JP2012106421A - Method for manufacturing gas barrier film, gas barrier film, and electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a gas barrier film which has high gas barrier performance, excellent bending resistance and smoothness, to provide the gas barrier film, and to provide an electronic device using the gas barrier film.SOLUTION: The gas barrier film 10 has a laminated structure of: a metal oxide-containing vapor deposition layer 2 which is formed on a base material 1 such as a resin film by a vapor deposition method such as a plasma CVD method; and a polysilazane reformed layer 3 formed thereon by applying a liquid containing polysilazane thereto followed by drying and irradiating it with vacuum ultraviolet ray. The gas barrier film is subjected to at least one of an excimer treatment of irradiating the vapor deposition layer 2 with vacuum ultraviolet ray and a plasma treatment of irradiating the polysilazane reformed layer 3 with plasma.

Description

  The present invention relates to a method for producing a gas barrier film, a gas barrier film, and an electronic apparatus using the gas barrier film.

Conventionally, a gas barrier film in which a thin film (gas barrier layer) containing a metal oxide such as aluminum oxide, magnesium oxide, or silicon oxide is formed on the surface of a plastic substrate or film is to prevent deterioration due to various gases such as water vapor and oxygen. It is used for packaging products that require shutoff of various gases. In addition to the packaging applications described above, it is also used for sealing electronic devices such as solar cells, liquid crystal display elements, and organic EL elements in order to prevent deterioration due to various gases.
As a method for producing such a gas barrier film, a method of forming a gas barrier layer on a substrate such as a film by a plasma CVD method (Chemical Vapor Deposition), or a polysilazane is mainly used. A method of forming a gas barrier layer by applying a surface treatment after applying a coating liquid containing as a main component on a substrate, or a method of using them together is known (for example, see Patent Documents 1 to 4).

For example, in the invention described in Patent Document 1, polysilazane is included in order to achieve both the thickening of the gas barrier layer in order to achieve high gas barrier properties and the suppression of cracks in the thickened gas barrier layer. Disclosed is a technique for laminating a thin film on a substrate by repeating a step of forming a polysilazane film by a wet method of applying a liquid and a step of irradiating the polysilazane film with vacuum ultraviolet light twice or more. Yes.
In the invention described in Patent Document 2, a gas barrier layer formed by laminating a silicon oxide layer formed by vacuum plasma CVD and a silicon oxide layer obtained by heat treatment after applying a liquid containing polysilazane is used as a resin. A technique for improving gas barrier performance by forming on a substrate is disclosed.
Further, in the invention described in Patent Document 3, a gas barrier layer and a surface smoothness of the gas barrier layer are formed by applying a perhydropolysilazane solution to a gas barrier layer obtained by an atmospheric pressure plasma CVD method to form a flattened film. A technique for achieving both is disclosed.
Moreover, in invention of patent document 4, by forming the hardened | cured material layer formed by apply | coating the liquid containing polysilazane on the base material, and the gas barrier layer formed by the plasma CVD method on the hardened | cured material layer, A technique for improving gas barrier performance is disclosed.

JP 2009-255040 A Japanese Patent No. 3511325 JP 2008-235165 A Japanese Patent Laid-Open No. 2003-118029

However, in the technique described in Patent Document 1, if the gas barrier layer is repeatedly laminated so as to obtain higher gas barrier properties, the flexibility of the gas barrier film may be lowered. In addition, the cutting edge may be broken like glass due to the stress applied when the gas barrier film is cut, and the effective area of the product is reduced due to the crack generated at the cutting edge. Could get worse.
In the technique described in Patent Document 2, the water vapor transmission rate of the gas barrier film is at a level that greatly exceeds 1 × 10 ⁻² [g / m ² / day], and various electronic devices such as organic EL elements are used. The function as a gas barrier sealing film was insufficient. In addition, since the heat treatment of polysilazane takes 1 hour at 160 ° C., there is a difficulty that the application range is limited to a resin base material having excellent heat resistance.
Further, in the technique described in Patent Document 3, the gas barrier property and the smoothness of the surface can be achieved at the same time, but the planarization film formed by applying the perhydropolysilazane solution does not have a sufficient gas barrier property. The gas barrier property could not be further improved by laminating the planarizing film.
Further, in the technique described in Patent Document 4, it is difficult to ensure smoothness of a gas barrier layer formed by a dry method such as a plasma CVD method, compared to a gas barrier layer formed by a wet method by coating. When used as a sealing substrate for an element, it sometimes causes a non-light emitting point called a dark spot.
Further, as a problem common to the above-mentioned Patent Documents 1 to 4, when a gas barrier layer mainly composed of a silicon oxide film is formed by applying an ultraviolet light irradiation treatment or a heat treatment after applying a polysilazane solution, silicon oxide is applied. If the unreacted polysilazane remains due to insufficient conversion reaction, the residual polysilazane becomes silicon oxide (SiO ₂ ) after the production of the gas barrier film as the environmental temperature is high and the long time elapses. In some cases, the reaction to be converted into a gas gradually proceeds, and the gas barrier layer may be partially destroyed by H ₂ O or NH ₃ generated by the reaction.

  An object of the present invention is to provide a gas barrier film manufacturing method and gas barrier film that have high gas barrier performance and excellent bending resistance and smoothness, and an electronic device using the gas barrier film.

In order to solve the above problems, the invention described in claim 1
A step of forming a vapor deposition layer containing a metal oxide on a base material by a vapor deposition method, and a step of forming a polysilazane modified layer by applying a liquid containing polysilazane and drying it, followed by irradiation with vacuum ultraviolet light. In the method for producing a gas barrier film having:
At least one of a step of performing an excimer treatment of irradiating the deposited layer with vacuum ultraviolet light and a step of performing a plasma treatment of the polysilazane modified layer is performed.

Invention of Claim 2 is a manufacturing method of the gas barrier film of Claim 1,
After the vapor deposition layer is formed on the substrate, the polysilazane modified layer is formed on the vapor deposition layer.

Invention of Claim 3 in the manufacturing method of the gas barrier film of Claim 1,
After the polysilazane modified layer is formed on the substrate, the vapor deposition layer is formed on the polysilazane modified layer.

The invention according to claim 4
A gas barrier film comprising a vapor-deposited layer containing a metal oxide formed by a vapor deposition method on a substrate, and a polysilazane modified layer formed by applying a liquid containing polysilazane and drying and then irradiating with vacuum ultraviolet light In
At least one of excimer treatment in which the deposited layer is irradiated with vacuum ultraviolet light and plasma treatment in which the polysilazane modified layer is irradiated with plasma is performed.

The invention according to claim 5 is the gas barrier film according to claim 4,
The polysilazane modified layer is formed on the vapor deposition layer formed on the substrate.

The invention according to claim 6 is the gas barrier film according to claim 4,
The vapor deposition layer is formed on the polysilazane modified layer formed on the substrate.

The invention according to claim 7 is an electronic device,
A gas barrier film according to any one of claims 4 to 6 and an electronic device sealed with the gas barrier film are provided.

  According to the present invention, it is possible to obtain a gas barrier film having high gas barrier properties, bending resistance and smoothness, and an electronic device having excellent gas barrier properties using the gas barrier film.

It is explanatory drawing which shows an example of the gas barrier film which concerns on this invention, and is the structure (a) which provided the vapor deposition layer and polysilazane modified layer to which the additional excimer process was given to the base material, a vapor deposition layer, and additional plasma to the base material Configuration (b) provided with a treated polysilazane modified layer, Configuration (c) provided with a deposited layer subjected to additional excimer treatment and a polysilazane modified layer subjected to additional plasma treatment on the substrate Is shown. It is explanatory drawing which shows an example of the gas barrier film which concerns on this invention, and is the structure (a) which provided the vapor deposition layer by which the polysilazane modified layer and the additional excimer process were performed to the base material, and an additional plasma process was performed to the base material. Configuration (b) provided with a modified polysilazane modified layer and a deposited layer, Configuration (c) provided with a polysilazane modified layer subjected to additional plasma treatment and a deposited layer subjected to additional excimer treatment on the substrate Is shown. It is the schematic which shows an example of the manufacturing apparatus of a gas barrier film. It is sectional drawing which shows an example of the organic electroluminescent panel which sealed the organic electroluminescent element using the gas barrier film.

  Hereinafter, preferred embodiments for carrying out the present invention will be described with reference to the drawings. However, although various technically preferable limitations for implementing the present invention are given to the embodiments described below, the scope of the invention is not limited to the following embodiments and illustrated examples.

A gas barrier film 10 according to the present invention was applied on a base material 1 such as a resin film by applying a vapor deposition layer 2 containing a metal oxide formed by a vapor deposition method such as a plasma CVD method, and a liquid containing polysilazane and then drying. And a polysilazane modified layer 3 formed by irradiation with vacuum ultraviolet light later. In particular, an excimer process for irradiating the deposited layer 2 with vacuum ultraviolet light and a plasma process for irradiating the polysilazane modified layer 3 with plasma. A gas barrier film to which at least one of the above is applied.
That is, the gas barrier film 10 includes a vapor-deposited layer 2a obtained by irradiating the vapor-deposited layer 2 with vacuum ultraviolet light and subjected to excimer treatment, and a polysilazane modified layer 3a obtained by irradiating the polysilazane-modified layer 3 with plasma and performing plasma treatment. At least one.

Specifically, as the gas barrier film (10) according to the present invention, as shown in FIG. 1, a gas barrier in which an evaporated layer 2a subjected to excimer treatment and a polysilazane modified layer 3 are sequentially laminated on a substrate 1. A film 11 (see FIG. 1 (a)), and a gas barrier film 12 (see FIG. 1 (b)) in which a deposited layer 2 and a polysilazane modified layer 3a subjected to plasma treatment are sequentially laminated on a substrate 1; There is a gas barrier film 13 (see FIG. 1 (c)) in which a deposited layer 2a subjected to excimer treatment and a polysilazane modified layer 3a subjected to plasma treatment are sequentially laminated on a substrate 1.
Moreover, as the gas barrier film (10) according to the present invention, as shown in FIG. 2, a gas barrier film 14 is formed by sequentially laminating a polysilazane modified layer 3 and an evaporated layer 2a subjected to excimer treatment on a substrate 1. (See FIG. 2 (a)), a gas barrier film 15 (see FIG. 2 (b)) formed by sequentially laminating a plasma-treated polysilazane modified layer 3a and a vapor deposition layer 2 on the substrate 1, and a base On the material 1, there is a gas barrier film 16 (see FIG. 2C) in which a polysilazane modified layer 3a subjected to plasma treatment and a vapor deposition layer 2a subjected to excimer treatment are sequentially laminated.
Thus, the vapor deposition layer 2 (2a) may be formed on the base material 1 first, and the polysilazane modified layer 3 (3a) may be formed on the vapor deposition layer 2 (2a). The polysilazane modified layer 3 (3a) may be formed first, and the vapor deposition layer 2 (2a) may be formed on the polysilazane modified layer 3 (3a). A gas barrier layer for blocking various gases is formed by the vapor deposition layer 2 (2a) and the polysilazane modified layer 3 (3a) formed on the substrate 1.
Further, a smooth layer or an anchor coat layer is formed on the base material 1 as an intermediate layer for improving the smoothness of the base material 1 and the adhesion of the vapor deposition layer 2 (2a) or the polysilazane modified layer 3 (3a) to the base material 1. It may be provided. In addition, a bleed-out prevention layer (protective layer) for preventing the surface of the substrate 1 from being scratched or soiled may be provided on the substrate 1.

  Hereinafter, the configuration of the gas barrier film 10 of the present invention will be described in detail.

(Gas barrier film)
As described above, the gas barrier film 10 is obtained by forming the gas barrier layer including the vapor deposition layer 2 (2a) and the polysilazane modified layer 3 (3a) on the base material 1.

(Base material)
The substrate 1 in the gas barrier film 10 of the present embodiment is a flexible bendable resin film. The substrate 1 is not particularly limited as long as it is a film material capable of holding a gas barrier layer having a gas barrier property (deposition layer 2 (2a) and polysilazane modified layer 3 (3a)).
Examples of the substrate 1 include acrylic acid ester, methacrylic acid ester, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, polyvinyl chloride (PVC), polyethylene ( PE), polypropylene (PP), polystyrene (PS), nylon (Ny), aromatic polyamide, polyetheretherketone, polysulfone, polyethersulfone, polyimide, polyetherimide resin film, organic-inorganic hybrid A heat-resistant transparent film (product name Sila-DEC, manufactured by Chisso Corporation) having silsesquioxane having a structure as a basic skeleton, and a resin film formed by laminating two or more layers of the above film materials are used. It is possible.
Among these resin films, films such as polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), and polycarbonate (PC) are preferably used in terms of cost and availability. Further, in terms of optical transparency, heat resistance, and adhesion to the vapor deposition layer 2 (2a) and the polysilazane modified layer 3 (3a), heat resistance having a silsesquioxane having an organic-inorganic hybrid structure as a basic skeleton. A transparent film is preferably used.
The thickness of the substrate 1 is preferably about 5 to 500 μm, and more preferably 25 to 250 μm.
Moreover, it is preferable that the base material 1 is transparent. If the substrate 1 is transparent and the various layers formed on the substrate 1 are also transparent, a gas barrier film having optical transparency can be obtained. If the base material 1 is light transmissive, it is possible to transmit the light emitted from the organic EL element or to allow the sunlight toward the solar cell to pass through. Therefore, the organic EL element and the solar cell are sealed. It can be suitably used as a sealing film (transparent substrate).

Moreover, the base material 1 using the resin material may be an unstretched film or a stretched film.
Moreover, the base material 1 which consists of said resin material can be manufactured by a conventionally well-known general manufacturing method. For example, an unstretched substrate that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding it with an annular die or a T-die, and quenching. Further, the unstretched base material is subjected to a known method such as uniaxial stretching, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, tubular simultaneous biaxial stretching, etc. A stretched substrate can be produced by stretching in the direction perpendicular to the flow direction of the substrate (horizontal axis). Although the draw ratio in this case can be suitably selected according to the resin used as the raw material of the base material, it is preferably 2 to 10 times in the vertical axis direction and the horizontal axis direction.
Moreover, in this base material 1, you may corona-treat before forming the vapor deposition layer 2 (2a).

Moreover, you may form the anchor-coat layer for improving the adhesiveness with the vapor deposition layer 2 (2a) and the polysilazane modified layer 3 (3a) on the surface of the base material 1 in this embodiment.
Examples of the anchor coating agent used in this anchor coat layer include polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicon resin, and alkyl titanate. One type or two or more types can be used in combination. Conventionally known additives can be added to these anchor coating agents. The anchor coat agent is coated on the substrate by a known method such as roll coat, gravure coat, knife coat, dip coat, spray coat, etc., and the solvent coat, diluent, etc. are removed by drying to remove the anchor coat layer. Can be formed.
The application amount of the anchor coating agent is preferably about 0.1 to 5 g / m ^{2 in} a dry state.

(Smooth layer)
Moreover, you may form a smooth layer in the surface of the base material 1 in this embodiment.
The smooth layer flattens the rough surface of the substrate 1 on which minute protrusions and the like exist, and prevents unevenness and pinholes from being generated on the deposited layer formed on the substrate 1 by protrusions on the surface of the substrate 1. Provided for. Such a smooth layer is formed, for example, by curing a photosensitive resin.
Examples of the photosensitive resin used for forming the smooth layer include a resin composition containing an acrylate compound having a radical reactive unsaturated bond, a resin composition containing an acrylate compound and a mercapto compound having a thiol group, and an epoxy. Examples thereof include resin compositions in which polyfunctional acrylate monomers such as acrylate, urethane acrylate, polyester acrylate, polyether acrylate, polyethylene glycol acrylate, and glycerol methacrylate are dissolved. Further, any mixture of the above resin compositions can be used, and any photosensitive resin containing a reactive monomer having one or more photopolymerizable unsaturated bonds in the molecule can be used. There is no particular limitation. The reactive monomer can be used as one or a mixture of two or more or as a mixture with other compounds.
The composition of the photosensitive resin contains a photopolymerization initiator. A photoinitiator can be used 1 type or in combination of 2 or more types.

The method for forming the smooth layer on the surface of the substrate 1 is not particularly limited. For example, a wet coating method such as a spin coating method, a spray method, a blade coating method, a dip method, or a dry coating method such as a vapor deposition method. It is preferable to form by a method.
Moreover, when forming a smooth layer, additives, such as antioxidant, a ultraviolet absorber, a plasticizer, can be added to above-described photosensitive resin as needed. In addition, an appropriate resin or additive may be used for improving the film formability on the formed smooth layer, preventing pinholes from being formed on the film formed on the smooth layer, or the like.
In addition, as a solvent used when forming a smooth layer using the coating liquid which melt | dissolved or disperse | distributed photosensitive resin in the solvent, alcohols, such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, are used. Terpenes such as α- or β-terpineol, ketones such as acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2-pyrrolidone, diethyl ketone, 2-heptanone, 4-heptanone, toluene, xylene, tetramethylbenzene, etc. Aromatic hydrocarbons, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dip Glycol ethers such as propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, Acetic esters such as ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 2-methoxyethyl acetate, cyclohexyl acetate, 2-ethoxyethyl acetate, 3-methoxybutyl acetate, diethylene glycol Dialkyl ether, dipropylene glyco Le dialkyl ethers, ethyl 3-ethoxypropionate, methyl benzoate, N, N- dimethylacetamide, N, may be mentioned N- dimethylformamide.

  The smoothness of the smooth layer is a value expressed by the surface roughness specified by JIS B 0601, and the maximum cross-sectional height Rt (p) is preferably 10 nm or more and 30 nm or less. When Rt is smaller than 10 nm, when the coating means comes into contact with the surface of the smooth layer by a coating method such as a wire bar or a wireless bar at the stage of applying a silicon compound (polysilazane solution) described later, the coating property is low. It may be damaged. Moreover, when Rt is larger than 30 nm, it may become difficult to smooth the unevenness | corrugation after apply | coating the silicon compound (polysilazane solution) mentioned later.

In addition, one of the preferred embodiments as an additive added when forming the smooth layer is a reactive silica particle (hereinafter simply referred to as “reactive silica particles”) in which a photosensitive group having photopolymerization reactivity is introduced into the photosensitive resin. (Also referred to as “reactive silica particles”). Here, examples of the photopolymerizable photosensitive group include a polymerizable unsaturated group represented by a (meth) acryloyloxy group. The photosensitive resin contains a photopolymerizable photosensitive group introduced on the surface of the reactive silica particles and a compound capable of photopolymerization, for example, an unsaturated organic compound having a polymerizable unsaturated group. It may be. Moreover, as a photosensitive resin, what adjusted solid content by mixing a general-purpose dilution solvent suitably with such a reactive silica particle or the unsaturated organic compound which has a polymerizable unsaturated group can be used.
Here, the average particle diameter of the reactive silica particles is preferably 0.001 to 0.1 μm. By making the average particle diameter in such a range, by using it in combination with a matting agent made of inorganic particles having an average particle diameter of 1 to 10 μm, which will be described later, optical properties satisfying a good balance between antiglare property and resolution. Further, it becomes easy to form a smooth layer having both hard coat properties. In addition, from the viewpoint of making it easier to obtain such an effect, it is more preferable to use reactive silica particles having an average particle diameter of 0.001 to 0.01 μm.
In the smooth layer in this embodiment, it is preferable to contain the inorganic particles as described above in a mass ratio of 20% to 60%. Addition of 20% or more improves adhesion with the gas barrier layer. On the other hand, if it exceeds 60%, the film may be bent, or cracks may occur when heat treatment is performed, and optical properties such as transparency and refractive index of the gas barrier film may be affected.
In the present embodiment, the polymerizable unsaturated group-modified hydrolyzable silane is chemically bonded to the silica particles by generating a silyloxy group by a hydrolysis reaction of the hydrolyzable silyl group. Such can be used as reactive silica particles. Examples of the hydrolyzable silyl group include a carboxylylate silyl group such as an alkoxylyl group and an acetoxysilyl group, a halogenated silyl group such as a chlorosilyl group, an aminosilyl group, an oxime silyl group, and a hydridosilyl group. Examples of the polymerizable unsaturated group include acryloyloxy group, methacryloyloxy group, vinyl group, propenyl group, butadienyl group, styryl group, ethynyl group, cinnamoyl group, malate group, and acrylamide group.
In the present embodiment, the thickness of the smooth layer is 1 to 10 μm, preferably 2 to 7 μm. By making it 1 μm or more, it becomes easy to make the smoothness as a gas barrier film having a smooth layer sufficient, and by making it 10 μm or less, it becomes easy to adjust the balance of optical properties of the gas barrier film, and the smooth layer is made to be a gas barrier. When the film is provided only on one side of the film, curling of the gas barrier film can be easily suppressed.

(Bleed-out prevention layer)
Moreover, you may form a bleed-out prevention layer in the surface of the base material 1 in this embodiment.
The bleed-out prevention layer has a smooth layer for the purpose of suppressing the phenomenon that unreacted oligomers migrate from the film base material to the surface when the film having the smooth layer is heated to contaminate the film surface. Provided on the opposite surface of the substrate 1. The bleed-out prevention layer may basically have the same configuration as the smooth layer as long as it has this function.
The unsaturated organic compound having a polymerizable unsaturated group that can be included in the bleed-out prevention layer includes a polyunsaturated organic compound having two or more polymerizable unsaturated groups in the molecule, or Mention may be made of monounsaturated organic compounds having one polymerizable unsaturated group.
As other additives, a matting agent may be contained. As the matting agent, inorganic particles having an average particle diameter of about 0.1 to 5 μm are preferable. As such inorganic particles, one or more of silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, zirconium oxide and the like can be used in combination. . The matting agent composed of inorganic particles is 2 parts by mass or more, preferably 4 parts by mass or more, more preferably 6 parts by mass or more and 20 parts by mass or less, preferably 18 parts per 100 parts by mass of the solid content of the hard coat agent. It is desirable that they are mixed in a proportion of not more than part by mass, more preferably not more than 16 parts by mass.

In addition, the bleed-out prevention layer may contain a thermoplastic resin, a thermosetting resin, an ionizing radiation curable resin, a photopolymerization initiator, and the like as other components of the hard coat agent and the mat agent.
Examples of the thermoplastic resin include cellulose derivatives such as acetylcellulose, nitrocellulose, acetylbutylcellulose, ethylcellulose, and methylcellulose, vinyl acetate and copolymers thereof, vinyl chloride and copolymers thereof, vinylidene chloride and copolymers thereof, and the like. Resins, acetal resins such as polyvinyl formal, polyvinyl butyral, acrylic resins and copolymers thereof, acrylic resins such as methacrylic resins and copolymers thereof, polystyrene resins, polyamide resins, linear polyester resins, polycarbonate resins, etc. Can be mentioned.
Examples of the thermosetting resin include a thermosetting urethane resin composed of an acrylic polyol and an isocyanate prepolymer, a phenol resin, a urea melamine resin, an epoxy resin, an unsaturated polyester resin, and a silicon resin.
The ionizing radiation curable resin is cured by irradiating an ionizing radiation (ultraviolet ray or electron beam) to an ionizing radiation curable paint in which one or more of photopolymerizable prepolymer or photopolymerizable monomer is mixed. Things can be used. Here, as the photopolymerizable prepolymer, an acrylic prepolymer having two or more acryloyl groups in one molecule and having a three-dimensional network structure by crosslinking and curing is particularly preferably used. As this acrylic prepolymer, urethane acrylate, polyester acrylate, epoxy acrylate, melamine acrylate and the like can be used. Further, as the photopolymerizable monomer, the polyunsaturated organic compounds described above can be used.
As photopolymerization initiators, acetophenone, benzophenone, Michler ketone, benzoin, benzylmethyl ketal, benzoin benzoate, hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2- (4-morpholinyl)- 1-propane, α-acyloxime ester, thioxanthone and the like can be mentioned.

The bleed-out prevention layer as described above is prepared by adding a hard coating agent, a matting agent, and other components added as necessary, and adding a predetermined dilution solvent to prepare a coating solution. It can form by apply | coating to the surface of the material 1 by a conventionally well-known coating method, and then irradiating with ionizing radiation and making it harden | cure. In addition, as a method of irradiating with ionizing radiation, a method of irradiating ultraviolet rays in a wavelength region of 100 to 400 nm, preferably 200 to 400 nm emitted from an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a metal halide lamp, or the like, or This can be performed by a method of irradiating an electron beam having a wavelength region of 100 nm or less emitted from a scanning or curtain type electron beam accelerator.
The thickness of the bleed-out prevention layer in this embodiment is 1 to 10 μm, preferably 2 to 7 μm. By making it 1 μm or more, it becomes easy to make the heat resistance as a gas barrier film sufficient, and by making it 10 μm or less, it becomes easy to adjust the balance of the optical properties of the gas barrier film, and the smooth layer is one of the gas barrier films. When provided on the surface, curling of the gas barrier film can be easily suppressed.

(Deposition layer)
In the gas barrier film 10 of the present embodiment, the vapor deposition layer 2 (2a) containing a metal oxide formed by a vapor deposition method is provided directly on the substrate 1, or via the polysilazane modified layer 3 (3a). And provided on the base material 1.
In particular, the vapor deposition layer 2 (2a) contains silicon oxide which is a metal oxide.

Examples of methods for forming a thin film such as a vapor deposition layer on the substrate 1 include physical vapor deposition and chemical vapor deposition.
The physical vapor deposition method is a method in which a thin film of a target substance (for example, a carbon film) is deposited on the surface of the substrate 1 in a gas phase by a physical technique. There are a heating method, electron beam evaporation, molecular beam epitaxy) method, ion plating method, sputtering method and the like.
On the other hand, chemical vapor deposition (chemical vapor deposition, chemical vapor deposition) is performed by supplying a base material 1 in a gas phase with a source gas containing a target thin film component mixed with an excited discharge gas. In this method, a thin film is deposited on the substrate 1 by a chemical reaction on the surface of the material or in the gas phase. In particular, there is a method of generating plasma etc. for the purpose of activating the chemical reaction. Known CVD methods such as thermal CVD method, catalytic chemical vapor deposition method, photo CVD method, plasma CVD method, atmospheric pressure plasma CVD method, etc. Etc.
In the present invention, as a method for forming a vapor deposition layer on the substrate 1, a plasma CVD method is preferable from the viewpoint of a film forming speed and a processing area, and an atmospheric pressure plasma CVD method that does not require a vacuum is more preferable. The atmospheric pressure plasma CVD method for performing plasma CVD processing at or near atmospheric pressure does not need to be reduced in pressure and has higher productivity than the plasma CVD method under vacuum, and has a higher plasma density. Therefore, the film formation rate is high, and furthermore, the gas mean free path is very short under a high pressure condition under atmospheric pressure as compared with the conditions of a normal CVD method, so that a very homogeneous film can be obtained.
The atmospheric pressure or the pressure in the vicinity thereof in the present invention is about 20 kPa to 110 kPa, and is preferably 93 kPa to 104 kPa in order to obtain the good effects described in the present invention. The excited gas as used in the present invention means that at least part of the molecules in the gas move from the existing state to a higher energy state by obtaining energy, and the excited gas molecules, radicalized gas This includes molecules and gas containing ionized gas molecules.

In the present invention, the method of forming the vapor deposition layer 2 containing a metal oxide is a method in which a source gas containing a metal element such as silicon is placed in a discharge space in which a high-frequency electric field is generated under atmospheric pressure or a pressure in the vicinity thereof. This is a plasma CVD method in which a secondary excitation gas is formed by mixing with an excited discharge gas, and an inorganic film (ceramic film) is formed on the substrate 1 by exposing the substrate 1 to this secondary excitation gas. That is, the pressure between the counter electrodes (discharge space) is set to atmospheric pressure or a pressure in the vicinity thereof, a discharge gas is introduced between the counter electrodes, a high-frequency voltage is applied between the counter electrodes, and the discharge gas is changed to a plasma state, followed by a plasma state The discharge gas and the raw material gas thus mixed are supplied outside the discharge space and supplied, and the substrate 1 is exposed to this mixed gas (secondary excitation gas) to form the vapor deposition layer 2 on the substrate 1.
In addition, the vapor deposition layer 2 containing the metal oxide formed by the plasma CVD method in this invention may be complex compounds, such as a metal oxide, a metal nitride, and a metal carbide.

The gas barrier layer obtained by the plasma CVD method or the atmospheric pressure plasma CVD method is a metal oxide ceramic film, or a metal oxide ceramic film by selecting conditions such as an organic or inorganic metal compound, decomposition gas, decomposition temperature, input power, etc. This is preferable because a ceramic film of a mixture of metal oxide and metal carbide, metal nitride, metal sulfide or the like can be formed separately. For example, if a silicon compound is used as a raw material compound and oxygen is used as a decomposition gas, a silicon oxide ceramic film is formed. Further, if a zinc compound is used as a raw material compound and carbon disulfide is used as a decomposition gas, a zinc sulfide ceramic film is formed. This is because highly active charged particles and active radicals exist in the plasma space at a high density, so that multistage chemical reactions are accelerated at high speed in the plasma space, and the elements present in the plasma space are thermodynamic. This is because it is converted into an extremely stable compound in a very short time.
As a raw material of such an inorganic film (ceramic film), as long as it has a typical or transition metal element, it may be in a gas, liquid, or solid state at normal temperature and pressure. In the case of gas, it can be introduced into the discharge space as it is, but in the case of liquid or solid, it is used after being vaporized by means such as heating, bubbling, decompression or ultrasonic irradiation. Moreover, you may dilute and use by a solvent and can use organic solvents, such as methanol, ethanol, n-hexane, and these mixed solvents. Since these diluted solvents are decomposed into molecular and atomic forms during the plasma discharge treatment, the influence on the film formation can be almost ignored.
In addition, as a decomposition gas for decomposing a raw material gas containing a metal element to obtain an inorganic compound, hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, ammonia gas, nitrous oxide gas , Nitrogen oxide gas, nitrogen dioxide gas, oxygen gas, water vapor, fluorine gas, hydrogen fluoride, trifluoroalcohol, trifluorotoluene, hydrogen sulfide, sulfur dioxide, carbon disulfide, chlorine gas and the like.
By appropriately selecting a source gas containing a metal element and a decomposition gas, a ceramic film of a metal oxide or a mixture of a metal oxide and a metal carbide, a metal nitride, a metal halide, a metal sulfide, etc. can be obtained. it can.

Then, when forming the vapor deposition layer 2, a discharge gas that tends to be in a plasma state is mixed with the reactive gas of the raw material gas and the decomposition gas, and the mixed gas is sent to the plasma discharge processing apparatus.
As such a discharge gas, nitrogen gas and / or 18th group atom of the periodic table, specifically, helium, neon, argon, krypton, xenon, radon, etc. are used. Among these, nitrogen, helium, and argon are preferably used, and nitrogen is particularly preferable because of low cost.
The vapor deposition layer 2 is formed by supplying the mixed gas which mixed discharge gas and reactive gas to a plasma discharge processing apparatus. Although the ratio of the discharge gas and the reactive gas varies depending on the properties of the film to be obtained, it is preferable to supply the reactive gas with the ratio of the discharge gas being 50% or more of the entire mixed gas.
In the ceramic film used as the gas barrier layer in the present invention, the inorganic compound contained in the ceramic film is SiOx, SiOxCy (x = 1.5 to 2.0, y = 0 to 0.5), or SiOxNy (x = 0). 0.1-2, y = 0.1-1.3), especially from the viewpoint of gas barrier properties, moisture permeability, light transmittance and suitability for atmospheric pressure plasma CVD, it is preferably SiOx or SiOxNy. preferable.
As described above, various inorganic films (ceramic films) can be formed by using the source gas (reactive gas) as described above together with the discharge gas. The vapor deposition layer 2 of the present invention may be composed of a plurality of layers in which these conditions are changed, and in the film thickness direction in which the ratio of the discharge gas and the reactive gas and the discharge conditions are continuously changed. It may be composed of a heterogeneous film.

Here, the atmospheric pressure plasma CVD method that can be suitably used in the method for producing a gas barrier film according to the present invention will be described in more detail.
In CVD (Chemical Vapor Deposition), volatilized and sublimated organometallic compounds adhere to the surface of the high-temperature support (base material 1), a thermal decomposition reaction takes place, and a thermally stable inorganic thin film is formed. Is generated. Such a normal CVD method (also referred to as a thermal CVD method) normally requires a substrate temperature of 500 ° C. or higher, and thus is difficult to use for film formation on a plastic substrate 1.
On the other hand, in the plasma CVD method, an electric field is applied to the space in the vicinity of the support (base material 1) to generate a space (plasma space) where gas in a plasma state exists, and the volatilized and sublimated organometallic compound is this plasma. After being introduced into the space and undergoing a decomposition reaction, it is sprayed onto the support (base 1) to form an inorganic thin film. In the plasma space, a high percentage of gas is ionized into ions and electrons, and although the temperature of the gas is kept low, the electron temperature is very high, so this high temperature electron or low temperature Is in contact with an excited state gas such as ions or radicals, the organometallic compound as the raw material of the inorganic film can be decomposed even at a low temperature. Therefore, it is a film forming method that can lower the temperature of the support (base material 1) for forming the inorganic material and can sufficiently form the film on the plastic base material 1 (resin film). According to this plasma CVD method, the film density when the ceramic film is formed on the resin film (base material 1) is dense, and a thin film having stable performance can be obtained. Moreover, the residual stress is a compressive stress, and a ceramic film having a range of 0.01 MPa or more and 20 MPa or less can be stably obtained.
Examples of the plasma discharge treatment apparatus applicable to the present invention include apparatuses described in JP-A-2004-68143, 2003-49272, WO 02/48428, etc. it can.

(Polysilazane modified layer)
In the gas barrier film 10 of the present embodiment, the polysilazane modified layer 3 (3a) is provided directly on the base material 1 or provided on the base material 1 via the vapor deposition layer 2 (2a). Yes.
The polysilazane modified layer 3 (3a) is formed by applying a liquid containing polysilazane and drying it, and then irradiating with vacuum ultraviolet light, and particularly contains silicon oxide.

(Application of liquid containing polysilazane)
“Polysilazane” used in the present invention is a polymer having a silicon-nitrogen bond, SiO ₂ having a bond such as Si—N, Si—H, N—H, etc., Si ₃ N ₄ and both intermediate solid solutions SiO _x. a ceramic precursor inorganic polymer N _y or the like.
As a coating method for coating the liquid containing polysilazane, a conventionally known appropriate method can be employed. Specific examples include a spin coating method, a roll coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, and a gravure printing method. The coating thickness can be appropriately set according to the purpose. For example, the coating thickness is preferably about 1 nm to 100 μm after drying, more preferably about 10 nm to 10 μm, and most preferably about 10 nm to 1 μm.

  The polysilazane is preferably a compound that is ceramicized at a relatively low temperature and denatured into silica so that the properties of the substrate 1 are not impaired. For example, the following general compounds described in JP-A-8-112879 A compound having a main skeleton composed of units represented by the formula (1) is preferred.

In the general formula (1), R ¹ , R ² and R ³ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group or an alkoxy group. To express.
In the present invention, perhydropolysilazane in which all of R ¹ , R ² , and R ³ are hydrogen atoms is particularly preferred from the viewpoint of the denseness as a gas barrier film to be obtained.
In addition, the organopolysilazane in which a part of the hydrogen atom bonded to Si is substituted with an alkyl group or the like has improved adhesion to the base material 1 as a base by having an alkyl group such as a methyl group, and The ceramic film made of hard and brittle polysilazane can have toughness, and there is an advantage that the occurrence of cracks can be suppressed even when the film thickness (average film thickness) is increased. Therefore, perhydropolysilazane and organopolysilazane may be appropriately selected according to the application, and may be used in combination.

Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on 6- and 8-membered rings. Its molecular weight is about 600 to 2000 (polystyrene conversion) in terms of number average molecular weight (Mn), and there are liquid or solid substances, and the state varies depending on the molecular weight. These are marketed in a solution state dissolved in an organic solvent, and the commercially available product can be used as it is as a polysilazane-containing coating solution.
As another example of polysilazane which becomes ceramic at low temperature, a silicon alkoxide-added polysilazane obtained by reacting a silicon alkoxide with a polysilazane having a main skeleton composed of a unit represented by the general formula (1) (for example, Japanese Patent Laid-Open No. Hei. No. 5-238827), glycidol-added polysilazane obtained by reacting glycidol (for example, see JP-A-6-122852), and alcohol-added polysilazane obtained by reacting alcohol (for example, JP-A-6-240208). Gazette), metal carboxylate-added polysilazanes obtained by reacting metal carboxylates (for example, see JP-A-6-299118), and acetylacetonate complexes obtained by reacting metal-containing acetylacetonate complexes Additional polysilazanes (for example, See JP -306329), a metal fine metal particles added polysilazane obtained by adding (e.g., JP-see JP 7-196986), and the like.
As the organic solvent for preparing the coating liquid containing polysilazane, it is not preferable to use an alcohol or water-containing one that easily reacts with polysilazane. Therefore, specifically, hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, halogenated hydrocarbon solvents, ethers such as aliphatic ethers and alicyclic ethers can be used. . Specifically, there are hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and turben, halogen hydrocarbons such as methylene chloride and trichloroethane, ethers such as dibutyl ether, dioxane and tetrahydrofuran. These organic solvents may be selected according to characteristics such as the solubility of polysilazane and the evaporation rate of the organic solvent, and a plurality of organic solvents may be mixed.
The polysilazane concentration in the polysilazane-containing coating solution varies depending on the film thickness of the target polysilazane modified layer and the pot life of the coating solution, but is preferably about 0.2 to 35% by mass.
In the polysilazane-containing coating solution, an amine or metal catalyst may be added to promote conversion to a silicon oxide compound. Specific examples include Aquamica NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL150A, NP110, NP140, and SP140 manufactured by AZ Electronic Materials.

The polysilazane modified layer 3 formed with the polysilazane-containing coating solution used in the present invention preferably has moisture removed before or during the modification treatment. Therefore, it may be divided into a first step aimed at removing the organic solvent in the polysilazane modified layer 3 and a second step aimed at removing water in the polysilazane modified layer.
In the first step, mainly the organic solvent is removed, and therefore, the drying conditions can be appropriately determined by a method such as heat treatment, and the conditions may be such that moisture is removed at this time. The heat treatment temperature is preferably a high temperature from the viewpoint of rapid processing, but it is preferable to appropriately determine the temperature and treatment time in consideration of thermal damage to the substrate 1 that is a resin film. For example, when a polyethylene terephthalate substrate having a glass transition temperature (Tg) of 70 ° C. is used as the substrate 1, the heat treatment temperature can be set to 150 ° C. or less. The treatment time is preferably set to a short time so that the solvent is removed and thermal damage to the substrate 1 is reduced. If the heat treatment temperature is 150 ° C. or less, the treatment time can be set within 30 minutes.
The second step is a step for removing moisture in the modified polysilazane modified layer 3, and a method for removing moisture is preferably maintained in a low humidity environment and dehumidified. Since humidity in a low-humidity environment varies depending on temperature, a preferable form is shown for the relationship between temperature and humidity by defining the dew point temperature. A preferable dew point temperature is 4 ° C. or less (temperature 25 ° C./humidity 25%), a more preferable dew point temperature is −8 ° C. (temperature 25 ° C./humidity 10%) or less, and a more preferable dew point temperature is −31 ° C. (temperature 25 ° C./temperature). Humidity 1%) or less. Moreover, you may dry under reduced pressure in order to make it easy to remove a water | moisture content. The pressure in the vacuum drying can be selected from normal pressure to 0.1 MPa.
As a preferable condition of the second step with respect to the condition of the first step, for example, when the solvent is removed at a temperature of 60 to 150 ° C. and a processing time of 1 to 30 minutes in the first step, the dew point of the second step is 4 ° C. or less. The treatment time can be selected from 5 minutes to 120 minutes under conditions for removing moisture.
The polysilazane modified layer 3 of the present invention is preferably subjected to a modification treatment while maintaining its state even after moisture is removed in the second step.

(Polysilazane modification treatment / vacuum ultraviolet irradiation treatment)
The polysilazane modification treatment in the present invention refers to a reaction in which part or all of the polysilazane compound is converted into silicon oxide or silicon oxynitride.
For this modification treatment, a known method based on the conversion reaction of polysilazane can be selected. The formation of a silicon oxide film or a silicon oxynitride film by a substitution reaction of a polysilazane compound requires a high temperature of 450 ° C. or higher, and is difficult to adapt to a flexible substrate using a resin film as the base material 1. Therefore, in producing the gas barrier film of the present invention, from the viewpoint of adapting to a plastic substrate, a conversion reaction using ultraviolet light capable of a conversion reaction at a lower temperature is preferable.

In the method for producing the gas barrier film 10 in the present invention, the polysilazane coating film from which moisture has been removed is modified by treatment with ultraviolet light irradiation. Ozone and active oxygen atoms generated by ultraviolet light (synonymous with ultraviolet light) have high oxidation ability, and it is possible to form a silicon oxide film or silicon oxynitride film having high density and insulation at low temperatures. It is.
This ultraviolet light irradiation excites and activates O ₂ and H ₂ O, UV absorbers, and polysilazane itself that contribute to ceramicization. And the ceramicization of the excited polysilazane is promoted, and the resulting ceramic film becomes dense. Irradiation with ultraviolet light is effective at any time after the formation of the coating film.
Any commonly used ultraviolet ray generator can be used for the vacuum ultraviolet ray irradiation treatment in the present invention. The ultraviolet light referred to in the present invention generally refers to ultraviolet light including electromagnetic waves having a wavelength of 10 to 200 nm called vacuum ultraviolet light.

In the irradiation with vacuum ultraviolet light, it is preferable to set the irradiation intensity and the irradiation time within a range in which the base material 1 carrying the pre-modified polysilazane layer to be irradiated is not damaged.
Taking the case where a plastic film is used as the substrate 1, for example, a 2 kW (80 W / cm × 25 cm) lamp is used, and the strength of the substrate surface is 20 to 300 mW / cm ² , preferably 50 to 200 mW / The distance between the substrate and the ultraviolet irradiation lamp is set so as to be cm ^2, and irradiation can be performed for 0.1 seconds to 10 minutes.
In general, when the substrate temperature during the ultraviolet irradiation treatment is 150 ° C. or higher, the characteristics of the substrate 1 are impaired in the case of a plastic film or the like, such as the substrate 1 being deformed or its strength deteriorated. become. However, in the case of a film having high heat resistance such as polyimide, a modification treatment at a higher temperature is possible. Therefore, there is no general upper limit for the substrate temperature at the time of ultraviolet irradiation, and a person skilled in the art can appropriately set the temperature depending on the type of the substrate 1. Moreover, there is no restriction | limiting in particular in ultraviolet irradiation atmosphere, What is necessary is just to implement in air.
Examples of such ultraviolet ray generating means include, but are not limited to, a metal halide lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a xenon arc lamp, a carbon arc lamp, an excimer lamp, and a UV light laser. In addition, when the polysilazane layer before modification is irradiated with the generated ultraviolet light, the polysilazane before modification is reflected after reflecting the ultraviolet light from the generation source with a reflector from the viewpoint of improving efficiency and uniform irradiation. It is desirable to hit the layer.
The ultraviolet irradiation can be adapted to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate 1 to be used. When the base material 1 having the polysilazane modified layer is in the form of a long film, it is converted into ceramics by continuously irradiating ultraviolet rays in the drying zone having the ultraviolet ray generation source as described above while being conveyed. be able to. The time required for ultraviolet irradiation is generally 0.1 seconds to 10 minutes, preferably 0.5 seconds to 3 minutes, although depending on the composition and concentration of the substrate 1 and polysilazane modified layer to be used.
Moreover, it is preferable that oxygen concentration at the time of irradiating with vacuum ultraviolet light (VUV) is 300 ppm to 10000 ppm (1%), and more preferably 500 ppm to 5000 ppm. By adjusting to such an oxygen concentration range, it is possible to prevent the formation of an oxygen-excess gas barrier layer and to prevent deterioration of the barrier property.
A dry inert gas is preferably used as a gas other than oxygen at the time of vacuum ultraviolet light (VUV) irradiation, and dry nitrogen gas is particularly preferable from the viewpoint of cost.
The oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.

Specifically, the modification treatment method for the polysilazane layer before modification in the present invention is treatment by irradiation with vacuum ultraviolet light. The treatment by vacuum ultraviolet light irradiation uses light energy of 100 to 200 nm, preferably light energy having a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in the polysilazane compound, and the bonding of atoms is called a photon process called a photon process. This is a method in which a silicon oxide film is formed at a relatively low temperature by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly by only the action. As a vacuum ultraviolet light source required for this, a rare gas excimer lamp is preferably used.
Note that rare gas atoms such as Xe, Kr, Ar, and Ne are called inert gases because they are chemically bonded and do not form molecules. However, rare gas atoms (excited atoms) that have gained energy by discharge or the like can be combined with other atoms to form molecules. When the rare gas is xenon,
e + Xe → e + Xe ^*
Xe ^* + Xe + Xe → Xe ₂ ^* + Xe
Then, when the excited excimer molecule Xe ₂ ^* transitions to the ground state, excimer light (vacuum ultraviolet light) of 172 nm is emitted.
A feature of the excimer lamp is that the radiation is concentrated on one wavelength, and since only the necessary light is not emitted, the efficiency is high. Further, since no extra light is emitted, the temperature of the object can be kept low. Furthermore, since no time is required for starting and restarting, instantaneous lighting and blinking are possible.

In order to obtain excimer light emission, a method using dielectric barrier discharge is known. Dielectric barrier discharge refers to lightning generated in a gas space by arranging a gas space between both electrodes via a dielectric (transparent quartz in the case of an excimer lamp) and applying a high frequency high voltage of several tens of kHz to the electrode. It is a similar very thin discharge called micro discharge. In addition to dielectric barrier discharge, electrodeless electric field discharge is also known as a method for efficiently obtaining excimer light emission. The electrodeless field discharge is a discharge due to capacitive coupling, and is also called an RF discharge. The lamp, the electrode, and the arrangement thereof may be basically the same as those of the dielectric barrier discharge, but the high frequency applied between the two electrodes is lit at several MHz. In the electrodeless field discharge, a spatially and temporally uniform discharge can be obtained in this way.
The Xe excimer lamp emits ultraviolet light having a short wavelength of 172 nm at a single wavelength, and thus has excellent luminous efficiency. Since this light has a large oxygen absorption coefficient, it can generate radical oxygen atom species and ozone at a high concentration with a very small amount of oxygen. In addition, it is known that the energy of light having a short wavelength of 172 nm for dissociating the bonds of organic substances has high ability. Due to the high energy of the active oxygen, ozone and ultraviolet radiation, the polysilazane film can be modified in a short time. Therefore, compared to low-pressure mercury lamps with a wavelength of 185 nm and 254 nm and plasma cleaning, the process time is shortened due to high throughput, the equipment area is reduced, and organic materials, plastic substrates, resin films, etc. that are easily damaged by heat are irradiated. It is possible.
In addition, since the excimer lamp has high light generation efficiency, it can be turned on with low power. In addition, light having a long wavelength that causes a temperature increase due to light is not emitted, and energy of a single wavelength is irradiated in the ultraviolet region, so that an increase in the surface temperature of the irradiation object is suppressed. For this reason, it is suitable for the irradiation to the gas barrier film which makes the base material 1 resin films, such as a polyethylene terephthalate considered that it is easy to receive the influence of a heat | fever.

(Plasma treatment)
In the gas barrier film 10 of the present embodiment, the polysilazane modified layer 3 that has been subjected to excimer treatment with vacuum ultraviolet light is preferably subjected to plasma treatment as an additional treatment to form a polysilazane modified layer 3a that has been subjected to plasma treatment. .
A known method can be used for the plasma treatment, but the plasma treatment as described in the above-mentioned “deposition layer” is preferable, and the plasma treatment under atmospheric pressure conditions is more preferable.
The plasma treatment applied as an additional treatment to the polysilazane modified layer 3 is different from the plasma at the time of vapor deposition layer formation in that the treatment is performed using a gas mainly composed of a vacuum or a discharge gas without substantially using a source gas. It is a point to do. Specifically, the fact that the source gas is not substantially used means that the average film thickness deposited by the source gas contained in the plasma atmosphere is 10% or less of the polysilazane modified layer 3, more preferably 1% or less. is there.
As conditions for this plasma treatment, it is preferable to appropriately adjust various treatment conditions such as applied power, interelectrode distance, and heating temperature so that the polysilazane modified layer 3 is not excessively etched by the plasma.
In the present invention, the additional plasma treatment applied to the polysilazane modified layer 3 further improves the gas barrier property of the polysilazane modified layer 3 by promoting modification of a region where the surface of the polysilazane modified layer 3 is insufficiently modified. It is a process for enhancing.
For example, when a foreign substance is present inside or on the surface of the polysilazane modified layer 3, the gas barrier property is lowered, or when this gas barrier film is used as a base material of an organic EL element, it is caused by the projection of the foreign substance. There is a concern that non-light-emitting points called dark spots may be generated due to the occurrence of a short circuit of the electrodes. Therefore, as in the manufacturing method of the present invention, by performing additional plasma treatment, foreign substances are reduced by the discharge energy, thereby repairing defects as a gas barrier layer or improving surface smoothness. Thus, the quality of the organic EL element can be improved. Moreover, when the gas barrier film 10 is bent by reducing the defect portion due to the foreign matter, the breakdown of the barrier function due to the concentration of stress on the defect portion can be greatly reduced.

(Excimer processing)
In the gas barrier film 10 of this embodiment, it is preferable to perform the excimer process as an additional process to the vapor deposition layer 2a formed by the plasma CVD method to obtain the vapor deposition layer 2a subjected to the excimer process.
A known method can be used for excimer treatment (vacuum ultraviolet light treatment), but vacuum ultraviolet light as described in the above-mentioned “polysilazane modified layer (polysilazane modified treatment / vacuum ultraviolet light irradiation treatment)” section. Light treatment is preferred, and vacuum ultraviolet light treatment with light energy having a wavelength of 100 to 180 nm is more preferred.
In the excimer treatment applied as an additional treatment to the vapor deposition layer 2, the oxygen concentration at the time of irradiation with vacuum ultraviolet light (VUV) is preferably 300 ppm to 50000 ppm (5%), more preferably 500 ppm to 10000 ppm. . By adjusting to such an oxygen concentration range, the amount of vacuum ultraviolet light received by the vapor deposition layer 2 is not significantly impaired, and oxygen in the atmosphere can be activated to appropriately generate ozone and oxygen radicals. In addition, it is preferable to use dry inert gas as gas other than these oxygen at the time of vacuum ultraviolet light (VUV) irradiation, and dry nitrogen gas is especially preferable from a viewpoint of cost. The oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.
In the present invention, the additional excimer treatment (vacuum ultraviolet light treatment) applied to the vapor deposition layer 2 is performed by promoting homogenization of a non-uniform region on the surface of the vapor deposition layer 2 containing the metal oxide formed by the vapor deposition method. This is a process for further improving the gas barrier property of the vapor deposition layer 2.
For example, when a foreign substance such as an organic substance is present inside or on the surface of the vapor deposition layer 2 containing a metal oxide formed by a vapor deposition method, the gas barrier property may be lowered, or the gas barrier film may be used as a base material for an organic EL element. When used, there is a concern that non-light-emitting points called dark spots frequently occur due to the occurrence of short-circuiting of electrodes due to the protrusions of the foreign matters. Therefore, by performing an additional excimer treatment as in the manufacturing method of the present invention, the foreign matter is decomposed and oxidized and removed by the vacuum ultraviolet light energy, ozone generated by the energy, active oxygen, etc. The quality of the organic EL element can be improved by repairing defects as a layer or increasing the surface smoothness.

(Gas barrier film manufacturing equipment, manufacturing process)
The gas barrier film manufacturing apparatus 100 used in the method for manufacturing a gas barrier film according to the present invention includes, for example, a roll-to-roller that winds and feeds the base material 1 and conveys the base material 1 as shown in FIG. A roll conveying means (1A, 1B, 1C), a plasma discharge processing unit 20 for forming a vapor-deposited layer containing a metal oxide by plasma CVD under atmospheric pressure, and performing plasma irradiation under atmospheric pressure; and polysilazane A polysilazane coating unit 30 that coats a liquid containing liquid, a drying unit 40 that dries and removes solvent and moisture, an excimer processing unit 50 that irradiates vacuum ultraviolet light, and the like.
Below, the outline | summary of the manufacturing method of the gas barrier film by this gas barrier film manufacturing apparatus 100 is demonstrated.

(Manufacturing method 1)
The substrate 1 wound in a roll shape on the first transport roller 1A is transported toward the second transport roller 1B while being guided by the support roller 1C.
First, atmospheric pressure plasma CVD is performed while supplying a source gas and a discharge gas in the plasma discharge processing unit 20, thereby forming a vapor deposition layer 2 containing a metal oxide on the substrate 1. Further, excimer treatment is performed on the vapor deposition layer 2 by irradiating the vacuum ultraviolet light with the excimer treatment unit 50 while conveying the substrate 1 on which the vapor deposition layer 2 is formed. In some cases, the vapor deposition layer 2 is not subjected to excimer treatment.
Then, the polysilazane coating unit 30 is formed on the vapor deposition layer 2 formed on the base material 1 while the base material 1 once wound around the second transport roller 1B is transported in the reverse direction toward the first transport roller 1A. After applying the liquid containing polysilazane, the solvent is removed by the drying unit 40 and drying is performed. Subsequently, the substrate 1 is conveyed, and the polysilazane coating film formed on the vapor deposition layer 2 on the substrate 1 is irradiated with excimer treatment by the excimer treatment unit 50 to perform the excimer treatment. Form. Further, the polysilazane modified layer 3 is subjected to plasma treatment in an atmosphere substantially made of a discharge gas by the plasma discharge treatment unit 20 while the substrate 1 is being conveyed. The polysilazane modified layer 3 may not be subjected to plasma treatment. Then, the completed gas barrier film (10) is wound around the first transport roller 1A.
The gas barrier films 11, 12, and 13 can be manufactured by such a manufacturing method in the order of steps.

(Manufacturing method 2)
The substrate 1 wound in a roll shape on the second transport roller 1B is transported toward the first transport roller 1A while being guided by the support roller 1C.
First, after a liquid containing polysilazane is applied onto the substrate 1 by the polysilazane coating unit 30, the solvent is removed by the drying unit 40 and drying is performed. Subsequently, the substrate 1 is conveyed, and the polysilazane coating film formed on the substrate 1 is irradiated with excimer treatment by the excimer treatment unit 50 to form the polysilazane modified layer 3. Further, the polysilazane modified layer 3 is subjected to plasma treatment in an atmosphere substantially composed of a discharge gas by the plasma discharge treatment unit 20 while conveying the substrate 1 on which the polysilazane modified layer 3 is formed. The polysilazane modified layer 3 may not be subjected to plasma treatment.
After that, while the substrate 1 once wound around the first transport roller 1A is transported in the reverse direction toward the second transport roller 1B, the raw material gas and the discharge gas are supplied by the plasma discharge processing unit 20 and large. Atmospheric pressure plasma CVD is performed, and the vapor deposition layer 2 containing a metal oxide is formed on the polysilazane modified layer 3 formed on the substrate 1. Further, the excimer treatment unit 50 is irradiated with vacuum ultraviolet light while carrying the substrate 1 on which the vapor deposition layer 2 is formed on the polysilazane modified layer 3, so that the vapor deposition layer 2 is subjected to excimer treatment. In some cases, the vapor deposition layer 2 is not subjected to excimer treatment. Then, the completed gas barrier film (10) is wound around the second transport roller 1B.
The gas barrier films 14, 15, and 16 can be manufactured by such a manufacturing method in the order of steps.

Excimer processing is performed by the excimer processing unit 50 on the vapor deposition layer 2 formed by the plasma discharge processing unit 20 by conveying the substrate 1 by roll-to-roll with the gas barrier film manufacturing apparatus 100 having such a configuration. The plasma discharge treatment unit 20 can be applied to the polysilazane modified layer 3 formed by performing the excimer treatment with the excimer treatment unit 50 on the polysilazane coating film formed by the polysilazane coating unit 30 and the drying unit 40. It is possible to carry out the step of performing plasma treatment.
In particular, the vapor deposition layer 2 formed on the substrate 1 by the plasma discharge treatment unit 20 is subjected to the excimer treatment by the excimer treatment unit 50 to form the vapor deposition layer 2a, and subsequently the polysilazane coating formed on the vapor deposition layer 2a is applied. The polysilazane modified layer 3 formed by subjecting the film to excimer treatment by the excimer treatment unit 50 can be subjected to plasma treatment by the plasma discharge treatment unit 20 to form the polysilazane modified layer 3a. Similarly, the polysilazane modified layer 3 formed by subjecting the polysilazane coating film formed on the substrate 1 to excimer treatment by the excimer treatment unit 50 is subjected to plasma treatment by the plasma discharge treatment unit 20 to form the polysilazane modified layer. 3a, and subsequently, the vapor deposition layer 2 formed by the plasma discharge treatment unit 20 on the polysilazane modified layer 3a can be subjected to an excimer treatment by the excimer treatment unit 50 to form the vapor deposition layer 2a.
Note that the order of arrangement of the plasma discharge processing unit 20, the polysilazane coating unit 30, the drying unit 40, and the excimer processing unit 50 is not limited to this order, and may be any order as long as desired processing is performed. It may be. Moreover, each unit is not limited to one, but may be a plurality.

(Organic EL panel as an electronic device)
Gas barrier film 10 (11-16) concerning the present invention can be used as a sealing film which seals electronic devices, such as a solar cell, a liquid crystal display element, and an organic EL element.
An example of the organic EL panel 9 which is an electronic device using the gas barrier film 10 as a sealing film is shown in FIG.
As shown in FIG. 4, the organic EL panel 9 includes a gas barrier film 10, a transparent electrode 4 such as ITO formed on the gas barrier film 10, and an organic EL formed on the gas barrier film 10 via the transparent electrode 4. An element 5 and a counter film 7 disposed via an adhesive layer 6 so as to cover the organic EL element 5 are provided. It can be said that the transparent electrode 4 forms part of the organic EL element 5.
The transparent electrode 4 and the organic EL element 5 are formed on the surface of the gas barrier film 10 on which the gas barrier layer (deposition layer 2 (2a), polysilazane modified layer 3 (3a)) is formed.
The counter film 7 may be a gas barrier film according to the present invention in addition to a metal film such as an aluminum foil. When a gas barrier film is used as the counter film 7, the surface on which the gas barrier layer (deposition layer 2 (2 a), polysilazane modified layer 3 (3 a)) is formed is attached to the organic EL element 5 with the adhesive layer 6. What should I do?

(Organic EL device)
The organic EL element 5 sealed with the gas barrier film 10 in the organic EL panel 9 will be described.
Although the preferable specific example of the layer structure of the organic EL element 5 is shown below, this invention is not limited to these.
(1) Anode / light emitting layer / cathode (2) Anode / hole transport layer / light emitting layer / cathode (3) Anode / light emitting layer / electron transport layer / cathode (4) Anode / hole transport layer / light emitting layer / electron Transport layer / cathode (5) Anode / anode buffer layer (hole injection layer) / hole transport layer / light emitting layer / electron transport layer / cathode buffer layer (electron injection layer) / cathode

(anode)
As the anode (transparent electrode 4) in the organic EL element 5, an electrode material made of a metal, an alloy, an electrically conductive compound or a mixture thereof having a high work function (4 eV or more) is preferably used. Specific examples of such electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO ₂ , and ZnO. Alternatively, an amorphous material such as IDIXO (In ₂ O ₃ —ZnO) capable of forming a transparent conductive film may be used.
For the anode, these electrode materials may be formed as a thin film by a method such as vapor deposition or sputtering, and the thin film may be formed into a desired shape pattern by photolithography, or if the pattern accuracy is not required ( The pattern may be formed through a mask having a desired shape when the electrode material is deposited or sputtered.
When light emission is taken out from the anode, it is desirable that the transmittance be larger than 10%. The sheet resistance as the anode is preferably several hundred Ω / □ or less. Moreover, although the film thickness of an anode is based also on material, it is 10-1000 nm normally, Preferably it is chosen in the range of 10-200 nm.

(cathode)
As the cathode in the organic EL element 5, a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, from the point of durability against electron injection and oxidation, etc., a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this, for example, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are suitable as the cathode.
The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet resistance as a cathode is preferably several hundred Ω / □ or less. The film thickness of the cathode is usually selected in the range of 10 nm to 5 μm, preferably 50 to 200 nm. In order to transmit the emitted light, if either one of the anode or the cathode of the organic EL element 5 is transparent or translucent, the light emission luminance is improved, which is convenient.
Moreover, after manufacturing the said metal quoted by description of the cathode with the film thickness of 1-20 nm, the transparent transparent or semi-transparent cathode is produced by producing the electroconductive transparent material quoted by description of the anode on it. By applying this, an element in which both the anode and the cathode are transmissive can be manufactured.

(Injection layer: electron injection layer, hole injection layer)
The injection layer includes an electron injection layer and a hole injection layer, and an electron injection layer and a hole injection layer are provided as necessary, between the anode and the light emitting layer or the hole transport layer, and between the cathode and the light emitting layer or the electron transport. Exist between the layers.
An injection layer is a layer provided between an electrode and an organic layer in order to reduce drive voltage and improve light emission luminance. “Organic EL element and its forefront of industrialization (issued by NTT Corporation on November 30, 1998) 2), Chapter 2, “Electrode Materials” (pages 123 to 166) in detail, and includes a hole injection layer (anode buffer layer) and an electron injection layer (cathode buffer layer).
The details of the anode buffer layer (hole injection layer) are also described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069, and the like. Examples thereof include a phthalocyanine buffer layer typified by phthalocyanine, an oxide buffer layer typified by vanadium oxide, an amorphous carbon buffer layer, and a polymer buffer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.
Details of the cathode buffer layer (electron injection layer) are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specifically, strontium Metal buffer layer typified by aluminum and aluminum, alkali metal compound buffer layer typified by lithium fluoride, alkaline earth metal compound buffer layer typified by magnesium fluoride, oxide buffer layer typified by aluminum oxide, etc. Is mentioned. The buffer layer (injection layer) is preferably a very thin film, and the film thickness is preferably in the range of 0.1 nm to 5 μm, although depending on the material.

(Light emitting layer)
The light emitting layer in the organic EL element 5 is a layer that emits light by recombination of electrons and holes injected from an electrode (cathode, anode) or an electron transport layer or a hole transport layer, and the light emitting portion is a light emitting layer. The interface between the light emitting layer and the adjacent layer may be used.
The light emitting layer of the organic EL element 5 preferably contains the following dopant compound (light emitting dopant) and host compound (light emitting host). Thereby, the luminous efficiency can be further increased.
(Luminescent dopant)
There are two types of luminescent dopants: a fluorescent dopant that emits fluorescence and a phosphorescent dopant that emits phosphorescence.
Representative examples of fluorescent dopants include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes. Stilbene dyes, polythiophene dyes, rare earth complex phosphors, and the like.
Typical examples of the phosphorescent dopant are preferably complex compounds containing metals of Group 8, Group 9, and Group 10 in the periodic table of elements, more preferably iridium compounds and osmium compounds, and most preferable among them. Is an iridium compound.
The light emitting dopant may be used by mixing a plurality of kinds of compounds.
(Light emitting host)
A light-emitting host (also simply referred to as a host) means a compound having the largest mixing ratio (mass) in a light-emitting layer composed of two or more kinds of compounds. It is also simply called a dopant). For example, if the light emitting layer is composed of two types of compound A and compound B and the mixing ratio is A: B = 10: 90, compound A is a dopant compound and compound B is a host compound. Further, if the light emitting layer is composed of three types of compound A, compound B and compound C and the mixing ratio is A: B: C = 5: 10: 85, compound A and compound B are dopant compounds, and compound C is a host compound.
The light emitting host is not particularly limited in terms of structure, but is typically a basic skeleton such as a carbazole derivative, a triarylamine derivative, an aromatic borane derivative, a nitrogen-containing heterocyclic compound, a thiophene derivative, a furan derivative, or an oligoarylene compound. Or a carboline derivative or a diazacarbazole derivative (herein, a diazacarbazole derivative is one in which at least one carbon atom of the hydrocarbon ring constituting the carboline ring of the carboline derivative is substituted with a nitrogen atom) And the like). Of these, carboline derivatives, diazacarbazole derivatives and the like are preferably used.
The light emitting layer can be formed by depositing the above compound by a known thinning method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, or an ink jet method. Although the film thickness as a light emitting layer does not have a restriction | limiting in particular, Usually, 5 nm-5 micrometers, Preferably it is chosen in the range of 5-200 nm. The light emitting layer may have a single layer structure in which the dopant compound and the host compound are one kind or two or more kinds, or may have a laminated structure having a plurality of layers having the same composition or different compositions.

(Hole transport layer)
The hole transport layer is made of a hole transport material having a function of transporting holes, and in a broad sense, a hole injection layer and an electron blocking layer are also included in the hole transport layer. The hole transport layer can be provided as a single layer or a plurality of layers.
The hole transport material has any one of hole injection or transport and electron barrier properties, and may be either organic or inorganic. For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, Examples thereof include stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers. The above-mentioned materials can be used as the hole transport material, but it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound. Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used. In addition, inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material.
The hole transport layer can be formed by thinning the hole transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. it can. Although there is no restriction | limiting in particular about the film thickness of a positive hole transport layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5-200 nm. The hole transport layer may have a single layer structure composed of one or more of the above materials.

(Electron transport layer)
The electron transport layer is made of an electron transport material having a function of transporting electrons, and in a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer. The electron transport layer can be provided as a single layer or a plurality of layers.
The electron transport material only needs to have a function of transmitting electrons injected from the cathode to the light emitting layer, and the material can be selected and used from conventionally known compounds. Examples include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, and the like. Furthermore, in the above oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, or a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as an electron transport material. Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used. In addition, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) aluminum Tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), and the like, and the central metals of these metal complexes are In, Mg, Metal complexes replaced with Cu, Ca, Sn, Ga or Pb can also be used as the electron transport material. In addition, metal-free or metal phthalocyanine, or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transporting material. Similarly to the hole injection layer and the hole transport layer, an inorganic semiconductor such as n-type-Si or n-type-SiC can also be used as the electron transport material.
The electron transport layer can be formed by thinning the electron transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. Although there is no restriction | limiting in particular about the film thickness of an electron carrying layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5-200 nm. The electron transport layer may have a single layer structure composed of one or more of the above materials.

(Method for producing organic EL element)
A method for producing the organic EL element 5 will be described.
Here, as an example of the organic EL element 5, a method for producing an organic EL element composed of an anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode will be described.
First, a desired electrode material, for example, a thin film made of an anode material is formed on the gas barrier film 10 to a thickness of 1 μm or less, preferably 10 to 200 nm, for example, by a method such as vapor deposition, sputtering, or plasma CVD. To produce an anode.
Next, an organic compound thin film of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer, which are organic EL element materials, is formed thereon. As a method for forming this organic compound thin film, there are a vapor deposition method, a wet process (spin coating method, casting method, ink jet method, printing method), etc., but a homogeneous film is easily obtained and pinholes are not easily generated. From the point of view, the vacuum deposition method, the spin coating method, the ink jet method, and the printing method are particularly preferable. Further, different film forming methods may be applied for each layer. When a vapor deposition method is employed for film formation, the vapor deposition conditions vary depending on the type of compound used, but generally a boat heating temperature of 50 to 450 ° C., a vacuum degree of 10 ⁻⁶ to 10 ⁻² Pa, and a vapor deposition rate of 0.01 to It is desirable to select appropriately within the range of 50 nm / second, substrate temperature −50 to 300 ° C., film thickness 0.1 nm to 5 μm, preferably 5 to 200 nm.
After these layers are formed, a thin film made of a cathode material is formed thereon by a method such as vapor deposition or sputtering so as to have a thickness of 1 μm or less, preferably in the range of 50 to 200 nm, and a cathode is provided. Thus, a desired organic EL element can be obtained.
The organic EL element 5 is preferably manufactured from the anode and the hole injection layer to the cathode consistently by a single evacuation, but may be taken out halfway and subjected to different film forming methods. At that time, it is necessary to consider that the work is performed in a dry inert gas atmosphere. In addition, it is also possible to reverse the production order and produce the cathode, the electron injection layer, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode in this order.
When a DC voltage is applied to the multicolor display device (organic EL panel 9) provided with the organic EL element 5 obtained in this manner, the voltage is about 2 to 40 V with the positive polarity of the anode and the negative polarity of the cathode. Luminescence can be observed by applying. An alternating voltage may be applied. The alternating current waveform to be applied may be arbitrary.

(Example)
Hereinafter, although the specific example is given and the gas barrier film of this invention is demonstrated in detail, this invention is not limited to these. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.

(Preparation of base material)
A 75 μm-thick polyester film (Cosmo Shine A4300, manufactured by Toyobo Co., Ltd.) with easy adhesion processing on both sides was used as a support, and as shown below, a bleed-out prevention layer was produced on one side and a smooth layer was produced on the opposite side. A substrate was used as the substrate 1.
Formation of a bleed-out prevention layer: After applying a UV curable organic / inorganic hybrid hard coat material OPSTAR Z7535 manufactured by JSR Corporation on one side of the support and applying a wire bar so that the film thickness after drying is 4 μm A bleed-out prevention layer was formed under drying conditions of 80 ° C. × 3 minutes and curing conditions of 1.0 J / cm ² using a high-pressure mercury lamp in an air atmosphere.
Formation of smooth layer; Subsequently, UV curable organic / inorganic hybrid hard coat material OPSTAR Z7501 manufactured by JSR Co., Ltd. was applied to the opposite surface of the support, and applied with a wire bar so that the film thickness after drying was 4 μm. Thereafter, a smooth layer was formed under drying conditions of 80 ° C. × 3 minutes and curing conditions of 1.0 J / cm ² using a high-pressure mercury lamp in an air atmosphere. The obtained smooth layer had a surface roughness specified by JIS B 0601 and a maximum cross-sectional height Rt (p) of 16 nm.
The base material on which such a bleed-out prevention layer and a smooth layer were formed was designated as “B0”.

Next, the bleed-out prevention layer is formed by an atmospheric pressure plasma method using a plasma discharge treatment unit 20 (for example, a roll-to-roll atmospheric pressure plasma discharge treatment apparatus described in FIG. 3 of JP-A-2008-56967). On the smooth layer surface of the base material “B0” on which the smooth layer was formed, a three-layered vapor deposition layer 2 was formed under the following conditions to prepare a sample “B1”.
The first to third vapor deposition layers 2 each contained a metal oxide (silicon oxide), and the thicknesses of the first to third vapor deposition layers 2 were a total of 160 nm of 100 nm, 30 nm, and 30 nm, respectively.
- first deposition layer discharge gas: _{N 2} gas reaction gas 1: 1% relative to the total gas and hydrogen gas
Reaction gas 2: 0.5% TEOS (tetraethoxysilane) with respect to the total gas
Film formation conditions;
1st electrode side Power supply type
Frequency 80kHz
Output density 8W / cm ²
Electrode temperature 115 ° C
Second electrode side Power supply type Pearl Industry 13.56MHz CF-5000-13M
Frequency 13.56MHz
Output density 10W / cm ²
Electrode temperature 95 ° C
・ Second deposition layer Discharge gas: N ₂ gas Reaction gas 1: 5% of oxygen gas with respect to the total gas
Reaction gas 2: TEOS is 0.1% of the total gas
Film formation conditions;
1st electrode side Power supply type HEIDEN Laboratory 100kHz (continuous mode) PHF-6k
Frequency 100kHz
Output density 10W / cm ²
Electrode temperature 120 ° C
Second electrode side Power supply type Pearl Industry 13.56MHz CF-5000-13M
Frequency 13.56MHz
Output density 10W / cm ²
Electrode temperature 95 ° C
Third deposited layer discharge gas: _{N 2} gas reaction gas 1: 1% relative to the total gas and hydrogen gas
Reaction gas 2: 0.5% of TEOS with respect to the total gas
Film formation conditions;
1st electrode side Power supply type
Frequency 80kHz
Output density 8W / cm ²
Electrode temperature 120 ° C
Second electrode side Power supply type Pearl Industry 13.56MHz CF-5000-13M
Frequency 13.56MHz
Output density 10W / cm ²
Electrode temperature 100 ° C

(Comparative Example 1, Sample 1)
On the surface of the sample “B1” on which the first to third vapor deposition layers 2 are formed, three vapor deposition layers 2 are repeatedly laminated under the same conditions as the first to third vapor deposition layers 2. A gas barrier film having a vapor deposition layer 2 containing a total of 6 layers of silicon oxide was produced. This was designated as Sample 1.
This sample 1 is a gas barrier film having a configuration in which two vapor deposition layers 2 are provided on a substrate 1.

(Comparative Example 2, Sample 2)
A polysilazane modified layer 3 was formed under the following conditions on the surface of the sample “B1” on which the first to third vapor deposition layers 2 were formed, and a gas barrier film was produced. This was designated as Sample 2.
This sample 2 is a gas barrier film having a configuration in which a vapor deposition layer 2 and a polysilazane modified layer 3 are provided on a substrate 1.
Polysilazane coating formation 10% by weight dibutyl ether solution of perhydropolysilazane (Aquamica NN120-10, manufactured by AZ Electronic Materials) and amine catalyst (Aquamica LExp. NAXCAT-10DB, manufactured by AZ Electronic Materials) ) N, N, N ′, N′-tetramethyl-1,6-diaminohexane in a 10% by weight dibutyl ether solution mixed in a 99: 1 ratio was dried with a wireless bar (average) ) The film was coated so that the film thickness was 0.10 μm, and dried for 1 minute with dry air at a temperature of 25 ° C. and a dew point of −5 ° C. to obtain a coated sample (coating process). A sample was obtained by treating the obtained coated sample with dry air at a temperature of 85 ° C. and a dew point of −5 ° C. for 2 minutes (drying step).
Excimer modification treatment The polysilazane modification layer 3 was formed by subjecting the sample after drying the polysilazane coating film to an excimer modification treatment using the following apparatus and conditions. The dew point temperature during the reforming treatment was -20 ° C. (excimer treatment step).
・ Modification processing equipment Excimer irradiation equipment MODEL: MECL-M-1-200 manufactured by M.D.
Wavelength: 172nm
Lamp filled gas: Xe
-Modification treatment conditions Excimer light intensity: 130 mW / cm ² (172 nm)
Distance between sample and light source: 2mm
Stage heating temperature: 80 ° C
Oxygen concentration in the irradiation device: 0.3%
Stage transport speed during excimer light irradiation: 10 mm / sec Stage transport count during excimer light irradiation: 3 reciprocations

(Example 1, Sample 3)
The surface of the polysilazane modified layer 3 of the sample 2 was subjected to additional atmospheric pressure plasma treatment under the following conditions using a plasma discharge treatment unit 20 (atmospheric pressure plasma discharge treatment apparatus) to produce a gas barrier film. This was designated as Sample 3.
This sample 3 is a gas barrier film having a configuration in which a vapor deposition layer 2 and a polysilazane modified layer 3a subjected to an additional atmospheric pressure plasma treatment are provided on a substrate 1, as shown in FIG. It corresponds to the gas barrier film 12.
・ Plasma treatment conditions Discharge gas: N2 gas Reactive gas: 5% of oxygen gas to the total gas
Film formation conditions;
1st electrode side Power supply type HEIDEN Laboratory 100kHz (continuous mode) PHF-6k
Frequency 100kHz
Output density 10W / cm2
Electrode temperature 100 ° C
Second electrode side Power supply type Pearl Industry 13.56MHz CF-5000-13M
Frequency 13.56MHz
Output density 10W / cm2
Electrode temperature 90 ° C
Sample transport speed: 10 cm / sec Sample transport frequency: 10 reciprocations

(Example 2, sample 4)
The surface of the sample “B1” on which the first to third vapor-deposited layers 2 are formed is subjected to additional vacuum ultraviolet light treatment (excimer treatment) under the following conditions, and then the method for producing the sample 2 is continued. Similarly, a polysilazane modified layer 3 was laminated to form a gas barrier film. This was designated as Sample 4.
This sample 4 is a gas barrier film having a structure in which a vapor deposition layer 2a subjected to an additional excimer treatment and a polysilazane modified layer 3 are provided on a substrate 1, and the gas barrier film shown in FIG. This corresponds to 11.
・ Excimer processing equipment:
Excimer irradiation device MODEL: MECL-M-1-200 manufactured by M.D.Com
Wavelength: 172nm
Lamp filled gas: Xe
-Excimer processing conditions Excimer processing was performed on the sample fixed on the operating stage by applying vacuum ultraviolet light under the following conditions.
Excimer light intensity: 130 mW / cm ² (172 nm)
Distance between sample and light source: 2mm
Stage heating temperature: 85 ° C
Oxygen concentration in the irradiation device: 1.0%
Stage transport speed during excimer light irradiation: 10 mm / second Stage transport count during excimer light irradiation: 4 reciprocations

(Example 3, sample 5)
The surface of the polysilazane modified layer 3 of the sample 4 was further subjected to the additional atmospheric pressure plasma treatment performed in the sample 3 to produce a gas barrier film. This was designated as Sample 5.
This sample 5 is a gas barrier film having a structure in which a vapor deposition layer 2a subjected to an additional excimer treatment and a polysilazane modified layer 3a subjected to an additional atmospheric pressure plasma treatment are provided on the substrate 1. It corresponds to the gas barrier film 13 shown in FIG.

(Comparative Example 3, Sample 6)
The smoothing layer after the base material “B0” on which the bleed-out prevention layer and the smoothing layer are formed is dried for 24 hours under dry air of 0.1 atm, 80 ° C. and 1 atm with a dew point of −30 ° C. On top of this, the polysilazane modified layer 3 was formed under the following conditions (same treatment as that of the sample 2) to prepare a sample “B2”.
-Polysilazane coating formation On a smooth layer of the base material "B0", a 10% by weight dibutyl ether solution of perhydropolysilazane (AQUAMICA NN120-10, manufactured by AZ Electronic Materials) and an amine catalyst (AQUAMICA LExp. NAXCAT) -10DB, manufactured by AZ Electronic Materials Co., Ltd.) N, N, N ', N'-tetramethyl-1,6-diaminohexane 10% by weight dibutyl ether solution mixed in a ratio of 99: 1 The sample was coated with a wireless bar so that the (average) film thickness after drying was 0.10 μm, and dried for 1 minute in dry air at a temperature of 25 ° C. and a dew point of −5 ° C. (coating) Process). A sample was obtained by treating the obtained coated sample with dry air at a temperature of 85 ° C. and a dew point of −5 ° C. for 2 minutes (drying step).
Excimer modification treatment The polysilazane modification layer 3 was formed by subjecting the sample after drying the polysilazane coating film to an excimer modification treatment using the following apparatus and conditions. The dew point temperature during the reforming treatment was -20 ° C. (excimer treatment step).
・ Modification processing equipment Excimer irradiation equipment MODEL: MECL-M-1-200 manufactured by M.D.
Wavelength: 172nm
Lamp filled gas: Xe
-Modification treatment conditions Excimer light intensity: 130 mW / cm ² (172 nm)
Distance between sample and light source: 2mm
Stage heating temperature: 80 ° C
Oxygen concentration in the irradiation device: 0.3%
Stage transport speed during excimer light irradiation: 10 mm / sec Stage transport count during excimer light irradiation: 3 reciprocations The surface of sample “B2” on which the polysilazane modified layer 3 is formed by performing the above processing is further subjected to the same conditions. The polysilazane modified layer 3 was repeatedly laminated to produce a gas barrier film having a polysilazane modified layer 3 having a two-layer structure. This was designated as Sample 6.
This sample 6 is a gas barrier film having a configuration in which two polysilazane modified layers 3 are provided on a substrate 1.

(Comparative Example 4, Sample 7)
Using the plasma discharge processing unit 20 (atmospheric pressure plasma discharge processing apparatus) on the surface of the sample “B2” in which one polysilazane modified layer 3 is formed, the atmospheric pressure under the same conditions as the sample “B1” is used. A gas barrier film in which the vapor deposition layer 2 having the first to third three-layer configuration was formed by a plasma method. This was designated as Sample 7.
This sample 7 is a gas barrier film having a configuration in which a polysilazane modified layer 3 and a vapor deposition layer 2 are provided on a substrate 1.

(Example 4, sample 8)
On the surface of the sample “B2” on which the polysilazane modified layer 3 is formed, an additional plasma treatment is performed using the plasma discharge treatment unit 20 (atmospheric pressure plasma discharge treatment apparatus) under the same conditions as the sample 3. After the application, a vapor barrier layer 2 containing a metal oxide (silicon oxide) was continuously formed by an atmospheric pressure plasma method under the same conditions as the sample “B1” to produce a gas barrier film. This was designated as Sample 8.
This sample 8 is a gas barrier film having a configuration in which a polysilazane modified layer 3a subjected to an additional atmospheric pressure plasma treatment and a vapor deposition layer 2 are provided on a base material 1, as shown in FIG. It corresponds to the gas barrier film 15.

(Example 5, sample 9)
The vapor deposition layer 2 containing a metal oxide (silicon oxide) is subsequently formed on the surface of the sample “B2” on which the polysilazane modified layer 3 is formed by the atmospheric pressure plasma method under the same conditions as the sample “B1”. After the lamination, an additional vacuum ultraviolet light treatment (excimer treatment) was applied to the vapor deposition layer 2 under the same conditions as the sample 4 to produce a gas barrier film. This was designated as Sample 9.
This sample 9 is a gas barrier film having a structure in which a polysilazane modified layer 3 and a vapor deposition layer 2a subjected to an additional excimer treatment are provided on a substrate 1, and the gas barrier film shown in FIG. It corresponds to 14.

(Example 6, sample 10)
The surface of the vapor deposition layer 2 of the sample 8 was further subjected to additional vacuum ultraviolet light treatment (excimer treatment) performed in the sample 4 to produce a gas barrier film. This was designated as Sample 10.
This sample 10 is a gas barrier film having a configuration in which a polysilazane modified layer 3a subjected to an additional atmospheric pressure plasma treatment and a vapor deposition layer 2a subjected to an additional excimer treatment are provided on the substrate 1. It corresponds to the gas barrier film 16 shown in FIG.

About the gas barrier film samples 1-10 produced as mentioned above, the performance evaluation as a gas barrier film was performed.
The performance evaluation of the gas barrier film was performed for four evaluation items of water vapor barrier properties (water vapor transmission rate), bending resistance, surface roughness (smoothness), and light emission spots of the organic EL element caused by the gas barrier film.

(Evaluation of water vapor barrier properties)
According to the following measurement method, the water vapor barrier property (water vapor transmission rate; WVTR) of the gas barrier film of each sample was evaluated.
・ Equipment Vapor deposition device: JE-400, a vacuum vapor deposition device manufactured by JEOL Ltd.
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor-impermeable metal: Aluminum (φ3-5mm, granular)
-Manufacture of cell for evaluating water vapor barrier property Calcium metal is deposited on the surface of the gas barrier layer (deposition layer, polysilazane modified layer) of the gas barrier film samples 1 to 10 using a vacuum deposition apparatus (JE-400 made by JEOL). I let you. After that, in a dry nitrogen gas atmosphere, the metal calcium vapor deposition surface is bonded and bonded to quartz glass having a thickness of 0.2 mm via a sealing ultraviolet curable resin (manufactured by Nagase ChemteX) and irradiated with ultraviolet rays. An evaluation cell was produced.
The obtained sample (evaluation cell) was stored under high temperature and high humidity of 40 ° C. and 90% RH, and permeated into the cell from the corrosion amount of metallic calcium based on the method described in JP-A-2005-283561. The amount of water was calculated.
In addition, in order to confirm that there is no permeation of water vapor from other than the barrier film surface, instead of the gas barrier film sample as a comparative sample, a sample in which metallic calcium is deposited using a quartz glass plate having a thickness of 0.2 mm, Similar storage at 40 ° C. and 90% RH was performed under high temperature and high humidity, and it was confirmed that corrosion of metallic calcium did not occur even after 10000 hours.
The moisture content of the gas barrier film of each sample thus measured was classified into the following five stages, and the water vapor barrier property was evaluated.
5: Water content is less than 1 × 10 ⁻⁵ g / m ² / day 4: Water content is 1 × 10 ⁻⁵ g / m ² / day or more, and less than 1 × 10 ⁻⁴ g / m ² / day 3: Water content The amount is 1 × 10 ⁻⁴ g / m ² / day or more and less than 1 × 10 ⁻³ g / m ² / day 2: The amount of water is 1 × 10 ⁻³ g / m ² / day or more, 1 × 10 ⁻² Less than g / m ² / day 1: Water content is 1 × 10 ⁻² g / m ² / day or more

(Evaluation of bending resistance)
After the gas barrier film of each sample was bent 100 times at an angle of 180 degrees so that the radius was 5 mm, the water vapor transmission rate was measured by the same method as above, and the water vapor before and after the bending treatment was measured. From the change in transmittance, the degree of deterioration resistance was measured according to the following equation, and the bending resistance was evaluated according to the following criteria.
Deterioration resistance = (water vapor permeability after bending test / water vapor permeability before bending test) × 100 (%)
The deterioration resistance was classified into the following five grades and evaluated.
5: Deterioration resistance is 95% or more 4: Deterioration resistance is 85% or more and less than 95% 3: Deterioration resistance is 50% or more and less than 85% 2: Deterioration resistance is 10% or more and less than 50% 1: Deterioration resistance is less than 10%

(Evaluation of surface roughness)
The surface roughness is calculated from an uneven cross-sectional curve continuously measured with an AFM (Atomic Force Microscope) and a detector having a stylus with a minimum tip radius. The average roughness of the amplitude of fine irregularities measured 10 times in the section.
The surface roughness (smoothness) was evaluated by classifying into the following five stages.
Ra: arithmetic average roughness (nm)
5: Less than 0.5 4: 0.5 or more, less than 1.0 3: 1.0 or more, less than 4.0 2: 4.0 or more, less than 8.0 1: 8.0 or more • Rt: Maximum cross section Height (nm)
Less than 5:10 4:10 or more, less than 20 3:20 or more, less than 50 2:50 or more, less than 100 1: 100 or more

(Evaluation of light emission spots of organic EL elements)
On the gas barrier layers (deposited layer, polysilazane modified layer) of the produced samples 1 to 10, a transparent conductive film was produced by the following method.
-Formation of transparent conductive film As the plasma discharge apparatus, an electrode having a parallel plate type was used. The gas barrier film of each sample was placed between the electrodes, and a mixed gas was introduced to form a thin film. In addition, as a ground (ground) electrode, a 200 mm × 200 mm × 2 mm stainless steel plate is coated with a high-density, high-adhesion alumina sprayed film, and then a solution obtained by diluting tetramethoxysilane with ethyl acetate is applied and dried. An electrode was used which was cured by ultraviolet irradiation and sealed, and the dielectric surface thus coated was polished, smoothed and processed to have an Rmax of 5 μm. Further, as the application electrode, an electrode obtained by coating a dielectric on a hollow square pure titanium pipe under the same conditions as the ground electrode was used. A plurality of application electrodes were prepared and provided to face the ground electrode to form a discharge space. Moreover, as a power source used for plasma generation, a high frequency power source CF-5000-13M manufactured by Pearl Industry Co., Ltd. was used, and 5 W / cm ² of power was supplied at a frequency of 13.56 MHz.
Then, a mixed gas having the following composition is caused to flow between the electrodes to form a plasma state, the gas barrier film is subjected to atmospheric pressure plasma treatment, and a tin-doped indium oxide (ITO) film having a thickness of 100 nm is formed on the gas barrier layer (ceramic film). To obtain Samples 1 to 10 with a transparent conductive film.
Discharge gas: Helium 98.5% by volume
Reactive gas 1: 0.25% by volume of oxygen
Reactive gas 2: Indium acetylacetonate 1.2% by volume
Reactive gas 3: Dibutyltin diacetate 0.05% by volume
-Preparation of organic EL element The obtained sample 1 to 10 with a transparent conductive film was used as a substrate of 100 mm x 100 mm, and after patterning, the gas barrier film substrate provided with the ITO transparent electrode was ultrasonicated with isopropyl alcohol. Washed and dried with dry nitrogen gas. This transparent support substrate is fixed to a substrate holder of a commercially available vacuum evaporation apparatus, while 200 mg of α-NPD (the following formula (2)) is put in a molybdenum resistance heating boat, and the host compound is put in another molybdenum resistance heating boat. 200 mg of CBP (the following formula (3)), 200 mg of bathocuproine (BCP (the following formula (4))) in another molybdenum resistance heating boat, and Ir-1 ( 100 mg of the following formula (5) was put, and 200 mg of Alq ₃ (the following formula (6)) was put in another resistance heating boat made of molybdenum, and attached to a vacuum deposition apparatus.

Next, after reducing the vacuum tank to 4 × 10 ⁻⁴ Pa, the heating boat containing α-NPD is heated by heating, vapor-deposited on a transparent support substrate at a vapor deposition rate of 0.1 nm / second, and hole transport A layer was provided. Further, the heating boat containing CBP and Ir-1 was energized and heated, and co-evaporated on the hole transport layer at a deposition rate of 0.2 nm / second and 0.012 nm / second, respectively, to provide a light emitting layer. . In addition, the substrate temperature at the time of vapor deposition was room temperature. Further, the heating boat containing BCP was energized and heated, and was deposited on the light emitting layer at a deposition rate of 0.1 nm / second to provide a hole blocking layer having a thickness of 10 nm. Further, the heating boat containing Alq ₃ is further heated by energization, and is deposited on the hole blocking layer at a deposition rate of 0.1 nm / second to further provide an electron transport layer having a thickness of 40 nm. It was. In addition, the substrate temperature at the time of vapor deposition was room temperature.
Then, 0.5 nm of lithium fluoride and 110 nm of aluminum were vapor-deposited, the cathode was formed, and the organic EL element samples 1-10 using the samples 1-10 with a transparent conductive film were produced, respectively.
-Sealing of organic EL element sample In an environment purged with nitrogen gas (inert gas), an aluminum vapor deposition surface of organic EL element samples 1 to 10 and an aluminum foil with a thickness of 100 μm face each other. Sealing was performed by using an epoxy adhesive manufactured by Chemtex Corporation.
・ Evaluation of organic EL device samples (dark spots, uneven brightness)
The encapsulated organic EL element samples 1 to 10 were energized in an environment of 40 ° C. and 90% RH, and the change in light emission unevenness such as generation of dark spots was observed from the 0th to the 120th.
The emission unevenness of each sample observed in this way was classified into the following five stages and evaluated.
On day 5: 0, dark spots and luminance unevenness were not observed, and after 120 days, the non-light-emitting area was 0.1% or less of the total light-emitting area, and all the generated dark spots could not be observed easily by visual observation ( 0.1 mm or less).
4: All dark spots generated on the 0th day have a size (0.1 mm or less) that cannot be easily observed by visual observation, luminance unevenness is not observed, and the non-light emitting area is 0% of the total light emitting area after 120 days. At 2% or less, the generated dark spots maintained a size (0.1 mm or less) that could not be observed visually.
The dark spots that occurred on the 3rd day were all in a size (0.1 mm or less) that could not be easily observed visually, and the non-light-emitting area exceeded 2% of the total light-emitting area after 120 days.
2: Dark spots and luminance unevenness that can be visually discerned were observed on the 0th day, and after 120 days, the non-light emitting area exceeded 2% of the total light emitting area.
Dark spots that can be visually discerned on day 1 and non-luminous areas with uneven brightness were observed exceeding 1% of the total light-emitting area, and non-light-emitting areas exceeded 10% of the total light-emitting area within 120 days .

  The above evaluation results (five-step evaluation) are shown in Table 1.

As shown in Table 1, the substrate 1 was subjected to additional excimer treatment compared to the gas barrier film (samples 1, 2, 6, and 7) of the comparative example in which the deposition layer 2 and the polysilazane modified layer 3 were provided on the substrate 1. The gas barrier films (samples 3 to 5 and samples 8 to 10) of the present invention provided with the applied vapor deposition layer 2a and the polysilazane modified layer 3a subjected to additional atmospheric pressure plasma treatment have water vapor barrier properties, bending resistance, It can be seen that the gas barrier film is excellent in smoothness, and is a gas barrier film in which emission spots of the organic EL element are reduced.
As described above, in the present invention, the additional excimer treatment applied to the vapor deposition layer 2 promotes the homogenization of the non-uniform region on the surface of the vapor deposition layer 2 and the additional plasma treatment applied to the polysilazane modified layer 3. The gas barrier film having improved gas barrier performance, bending resistance, and smoothness can be improved by improving the area where the surface of the polysilazane modified layer 3 is insufficiently modified. Obtainable.

In the above embodiment, the gas barrier layer (the vapor deposition layer 2 (2a) and the polysilazane modified layer 3 (3a)) is disposed on one side of the substrate 1, but the present invention is not limited thereto. It is not limited, The structure which arrange | positioned the gas barrier layer on both surfaces of the base material 1 may be sufficient.
In addition, it is needless to say that other specific detailed structures can be appropriately changed.

DESCRIPTION OF SYMBOLS 1 Base material 2 Vapor deposition layer 2a Vapor deposition layer (The vapor deposition layer to which the additional excimer process was performed)
3 Polysilazane modified layer 3a Polysilazane modified layer (polysilazane modified layer subjected to additional plasma treatment)
DESCRIPTION OF SYMBOLS 10, 11-16 Gas barrier film 1A, 1B, 1C Conveyance means 20 Plasma discharge processing unit 30 Polysilazane coating unit 40 Drying unit 50 Excimer processing unit 100 Gas barrier film manufacturing apparatus 5 Organic EL element (electronic device)
9 Organic EL panel (electronic equipment)

Claims (7)

A step of forming a vapor deposition layer containing a metal oxide on a base material by a vapor deposition method, and a step of forming a polysilazane modified layer by applying a liquid containing polysilazane and drying it, followed by irradiation with vacuum ultraviolet light. In the method for producing a gas barrier film having:
A method for producing a gas barrier film, comprising performing at least one of a step of performing an excimer treatment of irradiating the deposited layer with vacuum ultraviolet light and a step of performing a plasma treatment of the polysilazane modified layer.   The method for producing a gas barrier film according to claim 1, wherein the polysilazane modified layer is formed on the vapor deposition layer after the vapor deposition layer is formed on the substrate.   The method for producing a gas barrier film according to claim 1, wherein the deposited layer is formed on the polysilazane modified layer after the polysilazane modified layer is formed on the substrate. A gas barrier film comprising a vapor-deposited layer containing a metal oxide formed by a vapor deposition method on a substrate, and a polysilazane modified layer formed by applying a liquid containing polysilazane and drying and then irradiating with vacuum ultraviolet light In
A gas barrier film, wherein at least one of an excimer treatment in which the deposited layer is irradiated with vacuum ultraviolet light and a plasma treatment in which the polysilazane modified layer is irradiated with plasma are applied.   The gas barrier film according to claim 4, wherein the polysilazane modified layer is formed on the vapor deposition layer formed on the substrate.   The gas barrier film according to claim 4, wherein the vapor deposition layer is formed on the polysilazane modified layer formed on the base material.   An electronic apparatus comprising the gas barrier film according to any one of claims 4 to 6 and an electronic device sealed with the gas barrier film.

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