JP2014180837A - Gas barrier film and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier film having an unprecedentedly high gas barrier capacity and a method for manufacturing the same.SOLUTION: A gas barrier film 10 includes a substrate 1, an inorganic layer 2 configured atop the substrate 1, and an organic layer 3 configured atop the inorganic layer 2, whereas the organic layer 3 is formed by inorganic particles possessing polymerizable groups on surfaces thereof. It is desirable for the polymerizable groups to concomitantly include one, two, or more reactive groups selected from among acrylic groups, epoxy groups, vinyl groups, allyl groups, isocyanate groups, and silanol groups. This gas barrier film 10 can be manufactured by a method including a step of dry-film-forming the inorganic layer 2 atop the substrate 1 and a step of film-forming, atop the inorganic layer 2, the organic layer 3 by curing an organic layer-forming composition including at least inorganic particles possessing polymerizable groups on surfaces thereof.

Description

  The present invention relates to a gas barrier film having a high water vapor barrier property and an oxygen barrier property, a method for producing the same, and an apparatus provided with the gas barrier film.

  The gas barrier film is permeable to chemical components such as oxygen or water vapor that degrade the performance of organic electroluminescence elements (organic EL elements), liquid crystal display elements, thin film transistors, solar cells, touch panels, electronic paper, and other devices. It is preferably applied to prevent. Conventional gas barrier films include those in which an inorganic layer such as aluminum oxide or silicon oxide is provided on a plastic substrate, or those in which an organic layer is provided on a plastic substrate (for example, Patent Document 1) In addition, an organic layer is provided after an inorganic layer is provided on a plastic substrate (for example, Patent Document 2).

  The gas barrier film proposed in Patent Document 1 is provided with an organic layer for improving adhesion and flatness as a base layer of a gas barrier inorganic layer, and specifically, at least one of the substrates. In this order, an anchor coat layer containing a polyacrylic acid resin, a hard coat layer containing a (meth) acrylic resin reacted and cured by ultraviolet rays or an electron beam, and a barrier thin film layer made of an inorganic compound in this order. Are stacked.

  In addition, the gas barrier film proposed in Patent Document 2 is provided with an organic layer on the outermost surface to improve bending resistance and scratch resistance. Specifically, the gas barrier film is made of polysilazane on a base material. A barrier layer containing at least one silicon atom and oxygen atom formed by treating the layer is provided, and an overcoat layer having inorganic nanoparticles is provided on the barrier layer by a sol-gel method.

JP 2010-105321 A JP 2011-73417 A

  The various gas barrier films described above have higher gas barrier properties and production than the gas barrier films proposed in Patent Documents 1 and 2 and the like described above, particularly with the recent enhancement of performance and quality of electronic devices. Sex is required.

  This invention solves the said subject, The objective is to provide the gas-barrier film with higher gas-barrier property, and its manufacturing method. Another object of the present invention is to provide a packaging container formed of the gas barrier film and an apparatus including the gas barrier film.

  (1) A gas barrier film according to the present invention for solving the above problems has a base material, an inorganic layer provided on the base material, and an organic layer provided on the inorganic layer, The organic layer is formed of inorganic particles having a polymerization reactive group on the surface.

  In the gas barrier film according to the present invention, the polymerization reactive group is preferably one or more reactive groups selected from an acrylic group, an epoxy group, a vinyl group, an allyl group, an isocyanate group, and a silanol group.

  (2) A packaging container according to the present invention for solving the above-described problems has a base material, an inorganic layer provided on the base material, and an organic layer provided on the inorganic layer, The organic layer is formed of a gas barrier film formed of inorganic particles having a polymerization reactive group on the surface.

  (3) A display device according to the present invention for solving the above problems includes a base material, an inorganic layer provided on the base material, and an organic layer provided on the inorganic layer, The organic layer is provided with a gas barrier film formed of inorganic particles having a polymerization reactive group on the surface.

  The power generation device according to the present invention for solving the above-described problem has a base material, an inorganic layer provided on the base material, and an organic layer provided on the inorganic layer, and the organic layer is It comprises a gas barrier film formed of inorganic particles having a polymerization reactive group on the surface.

  (4) A method for producing a gas barrier film according to the present invention for solving the above problems includes a step of dry-forming an inorganic layer on a substrate and a step of forming an organic layer on the inorganic layer. And the organic layer is formed by curing the organic layer-forming composition containing at least inorganic particles having a polymerization reactive group on the surface.

  In the method for producing a gas barrier film according to the present invention, the prepolymerization reactive group is one or more reactive groups selected from an acrylic group, an epoxy group, a vinyl group, an allyl group, an isocyanate group, and a silanol group. Is preferred.

  In the method for producing a gas barrier film according to the present invention, the dry film formation is preferably a chemical vapor deposition method or a physical vapor deposition method.

  According to the present invention, a gas barrier film having higher gas barrier properties and a method for producing the same can be provided.

It is a typical sectional view showing an example of a gas barrier film concerning the present invention. It is typical sectional drawing which shows another example of the gas barrier film which concerns on this invention. It is typical sectional drawing which shows another example of the gas barrier film which concerns on this invention. It is typical sectional drawing which shows another example of the gas barrier film which concerns on this invention.

  Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist thereof.

[Gas barrier film and method for producing the same]
As shown in FIGS. 1 to 4, the gas barrier film 10 according to the present invention includes a base material 1, an inorganic layer 2 provided on the base material 1, and an organic layer 3 provided on the inorganic layer 2. have. The organic layer 3 is formed of inorganic particles having a polymerization reactive group on the surface.

  Such a gas barrier film 10 comprises a step of dry-forming at least one inorganic layer 2 on a substrate 1, and a curable resin and inorganic particles having a polymerization reactive group on the surface on the inorganic layer 2. The organic layer forming composition contained is cured to form the organic layer 3. The dry film formation is preferably a chemical vapor deposition method (CVD method) or a physical vapor deposition method (PVD method).

  In addition, although the inorganic layer 2 and the organic layer 3 are provided in that order on one surface S1 of the base material 1 as shown in FIG. 1, as shown in FIG. 2, the inorganic layer 2 (2a, 2b) May be two or more layers. Further, as shown in FIG. 3, inorganic layers 2, 2 'and organic layers 3, 3' may be provided in this order on both surfaces S1, S2 of the substrate 1, respectively. In addition, if the inorganic layer 2 and the organic layer 3 are provided on one surface S1, the other surface S2 may be provided with neither an inorganic layer nor an organic layer as shown in FIG. Only one of the layer 2 and the organic layer 3 may be provided. Moreover, as shown in FIG. 4, you may provide the primer layer 4 between the base material 1 and the inorganic layer 2, and although not shown in figure, it is between the base material of the other surface S2, and an inorganic layer or an organic layer. A primer layer may be provided.

  Hereinafter, while explaining the structure of the gas barrier film, the production method will also be explained.

<Base material>
Although the base material 1 will not be specifically limited if it is a film which can form the inorganic layer 2, From the viewpoint of actual use, the base material 1 which consists of a polyester-type resin, an olefin resin, a polycarbonate resin, a cellulose resin, etc. is mentioned. Can do. Examples of the polyester resin include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), copolymers thereof, and polycyclohexanedimethylene terephthalate (PCT). Among the polyester resins, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and copolymers thereof are preferable, and polyethylene naphthalate and polyethylene terephthalate are particularly preferable. Examples of the olefin-based resin include norbornene-based polymers, cyclopentene-based polymers, cyclobutene-based polymers, and the like. Among these, norbornene-based polymers can be preferably exemplified.

  When a polyester resin is applied as the material of the base material 1, all of it may be the polyester resin base material 1, and at least a polyester resin layer is formed on the surface on which the inorganic layer 2 is formed. Alternatively, the laminated substrate 1 may be used. In this laminated substrate 1, layers other than the polyester resin layer on the side where the inorganic layer 2 is formed may not be a polyester resin layer. As a layer other than the polyester-based resin layer, various resin layers can be selected in consideration of flexibility, strength, heat resistance, thermal expansion, light transmittance, and the like.

  Although the thickness of the base material 1 is not specifically limited, It is preferable that it is a grade of 10 micrometers or more and 500 micrometers or less. The substrate 1 may be referred to as a substrate film or a substrate sheet depending on its thickness. Moreover, the transparency of the base material 1 is not particularly limited, and can be arbitrarily selected according to the application. When more transparency is required, the total light transmittance is preferably 80% or more. The total light transmittance is a numerical value representing transparency of a general film, and is measured by a method according to JIS-K-7105 or JIS-K-7361, and specifically obtained by haze meter measurement. It is expressed by all the light quantities. The base material 1 may contain a colorant as necessary, and may contain an antioxidant, an ultraviolet absorber, and the like. In addition, a uniaxially or biaxially stretched film is preferable because both transparency and mechanical strength are high. Among these, a biaxially stretched film of polyethylene terephthalate is preferable in terms of heat resistance, mechanical strength, light transmittance, cost, and the like.

  Such a base material 1 may be prepared by purchasing a commercial item, or may be prepared by producing it on its own. As a manufacturing method of the substrate 1, a conventionally known manufacturing method can be applied, and examples thereof include a solution casting method, a melt extrusion method, and a calendar method.

  The surface of the substrate 1 is subjected to surface treatment to improve the adhesion with the inorganic layer 2 or the adhesion with the primer layer 4 (see FIG. 4) provided as necessary. Is preferred. Examples of the surface treatment include oxidation treatment, roughening treatment (roughening treatment), and easy adhesion coating treatment. Examples of the oxidation treatment include corona discharge treatment, plasma treatment, glow discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone ultraviolet irradiation treatment, and the like. Examples of the roughening treatment (roughening treatment) include a sand blast method and a solvent treatment method. These surface treatments are selected according to the type of the substrate 1, but generally, a corona discharge treatment method is preferably used from the viewpoints of effects and operability.

(Primer layer)
The primer layer 4 is an arbitrary layer, and is provided as necessary on the substrate 1 on the side where the inorganic layer 2 is provided, as shown in FIG. The primer layer 4 acts to improve the adhesion between the inorganic layer 2 and the primer layer 4. The primer layer 4 is not particularly limited, and can be formed by applying a resin composition for a primer layer used in a general laminated film on the substrate 1 and curing it.

  Examples of the resin material constituting the primer layer 4 include heat such as acrylic resin, vinyl chloride-vinyl acetate copolymer, polyamide resin, polyester resin, chlorinated polypropylene, chlorinated rubber, urethane resin, epoxy resin, and styrene resin. Preferred examples include fusible resins. The primer layer 4 is composed of one or more of these resins, and an acrylic resin alone is particularly preferable from the viewpoint of improving weather resistance. A crosslinking agent is used if necessary, and examples thereof include a melamine-based crosslinking agent and an epoxy-based crosslinking agent.

  The thickness of the primer layer 4 is usually in the range of 1 μm to 25 μm, and preferably in the range of 3 μm to 20 μm. If the thickness is 1 μm or more, sufficient adhesiveness can be obtained, and if the thickness is 25 μm or less, it is economically preferable. The primer layer 4 may contain various additives as required. For example, one or both of a light stabilizer and an ultraviolet absorber may be included, or other additives may be included.

<Inorganic layer>
The inorganic layer 2 is formed by depositing an inorganic layer material (inorganic layer forming material) on the substrate 1 or a primer layer 4 provided as necessary by dry film formation. The inorganic layer 2 functions as a gas barrier layer that blocks gas such as water vapor and oxygen. Therefore, the inorganic layer 2 can be referred to as a “gas-shielding inorganic compound layer” having gas barrier properties, and any inorganic compound layer having gas barrier properties can be provided as the inorganic layer 2.

  The inorganic layer 2 may be formed of various conventionally known inorganic compounds capable of forming a gas barrier layer. Examples of such inorganic compounds include inorganic oxides, inorganic oxynitrides, inorganic nitrides, inorganic oxide carbides, Examples thereof include one or more inorganic compounds selected from inorganic oxycarbonitrides and silicon zinc oxide. Specific examples include inorganic compounds containing one or more elements selected from silicon, aluminum, magnesium, titanium, tin, indium, cerium, and zinc, and more specifically, silicon. Inorganic oxides such as oxides, aluminum oxides, magnesium oxides, titanium oxides, tin oxides, silicon zinc alloy oxides and indium alloy oxides, inorganics such as silicon nitrides, aluminum nitrides and titanium nitrides Examples thereof include inorganic silicon oxynitrides such as nitrides and silicon oxynitrides. Particularly preferably, the inorganic layer 2 is a layer made of one or more selected from silicon oxide, silicon nitride, silicon oxynitride, and silicon zinc oxide. The inorganic layer 2 may use the said material independently, and may mix and use the said material in arbitrary ratios within the range of the summary of this invention.

  The inorganic layer 2 is formed by dry film formation. Examples of the dry film formation include a physical vapor deposition (PVD) method and a chemical vapor deposition (CVD) method.

  The PVD method is a method in which a solid raw material is used as a raw material, vaporized by heat or plasma energy, and thinned on a film formation substrate. For example, a vacuum deposition method, an electron beam deposition method, a reactive deposition method, an ion plating method, a glow discharge sputtering method, an ion beam sputtering method, a reactive sputtering method, and the like can be given. In addition, the CVD method is a method of depositing a film through adsorption, reaction, and dissociation on the surface of a deposition target substrate by applying energy such as heat, light, or electromagnetic waves to the source gas to perform excitation or decomposition. . Examples thereof include a thermal CVD method, a metal organic chemical vapor deposition (MOCVD) method, an RF plasma CVD method, an ECR plasma CVD method, a photo CVD method, a laser CVD method, and a mercury sensitization method.

  More specifically, (1) a vacuum vapor deposition method in which a raw material such as an inorganic oxide, inorganic nitride, inorganic oxynitride, or metal is heated and deposited on a substrate, and (2) oxygen gas is introduced into the raw material. Oxidation reactive vapor deposition method for oxidizing and vapor-depositing on the base material, (3) Sputtering method for depositing on the base material by introducing argon gas and oxygen gas into the target raw material and sputtering, and (4) Raw material with a plasma gun An ion plating method in which heating is performed with the generated plasma beam and vapor deposition is performed on the substrate, and (5) a plasma CVD method in which an organic silicon compound or the like is used as a raw material and a silicon oxide film is vapor deposited on the substrate can be used. Among these methods for forming the inorganic layer 2, the ion plating method or the plasma CVD is particularly preferable in terms of the adhesion between the inorganic layer 2 and the organic layer 3 and the deposition rate.

  The thickness of the inorganic layer 2 varies depending on the inorganic compound used, but is usually 5 nm or more and 5000 nm or less. From the viewpoint of gas barrier properties, it is preferably 10 nm or more, and from the viewpoint of suppressing the occurrence of cracks and the like, it is preferably 500 nm or less. The inorganic layer 2 may be a single layer or two or more inorganic layers 2 (2a, 2b) having a total thickness within the above range. In the case of two or more inorganic layers 2, the same materials may be combined or different materials may be combined.

<Organic layer>
The organic layer 3 is a layer formed on the inorganic layer 2 with inorganic particles having a polymerization reactive group on the surface. The organic layer 3 can be formed of only inorganic particles having a polymerization reactive group on the surface, or can be formed of a composition containing inorganic particles having a polymerization reactive group on the surface and a curable resin.

(Inorganic particles)
The inorganic particles have a polymerization reactive group on the surface. Examples of the constituent material of the inorganic particles include silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, zinc oxide, tungsten oxide, niobium oxide, molybdenum oxide, nickel oxide and the like. Among these, silicon oxide is preferable from the viewpoint of optical characteristics and adhesion.

  The polymerization reactive group is preferably a monomer, oligomer, or prepolymer constituting a thermosetting resin or an ionizing radiation curable resin described later. The inorganic particles having such a polymerization reactive group on the surface are polymerized and cured by heat or ionizing radiation to form the organic layer 3. Examples of the polymerization reactive group include an acrylic group, an epoxy group, a vinyl group, an allyl group, an isocyanate group, and a silanol group. Preferable polymerization reactive groups include acrylic groups or epoxy groups. In particular, inorganic particles having a polymerization-reactive group that cures with an electron beam on the surface are preferable. When such a polymerization-reactive group reacts and cures upon irradiation with an electron beam, the organic component becomes a denser three-dimensional crosslinked structure. The organic layer 3 in which inorganic particles are densely formed is formed.

  The average particle diameter of the inorganic particles having a polymerization reactive group on the surface is preferably 10 nm or more and 400 nm or less, and more preferably 10 nm or more and 250 nm or less. Inorganic particles within this range are effective in terms of optical properties (transparency) and improving the barrier properties by filling gaps in the inorganic layer. If the average particle diameter of the inorganic particles is less than 10 nm, the particles may aggregate and the coating film may be whitened. If it exceeds 400 nm, the organic layer 3 may be whitened.

  By forming the organic layer 3 on the inorganic layer 2 with these inorganic particles, the organic layer 3 is contracted by the curing reaction of the resin component derived from the polymerization reactive group, and the organic layer 3 It is considered that the inorganic layer 2 contracts due to the contraction and becomes dense, and as a result, the gas barrier property is enhanced. In addition, the inorganic particles contained in the organic layer 3 are considered to exhibit one or both of an anchoring action that reinforces the organic layer 3 and an action that penetrates cracks, defects, and the like of the inorganic layer 2. It is considered that the gas barrier property is enhanced.

  The kind of the polymerization reactive group on the surface of the inorganic particle can be easily specified by, for example, X-ray photoelectron spectroscopy or Fourier transform infrared spectroscopy. For example, it can be specified whether the polymerization reactive group is an acrylic group or an epoxy group.

  For inorganic particles having a polymerization reactive group on the surface, use a polymerization reaction of a precursor such as a metal complex to synthesize colloidally dispersed nanoparticles and replace the surface ligand with a polymerization reactive group. Can be produced. Such inorganic particles are generally commercially available, and examples thereof include Opstar (trade name) manufactured by JSR Corporation and organosilica sol manufactured by Nissan Chemical Industries, Ltd. The surface of the inorganic particle is chemically modified with a polymerization reactive group, and the thickness of the chemically modified polymerization reactive group is, for example, in the range of 1 nm to 10 nm.

(Curable resin)
The curable resin can constitute an organic layer forming composition together with the above-described inorganic particles. That is, the organic layer 3 may contain a curable resin in addition to the above-described polymerization reactive group. As the curable resin, a thermosetting resin or an ionizing radiation curable resin is used. Ionizing radiation is not only electron beams and ultraviolet rays, but also electromagnetic waves such as visible rays, X-rays and γ rays, and charged particle beams such as α rays. Ionizing radiation curable resins are irradiated with ionizing radiation. It is a resin that crosslinks and cures.

  Examples of thermosetting resins include epoxy resins, phenol resins, urea resins, unsaturated polyester resins, melamine resins, alkyd resins, polyimide resins, silicone resins, hydroxyl functional acrylic resins, carboxyl functional acrylic resins, and amide functionalities. A copolymer, a urethane resin, etc. can be mentioned, These can be used 1 type or 2 types or more. As an aspect of cross-linking curing of these resins, for example, epoxy resin can promote cross-linking curing by reaction with amine, acid catalyst, carboxylic acid, acid anhydride, hydroxyl group, dicyandiamide or ketimine; Crosslinking cure can be promoted by reaction of aldehyde with excess aldehyde; urea resin can promote crosslinking cure by polycondensation reaction under alkaline or acidic conditions; unsaturated polyester resin can co-condensate maleic anhydride with diol Crosslinking and curing can be promoted by reaction; melamine resin can promote crosslinking and curing by heat polycondensation reaction of methylolmelamine; alkyd resin can be crosslinked and cured by reaction by air oxidation of unsaturated groups introduced into side chains and the like. Can be promoted; polyimide resins can be reacted by reaction in the presence of acids or weak alkali catalysts or Crosslinking and curing can be promoted by a reaction with a product (in the case of a two-component type); the silicone resin can promote crosslinking and curing by a condensation reaction in the presence of a silanol group acid catalyst; Crosslinking and curing can be promoted by reaction with its own amino resin (in the case of 1-component type); carboxyl functional acrylic resin can promote crosslinking and curing by reaction with carboxylic acid such as acrylic acid or methacrylic acid and an epoxy compound; Amide functional copolymers can promote cross-linking and curing by reaction with hydroxyl groups or self-condensation reactions; urethane resins are hydroxyl group-containing resins such as polyester resins, polyether resins, acrylic resins and isocyanate compounds or modified products thereof Crosslinking hardening can be accelerated | stimulated by reaction with. A cross-linking agent or a curing agent utilizing these reactions is usually used.

  As the ionizing radiation curable resin, an electron beam curable resin curable with an electron beam or an ultraviolet curable resin curable with an ultraviolet ray is preferably used.

  As an electron beam curable resin, 1 type (s) or 2 or more types selected from the various polymerizable oligomers and prepolymers generally used as an electron beam curable resin can be used. Examples of polymerizable oligomers and prepolymers include oligomers or prepolymers having radically polymerizable unsaturated groups in the molecule. For example, epoxy (meth) acrylates, urethane (meth) acrylates, polyether urethanes ( Preferred examples include (meth) acrylate-based, caprolactone urethane (meth) acrylate-based, polyester (meth) acrylate-based, and polyether (meth) acrylate-based oligomers or prepolymers, and these are used singly or in combination. be able to. Among these, urethane acrylic copolymer resins such as polycarbonate-based urethane acrylate and polyester-based urethane acrylate are preferable from the viewpoint of cost and productivity. Here, “(meth) acrylate” means “acrylate or methacrylate”. The electron beam curable resin is particularly preferable because it does not require the use of a solvent or the like.

  A monofunctional (meth) acrylate such as methyl (meth) acrylate can be used together with the polyfunctional urethane (meth) acrylate. The monofunctional (meth) acrylate may be used in combination as a diluent or the like for adjusting the viscosity within a range that does not impair the object of the present invention. A monofunctional (meth) acrylate may be used individually by 1 type, may be used in combination of 2 or more type, and may use low-molecular-weight polyfunctional (meth) acrylate together.

  As the ultraviolet curable resin, for example, a radical polymerizable resin that can be crosslinked by irradiation with ultraviolet rays can be exemplified. For example, 1 type, or 2 or more types chosen from the monomer (monomer) which has radically polymerizable unsaturated groups, such as an acrylate group, a vinyl group, an allyl group, and an isopropenyl group, an oligomer, and a prepolymer can be mentioned. Examples of such oligomers and prepolymers include one or more selected from urethane acrylate, epoxy acrylate, polyester acrylate, polyether acrylate, polyethylene acrylate, polybutadiene acrylate, silicone acrylate, polyol acrylate, and the like.

  Examples of the monomer having a radical polymerizable unsaturated group include monofunctional monomers and polyfunctional monomers. Although it does not specifically limit as a monofunctional monomer, For example, vinyl monomers, such as N-vinyl pyrrolidone, N-vinyl caprolactone, vinyl imidazole, vinyl pyridine, styrene; Phenoxyethyl acrylate, lauryl acrylate, stearyl acrylate, butoxyethyl acrylate, Acrylate monomers such as methoxypolyethylene glycol acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, isooctyl acrylate, cyclohexyl acrylate, benzyl acrylate, N, N-dimethylacrylamide, N, N-dimethylaminopropyl acrylate, acryloylmorpholine; and acrylamide Derivatives. Polyfunctional monomers include pentaerythritol triacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, polytetramethylene glycol diacrylate, butane Diol diacrylate, hexanediol diacrylate, nonanediol diacrylate, pentanediol diacrylate, neopentyl glycol diacrylate, dimethylol-tricyclodecane diacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and the like Modified ethylene oxide, B propylene oxide-modified products, and caprolactam modified products and the like. One type of monomer may be used, or two or more types may be mixed and used. Moreover, the oligomer and prepolymer which the above-mentioned monomer couple | bonded and produced | generated may be sufficient. These monomers, oligomers and prepolymers may be used singly or in combination, or may be used alone or in combination according to the required performance or industrial productivity. Two or more kinds can be used in appropriate combination.

  In the present invention, a diluent such as a monofunctional (meth) acrylate such as methyl (meth) acrylate is used together with the monomer, oligomer and prepolymer for the purpose of adjusting the viscosity. They can be used in combination as long as the purpose is not impaired. A monofunctional (meth) acrylate may be used individually by 1 type, may be used in combination of 2 or more type, and may use low-molecular-weight polyfunctional (meth) acrylate together. Moreover, as a diluent, the applicability | paintability of a resin composition can also be ensured using said monomer. “(Meth) acrylate” means “acrylate or methacrylate”.

  The ultraviolet curable resin contains a photopolymerization initiator. Although it does not specifically limit as a photoinitiator, For example, an acetophenone type compound, an acyl phosphine oxide type compound, etc. can be mentioned. Examples of acetophenone compounds include acetophenone, hydroxyacetophenone, aminoacetophenone, 1-hydroxycyclohexyl phenyl ketone, oligo [2-hydroxy-2-methyl-1- {4- (1-methylvinyl) phenyl} propanone], 2 -Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 and the like can be mentioned. Examples of the acyl phosphine oxide compound include bis (2,4,6-trimethylbenzoyl) -phenyl phosphine oxide. 1 type may be used for a photoinitiator and it may use it in combination of 2 or more types. Moreover, it is preferable that the compounding quantity of a photoinitiator is 0.1 to 5 mass% with respect to the whole quantity of the ultraviolet curable resin composition for forming the organic layer 3. FIG. In addition, as a quantification method of a photoinitiator, it can obtain | require by the gas chromatography mass spectrometry, for example.

  The type of the curable resin contained in the organic layer 3 can be easily specified by, for example, X-ray photoelectron spectroscopy or Fourier transform infrared spectroscopy, as with the above-described polymerization reactive group.

  When the organic layer 3 contains inorganic particles and a curable resin, the inorganic particles in the organic layer 3 are preferably 13% by mass or more. If the inorganic particles in the organic layer 3 are less than 13% by mass, the gas barrier effect due to the presence of the inorganic particles may not be sufficiently obtained. The upper limit of the inorganic particles in the organic layer 3 is not particularly limited, and may be the organic layer 3 that does not include a curable resin and is formed using only the polymerization reactive group on the surface of the inorganic particles as an organic component.

(Other ingredients)
The thermosetting resin composition or the electron beam curable resin composition for forming the organic layer 3 may contain a weathering agent such as a light stabilizer or an ultraviolet absorber.

  When a radical is generated by the action of ultraviolet rays, the light stabilizer can capture and inactivate the radical, and can suppress the progress of photooxidative degradation of the organic layer 3. A light stabilizer will not be specifically limited if there exists such an effect. As the light stabilizer, for example, a hindered amine light stabilizer (HALS) is preferable. When a free radical that causes an oxidation reaction occurs, the free radical can be captured and stabilized catalytically.

  Specific examples of hindered amine light stabilizers include bis (1,2,2,6,2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2′-n-butylmalonate). 6-pentamethyl-4-piperidyl), bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, 2,4-bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4 -Yl) amino] -6- (2-hydroxyethylamine) -1,3,5-triazine), tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4- Butante La carboxylate, can be mentioned 1,2,2,6,6-pentamethyl-4-piperidinyloxy methacrylate. Further, a hindered amine light stabilizer having a reactive functional group may be used, and specific examples include 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate.

  When the organic layer 3 is formed of an electron beam curable resin composition, the ultraviolet absorber can be preferably contained in the composition. The ultraviolet absorber may be inorganic or organic. Preferable examples of the inorganic ultraviolet absorber include titanium oxide, cerium oxide, and zinc oxide having an average particle size of about 5 nm to 120 nm. Preferred examples of the organic ultraviolet absorber include benzotriazole, triazine, benzophenone, salicylate, and acrylonitrile. Of these, triazines are preferred because they have a high ultraviolet-absorbing ability and are not easily degraded by high energy such as ultraviolet rays.

  Specific examples of the triazine ultraviolet absorber include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] phenol, 1,3,5 -Triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tri [{3,5-bis- (1,1-dimethylethyl) -4-hydroxyphenyl} methyl], And benzotriazole-based ultraviolet absorbers. Specific examples of the benzotriazole ultraviolet absorber include 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole, Examples include 3- [3- (benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl] propionic acid ester of polyethylene glycol.

  In the case where the organic layer 3 is formed of an ultraviolet curable resin composition, an ultraviolet absorber may be included in the composition, but in this case, the wavelength of ultraviolet rays that the ultraviolet absorber mainly absorbs. And the wavelength of the ultraviolet rays to be irradiated in order to cure the ultraviolet curable resin. Even if an ultraviolet curable resin composition containing an ultraviolet absorber is used by shifting both ultraviolet wavelengths, the ultraviolet curable resin is cured by irradiating with ultraviolet rays having a predetermined wavelength to thereby form the organic layer 3. Can be formed.

  Further, the ionizing radiation curable composition may contain other additives as necessary within a range not impairing the effects of the present invention. Examples of additives include heat stabilizers, antifoaming agents, leveling agents, plasticizers, surfactants, antistatic agents, antioxidants, infrared absorbers, dyes (coloring dyes, coloring pigments), extender pigments, light Examples include diffusing agents and coupling agents.

  The ionizing radiation curable composition may contain a solvent from the viewpoint of adjusting the viscosity during production. Solvents include alcohols such as isopropyl alcohol, methanol and ethanol; ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; esters such as ethyl acetate and butyl acetate; halogenated hydrocarbons; aromatic carbonization such as toluene and xylene Mention may be made of hydrogen; or mixtures thereof. These solvents may be mixed and used at an arbitrary ratio within the scope of the gist of the present invention.

(Formation method)
The organic layer 3 is provided by applying a composition for forming an organic layer containing inorganic particles on the inorganic layer 2. Examples of the organic layer forming composition include a composition containing the above-described inorganic particles and a viscosity adjusting solvent, a composition containing the above-described inorganic particles and curable resin, and a viscosity adjusting solvent. In addition, you may make this composition contain various additives as needed. As the viscosity adjusting solvent, methyl ethyl ketone, toluene, and other general-purpose solvents can be arbitrarily selected and used by appropriately blending them.

  Examples of the method for applying the organic layer forming composition onto the inorganic layer 2 include a roll coating method, a gravure roll coating method, a kiss roll coating method, a reverse roll coating method, a Miya bar coating method, a gravure coating method, and a spin coating. Method, die coating method and the like.

  After the organic layer forming composition is applied, it is cured by applying a predetermined curing means. As the curing means, heat is applied in the case of thermosetting that the polymerization reactive group reacts with heat to cure, and ionizing radiation in the case of ionizing radiation curable that the polymerization reactive group reacts and cures with ionizing radiation. Irradiate (electron beam, ultraviolet ray, etc.).

  As an electron beam source, various electron beam accelerators such as a cockcroft Walton type, a bandegraft type, a resonant transformer type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type can be used. The acceleration voltage of the electron beam is, for example, 70 kV or more and 1000 kV or less, and preferably 90 kV or more and 200 kV or less. The irradiation amount of the electron beam is, for example, 1 Mrad or more and 30 Mrad or less, and preferably 2.5 Mrad or more and 25 Mrad or less.

  As the ultraviolet light source, for example, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, a metal halide lamp is used. As the wavelength of the ultraviolet light, a wavelength range of 190 nm or more and 380 nm or less can be used. What is necessary is just to adjust suitably the time which irradiates an ultraviolet-ray from the viewpoint which carries out reliable hardening of an organic layer, considering industrial productivity. Moreover, hardening by heating is normally performed by maintaining at a temperature range of 160 ° C. or higher and 240 ° C. or lower for 2 hours or longer.

  The organic layer 3 to be formed may be a single layer or two or more layers. The total thickness of the organic layer 3 is preferably in the range of 0.1 μm or more and 20 μm or less, regardless of whether it is a single layer or two or more layers, and is 0.5 μm from the viewpoint of surface properties and productivity. More preferably, it is in the range of 10 μm or less.

<Other layers>
The gas barrier film according to the present invention may be provided with a heat sealable resin layer (not shown). The heat-sealable resin layer may be provided on the surface S1 of the base material 1, may be provided on the surface S4 on the organic layer 3 side, or may be provided on both of them. The heat-sealable resin layer can be formed by applying and drying a composition containing a heat-sealable resin such as polyethylene or polypropylene.

  Moreover, you may provide another functional layer suitably on the other surface S2 of the base material 1, the organic layer 3, or between the inorganic layer 2 and the organic layer 3 according to a function and a use. Examples of other functional layers include mat layers, protective layers, antistatic layers, smoothing layers, adhesion improving layers, light shielding layers, antireflection layers, hard coat layers, stress relaxation layers, antifogging layers, antifouling layers, Examples include a printing layer and an adhesive layer.

[Packaging containers and equipment]
The packaging container according to the present invention is a container formed of the gas barrier film 10 according to the present invention, and the apparatus according to the present invention is a display device or a power generation device including the gas barrier film 10 according to the present invention. is there.

  Since the packaging container according to the present invention has a high water vapor barrier property and an oxygen gas barrier property, it is preferably used as a packaging material for foods and medical products, and a packaging material for electronic devices.

  Examples of the display device include an organic EL element, a liquid crystal display element, a touch panel, and electronic paper. Note that the configuration of each of these display devices is not particularly limited, and a conventionally known configuration can be adopted as appropriate, and the sealing means by the gas barrier film 10 applied to each of these display devices is also particularly limited. It can be a conventionally known means.

  Specifically, for example, as an organic EL element, a cathode and an anode are provided on the gas barrier film 10 according to the present invention, and an organic light emitting layer (also simply referred to as “light emitting layer”) is provided between both electrodes. The thing which has an organic layer to include can be mentioned. As a lamination | stacking aspect of the organic layer containing a light emitting layer, the aspect laminated | stacked in order of the positive hole transport layer, the light emitting layer, and the electron carrying layer from the anode side is preferable. Furthermore, a charge blocking layer or the like may be provided between the hole transport layer and the light-emitting layer, or between the light-emitting layer and the electron transport layer. Further, a hole injection layer may be provided between the anode and the hole transport layer, and an electron injection layer may be provided between the cathode and the electron transport layer. Further, the light emitting layer may be only one layer, or the light emitting layer may be divided like a first light emitting layer, a second light emitting layer, a third light emitting layer, and the like. Furthermore, each layer may be divided into a plurality of secondary layers. Since the organic EL element is a light emitting element, at least one of the anode and the cathode is preferably transparent.

  Examples of the power generation device include a solar cell element (solar cell module). The configuration of the power generation device is not particularly limited, and a conventionally known configuration can be appropriately employed. Furthermore, the sealing means by the gas barrier film 10 applied to such a power generator is not particularly limited, and can be a conventionally known means. For example, the gas barrier film 10 can be used as a back surface protection sheet or a surface protection sheet of a solar cell element.

  Specifically, for example, as a solar cell module, an example in which the gas barrier film 10 according to the present invention is used as a solar cell back sheet can be given. Such solar cell modules are, in order from the sunlight side in the thickness direction, a front substrate (having high light transmittance such as glass or film), filler, solar cell element, lead wire, terminal, terminal box, solar In the configuration of the battery back sheet, they are fixed to exterior materials (aluminum frames or the like) at both ends via a sealing material. Examples of the solar cell backsheet include an example in which a gas barrier film 10 is sandwiched between a back surface sealing film and a film disposed on the outer layer side, and is disposed on the outer layer side. An example of using the gas barrier film 10 as a film to be used can be given. Moreover, the example which uses the gas-barrier film 10 as a surface protection sheet of a front base material can be given. Since the film disposed on the surface protective sheet or the outer layer side of such a solar cell element is required to have weather resistance, the gas barrier film 10 having high weather resistance can be preferably applied.

  EXAMPLES The present invention will be described more specifically with reference to examples. However, the present invention is not limited to the description of the following examples unless it exceeds the gist.

[Example 1]
A roll-rolled biaxially stretched polyethylene terephthalate film (PET film, thickness 12 μm, manufactured by Unitika Co., Ltd.) was prepared as the substrate 1 and mounted in a chamber of a plasma CVD apparatus equipped with a winding mechanism. Next, the pressure in the chamber of the plasma CVD apparatus was reduced to an ultimate vacuum of 3.0 × 10 ⁻⁵ Torr (4 × 10 ⁻³ Pa) by an oil rotary pump and an oil diffusion pump. Further, hexamethyldisiloxane (HMDSO) (SH200, 0.65CSt, manufactured by Toray Dow Corning Silicone Co., Ltd.) and oxygen gas were prepared as source gases. Next, an electrode was disposed near the coating drum in the chamber so as to face the coating drum, and high-frequency power with a frequency of 40 kHz (input power of 12 kW) was applied between the coating drum and the electrode. Then, by introducing HMDSO gas 1200 sccm, oxygen gas 2400 sccm, He gas 1200 sccm from the gas inlet provided near the electrode in the chamber, and controlling the opening and closing of the valve between the vacuum pump and the chamber, The inside was maintained at 5 × 10 ⁻² Torr (6.7 Pa), and an inorganic layer 2 made of a silicon oxide film (also referred to as a CVD silica film) was formed on the substrate 1.

Next, silica nanoparticles (silicon oxide particles, trade name: Opster Z7537, manufactured by JSR Corporation) having an average particle diameter of 20 nm having a polymerization reactive group on the surface are prepared as inorganic particles. (MEK): Diluted to a solid content of 18% by mass with a solvent of toluene = 1: 1, and a reactive silica solution having a ratio of inorganic particles in the solid content of 100% by mass was prepared as the organic layer forming composition. Then, the organic layer forming composition onto a CVD silica film described above, after the thickness has been applied so that 1 g / ^{m 2,} dried for 1 minute at 120 ° C., voltage 120 kV, the electron beam dose 5Mrad Irradiated to cure. Thus, the organic layer 3 was formed on the inorganic layer 2 to obtain a gas barrier film of Example 1.

[Example 2]
As an organic layer forming composition, silica nanoparticles having an average particle size of 20 nm having a polymerization reactive group on the surface (trade name: Opstar Z7537, manufactured by JSR Corporation) and an acrylic monomer (trade name: OELV30, manufactured by DNPFC Corporation) The organic layer forming composition was used so that the solid content was 18% by mass and the proportion of the inorganic particles in the solid content was 66% by mass. Other than that was carried out similarly to Example 1, and obtained the gas-barrier film of Example 2.

[Example 3]
As the composition for forming an organic layer, an average particle diameter having a polymerization reactive group on the surface is 20 nm silica nanoparticles (trade name: Opstar Z7537, manufactured by JSR Corporation) and an acrylic monomer (trade name: OELV30, curable resin). DNPFC Co., Ltd.) was mixed, and the organic layer forming composition was used so that the solid content was 18% by mass and the proportion of the inorganic particles in the solid content was 50% by mass. Other than that was carried out similarly to Example 1, and obtained the gas-barrier film of Example 3.

[Example 4]
As an organic layer forming composition, silica nanoparticles having an average particle size of 20 nm having a polymerization reactive group on the surface (trade name: Opstar Z7537, manufactured by JSR Corporation) and an acrylic monomer (trade name: OELV30, manufactured by DNPFC Corporation) And an organic layer forming composition having a solid content of 18% by mass and a ratio of inorganic particles in the solid content of 33% by mass was used. Other than that was carried out similarly to Example 1, and obtained the gas-barrier film of Example 4.

[Example 5]
As an organic layer forming composition, silica nanoparticles having an average particle size of 20 nm having a polymerization reactive group on the surface (trade name: Opstar Z7537, manufactured by JSR Corporation) and an acrylic monomer (trade name: OELV30, manufactured by DNPFC Corporation) And an organic layer forming composition in which the solid content was 18% by mass and the ratio of the inorganic particles in the solid content was 13% by mass was used. Other than that was carried out similarly to Example 1, and obtained the gas-barrier film of Example 5.

[Example 6]
In Example 1, silica nanoparticles (trade name: MIBK-SD, manufactured by Nissan Chemical Industries, Ltd.) having an average particle diameter of 12 nm having a polymerization reactive group on the surface were used as inorganic particles. Other than that was carried out similarly to Example 1, and obtained the gas-barrier film of Example 6.

[Example 7]
In Example 3, DPHA (trade name: KAYARAD, manufactured by Nippon Kayaku Co., Ltd.), which is a hexafunctional acrylic monomer, was used as the curable resin instead of the acrylic monomer. Other than that was carried out similarly to Example 3, and obtained the gas-barrier film of Example 7.

[Example 8]
In Example 3, a trifunctional acrylic monomer DPHA (trade name: KAYARAD, manufactured by Nippon Kayaku Co., Ltd.) was used as the curable resin instead of the acrylic monomer. Other than that was carried out similarly to Example 3, and obtained the gas-barrier film of Example 8.

[Example 9]
Instead of the silicon oxide film formed as the inorganic layer 2 in Example 1, an aluminum oxide film was formed by the following method. Other than that was carried out similarly to Example 1, and obtained the gas-barrier film of Example 9.

A roll-rolled biaxially stretched polyethylene terephthalate film (PET film, thickness 12 μm, manufactured by Unitika Ltd.) was prepared as the substrate 1 and mounted in a chamber of a PVD apparatus equipped with a winding mechanism. Next, the pressure in the chamber of the PVD apparatus was reduced to an ultimate vacuum of 3.0 × 10 ⁻⁵ Torr (4 × 10 ⁻³ Pa) with an oil rotary pump and an oil diffusion pump. Further, aluminum (purity 99.999%, particle size 3 to 5 μm, manufactured by Kojundo Chemical Laboratory Co., Ltd.) was placed in the crucible as a raw material (evaporation source). Next, oxygen gas is introduced at a flow rate of 12000 sccm in the vicinity of the coating drum in the chamber, and the opening and closing of a valve between the vacuum pump and the chamber is controlled, so that the pressure in the chamber during film formation is 3 ×. The pressure was kept at 10 ⁻⁴ Torr (4 × 10 ⁻² Pa). Then, using a Pierce electron gun, 10 kW of power was applied to evaporate the evaporation source in the crucible, an aluminum oxide thin film was formed on the PET film running in the coating drum, and the inorganic layer 2 was formed.

[Example 10]
Instead of the silicon oxide film formed as the inorganic layer 2 in Example 6, the same aluminum oxide film as in Example 9 was formed. Other than that was carried out similarly to Example 6, and obtained the gas-barrier film of Example 10.

[Example 11]
In Example 2, a polymerization initiator (trade name: Irg. 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) was blended in the composition for forming an organic layer, and ultraviolet rays were irradiated as a curing means under the condition of 300 mJ. Other than that was carried out similarly to Example 2, and obtained the gas-barrier film of Example 11.

[Comparative Example 1]
In Example 1, the organic layer 3 was not formed on the inorganic layer 2. Other than that was carried out similarly to Example 1, and obtained the gas-barrier film of the comparative example 1.

[Comparative Example 2]
In Example 9, the organic layer 3 was not formed on the inorganic layer 2. Other than that was carried out similarly to Example 9, and obtained the gas-barrier film of the comparative example 2.

[Comparative Example 3]
In Example 1, silica nanoparticles having a polymerization reactive group on the surface are not used, only a polyfunctional acrylic monomer (trade name: OELV30, manufactured by DNPFC Co., Ltd.) is used, and the proportion of inorganic particles in the solid content is 0. The organic layer 3 was formed so that it might become mass%. Other than that was carried out similarly to Example 1, and obtained the gas-barrier film of the comparative example 1.

[Comparative Example 4]
Instead of the silicon oxide film formed as the inorganic layer 2 in Example 1, the same aluminum oxide film as in Example 9 was formed. Moreover, the silica nanoparticle which has a polymerization reactive group on the surface is not used, but only the hexafunctional acrylic monomer DPHA (trade name: KAYARAD, manufactured by Nippon Kayaku Co., Ltd.) is used, and the ratio of inorganic particles in the solid content is 0. The organic layer 3 was formed so that it might become mass%. Other than that was carried out similarly to Example 1, and obtained the gas-barrier film of the comparative example 4.

[Comparative Example 5]
In Example 2, silica nanoparticles having no polymerization reactive group (non-reactive silica particles, trade name: E-65, manufactured by CI Kasei Co., Ltd.) are used as the organic layer 3, and ultraviolet rays are used as a curing means for the organic layer. Was irradiated under the condition of 300 mJ. Other than that was carried out similarly to Example 2, and obtained the gas-barrier film of the comparative example 5.

[Comparative Example 6]
In Example 2, as the organic layer 3, silica nanoparticles having no polymerization reactive group (non-reactive silica particles, trade name: E-65, manufactured by C-I Kasei Co., Ltd.) are used, and as a curing means of the organic layer, The same electron beam as in Example 2 was irradiated under the same conditions. Other than that was carried out similarly to Example 2, and obtained the gas-barrier film of the comparative example 6.

[Evaluation of gas barrier properties]
About the gas barrier film of Examples 1-11 and Comparative Examples 1-6, water vapor permeability (WVTR) and oxygen gas permeability (OTR) were evaluated. The water vapor permeability was evaluated using a water vapor permeability measuring device (manufactured by MOCON, PERMATRAN-W3 / 31) at a temperature of 40 ° C. and a humidity of 100% RH. The oxygen gas permeability was evaluated using an oxygen gas permeability measuring device (manufactured by MOCON, OXTRAN 2/20) under the conditions of a temperature of 23 ° C. and a humidity of 100% RH.

  As shown in Table 1, the gas barrier films of Examples 1 to 11 showed good gas barrier properties. On the other hand, the gas barrier films of Comparative Examples 1 to 6 did not have sufficient gas barrier properties. As a result, since the organic layer 3 is formed of inorganic particles having a polymerization reactive group on the surface, the organic layer 3 contracts due to the curing reaction of the resin component derived from the polymerization reactive group, and the organic layer It is considered that the inorganic layer 2 also shrinks and becomes dense due to the shrinkage of 3, and as a result, the gas barrier property is enhanced. In addition, the inorganic particles contained in the organic layer 3 are considered to exhibit one or both of an anchoring action that reinforces the organic layer 3 and an action that penetrates cracks, defects, and the like of the inorganic layer 2. It is considered that the gas barrier property is enhanced.

DESCRIPTION OF SYMBOLS 1 Base material 2, 2 'Inorganic layer 3, 3' Organic layer 4 Primer layer 10, 10A, 10B, 10C, 10D Gas barrier film S1 One side of base material S2 Other side of base material S3 Surface of gas barrier film S4 Gas barrier Other surface of adhesive film

Claims (8)

  A base material, an inorganic layer provided on the base material, and an organic layer provided on the inorganic layer, wherein the organic layer is formed of inorganic particles having a polymerization reactive group on the surface. A gas barrier film characterized by comprising:   The gas barrier film according to claim 1, wherein the polymerization reactive group includes one or more reactive groups selected from an acrylic group, an epoxy group, a vinyl group, an allyl group, an isocyanate group, and a silanol group.   It has a base material, an inorganic layer provided on the base material, and an organic layer provided on the inorganic layer, and the organic layer is formed of inorganic particles having a polymerization reactive group on the surface. A packaging container formed of a gas barrier film.   It has a base material, an inorganic layer provided on the base material, and an organic layer provided on the inorganic layer, and the organic layer is formed of inorganic particles having a polymerization reactive group on the surface. A display device comprising a gas barrier film.   It has a base material, an inorganic layer provided on the base material, and an organic layer provided on the inorganic layer, and the organic layer is formed of inorganic particles having a polymerization reactive group on the surface. A power generation device comprising a gas barrier film.   A step of dry-forming an inorganic layer on a substrate and a step of forming an organic layer on the inorganic layer. In the organic layer-forming step, the organic layer is polymerized on the surface. A method for producing a gas barrier film, comprising curing and forming a composition for forming an organic layer containing at least inorganic groups having a group.   The method for producing a gas barrier film according to claim 6, wherein the prepolymerization reactive group is one or more reactive groups selected from an acrylic group, an epoxy group, a vinyl group, an allyl group, an isocyanate group, and a silanol group. . The method for producing a gas barrier film according to claim 6 or 7, wherein the dry film formation is a chemical vapor deposition method or a physical vapor deposition method.

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