TW201441051A - Gasbarrier film and producing method thereof - Google Patents

Abstract

An object of the present invention is to provide a gasbarrier film having higher gasbarrier properties and a producing method of the gasbarrier film. The present invention attains the object by providing a gasbarrier film 10 comprising: a substrate 1, an inorganic layer 2 provided on the substrate 1, and an organic layer 3 provided on the inorganic layer 2, wherein the organic layer 3 is formed by inorganic particles having a polymerization reactive group on its surface. At that time, the polymerization reactive group preferably contains one or two or more reactive groups selected from the group consisting of an acrylic group, an epoxy group, a vinyl group, an allyl group, an isocyanate group, and a silanol group. This gasbarrier film 10 can be produced by a method comprising steps of: forming a film by a dry system in which the inorganic layer 2 is formed on the substrate 1; and curing an organic layer-forming composition, containing at least inorganic particles which has a polymerization reactive group on their surfaces, to form the organic layer 3 on the inorganic layer 2.

Description

Gas barrier film and method of producing the same

The present invention relates to a gas barrier film having a high water vapor barrier property and oxygen barrier property, a method for producing the same, and a device comprising the gas barrier film.

The gas barrier film is preferably applied to an organic electroluminescence device (organic EL device), a liquid crystal display device, a thin film transistor, a solar cell, a touch panel, an electronic paper, or the like to prevent deterioration of oxygen such as performance. Or the penetration of chemical components such as water vapor. As a gas barrier film of the prior art, an inorganic layer such as alumina or yttrium oxide is provided on a plastic substrate, and an inorganic layer is provided after the organic layer is provided on the plastic substrate (for example, Patent Document 1). After the inorganic layer is provided on the plastic substrate, an organic layer is provided (for example, Patent Document 2).

The gas barrier film proposed in Patent Document 1 is provided with an organic layer having improved adhesion and flatness as a bottom layer of the gas barrier inorganic layer, and specifically, a layered layer is formed on at least one side of the substrate. A hard coat layer containing a (meth)acrylic resin and a barrier film layer containing an inorganic compound, which are obtained by curing a fixed coating of an acrylic resin and curing it by ultraviolet rays or electron beams.

Further, the gas barrier film proposed in Patent Document 2 is one in which an organic layer is provided on the outermost surface to improve bending resistance or damage resistance, and specifically, a pair of polyazulidine is provided on a substrate. a barrier layer containing at least one layer containing a ruthenium atom and an oxygen atom formed by the treatment, and further provided on the barrier layer by a sol-gel method to have an inorganic layer The protective layer of nano particles.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-105321

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2011-73417

In the above-mentioned various gas barrier films, in particular, in recent years, higher performance and higher quality of electronic devices are required, and higher gas barrier properties are required as compared with the gas barrier films proposed in Patent Documents 1 and 2 and the like. Sex and productive.

The present invention has been made in view of the above problems, and an object thereof is to provide a gas barrier film having a higher gas barrier property and a method for producing the same. Further, 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) The gas barrier film of the present invention for solving the above problems is characterized in that it comprises a substrate, an inorganic layer provided on the substrate, and an organic layer provided on the inorganic layer, and the organic layer It is formed of inorganic particles having a polymerizable reactive group on the surface.

In the gas barrier film of the present invention, the polymerization reactive group is preferably one or more selected from the group consisting of an acryloyl group, an epoxy group, a vinyl group, an allyl group, an isocyanate group, and a stanol group. Reactive group.

(2) A packaging container according to the present invention for solving the above problems is characterized in that it is formed of a gas barrier film comprising a substrate and disposed on the substrate An inorganic layer on the 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.

(3) A display device according to the present invention for solving the above problems, comprising: a gas barrier film comprising a substrate, an inorganic layer provided on the substrate, and an inorganic layer disposed on the inorganic layer The organic layer is formed, and the organic layer is formed of inorganic particles having a polymerizable reactive group on the surface.

A power generating device according to the present invention for solving the above problems is characterized in that it has a gas barrier film comprising a substrate, an inorganic layer provided on the substrate, and an organic layer provided on the inorganic layer. And the above organic layer is formed of inorganic particles having a polymerization reactive group on the surface.

(4) A method for producing a gas barrier film of the present invention for solving the above problems, comprising the steps of: forming a inorganic layer by dry film formation on a substrate, and forming an organic layer on the inorganic layer; In the film formation step of the organic layer, the organic layer forming composition is cured by at least an inorganic layer-forming composition containing at least a polymerizable reactive group on the surface.

In the method for producing a gas barrier film of the present invention, it is preferred that the prepolymerization reactive group is one selected from the group consisting of an acryloyl group, an epoxy group, a vinyl group, an allyl group, an isocyanate group, and a stanol group. Two or more reactive groups.

In the method for producing a gas barrier film of the present invention, it is preferred that the dry film formation is a chemical vapor deposition method or a physical vapor deposition method.

According to the present invention, it is possible to provide a gas barrier film having a higher gas barrier property and a method for producing the same.

1‧‧‧Substrate

2, 2', 2a, 2b‧‧‧ inorganic layer

3, 3'‧‧‧ organic layer

4‧‧‧Undercoat

10, 10A, 10B, 10C, 10D‧‧‧ gas barrier film

One side of S1‧‧‧ substrate

The other side of the S2‧‧‧ substrate

Surface of S3‧‧‧ gas barrier film

The other surface of the S4‧‧‧ gas barrier film

Fig. 1 is a schematic cross-sectional view showing an example of a gas barrier film of the present invention.

Fig. 2 is a schematic cross-sectional view showing another example of the gas barrier film of the present invention.

Fig. 3 is a schematic cross-sectional view showing still another example of the gas barrier film of the present invention.

Fig. 4 is a schematic cross-sectional view showing still another example of the gas barrier film of the present invention.

Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the embodiments described below, and various modifications can be made without departing from the spirit and scope of the invention.

[Gas barrier film and method of producing the same]

As shown in FIGS. 1 to 4, the gas barrier film 10 of the present invention comprises a substrate 1, an inorganic layer 2 provided on the substrate 1, and an organic layer 3 provided on the inorganic layer 2. Further, the organic layer 3 is formed of inorganic particles having a polymerization reactive group on the surface.

The gas barrier film 10 is produced by a method comprising the steps of: dry forming a film on the substrate 1 to form at least one inorganic layer 2; and on the inorganic layer 2, containing a curable resin. The organic layer forming composition of the inorganic particles having a polymerization reactive group on the surface thereof is cured to form the film organic layer 3. The dry film formation is preferably a chemical vapor deposition method (CVD method) or a physical vapor deposition method (PVD method).

Further, as shown in FIG. 1, the inorganic layer 2 and the organic layer 3 are sequentially provided on one surface S1 of the substrate 1, and as shown in FIG. 2, the inorganic layer 2 (2a, 2b) may be two or more layers. Further, as shown in FIG. 3, the inorganic layers 2, 2' and the organic layers 3, 3' may be sequentially provided on both surfaces S1, S2 of the substrate 1. Further, if the inorganic layer 2 and the organic layer 3 are provided on one surface S1, the inorganic layer 2 and the organic layer may be provided on the other surface S2 as shown in Fig. 1, or only the inorganic layer 2 and the organic layer may be provided. Any of the layers 3. Also, as shown in FIG. 4, on the substrate 1 The undercoat layer 4 is provided between the inorganic layer 2 and the inorganic layer 2, although not shown, an undercoat layer may be provided between the substrate of the other surface S2 and the inorganic layer or the organic layer.

Hereinafter, the configuration of the gas barrier film will be described, and the manufacturing method will also be described.

<Substrate>

The base material 1 is not particularly limited as long as it is a film that can form the inorganic layer 2, and examples thereof include a polyester resin, an olefin resin, a polycarbonate resin, a cellulose resin, and the like. Substrate 1. Examples of the polyester resin include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and copolymerization of the polyester resins. Fit, and poly(cyclohexanedimethylene terephthalate (PCT), etc. Among the polyester resins, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and the like, and especially the polyethylene naphthalate are preferred. Ester and polyethylene terephthalate. As the olefin resin, a drop can be mentioned. An olefin polymer, a cyclopentene polymer, a cyclobutene polymer, etc., among which, a An olefinic polymer.

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

The thickness of the substrate 1 is not particularly limited, but is preferably about 10 μm or more and 500 μm or less. The substrate 1 is sometimes referred to as a base film or a substrate sheet depending on its thickness. Further, the transparency of the substrate 1 is not particularly limited, and may be arbitrarily selected depending on the use thereof. to When the transparency is further required, the total light transmittance is preferably 80% or more. Further, the total light transmittance is a value indicating the transparency of a general film, and is measured by a method according to JIS-K-7105 or JIS-K-7361, specifically, by a haze meter. It is expressed by the total amount of light. The base material 1 may contain a coloring agent as needed, and may contain an antioxidant, an ultraviolet absorber, or the like. Further, a film which is uniaxially stretched or biaxially stretched is preferred because it has high transparency and mechanical strength. Among them, the biaxially stretched film of polyethylene terephthalate is preferable in terms of heat resistance, mechanical strength, light transmittance, and cost.

Such a substrate 1 can be prepared by purchasing a commercially available product, or can be prepared by itself. As a method of producing the substrate 1, a conventionally known production method can be applied, and examples thereof include a solution casting method, a melt extrusion method, and a calendering method.

In order to improve the adhesion to the inorganic layer 2 or the adhesion to the undercoat layer 4 (see FIG. 4) as needed, the surface of the substrate 1 is preferably subjected to surface treatment as needed. Examples of the surface treatment include oxidation treatment, unevenness 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, and ozone ultraviolet irradiation treatment. Examples of the roughening treatment (roughening treatment) include a sand blast method, a solvent treatment method, and the like. These surface treatments are selected depending on the type of the substrate 1. In general, it is preferable to use a corona discharge treatment method in terms of effects and workability.

(primer coating)

The undercoat layer 4 is an arbitrary layer, and as shown in FIG. 4, it may be provided on the substrate 1 on the side where the inorganic layer 2 is provided as needed. The undercoat layer 4 functions to improve the adhesion to the inorganic layer 2 . The undercoat layer 4 is not particularly limited, and a resin composition for an undercoat layer used in a general laminated film can be applied onto a substrate 1 and cured.

Examples of the resin material constituting the undercoat layer 4 include an acrylic resin, a vinyl chloride-vinyl acetate copolymer, a polyamide resin, a polyester resin, a chlorinated polypropylene, a chlorinated rubber, and an amine group. A hot melt adhesive resin such as ethyl formate resin, epoxy resin or styrene resin. The undercoat layer 4 contains one or two or more kinds of resins of these resins, and is preferably an acrylic resin monomer in terms of improving weather resistance. A crosslinking agent can be used as needed, for example, a melamine-based crosslinking agent or an epoxy-based crosslinking agent.

The thickness of the undercoat layer 4 is usually in the range of 1 μm or more and 25 μm or less, preferably in the range of 3 μm or more and 20 μm or less. When the thickness is 1 μm or more, sufficient adhesion can be obtained, and when the thickness is 25 μm or less, it is economically preferable. The undercoat layer 4 may also contain various additives as needed. For example, one or both of a light stabilizer or an ultraviolet absorber may be contained, and other additives may be contained.

<Inorganic layer>

The inorganic layer 2 is formed on the substrate 1 or, if necessary, on the undercoat layer 4, by depositing a material for forming an inorganic layer (a material for forming an inorganic layer) by dry film formation. The inorganic layer 2 functions as a gas barrier layer that blocks a gas such as water vapor or oxygen. Therefore, the inorganic layer 2 can be referred to as a "gas barrier inorganic compound layer" having gas barrier properties, and can be provided as the inorganic layer 2 as long as it is a gas barrier property of various inorganic compound layers.

The inorganic layer 2 may be formed of various conventionally known inorganic compounds which can form a gas barrier layer, and examples of such an inorganic compound include inorganic oxides, inorganic nitrogen oxides, inorganic nitrides, and inorganic carbons. One or two or more inorganic compounds of an oxide, an inorganic oxycarbonitride, and cerium oxide oxide. Specifically, an inorganic compound containing one or two or more elements selected from the group consisting of ruthenium, aluminum, magnesium, titanium, tin, indium, antimony, and zinc may be mentioned, and more specifically, 矽Oxide, aluminum oxide, magnesium Inorganic oxides such as oxides, titanium oxides, tin oxides, antimony-zinc alloy oxides and indium alloy oxides; inorganic nitrides such as niobium nitrides, aluminum nitrides, and titanium nitrides; inorganic nitrogens such as niobium oxynitride Oxide. In particular, the inorganic layer 2 is a layer containing one or more selected from the group consisting of cerium oxide, cerium nitride, cerium oxynitride, and cerium oxide. The above-mentioned materials may be used singly in the inorganic layer 2, and the above materials may be used in an arbitrary ratio within the scope of the gist of the present invention.

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

The PVD method is a method in which a solid raw material is used as a raw material and is vaporized by heat of a heat or plasma to form a film on a film-forming substrate. For example, a vacuum vapor deposition method, an electron beam vapor deposition method, a reactive vapor 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. Further, the CVD method is a method in which energy such as heat, light, or electromagnetic waves is excited or decomposed by a material gas, and a film is deposited by adsorption, reaction, and dissociation on the surface of a film-forming substrate. For example, a thermal CVD method, an organic metal vapor deposition (MOCVD) method, a radio frequency (RF) radio frequency plasma CVD method, an electron coupling resonance (ECR) electro-electrochemical CVD method, a photo CVD method, Laser CVD method, mercury sensitization method, and the like.

More specifically, the following method can be used: (1) a vacuum evaporation method in which a raw material such as an inorganic oxide, an inorganic nitride, an inorganic nitrogen oxide, or a metal is heated and vapor-deposited on a substrate; (2) in a raw material a oxidative reactive vapor deposition method in which oxygen is introduced to oxidize and vapor-deposited on a substrate; (3) a sputtering method in which argon gas and oxygen gas are introduced into the target material to deposit on the substrate; (4) An ion plating method in which a raw material is heated by a plasma beam generated by a plasma gun and evaporated on a substrate; (5) an organic germanium compound or the like is used as a raw material, and oxygen is vapor-deposited on the substrate. Plasma CVD method for ruthenium film. Among the methods for forming the inorganic layer 2, in particular, the adhesion between the inorganic layer 2 and the organic layer 3 and the vapor deposition rate are particularly preferably ion plating or plasma CVD.

The thickness of the inorganic layer 2 varies depending on the inorganic compound to be used, and 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 generation of cracks or the like, it is preferably 500 nm or less. Further, the inorganic layer 2 may be one layer, or may be an inorganic layer 2 (2a, 2b) having a total thickness of two or more layers within the above range. In the case of the inorganic layer 2 of 2 or more layers, the same materials may be combined with each other, or different materials may be combined with each other.

<organic layer>

The organic layer 3 is a layer formed on the inorganic layer 2 by inorganic particles having a polymerization reactive group on the surface. The organic layer 3 may be formed only of inorganic particles having a polymerization reactive group on the surface, or may 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 cerium oxide, aluminum oxide, titanium oxide, zirconium oxide, zinc oxide, tungsten oxide, cerium oxide, molybdenum oxide, and nickel oxide. Among them, from the viewpoint of optical properties and adhesion, cerium oxide is preferred.

The polymerization reactive group is preferably a monomer, oligomer or prepolymer which constitutes the following thermosetting resin or ionizing radiation curable resin. Such inorganic particles having a polymerizable reactive group on the surface are hardened by polymerization by heat or ionizing radiation, thereby forming Into the organic layer 3. Examples of the polymerization reactive group include an acrylonitrile group, an epoxy group, a vinyl group, an allyl group, an isocyanate group, and a stanol group. The preferred polymerization reactive group may, for example, be an acrylonitrile group or an epoxy group. In particular, inorganic particles having a polymerizable reactive group which is hardened by an electron beam are used, and such a polymerizable reactive group is hardened by reaction by electron beam irradiation, whereby the organic component becomes a dense three-dimensional crosslinked structure. The organic layer 3 in which the film-forming inorganic particles are densely adhered to each other.

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, more preferably 10 nm or more and 250 nm or less. The inorganic particles in this range are more effective in terms of optical properties (transparency) and filling of the gap between the inorganic layers to improve the barrier properties. When the average particle diameter of the inorganic particles is less than 10 nm, the particles may be agglomerated and the coating film may be whitened. When the average particle diameter exceeds 400 nm, the organic layer 3 may be whitened.

It is considered that the organic layer 3 is formed on the inorganic layer 2 by using such inorganic particles, and the organic layer 3 is shrunk by a hardening reaction of a resin component derived from a polymerization reactive group, and the inorganic layer 2 is also passed through the organic layer. The contraction of 3 shrinks and becomes dense, and as a result, the gas barrier property is improved. In addition, it is considered that the inorganic particles contained in the organic layer 3 exhibit either an anchoring effect of strengthening the organic layer 3 or an effect of causing cracks or defects into the inorganic layer 2, or both. It is considered that the result is improved in gas barrier properties.

The kind of the polymerization reactive group present on the surface of the inorganic particles can be easily specified by, for example, X-ray photoelectron spectroscopy or Fourier transform infrared spectroscopy. For example, the polymerization reactive group may be specifically an acryloyl group or an epoxy group.

The inorganic particles having a polymerizable reactive group on the surface can be produced by synthesizing a colloid-dispersed nanoparticle by a polymerization reaction of a precursor such as a metal complex, and substituting a ligand on the surface for a polymerization reactive group. . Such inorganic particles are generally found in the city For example, Opstar (trade name) manufactured by JSR Co., Ltd., or organic cerium sol manufactured by Nissan Chemical Industries Co., Ltd., etc., may be mentioned. The polymerization reactive group is chemically modified on the surface of the inorganic particles, and the thickness of the chemically modified polymerization reactive group is, for example, in the range of 1 nm or more and 10 nm.

(curable resin)

The curable resin can constitute a composition for forming an organic layer together with the above inorganic particles. In other words, the organic layer 3 may contain a curable resin in addition to the above-mentioned polymerization reactive group. As the curable resin, a thermosetting resin or an ionizing radiation curable resin can be used. The ionizing radiation is a charged particle beam such as an electromagnetic wave such as a visible light beam, an X-ray or a gamma ray, or an α-ray, in addition to an electron beam and an ultraviolet ray. The ionizing radiation-curable resin is obtained by irradiating an ionizing radiation. A resin that is hardened together.

Examples of the thermosetting resin include an epoxy resin, a phenol resin, a urea resin, an unsaturated polyester resin, a melamine resin, an alkyd resin, a polyimide resin, a polyoxyxylene resin, and a hydroxyl functional acrylic acid. The resin, the carboxyl functional acrylic resin, the guanamine functional copolymer, the urethane resin, and the like may be used alone or in combination of two or more. As a cross-linking hardening of the resins, for example, an epoxy resin can promote cross-linking hardening by reaction with an amine, an acid catalyst, a carboxylic acid, an acid anhydride, a hydroxyl group, a dicyandiamide or a ketimine; The resin can promote cross-linking hardening by the reaction of an alkali catalyst with an excess of aldehyde; the urea resin can promote cross-linking hardening by a polycondensation reaction under basic or acidic; the unsaturated polyester resin can be quenched by The co-condensation reaction of the dianhydride with the diol promotes cross-linking hardening; the melamine resin can promote cross-linking hardening by heating polycondensation reaction of methylol melamine; the alkyd resin can be introduced into the unsaturated group such as a side chain Promoting cross-linking hardening by mutual oxidation of air; polyimine resin can be reacted by the presence of acid or weak base catalyst, or by The reaction of the isocyanate compound (in the case of the two-liquid type) promotes cross-linking hardening; the polyoxynoxy resin can promote cross-linking hardening by the condensation reaction of stanol in the presence of an acid catalyst; the hydroxy-functional acrylic resin can be borrowed Promoting cross-linking hardening by reaction of a hydroxyl group with an amine-based resin (in the case of a one-liquid type); a carboxyl-functional acrylic resin can be promoted by a reaction of a carboxylic acid such as acrylic acid or methacrylic acid with an epoxy compound Cross-linking hardening; the guanamine functional copolymer can promote cross-linking hardening by reaction with a hydroxyl group or self-condensation reaction; the urethane resin can be obtained by a polyester resin containing a hydroxyl group, a polyether resin, an acrylic resin The reaction of the resin with an isocyanate compound or a modified substance thereof promotes crosslinking hardening. Crosslinking agents or hardeners that utilize such reactions are typically employed.

As the ionizing radiation curable resin, an electron beam curable resin which is cured by an electron beam or an ultraviolet curable resin which is cured by ultraviolet rays is preferably used.

As the electron beam curable resin, one or two or more kinds selected from various polymerizable oligomers and prepolymers which are generally used as an electron beam curable resin can be used. Examples of the polymerizable oligomer and the prepolymer include an oligomer or a prepolymer having a radical polymerizable unsaturated group in the molecule, and for example, an epoxy (meth)acrylate system is preferably used. (meth)acrylic acid ethyl methacrylate, (meth)acrylic acid polyether urethane type, (meth)acrylic acid caprolactone ethyl methacrylate type, polyester (meth) acrylate type An oligomer or a prepolymer such as a polyether (meth) acrylate or the like may be used alone or in combination of two or more. Among these, from the viewpoint of cost or productivity, a urethane-acrylic acid copolymer resin such as polycarbonate urethane acrylate or polyester urethane acrylate is preferred. . Here, "(meth)acrylate" means "acrylate or methacrylate". The electron beam curable resin is preferred in that it does not require the use of a solvent or the like.

Can be used together with polyfunctional ethyl (meth) acrylate (A) Monofunctional (meth) acrylate such as methyl acrylate. The monofunctional (meth) acrylate can be used as a diluent for adjusting the viscosity and the like, and can be used together without departing from the object of the present invention. The monofunctional (meth) acrylate may be used singly or in combination of two or more kinds, and a polyfunctional (meth) acrylate having a low molecular weight may be used in combination.

The ultraviolet curable resin is, for example, a radical polymerizable resin which is crosslinkable and polymerizable by irradiation of ultraviolet rays. For example, one or two kinds of monomers (oliomers), oligomers, and prepolymers selected from a radical polymerizable unsaturated group such as an acrylate group, a vinyl group, an allyl group, or an isopropenyl group may be mentioned. the above. Examples of such oligomers and prepolymers include ethyl amide acrylate, epoxy acrylate, polyester acrylate, polyether acrylate, polyethylene acrylate, and polybutadiene acrylate. One or more of polyoxy acrylate and polyol acrylate.

Examples of the monomer having a radical polymerizable unsaturated group include a monofunctional monomer and a polyfunctional monomer. The monofunctional monomer is not particularly limited, and examples thereof include a vinyl monomer such as N-vinylpyrrolidone, N-vinylcaprolactone, vinylimidazole, vinylpyridine or styrene; Ethyl ethyl ester, lauryl acrylate, stearyl acrylate, butoxyethyl acrylate, methoxy polyethylene glycol acrylate, tetrahydrofurfuryl acrylate, acrylic acid Ester, isooctyl acrylate, cyclohexyl acrylate, benzyl acrylate, N,N-dimethyl decylamine, N,N-dimethylaminopropyl acrylate, propylene fluorenyl An acrylate monomer such as a phenyl group; and a acrylamide derivative. Examples of the polyfunctional monomer include pentaerythritol triacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, and tripropylene glycol diacrylic acid. Ester, polypropylene glycol diacrylate, polytetramethylene glycol diacrylate, butanediol diacrylate, hexanediol diacrylate, decanediol diacrylate, pentanediol diacrylate, neopentyl Alcohol diacrylate, dimethylol-tricyclodecane diacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and the like, and the ethylene oxide modified product, propylene oxide modified product, and Caprolactone modification and the like. One type of the monomers may be used alone or two or more types may be used in combination. Further, it may be an oligomer or a prepolymer which is formed by bonding the above monomers. The monomer, the oligomer, and the prepolymer may be used singly or in combination according to the required performance or industrial productivity, or one or two or more of them may be appropriately combined. And use.

Further, in the present invention, in order to adjust the viscosity and the like, a monofunctional group such as methyl (meth) acrylate may be suitably used together with the above monomers, oligomers and prepolymers within the range which does not impair the object of the present invention. A diluent for a (meth) acrylate. The monofunctional (meth) acrylate may be used singly or in combination of two or more kinds, and a polyfunctional (meth) acrylate having a low molecular weight may be used in combination. Further, as the diluent, the above monomer can also be used to ensure the coatability of the resin composition. In addition, "(meth)acrylate" means "acrylate or methacrylate."

The ultraviolet curable resin contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited, and examples thereof include an acetophenone-based compound and a mercaptophosphine oxide-based compound. Examples of the acetophenone-based compound include acetophenone, hydroxyacetophenone, aminoacetophenone, 1-hydroxycyclohexyl phenyl ketone, and oligomeric [2-hydroxy-2-methyl-1- {4-(1-methylvinyl)phenyl}acetone], 2-methyl-1-(4-methylthienyl)-2- Lolinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4- Examples of the fluorenyl phosphine oxide-based compound include bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide and the like. One type of the photopolymerization initiator may be used, or two or more types may be used in combination. In addition, the blending amount of the photopolymerization initiator is preferably 0.1% by mass or more and 5% by mass or less based on the total amount of the ultraviolet curable resin composition for forming the organic layer 3. Further, the quantitative method of the photopolymerization initiator can be determined, for example, by gas chromatography mass spectrometry.

Regarding the curable resin contained in the organic layer 3, the above polymerization reaction Similarly, the type can be easily specified by, for example, X-ray photoelectron spectroscopy or Fourier transform infrared spectroscopy.

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. When the inorganic particles in the organic layer 3 are less than 13% by mass, the effect of the gas barrier properties obtained by the presence of the inorganic particles may not be sufficiently obtained. In addition, the upper limit of the inorganic particles in the organic layer 3 is not particularly limited, and the organic layer 3 may be formed by using only a polymerizable reactive group on the surface of the inorganic particles as an organic component, which does not contain a curable resin.

(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 the light stabilizer generates a radical by the action of ultraviolet rays, the radical can be trapped and inertized, and the progress of photooxidation deterioration of the organic layer 3 can be suppressed. The light stabilizer is not particularly limited as long as it exhibits such effects. As the light stabilizer, for example, a hindered amine light stabilizer (HALS) is preferable, and when a radical which causes an oxidation reaction is generated, the radical can be trapped in a catalyst form to be stabilized.

Specific examples of the hindered amine light stabilizer include 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2'-n-butylmalonic acid bis (1, 2,2,6,6-pentamethyl-4-piperidinyl), bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, sebacic acid Bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester, sebacic acid methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) Ester, 2,4-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-(2- Hydroxyethylamine)-1,3,5-three , 1,2,3,4-butane tetracarboxylic acid hydrazine (2,2,6,6-tetramethyl-4-piperidyl) ester, methacrylic acid (1,2,2,6,6 - pentamethyl-4-piperidinyl) and the like. Further, a hindered amine light stabilizer having a reactive functional group may be used, and specific examples thereof include (1,2,2,6,6-pentamethyl-4-piperidyl)methacrylate. Wait.

When the ultraviolet absorber is used to form the organic layer 3 by the electron beam curable resin composition, it can be preferably contained in the composition. The ultraviolet absorber may be inorganic or organic. As the inorganic ultraviolet absorber, titanium oxide, cerium oxide, zinc oxide or the like having an average particle diameter of about 5 nm or more and 120 nm or less is preferably used. As the organic ultraviolet absorber, for example, a benzotriazole system or a trisole is preferably mentioned. A benzophenone type, a salicylate type, an acrylonitrile type, etc. Among them, it is more preferable that the ultraviolet absorbing ability is high, and the high energy such as ultraviolet rays is not easily deteriorated. system.

As three It is a UV absorber, and specifically, 2-(4,6-diphenyl-1,3,5-3 -2-yl)-5-[(hexyl)oxy]phenol, 1,3,5-three -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-based ultraviolet absorber include 2-(2-hydroxy-5-methylphenyl)benzotriazole and 2-(2-hydroxy-3,5-di- 3-[3-(benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl]propionate of the third amylphenyl)benzotriazole and polyethylene glycol .

Further, when the organic layer 3 is formed by using the ultraviolet curable resin composition, the composition may contain an ultraviolet absorber. In this case, it is necessary to make the wavelength of the ultraviolet light mainly absorbed by the ultraviolet absorber and The ultraviolet curable resin is cured and the wavelength of the ultraviolet ray to be irradiated is shifted. When the ultraviolet curable resin composition containing the ultraviolet absorber is used, when the ultraviolet curable resin composition containing the ultraviolet absorber is used, the ultraviolet curable resin can be cured by irradiation of ultraviolet rays having a predetermined wavelength to form the organic layer 3.

Further, in the ionizing radiation curable composition, other additives may be contained as needed within the range which does not impair the effects of the present invention. As an additive, for example, Heat stabilizers, antifoaming agents, leveling agents, plasticizers, surfactants, antistatic agents, antioxidants, infrared absorbers, pigments (staining dyes, coloring pigments), extender pigments, light diffusing agents, coupling agents, and the like.

The ionizing radiation curable composition may contain a solvent in view of viscosity adjustment at the time of production. Examples of the solvent 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; and halogenation. a hydrocarbon; an aromatic hydrocarbon such as toluene or xylene; or a mixture thereof. Such a solvent can be used in combination in any ratio within the scope of the gist of the present invention.

(formation method)

The organic layer 3 is provided by applying an organic layer-forming composition containing inorganic particles to the inorganic layer 2. The composition for forming the organic layer may be a composition containing the inorganic particles and the solvent for adjusting the viscosity, a composition containing the inorganic particles, a curable resin, and a solvent for adjusting the viscosity. Further, various additives may be contained in the composition as needed. As the solvent for viscosity adjustment, methyl ethyl ketone, toluene, and other general-purpose solvents can be arbitrarily selected and used as appropriate.

Examples of the method of applying the composition for forming an organic layer to the inorganic layer 2 include a roll coating method, a gravure roll coating method, a contact roll coating method, and a reverse roll coating method. , bar coating method, gravure coating method, spin coating method, and die coating method.

After coating the composition for forming an organic layer, it is cured by a predetermined hardening means. When the polymerization reactive gene heat is reacted and the thermosetting property is hardened, the heat is applied, and when the polymerization reactive ionizing radiation is reacted and the ionizing radiation is hardened, the ionizing radiation is irradiated (electron beam or UV, etc.).

As the electron beam source of the electron beam, Cockcroft Walton type, Van de Graaff type, resonant transformer type, insulated core transformer type, linear type, high frequency high voltage can be used. Various electron beam accelerators such as accelerator type and high frequency type. The acceleration voltage of the electron beam is, for example, 70 kV or more and 1000 kV or less, 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, preferably 2.5 Mrad or more and 25 Mrad or less.

As the ultraviolet source, for example, a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black fluorescent lamp, or a metal halide lamp can be used. As the wavelength of the ultraviolet light, a wavelength region of 190 nm or more and 380 nm or less can be used. The time for irradiating the ultraviolet ray may be appropriately adjusted from the viewpoint of industrial productivity and the actual hardening of the organic layer. Further, curing by heating is usually carried out by maintaining the temperature in the range of 160 ° C or more and 240 ° C or less for 2 hours or more.

The organic layer 3 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 in terms of the single layer or the two layers or more, and more preferably 0.5 μm from the viewpoint of surface properties or productivity. Above and within the range of 10 μm or less.

<other layer>

A heat-sealable resin layer (not shown) may be provided on the gas barrier film of the present invention. The heat-sealable resin layer may be provided on the surface S1 of the substrate 1, may be provided on the surface S4 on the side of the organic layer 3, or may be provided on both. Further, the heat-sealable resin layer can be formed by applying and drying a composition containing a resin such as heat-sealing polyethylene or polypropylene.

Further, another functional layer may be appropriately provided on the other surface S2 of the substrate 1, on the organic layer 3, or between the inorganic layer 2 and the organic layer 3, depending on the function and use. Examples of the other functional layer include a matte layer, a protective layer, an antistatic layer, a smoothing layer, an adhesion improving layer, a light shielding layer, an antireflection layer, a hard coat layer, a stress relaxation layer, an antifogging layer, and an antifouling layer. Printed layer, adhesive layer, etc.

[Packaging container, device]

The packaging container of the present invention is a container formed of the gas barrier film 10 of the present invention, and the apparatus of the present invention includes the display device or the power generating device of the gas barrier film 10 of the present invention.

Since the packaging container of the present invention has high water vapor barrier property and oxygen barrier property, it is preferably used as a packaging material for foods or medical products, and packaging materials for electronic devices and the like.

Examples of the display device include an organic EL element, a liquid crystal display element, a touch panel, and electronic paper. In addition, the configuration of each of the display devices is not particularly limited, and a conventionally known configuration can be suitably employed, and the sealing means applied to the gas barrier film 10 of each of the display devices is not particularly limited, and may be employed. A previously known means.

Specifically, for example, as the organic EL element, the gas barrier film 10 of the present invention has a cathode and an anode, and has an organic light-emitting layer (also referred to simply as a "light-emitting layer") between the electrodes. Layer. As a laminated aspect of the organic layer including the light-emitting layer, it is preferable that a hole transport layer, a light-emitting layer, and an electron transport layer are sequentially laminated from the anode side. Further, 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, or an electron injection layer may be provided between the cathode and the electron transport layer. Moreover, the luminescent layer may be only one layer, and the first luminescent layer, the second luminescent layer and the third illuminating layer may also be used. The light-emitting layer is divided by a layer or the like. Furthermore, each layer can also be divided into several secondary layers. Further, since the organic EL element is a light-emitting element, it is preferable that at least one of the anode and the cathode is transparent.

As a power generation device, a solar cell element (solar cell module) is mentioned, for example. The configuration of the power generating device is not particularly limited, and a conventionally known configuration can be suitably employed. Further, the sealing means applied to the gas barrier film 10 used in such a power generating device is not particularly limited, and a conventionally known means can be employed. For example, the gas barrier film 10 can be used as a back protective sheet or a front protective sheet of a solar cell element.

Specifically, for example, as the solar cell module, an example in which the gas barrier film 10 of the present invention is used as a solar cell underlayer sheet can be cited. The solar cell module is sequentially oriented in the thickness direction from the sunlight side to the front substrate (such as glass or film with high light penetration), filling materials, solar cell components, leads, terminals, terminal boxes, and the sun. A structure of a battery back sheet, and a packaging material (aluminum frame or the like) fixed to both ends via a sealing material. The solar cell underlayer sheet may be configured by sandwiching the gas barrier film 10 between the film for back sealing and the film disposed on the outer layer side, and the gas barrier film 10 may be used as the separator. An example of a film on the outer side. Further, an example in which the gas barrier film 10 is used as the surface protective sheet of the front substrate can be mentioned. Since the surface protective sheet of such a solar cell element or the film disposed on the outer layer side is required to have weather resistance, the gas barrier film 10 having high weather resistance can be preferably used.

[Examples]

The present invention will be specifically described by way of examples, but the present invention is not limited to the description of the examples below as long as it does not exceed the gist of the invention.

[Example 1]

A roll-shaped biaxially stretched polyethylene terephthalate film (PET film, thickness: 12 μm, manufactured by Unitika Co., Ltd.) was prepared as a substrate 1 and mounted on a plasma CVD apparatus equipped with a winding mechanism. Inside the chamber. Next, the chamber of the plasma CVD apparatus was decompressed 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, hexamethyldioxane (HMDSO) (SH200, 0.65 CSt, manufactured by Dow Corning Toray Silicone Co., Ltd.) and oxygen were prepared as raw material gases. Next, an electrode was placed in the vicinity of the coating drum in the chamber so as to face the coating drum, and high-frequency electric power (input electric power 12 kW) having a frequency of 40 kHz was applied between the coating drum and the electrode. Then, from the gas introduction port provided near the electrode in the chamber, 1200 sccm of HMDSO gas, 2400 sccm of oxygen gas, 1200 sccm of helium gas are introduced, and the opening and closing of the valve existing between the vacuum pump and the chamber is controlled, thereby keeping the chamber 5 ×10 ^-2 Torr (6.7 Pa), an inorganic layer 2 containing a hafnium oxide film (also referred to as a CVD ceria film) was formed on the substrate 1.

Next, as the inorganic particles, a cerium oxide nanoparticle (manganese oxide particle, trade name: Opstar Z7537, manufactured by JSR Co., Ltd.) having an average particle diameter of 20 nm on the surface of the polymerization-reactive group was prepared as an inorganic particle, and methyl ethyl ketone was used. (MEK): a solvent of toluene = 1:1, the inorganic particles are diluted to a solid content of 18% by mass, and a reactive cerium oxide solution having a ratio of inorganic particles in the solid content of 100% by mass is used as an organic layer forming composition. Adjust for things. Then, the organic layer-forming composition was applied onto the CVD cerium oxide film so that the film thickness became 1 g/m ² , and then dried at 120 ° C for 1 minute, and irradiated with a voltage of 120 kV and a dose of 5 Mrad. The bundle hardens it. Thus, the organic layer 3 was formed on the inorganic layer 2, and the gas barrier film of Example 1 was obtained.

[Embodiment 2]

The following is used as a composition for forming an organic layer: having a polymerizable reactive group on the surface The cerium oxide nanoparticle (trade name: Opstar Z7537, manufactured by JSR Co., Ltd.) having an average particle diameter of 20 nm is mixed with an acrylic monomer (trade name: OELV30, manufactured by DNPFC Co., Ltd.) to form a solid component. The ratio of the inorganic particles in the solid content of 18% by mass was 66% by mass. A gas barrier film of Example 2 was obtained in the same manner as in Example 1 except the above.

[Example 3]

The composition for forming an organic layer is as follows: a cerium oxide nanoparticle having an average particle diameter of 20 nm having a polymerization reactive group on the surface (trade name: Opstar Z7537, manufactured by JSR Co., Ltd.) and a curable resin. The acrylic monomer (trade name: OELV30, manufactured by DNPFC Co., Ltd.) was mixed so that the solid content was 18% by mass, and the ratio of the inorganic particles in the solid portion was 50% by mass. A gas barrier film of Example 3 was obtained in the same manner as in Example 1 except the above.

[Example 4]

The composition for forming an organic layer is as follows: cerium oxide nanoparticles (trade name: Opstar Z7537, manufactured by JSR Co., Ltd.) having an average particle diameter of 20 nm having a polymerization reactive group on the surface, and an acrylic monomer ( The product name: OELV30, manufactured by DNPFC Co., Ltd.) was mixed so that the solid content was 18% by mass, and the ratio of the inorganic particles in the solid portion was 33% by mass. A gas barrier film of Example 4 was obtained in the same manner as in Example 1 except the above.

[Example 5]

The following is used as a composition for forming an organic layer: having a polymerizable reactive group on the surface The cerium oxide nanoparticle (trade name: Opstar Z7537, manufactured by JSR Co., Ltd.) having an average particle diameter of 20 nm is mixed with an acrylic monomer (trade name: OELV30, manufactured by DNPFC Co., Ltd.) to form a solid component. The ratio of the inorganic particles in the solid content of 18% by mass was 13% by mass. A gas barrier film of Example 5 was obtained in the same manner as in Example 1 except the above.

[Embodiment 6]

In Example 1, as the inorganic particles, cerium oxide nanoparticles (trade name: MIBK-SD, manufactured by Nissan Chemical Industries, Ltd.) having an average particle diameter of 12 nm on the surface of the polymerization-reactive group were used. A gas barrier film of Example 6 was obtained in the same manner as in Example 1 except the above.

[Embodiment 7]

In the example 3, a 6-functional acrylic monomer DPHA (trade name: KAYARAD, manufactured by Nippon Kayaku Co., Ltd.) was used as the curable resin instead of the acrylic monomer. A gas barrier film of Example 7 was obtained in the same manner as in Example 3 except for the above.

[Embodiment 8]

In the third embodiment, a trifunctional acrylic monomer PETA (trade name: KAYARAD, manufactured by Nippon Kayaku Co., Ltd.) was used as the curable resin instead of the acrylic monomer. A gas barrier film of Example 8 was obtained in the same manner as in Example 3 except the above.

[Embodiment 9]

In Example 1, instead of the ruthenium oxide film formed as the inorganic layer 2, an aluminum oxide film was formed by the following method. A gas barrier film of Example 9 was obtained in the same manner as in Example 1 except the above.

A roll-shaped 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 PVD device having a winding mechanism. . Next, the chamber of the PVD apparatus was decompressed to a limit vacuum of 3.0 × 10 ^-5 Torr (4 × 10 ^-3 Pa) by an oil rotary pump and an oil diffusion pump. Further, as a raw material (evaporation source), aluminum (purity: 99.999%, particle size: 3 to 5 μm, manufactured by High Purity Chemical Research Co., Ltd.) was placed in a crucible. Next, in the vicinity of the coating drum in the chamber, oxygen is introduced at a flow rate of 12,000 sccm, and the opening and closing of the valve existing between the vacuum pump and the chamber is controlled, thereby maintaining the pressure in the chamber at the time of film formation to 3 × 10 ^{- 4} Torr (4 × 10 ^-2 Pa). Then, using a Pierce type electron gun, electric power of 10 kW was applied to evaporate the evaporation source in the crucible, and an aluminum oxide film was formed on the PET film which was moved in the coating drum to form the inorganic layer 2.

[Embodiment 10]

In Example 6, an aluminum oxide film similar to that of Example 9 was formed instead of the ruthenium oxide film formed as the inorganic layer 2. A gas barrier film of Example 10 was obtained in the same manner as in Example 6 except the above.

[Example 11]

In Example 2, a polymerization initiator (trade name: Irg. 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) was blended as a hardening agent in the composition for forming an organic layer. Means to irradiate ultraviolet rays at a condition of 300 mJ. A gas barrier film of Example 11 was obtained in the same manner as in Example 2 except for the above.

[Comparative Example 1]

In Example 1, the organic layer 3 was not formed on the inorganic layer 2. A gas barrier film of Comparative Example 1 was obtained in the same manner as in Example 1 except the above.

[Comparative Example 2]

In Example 9, the organic layer 3 was not formed on the inorganic layer 2. A gas barrier film of Comparative Example 2 was obtained in the same manner as in Example 9 except the above.

[Comparative Example 3]

In Example 1, the cerium oxide nanoparticles having a polymerizable reactive group on the surface were not used, and only the polyfunctional acrylic monomer (trade name: OELV30, manufactured by DNPFC Co., Ltd.) was used, and the inorganic substance in the solid portion was used. The ratio of the particles was 0% by mass to form the organic layer 3. A gas barrier film of Comparative Example 1 was obtained in the same manner as in Example 1 except the above.

[Comparative Example 4]

In Example 1, an aluminum oxide film similar to that of Example 9 was formed instead of the ruthenium oxide film formed as the inorganic layer 2. Further, without using a cerium oxide nanoparticle having a polymerizable reactive group on the surface, only the hexafunctional acrylic monomer DPHA (trade name: KAYARAD, manufactured by Nippon Kayaku Co., Ltd.) is used, and the inorganic particles in the solid portion are used. The ratio was 0% by mass to form the organic layer 3. A gas barrier film of Comparative Example 4 was obtained in the same manner as in Example 1 except the above.

[Comparative Example 5]

In Example 2, cerium oxide nanoparticles (non-reactive cerium oxide particles, trade name: E-65, manufactured by CIKasei Co., Ltd.) having no polymerizable group were used as the organic layer 3 as organic The layer is hardened by irradiating ultraviolet rays at a condition of 300 mJ. A gas barrier film of Comparative Example 5 was obtained in the same manner as in Example 2 except the above.

[Comparative Example 6]

In Example 2, cerium oxide nanoparticles (non-reactive cerium oxide particles, trade name: E-65, manufactured by CIKasei Co., Ltd.) having no polymerizable group were used as the organic layer 3 as organic The electron beam of the same layer was irradiated under the same conditions as the hardening means of the layer. A gas barrier film of Comparative Example 6 was obtained in the same manner as in Example 2 except the above.

[Evaluation of gas barrier properties]

Water vapor permeability (WVTR) and oxygen permeability (OTR) were evaluated for the gas barrier films of Examples 1 to 11 and Comparative Examples 1 to 6. The water vapor permeability evaluation was carried out using a water vapor permeability measuring apparatus (manufactured by MOCON Corporation, PERMATRAN-W3/31) at a temperature of 40 ° C and a humidity of 100% RH. Further, the oxygen permeability evaluation was carried out under the conditions of a temperature of 23 ° C and a humidity of 100% RH using an oxygen permeability measuring device (OXTRAN 2/20, manufactured by MOCON Corporation).

As shown in Table 1, the gas barrier films of Examples 1 to 11 exhibited good gas barrier properties. On the other hand, the gas barrier properties of the gas barrier films of Comparative Examples 1 to 6 were not sufficient. This result is considered to be because the organic layer 3 is formed of inorganic particles having a polymerization reactive group on the surface, and therefore the organic layer 3 is shrunk by the hardening reaction of the resin component derived from the polymerization reactive group, and the inorganic layer 2 is also The organic layer 3 shrinks and contracts, thereby becoming dense, and as a result, gas barrier properties are improved. In addition, it is considered that the inorganic particles contained in the organic layer 3 exhibit either a fixing action for strengthening the organic layer 3 and a function of cracking or defects entering the inorganic layer 2, and the like. Improve gas barrier properties.

1‧‧‧Substrate

2‧‧‧Inorganic layer

3‧‧‧Organic layer

One side of S1‧‧‧ substrate

The other side of the S2‧‧‧ substrate

Surface of S3‧‧‧ gas barrier film

Claims (8)

A gas barrier film comprising: a substrate, an inorganic layer disposed on the substrate, and an organic layer disposed on the inorganic layer; and the organic layer is an inorganic layer having a polymerization reactive group on the surface The particles are formed. The gas barrier film of claim 1, wherein the polymerization reactive group comprises one or two selected from the group consisting of an acryloyl group, an epoxy group, a vinyl group, an allyl group, an isocyanate group, and a stanol group. More than one reactive group. A packaging container characterized by comprising a gas barrier film comprising a substrate, an inorganic layer disposed on the substrate, and an organic layer disposed on the inorganic layer, wherein the organic layer is It is formed of inorganic particles having a polymerizable reactive group on the surface. A display device comprising a gas barrier film comprising a substrate, an inorganic layer disposed on the substrate, and an organic layer disposed on the inorganic layer, wherein the organic layer is a surface It is formed of inorganic particles having a polymerization reactive group. A power generating device comprising a gas barrier film comprising a substrate, an inorganic layer disposed on the substrate, and an organic layer disposed on the inorganic layer, wherein the organic layer is a surface It is formed of inorganic particles having a polymerization reactive group. A method for producing a gas barrier film, comprising the steps of: a step of dry-forming a inorganic layer on a substrate; and a step of forming an organic layer on the inorganic layer; and a film forming step of the organic layer In the middle, the organic layer-forming composition containing at least the inorganic particles having a polymerization reactive group on the surface thereof is cured to form the organic layer. The method for producing a gas barrier film according to the sixth aspect of the invention, wherein the prepolymerization group is selected from the group consisting of a propylene group, an epoxy group, a vinyl group, an allyl group, an isocyanate group and a stanol group. Kinds or more than two kinds of reactive groups. 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.