by a cross-cut (cross-cut) method in JIS K5600-5-6 (ISO 2409). The evaluation results are shown in the column of “Adhesion” in Table 2.

5: Number of peeled mass 0-5 / 100
4: Peeling mass number 6 to 10/100
3: Peeling mass number 11-30 / 100
2: Number of peeled masses 31-50 / 100
1: Peeling mass number 51 or more / 100.

<Storage stability (flexibility): Evaluation of water vapor permeability after flex test>
Each gas barrier film sample was bent 100 times at an angle of 180 degrees so that the radius of curvature was 10 mm, and then the permeated moisture was measured in the same manner as in [Evaluation of water vapor barrier property] in (1) above. The amount of deterioration was measured from the change in the amount of permeated water before and after the bending treatment, and the degree of deterioration resistance was measured according to the following formula, and the storage stability (bending resistance) was evaluated according to the following criteria. The evaluation results are shown in the column of “flex resistance” in Table 2.

Deterioration resistance = (water permeation before bending test / water permeation after bending test) × 100 (%)
The evaluation criteria for flex resistance are as follows:
5: Deterioration resistance is 90% or more
4: Deterioration resistance is 80% or more and less than 90% 3: Deterioration resistance is 60% or more and less than 80% 2: Deterioration resistance is 30% or more and less than 60% 1: Deterioration resistance is less than 30%.

<Gas barrier properties; measurement of permeated water content>
The permeated water amount (g / m ² · day) of each gas barrier film was evaluated by the Ca method described below, and ranked as follows.

  Using a vacuum vapor deposition device (manufactured by JEOL Ltd., vacuum vapor deposition device JEE-400) on the surface of the barrier layer of the sample, the portion to be vapor-deposited of the gas barrier film sample before attaching the transparent conductive film (9 locations of 12 mm x 12 mm) The metal calcium (granular form) was vapor-deposited (deposition film thickness 80 nm). Then, the mask was removed in a vacuum state, and metal aluminum (φ3 to 5 mm, granular), which is a water vapor impermeable metal, was deposited on the entire surface of one side of the sheet from another metal deposition source. After aluminum sealing, the vacuum state is released, and immediately facing the aluminum sealing side through a UV-curable resin for sealing (made by Nagase ChemteX) on quartz glass with a thickness of 0.2 mm in a dry nitrogen gas atmosphere The cell for evaluation was produced by irradiating with ultraviolet rays.

  The obtained sample is stored under high temperature and high humidity of 60 ° C. and 90% RH, and the amount of moisture permeated into the cell is calculated from the corrosion amount of metallic calcium based on the method described in JP-A-2005-283561. did.

  In addition, in order to confirm that there is no permeation of water vapor from other than the gas barrier film surface, a sample obtained by depositing metallic calcium using a quartz glass plate having a thickness of 0.2 mm instead of the gas barrier film sample as a comparative sample Was stored under the same high temperature and high humidity conditions of 85 ° C. and 85% RH, and it was confirmed that no corrosion of metallic calcium occurred even after 300 hours.

The permeated water amount (g / m ² · day; “WVTR” in the table) of each gas barrier film measured as described above was evaluated by the Ca method and ranked as follows. In addition, if it is rank 3 or more, there is no problem in actual use and it is a pass product. The evaluation results are shown in the column of “Gas barrier performance” in Table 2.

(Rank evaluation)
Less than 5: 1 × 10 ⁻⁴ g / m ² / day 4: 1 × 10 ⁻⁴ g / m ² / day or more and less than 5 × 10 ⁻⁴ g / m ² / day 3: 5 × 10 ⁻⁴ g / day m ² / day or more, less than 1 × 10 ⁻³ g / m ² / day 2: 1 × 10 ⁻³ g / m ² / day or more, less than 1 × 10 ⁻² g / m ² / day 1: 1 × 10 ^-2 g ^/ m 2 / day or more.

<Performance evaluation of organic light emitting device (OLED)>
Using the gas barrier film obtained in each of Examples and Comparative Examples, bottom emission type organic electroluminescence device (organic EL device) so that the area of the light emitting region is 5 cm × 5 cm by the method shown below. Was made. For each gas barrier film, four elements were produced.

(Formation of underlayer and first electrode)
The gas barrier film is fixed to a substrate holder of a commercially available vacuum deposition apparatus, compound 118 is placed in a resistance heating boat made of tungsten, and the substrate holder and the heating boat are attached in the first vacuum chamber of the vacuum deposition apparatus. It was. Moreover, silver (Ag) was put into the resistance heating boat made from tungsten, and it attached in the 2nd vacuum chamber of a vacuum evaporation system.

Next, after depressurizing the first vacuum chamber of the vacuum deposition apparatus to 4 × 10 ⁻⁴ Pa, the heating boat containing the compound 118 was energized and heated, and the deposition rate was 0.1 nm / second to 0.2 nm / second. The underlayer of the first electrode was provided with a thickness of 10 nm.

Next, the base material formed up to the underlayer was transferred to the second vacuum chamber while being vacuumed, and the second vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa, and then the heating boat containing silver was energized and heated. Thus, a first electrode made of silver having a thickness of 8 nm was formed at a deposition rate of 0.1 nm / second to 0.2 nm / second.

(Organic functional layer-second electrode)
Subsequently, the pressure was reduced to 1 × 10 ⁻⁴ Pa using a commercially available vacuum deposition apparatus, and then the compound HT-1 was deposited at a deposition rate of 0.1 nm / second while moving the base material. A transport layer (HTL) was provided.

  Next, compound A-3 (blue light-emitting dopant), compound A-1 (green light-emitting dopant), compound A-2 (red light-emitting dopant) and compound H-1 (host compound), compound A-3 is film thickness In contrast, the vapor deposition rate was changed depending on the location so that it was linearly 35 wt% to 5 wt%, and the compound A-1 and the compound A-2 each had a concentration of 0.2 wt% without depending on the film thickness. Thus, at a deposition rate of 0.0002 nm / sec, the compound H-1 was co-deposited to a thickness of 70 nm by changing the deposition rate from 64.6 wt% to 94.6 wt% depending on the location. A light emitting layer was formed.

  Thereafter, Compound ET-1 was deposited to a thickness of 30 nm to form an electron transport layer, and potassium fluoride (KF) was further formed to a thickness of 2 nm. Furthermore, aluminum 110nm was vapor-deposited and the 2nd electrode was formed.

  The compound 118, compound HT-1, compound A-1 to compound 3, compound H-1, and compound ET-1 are the compounds shown below.

(Solid sealing)
Next, an aluminum foil with a thickness of 25 μm is used as a sealing member, and a thermosetting sheet adhesive (epoxy resin) is bonded as a sealing resin layer on one surface of the aluminum foil with a thickness of 20 μm. The stopper member was used to superimpose the sample up to the second electrode. At this time, the adhesive forming surface of the sealing member and the organic functional layer surface of the element were continuously overlapped so that the end portions of the extraction electrodes of the first electrode and the second electrode were exposed.

  Next, the sample was placed in a decompression device, and the laminated base material and the sealing member were pressed and held for 5 minutes under a decompression condition of 0.1 MPa at 90 ° C. Subsequently, the sample was returned to an atmospheric pressure environment and further heated at 120 ° C. for 30 minutes to cure the adhesive.

  The sealing step is performed under atmospheric pressure and in a nitrogen atmosphere with a water content of 1 ppm or less in accordance with JIS B 9920: 2002. The measured cleanliness is class 100, the dew point temperature is −80 ° C. or less, and the oxygen concentration is 0.00. It was performed at an atmospheric pressure of 8 ppm or less. In addition, the description regarding formation of the lead-out wiring from an anode and a cathode is abbreviate | omitted.

(Dark spot (DS) evaluation)
The organic EL device obtained as described above was energized for 100 hours in an environment of 85 ° C. and 85% RH, and the dark spot having a dark spot generated in 100 hours had a circle-equivalent diameter. The number of dark spots that are 300 μm or more / four devices were determined. The measurement results are shown in the column of “DS at 100 hr” in Table 2.

(Rank evaluation)
5: Less than 20 4:20 or more, less than 40 3:40 or more, less than 60 2:60 or more, less than 80 1:80 or more.

  From the said result, it turns out that the gas barrier film (gas barrier films 1-11) of this invention has high adhesiveness and bending resistance, and has the outstanding water vapor | steam barrier property (gas barrier performance). Moreover, since the gas barrier film of this invention has the outstanding gas barrier performance, even when it is a case where it applies to an electronic device, it turns out that it is excellent in durability in a high temperature, high humidity environment.

1 gas barrier film,
2 base material,
3 barrier layers,
31 manufacturing equipment,
32 Feeding roller,
33, 34, 35, 36 transport rollers,
39, 40 ... film forming roller,
41 gas supply pipe,
42 Power supply for plasma generation,
43, 44 Magnetic field generator,
45 take-up roller,
111 gas barrier film,
110 resin base material,
120 gas barrier layer,
120a first inorganic barrier layer,
120b Second inorganic barrier layer.

Claims (7)

On the resin substrate,
A first inorganic barrier layer formed by applying vacuum ultraviolet light to a coating film obtained by applying and drying a coating liquid containing polysilazane;
A second inorganic barrier layer formed by plasma enhanced chemical vapor deposition, disposed in contact with the first gas barrier layer,
The second inorganic barrier layer includes one or more metals selected from the group consisting of Al, Ti, Zr, Ta, Nb, Hf, Ru and Y,
The content of the metal of the second inorganic barrier layer is 25 to 50 at% with respect to 100 at% of the total amount of elements in the entire layer,
The carbon content of the second inorganic barrier layer is 0.1 to 10 at% with respect to 100 at% of the total amount of elements in the entire layer.   2. The gas barrier film according to claim 1, wherein the nitrogen content of the first inorganic barrier layer is 10 to 40 at% with respect to 100 at% of the total amount of silicon, oxygen and nitrogen. The gas barrier film according to claim 1 or 2, wherein the vacuum ultraviolet ray has an irradiation energy of 1.0 J / cm ² or more.   The second inorganic barrier layer is formed of at least one selected from the group consisting of metal alkoxides, metal amino compounds, metal chlorides, metal cyclopentadienyl compounds, metal alkoxy β-diketone complexes, and metal alkoxyimide complexes. The gas barrier film according to any one of claims 1 to 3.   The gas barrier film according to claim 1, wherein the metal is Nb.   The gas barrier film according to claim 1, wherein the plasma chemical vapor deposition method is performed by a plasma CVD apparatus having a counter roll electrode.   The electronic device which has a gas barrier film of any one of Claims 1-6.