JP2013039706A - Method for producing steam barrier film, steam barrier film and electronic equipment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing steam barrier film which is highly durable and has an excellent steam barrier ability, a steam barrier film having such excellent performance, and electronic equipment having an excellent steam barrier ability using the steam barrier film.SOLUTION: In the steam barrier film 10 in which a steam barrier layer 4 and a protection layer 5 are piled up on a base material 1, a low-permeability region Rb having a lower permeability than the center side is formed at least on a part of the periphery of the steam barrier film 10. Preferably the low-permeability region Rb is formed all over the periphery.

Description

  The present invention relates to a method for producing a water vapor barrier film, a water vapor barrier film, and an electronic apparatus using the water vapor 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 prevents deterioration due to various gases such as water vapor and oxygen. Therefore, it is used in applications for packaging articles 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. A gas barrier film is superior in flexibility to a glass substrate, and is advantageous in terms of roll-type production suitability, weight reduction and handling of electronic devices.
As a method for producing such a gas barrier film, mainly a method of forming a gas barrier layer on a substrate such as a film by a plasma CVD method (Chemical Vapor Deposition: chemical vapor deposition method) A method is known in which a gas barrier layer is formed by applying a surface treatment after applying a coating liquid containing polysilazane as a main component onto a substrate (for example, see Patent Documents 1 and 2).
For example, in the invention described in Patent Document 1, 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, Regarding a technique of laminating a thin film on a substrate by repeating a process of forming a polysilazane film by a wet method of applying a liquid containing polysilazane and a process of irradiating the polysilazane film with vacuum ultraviolet light at least twice each. It is disclosed.

However, as in Patent Document 1, in the case of a film having a gas barrier layer on the outermost surface, the film surface is scratched by surface contact during production or handling, and the gas barrier layer is damaged. There is a concern that the barrier properties may be lowered. In addition, the gas barrier layer has low adhesiveness with a sealing agent (sealing agent mainly composed of organic resin components) for use in sealing electronic devices, ensuring long-term sealing and long-term durability of electronic devices. It was difficult to do. Furthermore, in order to obtain higher gas barrier properties, it is necessary to increase the amount of ultraviolet light that modifies the polysilazane film and to stack a plurality of gas barrier layers. The larger the size, the lower the flexibility as a flexible barrier film, and the trade-off relationship that durability against physical stress such as bending is reduced cannot be overcome.
In Patent Document 2, the protective layer is provided on the gas barrier layer to improve the handling durability of the barrier film. On the other hand, when sealing a device that deteriorates due to moisture such as an organic EL element, a resin is used. Water vapor that has permeated and diffused into the protective layer from the end of the protective layer may reach the organic EL element (device) and act. For example, when water vapor acts on the organic EL element, there is a problem that a point-like non-light-emitting portion called a luminance drop or a dark spot is generated. In addition, if the moisture previously contained in the protective layer made of an acrylate film or a methacrylate film is not removed before the organic EL element sealing step with the barrier film, the initial light emitting performance is deteriorated. A processing step for removing moisture for a certain period of time in an environment with heating was required.

Further, a method of manufacturing an organic EL light emitting device by sealing an organic EL element with a flexible plate having a gas barrier layer having a different thickness for each region is known. (For example, refer to Patent Document 3).
However, since the technique of Patent Document 3 is a technique aimed at increasing the ultraviolet transmittance by reducing the thickness of the gas barrier layer around the flexible plate, water vapor permeation from the film edge is suppressed. On the contrary, there was a risk of increasing.

  And the technique of patent document 4 is mentioned as a technique which suppresses water vapor permeation from the edge part of a barrier film regarding the organic EL light-emitting device formed by sealing an organic EL element with a barrier film.

JP 2009-255040 A Japanese Patent No. 4506365 JP 2008-84599 A JP 2010-244696 A

  However, in the method of Patent Document 4, it is necessary to form two or more gas barrier layers for each organic EL element to be sealed. Each time a plurality of gas barrier layers are formed, a plasma CVD method or an ion plating method is used. Since it is necessary to carry out a process using a method, there is a disadvantage that productivity is low.

  An object of the present invention is to provide a water vapor barrier film having high durability and good water vapor barrier performance, a method for producing the water vapor barrier film, and an electronic device using the water vapor barrier film.

In order to solve the above problems, the invention described in claim 1
A water vapor barrier film in which a water vapor barrier layer and a protective layer are laminated on a substrate,
It has a low transmission region having a lower water vapor transmission rate than at the center side of the water vapor barrier film in at least a part of the peripheral edge of the water vapor barrier film.

The invention according to claim 2 is the water vapor barrier film according to claim 1,
The low transmission region is formed in at least one of the water vapor barrier layer and the protective layer.

Invention of Claim 3 in the water vapor | steam barrier film of Claim 1 or 2,
The water vapor transmission rate in the central region of the water vapor barrier film is 3 to 20 times the water vapor transmission rate in the low transmission region.

Invention of Claim 4 is the water vapor | steam barrier film as described in any one of Claims 1-3,
The water vapor barrier layer is a layer obtained by applying a predetermined modification to a layer obtained by applying a coating solution containing at least polysilazane on the base material and drying the coating solution.

Invention of Claim 5 is the water vapor | steam barrier film as described in any one of Claims 1-4,
The protective layer contains a metal compound containing at least one of Si, Ti, and Zr.

Invention of Claim 6 is the water vapor | steam barrier film as described in any one of Claims 1-5,
The low-permeability region is provided over the entire periphery of the water vapor barrier film.

Invention of Claim 7 is a manufacturing method of a water vapor | steam barrier film, Comprising:
A coating solution containing at least polysilazane is coated on the substrate and dried, and then subjected to a predetermined modification treatment to form a water vapor barrier layer. Next, at least one of Si, Ti, and Zr is formed on the water vapor barrier layer. After applying and drying a coating solution containing a metal compound containing two, a predetermined reforming treatment is performed to form a protective layer, and the water vapor barrier layer and the protection in a portion corresponding to the edge of the substrate At least one of the layers is subjected to additional modification treatment to form a low-permeability region having a lower water vapor transmission rate than the other regions.

Invention of Claim 8 in the manufacturing method of the water vapor | steam barrier film of Claim 7,
The modification treatment is a heat treatment or an ultraviolet irradiation treatment.

Invention of Claim 9 is an electric equipment, Comprising:
The water vapor barrier film according to any one of claims 1 to 6, or the water vapor barrier film obtained by the method for producing a water vapor barrier film according to claim 7 or 8, and an electron sealed by the water vapor barrier film. A device is provided.

The invention according to claim 10 is the electronic apparatus according to claim 9,
The electronic device is arranged on the center side of the water vapor barrier film rather than the low transmission region of the water vapor barrier film.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the water vapor | steam barrier film which has high durability and favorable water vapor | steam barrier performance is implement | achieved, the water vapor | steam barrier film which has such outstanding performance, and the water vapor | steam barrier property using the water vapor | steam barrier film Can be obtained.

It is explanatory drawing which shows an example of the water vapor | steam barrier film which concerns on this invention, and is a schematic perspective view (a) and a perspective view (b) which shows a partially broken view of FIG. 1 (a). It is the schematic which shows an example of the manufacturing apparatus of a water vapor | steam barrier film. It is explanatory drawing regarding manufacture of a water vapor | steam barrier film, and is the top view (b) of the water vapor | steam barrier film obtained through the process (a) which performs an excimer process to the cutting | disconnection edge part of a film, and the process. It is explanatory drawing which shows an example of the pattern of the low permeation | transmission area | region provided in the water vapor | steam barrier film, and the modification process was given to all four sides of a film (a), and the modification process was carried out to two sides which a film opposes What was applied (b), one that was modified on three sides of the film (c), one that was modified on two adjacent sides of the film (d), and one that was modified on one side of the film It has been subjected to quality treatment (e). It is sectional drawing which shows an example of the organic electroluminescent panel which sealed the organic electroluminescent element using the water vapor | steam 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.

The water vapor barrier film of the present invention is a water vapor barrier film having at least a water vapor barrier layer and a protective layer on a substrate. For example, a water vapor barrier layer and a protective layer are laminated on a substrate such as a resin film. .
The protective layer is provided on the water vapor barrier layer, and is a layer for imparting strength against stress during bending or protecting the water vapor barrier layer from scratches due to contact.
In particular, the water vapor barrier film of the present invention is characterized in that it has a low transmission region having a water vapor transmission rate lower than that at the center side of the water vapor barrier film in at least a part of the peripheral edge of the water vapor barrier film. The low-permeability region of the water vapor barrier film is a water vapor barrier layer and a protective layer provided by being laminated on the base material, and is a portion corresponding to the peripheral portion of the water vapor barrier film with respect to the water vapor barrier layer and the protective layer. This is a region formed by subjecting at least one of the water vapor barrier layer and the protective layer to a predetermined modification treatment (for example, heat treatment, ultraviolet irradiation treatment).
Moreover, you may provide a smooth layer and an anchor coat layer on the surface of a base material as an intermediate | middle layer for improving the smoothness of a base material, or the adhesiveness of the water vapor | steam barrier layer with respect to a base material.
In addition, a scratch-resistant layer to prevent the base material from being scratched or soiled, or a low molecular weight component such as a monomer or oligomer is deposited from the inside to the surface when the resin base material is heated, so-called bleed. A bleed-out prevention layer for the purpose of suppressing the out may be provided on the surface of the substrate.

Specifically, the water vapor barrier film 10 according to the present invention includes, for example, a smooth layer 3 on one surface of the substrate 1 as shown in FIGS. 1 (a) and 1 (b), and on the smooth layer 3, A gas barrier layer having a two-layer structure in which a water vapor barrier layer 4 and a protective layer 5 are sequentially laminated is provided. In addition, a bleed-out preventing layer 2 is provided on the other surface of the substrate 1.
Further, a low transmission region Rb having a lower water vapor transmission rate than the central region Rc of the water vapor barrier film 10 is formed at the peripheral edge of the water vapor barrier film 10.
The low-permeability region Rb of the water vapor barrier film 10 is provided over the entire periphery, and has a substantially rectangular frame shape (substantially rectangular shape).
The low-permeability region Rb only needs to be formed by modifying at least one of the water vapor barrier layer 4 and the protective layer 5. In this water vapor barrier film 10, the low light transmission region Rb is formed over two layers of the water vapor barrier layer 4 and the protective layer 5. ing.

  Hereinafter, the structure of the water vapor | steam barrier film 10 of this invention is demonstrated in detail.

(Base material)
The base material 1 in the barrier film of this embodiment is a flexible and foldable film base material. The substrate 1 is not particularly limited as long as it is a film material capable of holding a constituent layer having water vapor barrier properties and various functional layers.

Examples of the resin material used for the substrate 1 include acrylic ester, methacrylic 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, etc. , A heat-resistant transparent film (product name: SILPLUS, manufactured by Nippon Steel Chemical Co., Ltd.) having silsesquioxane having an organic-inorganic hybrid structure as a basic skeleton, and a resin film formed by laminating two or more layers of the above film materials. It can be used Lum and the like.
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.
In addition, when a high temperature treatment is required in the processing step for sealing the device, a transparent polyimide film having both heat resistance and transparency, for example, a transparent polyimide film type HM manufactured by Toyobo Co., Ltd., Mitsubishi Gas Chemical Co., Ltd. A transparent polyimide-based film, Neoprim L L-3430, etc., can be 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 water vapor 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 each of the vertical axis direction and the horizontal axis direction.

(Anchor coat layer)
Moreover, you may form the anchor coat layer for improving the adhesiveness with the water vapor | steam barrier layer 4 or the smooth layer 3 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, two or more can be used in combination. Conventionally known additives can be added to these anchor coating agents. The anchor coating agent is coated on the substrate by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, and the like, and the anchor coating layer is formed by removing the solvent, diluent, etc. 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 provide the smooth layer 3 in the surface of the base material 1 in this embodiment. The smooth layer 3 is formed on one surface of the substrate 1.
The smooth layer 3 flattens the rough surface of the substrate 1 on which minute protrusions and the like exist, and unevenness and pinholes do not occur in the water vapor barrier layer 4 formed on the substrate 1 by the protrusions on the surface of the substrate 1. It is provided to make it. Such a smooth layer 3 is formed, for example, by curing a photosensitive resin.
Examples of the photosensitive resin used for forming the smooth layer 3 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, Examples thereof include a resin composition in which a polyfunctional acrylate monomer such as epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, polyethylene glycol acrylate, or glycerol methacrylate is 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 3 on the surface of the substrate 1 is not particularly limited, but 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 method such as a vapor deposition method. It is preferably formed by a coating method.
Moreover, when forming the smooth layer 3, 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 3 or preventing the occurrence of pinholes in the film formed on the smooth layer 3.
In addition, as a solvent used when forming the smooth layer 3 using the coating liquid which melt | dissolved or disperse | distributed photosensitive resin in the solvent, alcohol, such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, is 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, di 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 glycol Lumpur dialkyl ethers, ethyl 3-ethoxypropionate, methyl benzoate, N, N- dimethylacetamide, N, may be mentioned N- dimethylformamide.

  The smoothness of the smooth layer 3 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, it is applied when the coating means comes into contact with the surface of the smooth layer by a coating method such as a wire bar or wireless bar at the stage of applying a silicon compound solution (polysilazane coating solution) described later. May be impaired. Moreover, when Rt is larger than 30 nm, it may become difficult to smooth the unevenness | corrugation after apply | coating the silicon compound solution (polysilazane coating liquid) mentioned later.

In addition, one of the preferred embodiments as an additive to be added when forming the smooth layer 3 is a reactive silica particle (hereinafter simply referred to as “photosensitive resin group having a photopolymerization reactivity” introduced into the surface thereof). (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. It becomes easy to form the smooth layer 3 having both hard coat properties. 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 size of 0.001 to 0.01 μm.
The smooth layer 3 in the present embodiment preferably contains 20% or more and 60% or less of the inorganic particles as described above as a mass ratio. By adding 20% or more, the adhesion with the water vapor barrier layer 4 is improved. On the other hand, if it exceeds 60%, the film may be bent or cracked when heat-treated, or optical properties such as transparency and refractive index of the water vapor 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 smooth layer 3 has a thickness of 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 water vapor barrier film having the smooth layer 3 sufficiently, and by making it 10 μm or less, it becomes easy to adjust the balance of the optical characteristics of the water vapor barrier film, and smoothness. When the layer 3 is provided only on one surface of the water vapor barrier film, curling of the water vapor barrier film can be easily suppressed.

(Water vapor barrier layer)
The water vapor barrier layer 4 in the present embodiment is subjected to a modification process such as a vapor deposition layer having a water vapor barrier property formed by a vapor deposition method or a coating film that is dried by applying a liquid containing polysilazane and irradiating with vacuum ultraviolet light. A layer converted into a polysilazane modified layer having a water vapor barrier property by applying can be used.

(Deposition layer as a water vapor barrier layer)
Examples of the method for forming a vapor deposition layer, which is a thin film serving as the water vapor barrier layer 4, 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 method. Resistance heating method, electron beam evaporation method, 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.

(Coating reforming layer as a water vapor barrier layer)
As a method for forming a coating film reforming layer, which is a thin film that forms the water vapor barrier layer 4 on the substrate 1, for example, a vacuum ultraviolet light is irradiated to a coating film (polysilazane-containing layer) that has been applied and dried with a liquid containing polysilazane. The method of converting into the polysilazane modified layer which has water vapor | steam barrier property by performing the ultraviolet irradiation process to perform, the heat processing which irradiates a heat ray, etc. is mentioned.
For example, the water vapor barrier layer 4 in the present embodiment is modified such that a polysilazane-containing layer formed by applying a liquid containing a polysilazane (first coating liquid) on the substrate 1 and drying is irradiated with vacuum ultraviolet light. It can be formed by processing and modifying the polysilazane-containing layer into the water vapor barrier layer 4. In addition, the protective layer 5 described later is laminated on the polysilazane-containing layer formed by coating and drying, and the polysilazane-containing material is subjected to a modification treatment such as irradiation of vacuum ultraviolet light from the coating surface side of the protective layer 5 The layer can be formed by modifying the water vapor barrier layer 4.

(Application of liquid containing polysilazane)
The water vapor barrier layer 4 in the present embodiment is formed by applying a liquid containing polysilazane (first coating liquid) and forming a coating film.
By "polysilazane" as used in the present invention, silicon - a polymer with a nitrogen bonds, Si-N, Si-H , SiO 2 having a bond such as _{N-H, Si} 3 N ₄ and both of the intermediate solid solution 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. Represent.
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 denseness as the resulting polysilazane-containing layer (water vapor barrier layer 4).
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-containing layer (water vapor barrier layer 4) 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 a metal catalyst may be added in order to accelerate the reaction of converting polysilazane into 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.

(catalyst)
In order to modify the polysilazane-containing layer into the water vapor barrier layer 4, a catalyst that promotes a reaction for converting at least a part of the polysilazane in the polysilazane-containing layer into a silicon oxide compound may be used.
The catalyst preferably used in the present invention is at least one selected from the group of nickel, titanium, platinum, rhodium, cobalt, iron, ruthenium, osmium, palladium, iridium, and aluminum described in JP-A-10-279362. Metal carboxylates obtained by reacting metal carboxylates containing these metals, acetylacetonate complexes containing nickel, platinum, palladium or aluminum, and fine particles of metals including Au, Ag, Pd, Ni, Also, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, butylamine, dibutylamine, tributylamine, pentylamine, dipentylamine, tripentylamine , Hexylamine, dihexylamine, trihexylamine, heptylamine, diheptylamine, triheptyl, octylamine, dioctylamine, trioctylamine, phenylamine, diphenylamine, triphenylamine, and the like. The hydrocarbon chain contained in these amine compounds may be a straight chain or a branched chain. Specific examples of pyridines include pyridine, α-picoline, β-picoline, γ-picoline, piperidine, lutidine, pyrimidine, pyridazine, and the like. Furthermore, DBU (1,8-diazabicyclo [5.4.0] -7-undecene), DBN (1,5-diazabicyclo [4.3.0] -5-nonene), and the like can also be used. Specific examples of the acid compound include organic acids such as acetic acid, propionic acid, butyric acid, valeric acid, maleic acid and stearic acid, and inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid and hydrogen peroxide.
The addition amount of these catalysts to polysilazane is preferably 0 ppm or more and less than 5% with respect to the weight of polysilazane as a solid content concentration ratio in the liquid containing polysilazane (first coating solution). More preferably, it is 100 ppm or more and 3% or less.

In the polysilazane-containing layer formed by the polysilazane-containing coating liquid (first coating liquid) used in the present invention, the amount of water contained before or during the modification treatment is preferably controlled.
Examples of the supply of moisture that can enter the polysilazane-containing layer before or during the modification treatment include migration from the surface of the coated substrate or absorption of water vapor in the atmosphere. Control of moisture transferred from the substrate side into the polysilazane-containing layer is to store the substrate in a constant temperature and humidity environment before applying the polysilazane-containing coating solution, and control the moisture content to a desired value. Can do. The desired value varies depending on the humidity in the atmosphere to be described later, but is usually 1000 ppm or less, preferably 300 ppm or less as a weight.
In the step of applying and drying the polysilazane-containing coating solution (first coating solution) on the substrate, the organic solvent is mainly removed, so that the drying conditions can be appropriately determined by a method such as heat treatment, and the heat treatment temperature is rapid. Although it is preferable that it is high temperature from a viewpoint of a process, it is preferable to determine suitably temperature and processing time in consideration of the heat damage with respect to the base material 1 which 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 atmosphere in the step of applying and drying the polysilazane-containing coating liquid (first coating liquid) on the substrate is preferably controlled to be relatively low humidity, but the humidity in a low humidity environment changes with temperature, The relationship between temperature and humidity is shown in a preferred form by 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.

(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.
The reforming process can be selected known method based on the conversion reaction of the polysilazane. 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 barrier film of the present invention, a conversion reaction using ultraviolet light that can be converted at a lower temperature is preferable from the viewpoint of adaptation to a plastic substrate.

In the method for producing a barrier film in the present invention, the polysilazane coating film (polysilazane-containing layer) 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 can 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-containing layer is not damaged.
Taking the case where a plastic film is used as the base material 1, for example, a 2 kW (80 W / cm × 25 cm) lamp is used, and the strength of the base material 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 it can be appropriately set by those skilled in the art depending on the type of 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, metal halide lamps, high pressure mercury lamps, low pressure mercury lamps, xenon arc lamps, carbon arc lamps, excimer lamps, and UV light lasers. In addition, when irradiating the polysilazane-containing layer before modification with the generated ultraviolet light, from the viewpoint of achieving efficiency improvement and uniform irradiation, the ultraviolet light from the generation source is reflected by the reflector and then before modification. It is desirable to apply to the polysilazane-containing 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 substrate 1 having a polysilazane-containing layer is in the form of a long film, it is converted into ceramics by continuously irradiating ultraviolet rays in a drying zone equipped with an ultraviolet ray source as described above while being conveyed. Can do. The time required for ultraviolet irradiation is generally 0.1 seconds to 10 minutes, preferably 0, although it depends on the composition and concentration of the substrate 1 and the polysilazane modified layer (polysilazane-containing layer, water vapor barrier layer 4) to be used. .5 seconds to 3 minutes.
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 formation of the oxygen-rich water vapor barrier layer 4 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-containing 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 placing 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 and electrodes and their arrangement 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 and plasma cleaning that emit ultraviolet rays with wavelengths of 185 nm and 254 nm, 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 used. Can be irradiated.
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 barrier film which makes the base material 1 resin films, such as a polyethylene terephthalate considered to be easy to receive the influence of a heat | fever.

(Protective layer)
The protective layer 5 in this embodiment is laminated for the purpose of protecting the water vapor barrier layer 4 formed on the substrate 1.
The protective layer 5 can be formed by applying a second coating solution on the water vapor barrier layer 4 and drying it. In addition, the coating layer dried by applying the second coating liquid is subjected to a predetermined modification process (for example, an ultraviolet irradiation process for irradiating vacuum ultraviolet light, a heating process for irradiating heat rays) to form the protective layer 5. You may do it.

The compound used for the protective layer 5 of the present invention is an organic or inorganic compound, and is preferably a transparent film in the ultraviolet to visible light region. Examples of the organic resin include polyester resins, isocyanate resins, urethane resins, acrylic resins. Resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicon resin, acetal resin, and the like can be used alone or in combination. Conventionally known additives can be added to these resins. The above compound material (resin) is anchored by coating on a plastic film by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, etc., and drying and removing the solvent, diluent, etc. Can be coated. The coating amount is preferably about 0.01 to 1 g / m ² (dry state).
In addition, the protective layer 5 used in the present invention is more preferably an inorganic compound in view of the purpose of reducing the water vapor transmission rate in the protective layer 5 and less coloring due to absorption of vacuum ultraviolet light or irradiation with vacuum ultraviolet light. Used. What is preferably used as the inorganic compound is a metal compound containing at least one of Si, Ti, and Zr, and examples thereof include metal alkoxides, silane compounds, silazane compounds, and metal halides.

Although the specific example of the compound which can be used for the protective layer 5 below is shown, it is not limited to these. The following compounds may be used alone or in combination, and may be a composition mixed with other organic or inorganic compounds.
For example, tetrachlorosilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltri Ethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, decyltrimethoxysilane, trifluoropropyltrimethoxysilane, hexamethyldisilazane, par Hydropolysilazane, methylpolysilazane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxysilane) Hexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p- Styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyl Riethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3- Examples thereof include silane compounds such as mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, tetraisocyanatesilane, and methyltriisocyanatesilane.

  Or the organic titanium compound etc. which are shown by following General formula (2) (3) (4) are mentioned. In the general formula, R is an alkyl group.

  In addition, titanium tetra-2-ethylhexoxide, titanium diisopropoxybis (acetylacetonate), titanium tetraacetylacetonate, titanium dioctyloxybis (octylene glycolate), titanium diisopropoxybis (ethylacetoacetate) ), Titanium diisopropoxybis (triethanolaminate), titanium lactate ammonium salt, titanium lactate, titanium lactate, polyhydroxy titanium stearate and the like.

  Or the organic zirconium compound etc. which are shown by following General formula (5) (6) (7) are mentioned. In the general formula, R is an alkyl group.

  Further, zirconium tetranormal propoxide, zirconium tetranormal butoxide, zirconium tetraacetylacetonate, zirconium tributoxymonoacetylacetonate, zirconium monobutoxyacetylacetonate bis (ethylacetoacetate), zirconium dibutoxybis (ethylacetoacetate), Organic zirconium compounds such as zirconium tetraacetylacetonate, zirconium tributoxy monostearate and the like can be mentioned.

Moreover, polysilazane is mentioned as one of the compounds preferably used for the protective layer 5. When polysilazane is used for forming the protective layer 5, it is preferable to contain a catalyst added to the water vapor barrier layer 4 (polysilazane-containing layer). For example, the amount of catalyst contained in the coating liquid (second coating liquid) for forming the protective layer 5 is based on the weight of polysilazane as a solid content concentration ratio in the liquid containing polysilazane (second coating liquid). It is preferably 0.1% or more and 10% or less. More preferably, it is 0.5% or more and 5% or less.
When polysilazane is used as the protective layer 5, it is preferable to mix the aforementioned different inorganic compounds in order to enhance the flexibility of the protective layer 5 and the ability to relieve heat shrinkage stress. Thereby, it becomes easy to achieve both the water vapor barrier property of the protective layer 5 and the protection of the adjacent water vapor barrier layer 4.

(Other components that can be included in the protective layer)
An organic or inorganic compound that is solid at room temperature can be added to the protective layer 5. In particular, when the compound is liquid at room temperature, a known thermoplastic resin, heat or photo-curable resin, or inorganic fine particle compound may be used as long as the additive is stably held in the protective layer 5. it can.

(Lamination method of protective layer)
The protective layer 5 of the present invention is laminated on the water vapor barrier layer 4 (polysilazane-containing layer) provided on the substrate 1.
As a method for forming the protective layer 5, when an inorganic compound reactive with moisture is used, a solution (second coating solution) obtained by dissolving and dispersing the compound in a solvent having a low moisture content is used in a low humidity environment. It is preferable to form by applying and drying. Here, since the humidity in the low humidity environment varies depending on the temperature, the relationship between the temperature and the humidity shows a preferable form by the definition of 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, the thickness of the protective layer 5 of this invention is 1 nm or more and 1000 nm or less normally, Preferably they are 10 nm or more and 500 nm or less. If the thickness of the protective layer 5 of this invention exists in the said range, it will become easy to ensure the uniformity of a coating film, and it can protect from the abrasion at the time of the water vapor | steam barrier layer 4, and the stress at the time of bending.

(Water vapor barrier properties and water vapor transmission rates are different)
As shown in FIGS. 1A and 1B, a low transmission region Rb having a lower water vapor transmission rate than the central region Rc of the water vapor barrier film 10 is formed at the edge (peripheral part) of the water vapor barrier film 10. ing. In the present embodiment, the low transmission region Rb is formed over two layers of the water vapor barrier film 10 and the protective layer 5 in the water vapor barrier film 10.
This low transmission region Rb is an additional modification process (for example, an ultraviolet irradiation process for irradiating vacuum ultraviolet light, a heating process for irradiating heat rays) to the water vapor barrier layer 4 or the protective layer 5 corresponding to the edge of the film. This is a region that has been modified so that the water vapor transmission rate is lower than that of the region that is not subjected to additional modification treatment.
Here, the edge part in the water vapor | steam barrier film 10 with respect to the full width L of a sheet-like film is the distance l which went to the inside from the edge of at least one side as 1/20% as a ratio of 1 / L. It is preferable that the region satisfies the condition. By adjusting the low-permeability region Rb of the water vapor barrier film 10 within this range, it becomes easy to achieve both sufficient water vapor barrier properties and durability against bending.
Generally, when the degree of modification of the water vapor barrier layer 4 or the protective layer 5 is increased, the water vapor barrier property is improved, but at the same time, the hardness of the modified film is increased. Therefore, when additional modification treatment is performed on a wide region, the bending followability of the low-permeability region Rb in the water vapor barrier layer 4 or the protective layer 5 on the substrate 1 tends to be reduced. By limiting the region for forming Rb to the partial range described above, the flexibility of the water vapor barrier film 10 can be maintained.
And the water vapor transmission rate of the center side area | region Rc of the water vapor | steam barrier film 10 is 3 to 20 times the water vapor transmission rate of the low transmission area | region Rb. That is, the water vapor transmission rate of the low transmission region Rb in the water vapor barrier film is 1/3 to 1/20 of the central region Rc.

The boundary between the central region Rc and the low-permeability region Rb of the water vapor barrier film 10 is masked on the central side of the water vapor barrier film, and an additional modification process is performed only on the edge (periphery) of the water vapor barrier film. Therefore, it may be a boundary that can be divided into two regions with different values of water vapor transmission rate depending on the presence or absence of the additional modification treatment, and is added from the edge (periphery) side of the water vapor barrier film. Even if it is a boundary where the value of the water vapor transmission rate gradually changes with the degree and degree of the additional modification process continuously varying from the edge of the film toward the inside by the modification process of Good.
In the case of a water vapor barrier film in which the degree of the additional modification treatment is continuously different from the end of the film toward the inside, and the value of the water vapor transmission rate is gradually changed, the condition based on the ratio of l / L described above ( 1% ≦ l / L ≦ 20%), the boundary between the central region Rc and the low transmission region Rb can be determined, and the water vapor transmission rate of each region can be measured.

(Bleed-out prevention layer)
Moreover, you may form the bleed-out prevention layer 2 in the surface of the lower surface side of the base material 1 in this embodiment.
The bleed-out prevention layer 2 is smooth for the purpose of suppressing a phenomenon in which unreacted oligomers migrate from the substrate 1 to the surface thereof when the film having the smooth layer 3 is heated to contaminate the film surface. It is provided on the opposite surface of the substrate 1 having the layer 3. The bleed-out prevention layer 2 may basically have the same configuration as the smooth layer 3 as long as it has this function.
Examples of the unsaturated organic compound having a polymerizable unsaturated group that can be included in the bleedout prevention layer 2 include a polyunsaturated organic compound having two or more polymerizable unsaturated groups in the molecule, or in the molecule And 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.

The bleed-out prevention layer 2 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 2 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 base 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 2 in this embodiment is 1 to 10 μm, preferably 2 to 7 μm. By setting the thickness to 1 μm or more, the heat resistance as the water vapor barrier film is easily made sufficient. By making the thickness 10 μm or less, it becomes easy to adjust the balance of the optical characteristics of the water vapor barrier film, and it is easy to suppress curl of the water vapor barrier film when the smooth layer 3 is provided on one surface of the water vapor barrier film. become able to.

(Water vapor barrier film manufacturing equipment)
An example of the manufacturing apparatus used for manufacture of the water vapor | steam barrier film 10 which concerns on this invention is shown in FIG. In addition, a water vapor | steam barrier film manufacturing apparatus is not limited to this embodiment.
For example, as shown in FIG. 2, the water vapor barrier film manufacturing apparatus 100 includes a roll-to-roll transport means (1 </ b> A, 1 </ b> B, 1 </ b> C) that winds and feeds the base material 1 to transport the base material 1. A first coating unit 40 for coating a first coating solution for a water vapor barrier layer containing at least polysilazane, a first drying unit 50 for drying and removing a solvent and moisture, and an excimer lamp for irradiating vacuum ultraviolet light A first excimer processing unit 60 provided with 60a, a second coating unit 70 for coating the second coating liquid for the protective layer, a second drying unit 80 for drying and removing the solvent and moisture, and a vacuum A second excimer processing unit 90 provided with excimer lamps 90a and 90b for irradiating ultraviolet light is provided. The excimer lamp 90a of the second excimer processing unit 90 is arranged in a direction perpendicular to the transport direction, and the excimer lamp 90b of the second excimer processing unit 90 is parallel to the transport direction, and It is arranged at a position corresponding to the edge.
Below, the outline | summary of the manufacturing method of the water vapor | steam barrier film by this water vapor | steam barrier film manufacturing apparatus 100 is demonstrated.

(Manufacturing process and manufacturing method of water vapor barrier film)
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. A smoothing layer 3 is formed on the upper surface of the substrate 1 and a bleed-out preventing layer 2 is formed on the lower surface.
First, after applying a first coating solution having a composition containing, for example, polysilazane and a catalyst on the smooth layer 3 formed on the substrate 1 with the first coating unit 40, the solvent is removed with the first drying unit 50. Dry to form a polysilazane-containing layer. After forming the polysilazane-containing layer on the substrate 1, the first excimer processing unit 60 irradiates vacuum ultraviolet light to perform excimer treatment (modification treatment), thereby modifying the polysilazane-containing layer to form the water vapor barrier layer 4. Form.
Subsequently, the substrate 1 is transported, and the second coating unit 70 for the protective layer having the above-described composition is formed on the water vapor barrier layer 4 formed on the smooth layer 3 of the substrate 1 by the second coating unit 70. After the liquid is applied, the solvent is removed by the second drying unit 80 and dried to form the protective layer 5.
Further, the substrate 1 is conveyed, and from the side of the protective layer 5 formed on the substrate 1, the second excimer processing unit 90 irradiates the vacuum ultraviolet light to perform the excimer treatment, and the water vapor barrier layer 4 and the protective layer. 5 is batch-modified. In the second excimer processing unit 90, the excimer lamp 90a arranged in the direction perpendicular to the transport direction contributes to the reforming process for the entire film. On the other hand, in the second excimer processing unit 90, the excimer lamp 90 b arranged in a direction parallel to the transport direction is modified only in a part of the water vapor barrier layer 4 and the protective layer 5 corresponding to the edge of the substrate 1. It advances and contributes to the additional modification | reformation process for forming the low permeable area | region Rb whose water vapor transmission rate is lower than the center side of the water vapor | steam barrier film 10. FIG. In addition, it is preferable to form the low transmission region Rb so that (water vapor transmission rate of the central region Rc) / (water vapor transmission rate of the low transmission region Rb) is 3 times or more and 20 times or less. By setting the ratio of the water vapor transmission rate within this range, it is possible to achieve both sufficient water vapor barrier properties and durability against bending.
And the completed water vapor | steam barrier film (10a) is wound up by the 2nd conveyance roller 1B. The water vapor barrier film 10 is obtained by cutting the long water vapor barrier film (10a) wound around the transport roller 1B into a desired size.
The water vapor barrier film 10 can be manufactured by such a manufacturing method in the order of steps.
In addition, the excimer processing unit of the water vapor barrier film manufacturing apparatus 100 in this embodiment is replaced with a heat processing unit including an infrared heater, an infrared lamp, a halogen lamp, etc. It may be a method.

The water vapor barrier film 10 of the present invention is characterized by having a low transmission region Rb having a lower water vapor transmission rate than the central side of the water vapor barrier film 10 in at least a part of the peripheral portion thereof. The low transmission region Rb is provided in a frame shape over the entire periphery of the water vapor barrier film 10.
As a method for producing such a water vapor barrier film 10, the long water vapor barrier film (10a) produced by the water vapor barrier film production apparatus 100 described above is cut out to a desired size, for example, as shown in FIG. As shown, an excimer process for selectively irradiating vacuum ultraviolet light using an excimer lamp 90c may be performed on both ends of the cut portion to perform an additional modification process. By doing so, as shown in FIG. 3 (b), it is possible to manufacture the water vapor barrier film 10 in which the low transmission region Rb is provided in a frame shape over the entire periphery.
As described above, the side surface of the water vapor barrier film 10 is subjected to an additional reforming process that forms a low-permeability region Rb having a lower water vapor transmission rate than the center side of the water vapor barrier film 10 on at least a part of the peripheral edge of the film. Water vapor permeation from the (end face), in particular, water vapor permeation and diffusion in the protective layer 5 film can be suppressed, and while maintaining the flexibility of the water vapor barrier film 10, the water vapor barrier film 10 having high water vapor barrier properties is provided. Can be manufactured.

In addition, the water vapor | steam barrier film which has the low permeable area | region Rb whose water vapor permeability is lower than the center side in at least one part of a peripheral part is not restricted to the water vapor | steam barrier film 10 shown to Fig.4 (a). An additional modification process using an excimer lamp or the like may be performed on any edge of the film.
For example, a figure in which a low-permeation region Rb is applied to a pair of opposing edges formed by cutting out a long water vapor barrier film (10a) produced by the water vapor barrier film production apparatus 100 to a desired size. The water vapor barrier film 11 shown in 4 (b) may be used.
Moreover, the water vapor | steam barrier film 12 shown in FIG.4 (c) by which the low permeable area | region Rb was given to the three edge parts of the film may be sufficient.
Moreover, the water vapor | steam barrier film 13 shown in FIG.4 (d) by which the low-permeability area | region Rb was given to the two adjacent edge parts of a film may be sufficient.
Moreover, the water vapor | steam barrier film 14 shown in FIG.4 (e) by which the low permeable area | region Rb was given to one edge part of the film may be sufficient.

(Organic EL panel as an electronic device)
The water vapor barrier film 10 according to the present invention can be used as a sealing film for sealing electronic devices such as solar cells, liquid crystal display elements, and organic EL elements.
An example of the organic EL panel 20 which is an electronic device using this water vapor | steam barrier film 10 as a sealing film is shown in FIG.
As shown in FIG. 5, the organic EL panel 20 is formed on the water vapor barrier film 10, the transparent electrode 6 such as ITO formed on the water vapor barrier film 10, and the transparent electrode 6. The organic EL element 7 and a counter film 9 disposed via an adhesive layer 8 so as to cover the organic EL element 7 are provided. The transparent electrode 6 may form part of the organic EL element 7.
A transparent electrode 6 and an organic EL element 7 are formed on the surface of the water vapor barrier film 10 on which the water vapor barrier layer 4 and the protective layer 5 are formed. In particular, the organic EL element 7 which is an electronic device is disposed and sealed on the central region Rc on the central side of the water vapor barrier film rather than the low transmission region Rb of the water vapor barrier film 10.
As described above, in the organic EL panel 20, the organic EL element 7 is disposed and sealed on the central side region Rc on the central side of the water vapor barrier film 10 in which the low-permeation region Rb having a low water vapor transmission rate is formed at the peripheral edge thereof. Therefore, water vapor permeation from the side surface (end surface) of the water vapor barrier film 10, particularly water vapor permeation in the protective layer 5 film is suppressed by the low transmission region Rb, and water vapor hardly acts on the organic EL element 7. ing.
That is, in the organic EL panel 20, the water vapor permeation from the upper surface and the lower surface is suppressed by the water vapor barrier film 10 and the counter film 9, and the water vapor permeation from the side surface (end surface) of the water vapor barrier film 10 is a low transmission region Rb. Therefore, the organic EL element 7 sealed between the water vapor barrier film 10 and the counter film 9 is suitably sealed so as not to be exposed to water vapor.
In the organic EL panel 20, the organic EL element 7 is suitably sealed so as not to be exposed to water vapor, and the organic EL element 7 is hardly deteriorated, so that the organic EL panel 20 can be used for a long time. It becomes possible, and the lifetime of the organic EL panel 20 is extended.
In addition, the opposing film 9 may use the water vapor | steam barrier film which concerns on this invention other than metal films, such as aluminum foil. When a water vapor barrier film is used as the counter film 9, the surface on which the water vapor barrier layer 4 and the protective layer 5 are formed may be attached to the organic EL element 7 with the adhesive layer 8.

(Organic EL device)
The organic EL element 7 sealed with the water vapor barrier film 10 in the organic EL panel 20 will be described.
Although the preferable specific example of the layer structure of the organic EL element 7 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 6) in the organic EL element 7, 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 7, 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 7 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 desirably a very thin film, and although it depends on the material, the film thickness is preferably in the range of 0.1 nm to 5 μm.

(Light emitting layer)
The light emitting layer in the organic EL element 7 is a layer that emits light by recombination of electrons and holes injected from the electrode (cathode, anode) or electron transport layer or hole transport layer, and the light emitting portion is the 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 7 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 it is also possible to use these materials are introduced in a polymer chain or a polymer having the material as the polymer main chain. Further, it is possible to p-type -Si, inorganic compounds such as p-type -SiC used hole injection material, a 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. There is no particular limitation on the thickness of the hole transporting layer is usually about 5 nm to 5 [mu] m, preferably 5 to 200 nm. The hole transport layer may have a single layer structure comprising one kind or two or more kinds 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, and 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 7 will be described.
Here, as an example of the organic EL element 7, a method for manufacturing 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 barrier film 10 by a method such as vapor deposition, sputtering, or plasma CVD so as to have a film thickness of 1 μm or less, preferably 10 to 200 nm. 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 7 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 20) including the organic EL element 7 obtained in this manner, the voltage is about 2 to 40 V with the anode being positive and the cathode being negative. Luminescence can be observed by applying. An alternating voltage may be applied. The alternating current waveform to be applied may be arbitrary.

  Hereinafter, although the specific example is given and the water vapor | steam 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 100 μm thick polyester film (Cosmo Shine A4300, manufactured by Toyobo Co., Ltd.), which is a thermoplastic resin support and easily bonded on both sides, is used as a base material 1 to prevent bleeding out on one side as shown below. Layer 2 and smooth layer 3 on the opposite surface were prepared and used.
(Formation of bleed-out prevention layer)
A UV curable organic / inorganic hybrid hard coat material OPSTAR Z7535 manufactured by JSR Corporation was applied to one side of the substrate 1 with a wire bar so that the film thickness after drying was 4 μm, and then a high-pressure mercury lamp in the air. Curing was carried out under curing conditions of use 1.0 J / cm ² and drying conditions of 80 ° C. × 3 minutes to form a bleed-out prevention layer 2.
(Formation of smooth layer)
Subsequently, a UV curable organic / inorganic hybrid hard coat material OPSTAR Z7501 manufactured by JSR Corporation was applied to the opposite surface of the substrate 1 with a wire bar so that the film thickness after drying was 4 μm, and then a drying condition of 80 The film was dried at 3 ° C. for 3 minutes, and then cured under a curing condition of 1.0 J / cm ² using a high-pressure mercury lamp in an air atmosphere to form a smooth layer 3.
With the surface roughness defined by JIS B 0601 of the obtained smooth layer 3, the maximum cross-sectional height Rt (p) was 16 nm.
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, and the measurement direction is 30 μm with a stylus with a minimum tip radius. This is the average roughness for the amplitude of fine irregularities, measured many times in the section.
Thus, the base material 1 on which the bleed-out prevention layer 2 and the smooth layer 3 were formed was designated as “B0”.

  Next, a 10% by weight dibutyl ether solution of perhydropolysilazane (Aquamica NN120-10, manufactured by AZ Electronic Materials Co., Ltd.) and an amine catalyst N, N, N ′, N′-tetramethyl-1,6-diamino A liquid (first coating liquid) in which a 10% by mass dibutyl ether solution of hexane was mixed at a ratio of 99: 1 was measured with a wireless bar so that the (average) film thickness after drying was 150 nm. ”And dried with dry air at a temperature of 50 ° C. and a dew point of −5 ° C. for 1 minute to obtain a coated sample (coating step). The obtained coated sample was treated with dry air at a temperature of 95 ° C. and a dew point of −5 ° C. for 2 minutes to obtain a sample “B1” in which a polysilazane-containing layer was formed on the smooth layer 3 on the upper surface of the substrate 1.

[First embodiment]
(Comparative example, sample 1)
The surface of the sample B1 was irradiated with vacuum ultraviolet light (excimer modification treatment) under the following apparatus and conditions to modify the polysilazane-containing layer to form the water vapor barrier layer 4.
Excimer modification treatment The sample after the polysilazane coating film is dried and the polysilazane-containing layer is formed is subjected to an excimer modification treatment with the following equipment and conditions to modify the polysilazane-containing layer to form a water vapor barrier layer 4 Formed. The dew point temperature during the reforming treatment was -20 ° C. (excimer treatment step).
-Reforming treatment apparatus Eximer irradiation apparatus MODEL: MECL-M-1-200 manufactured by M.D.
Wavelength: 172nm
Lamp filled gas: Xe
-Modification treatment conditions Average excimer light intensity: 130 mW / cm ² (172 nm)
Distance between sample and light source: 3 mm
Stage heating temperature: 90 ° C
Oxygen concentration in the irradiation device: 0.2%
Stage transfer speed during excimer light irradiation: 10 mm / sec Stage transfer count during excimer light irradiation: 6 reciprocations

Furthermore, a 10% by mass dibutyl ether solution of perhydropolysilazane (Aquamica NN120-10, manufactured by AZ Electronic Materials Co., Ltd.) and an amine catalyst N, N, N are formed on the surface of the sample (on the water vapor barrier layer 4). A 10% by mass dibutyl ether solution of ', N'-tetramethyl-1,6-diaminohexane and a 10% by mass dibutyl ether solution of methyltriethoxysilane (KBE-13, manufactured by Shin-Etsu Chemical Co., Ltd.) The liquid (second coating liquid) mixed at a ratio of 3 to 15 was applied with a wireless bar so that the (average) film thickness after drying was 400 nm, and the temperature was 25 ° C. and the dew point was −5 ° C. Was dried with dry air for 1 minute to obtain a coated sample (coating step). The obtained coating sample was treated with dry air at a temperature of 85 ° C. and a dew point of −5 ° C. for 2 minutes to form a polysilazane-containing protective layer coating film before modification.
Subsequently, the sample after drying the polysilazane-containing protective layer coating film is subjected to an excimer modification treatment uniformly on the entire surface of the coating film with the following apparatus and conditions to modify the protective layer coating film. The protective layer 5 which is a polysilazane-containing modified layer was formed. The dew point temperature during the reforming treatment was -20 ° C. (excimer treatment step).
In this way, Sample 1 was obtained. In this sample 1, the low transmission region Rb is not formed.
・ 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: 95 ° C
Oxygen concentration in the irradiation device: 0.3%
Stage transfer speed during excimer light irradiation: 10 mm / sec Stage transfer number during excimer light irradiation: 2 reciprocations

(Comparative example, sample 2)
Produced in the same manner as in Sample 1 except that the number of stage transports during excimer light irradiation in the excimer modification treatment performed on the polysilazane-containing protective layer coating film (protective layer 5) was changed from 2 reciprocations to 5 reciprocations. This was designated as Sample 2. Also in this sample 2, the low transmission region Rb is not formed.

(Invention, Sample 3)
The sample 1 is cut into a 10 cm × 8 cm rectangle, and an excimer lamp is fixedly arranged so that the central axis of the lamp tube is placed at a position 5 mm inside from one end of the cut sample, and the excimer lamp is held for 6 seconds. By turning on the light, the edge of the cut sample was selectively irradiated with excimer light for additional modification.
Further, the same excimer treatment was performed on the remaining three sides, and a sample in which the entire periphery of the peripheral portion was additionally modified to form the low transmission region Rb was designated as sample 3.

(Invention, Sample 4)
Except that the formation of the water vapor barrier layer 4 in the sample 3 was changed to the vapor deposition layer formation by the following plasma CVD, and the excimer modification treatment for the polysilazane-containing layer of the sample B1 became unnecessary due to the change. Sample 4 was prepared in the same manner as Sample 3. Note that the additional reforming process is also performed on the entire periphery of the peripheral edge of the sample 4 to form a low transmission region Rb.
Using a plasma discharge treatment unit (for example, a roll-to-roll atmospheric pressure plasma discharge treatment apparatus described in FIG. 3 of JP-A-2008-56967), the substrate 1 “B0” is smoothed by an atmospheric pressure plasma method. On the layer 3, the water vapor | steam barrier layer 4 which consists of a vapor deposition layer of a 3 layer structure on the following conditions was formed, and sample "B2" was produced.
The first to third vapor-deposited layers each contained a metal oxide (silicon oxide), and the thickness of the first to third vapor-deposited layers was 150 nm, 25 nm, and 30 nm, respectively, for a total of 205 nm.
- 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 110 ° 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
・ 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 100 ° 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 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 105 ° C
Measurement of water vapor transmission rate of sample “B2” The water vapor transmission rate of the sample “B2” after humidity control was determined according to MOCON method using PERMATRAN-W3 / 33 manufactured by MOCON, and JIS standard K7129 method (temperature 40 ° C. , Humidity 90% RH). The measured water vapor transmission rate was below the detection limit of 0.01 g / m ² / day.

(Invention, Sample 5)
In the sample 3, the vacuum ultraviolet treatment (excimer treatment) for additionally modifying the edge portion was changed to a heat treatment using an infrared heater.
Then, using a heat insulating material of 8 cm × 6 cm (pyro blanket (heat insulating material manufactured by Insulflex)) as a mask material, a mask is formed so that heating is possible from the four sides of the sample cut to a 10 cm × 8 cm rectangle to the inside 1 cm. By placing the material in the center of the sample and performing the heat treatment continuously for 4 hours so that the temperature of the irradiated surface becomes 90 ° C., a low transmission region Rb is formed at the peripheral edge of the cut sample, and the sample 5 is Produced.

(Invention, Sample 6)
Sample 6 was prepared in the same manner as Sample 3 except that the excimer lamp lighting time of vacuum ultraviolet treatment (excimer treatment) for additional modification of the edge portion was changed from 6 seconds to 5 seconds.

(Invention, Sample 7)
Regarding the formation of the protective layer 5 in Sample 3, Sample 7 was prepared in the same manner except that the second coating solution composition and the modification treatment conditions were changed as follows.
-2nd coating liquid composition 10 mass% dibutyl ether solution of perhydropolysilazane (Aquamica NN120-10, AZ Electronic Materials Co., Ltd.) and amine catalyst N, N, N ', N'-tetramethyl- A ratio of 87: 3 to 10: a 10 mass% dibutyl ether solution of 1,6-diaminohexane and a 10 mass% toluene solution of zirconium tetraacetylacetonate (Orgatechx ZC-150, manufactured by Matsumoto Fine Chemical Co., Ltd.) Liquid mixed with.
-Modification treatment conditions Excimer light intensity: 130 mW / cm ² (172 nm)
Distance between sample and light source: 2mm
Stage heating temperature: 95 ° 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

(Invention, Sample 8)
Regarding the formation of the protective layer 5 in Sample 3, Sample 8 was prepared in the same manner except that the second coating solution composition and the modification treatment conditions were changed as follows.
-2nd coating liquid composition The liquid which diluted the 25 mass% toluene-butanol solution of the titanium oligomer (Orgatechs PC-685 made by Matsumoto Fine Chemical Co., Ltd.) to 10% with butanol.
-Modification treatment conditions Excimer light intensity: 130 mW / cm ² (172 nm)
Distance between sample and light source: 2mm
Stage heating temperature: 95 ° 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

(Invention, Sample 9)
Regarding the formation of the protective layer 5 in Sample 3, Sample 9 was prepared in the same manner except that the second coating solution composition and the modification treatment conditions were changed as follows.
-Second coating liquid composition A liquid obtained by diluting a 20% by mass solution of methylpolysiloxane, silica-based isopropyl alcohol, methanol, and isobutyl alcohol mixed solvent solution (Grasca HPC7003 JSR Co., Ltd.) to 10% with butanol.
-Modification treatment conditions Excimer light intensity: 130 mW / cm ² (172 nm)
Distance between sample and light source: 2mm
Stage heating temperature: 110 ° 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

(Invention, Sample 10)
Regarding the formation of the protective layer 5 in Sample 3, Sample 10 was prepared in the same manner except that the second coating solution composition and the modification treatment conditions were changed as follows.
-Second coating liquid composition Polysilsesquioxane (SR-) comprising 10% by mass dibutyl ether solution of N, N, N ', N'-tetramethyl-1,6-diaminohexane and the following structural formula (8) 13 A liquid prepared by mixing a 10% by weight methyl ethyl ketone solution (manufactured by Konishi Chemical Co., Ltd.) in a 1:99 ratio.
-Modification treatment conditions Excimer light intensity: 130 mW / cm ² (172 nm)
Distance between sample and light source: 2mm
Stage heating temperature: 105 ° C
Oxygen concentration in the irradiation device: 0.1%
Stage transport speed during excimer light irradiation: 10 mm / sec Stage transport count during excimer light irradiation: 3 reciprocations

[Second Embodiment]
(Comparative Example, Sample 11)
A sample 11 (comparative example) was prepared in the same manner except that the modification conditions of the water vapor barrier layer 4 in the sample 1 of the first example described above were changed as follows. In this sample 11, the low transmission region Rb is not formed.
-Modification treatment conditions Average excimer light intensity: 130 mW / cm ² (172 nm)
Distance between sample and light source: 3 mm
Stage heating temperature: 90 ° C
Oxygen concentration in the irradiation device: 0.2%
Stage transport speed during excimer light irradiation: 10 mm / sec Stage transport count during excimer light irradiation: 5 reciprocations

(Invention, Samples 12-16)
The sample 11 is cut into a rectangle of 10 cm × 8 cm, an excimer lamp is fixedly arranged so that the central axis of the lamp tube is arranged at a position 5 mm inside from one end of the cut sample, and the excimer lamp is turned on. Thus, the excimer light was selectively irradiated to the edge of the cut out sample to perform additional modification. By adjusting the point time of this excimer lamp, the degree of modification of the low transmission region Rb by the additional modification process was adjusted to be different.
Further, the same excimer treatment was performed on the remaining three sides, and samples having the low permeation region Rb formed by additionally modifying the entire periphery of the peripheral portion were designated as Samples 12 to 16 (present invention).
The excimer lamp lighting conditions (point time, etc.) for samples 12 to 16 are shown below.
Sample 12: 4 seconds Sample 13: 7 seconds Sample 14: 12 seconds Sample 15: 20 seconds Sample 16: 30 seconds

[Third embodiment]
(Invention, Samples 17-19)
Samples 17 to 19 (invention) were prepared in the same manner except that the edge additional modification treatment in the sample 6 of the first example described above was changed as follows.
Sample 6 is obtained by subjecting all four sides of a 10 cm × 8 cm rectangular sample to a modification treatment (see FIG. 4A).
・ Sample 17
A 10 cm × 8 cm rectangular sample not subjected to the modification treatment on one side on the 8 cm side (see FIG. 4C).
・ Sample 18
A 10 cm × 8 cm rectangular sample not subjected to the modification process on the two sides on the 8 cm side (see FIG. 4B).
・ Sample 19
In a 10 cm × 8 cm rectangular sample, no modification treatment is performed on two sides on the 8 cm side and one side on the 10 cm side (see FIG. 4E).

About the water vapor | steam barrier film samples 1-19 produced as mentioned above, the performance evaluation as a water vapor | steam barrier film was performed.
The performance evaluation of the water vapor barrier film was performed for two evaluation items of water vapor barrier property (water vapor transmission rate; WVTR) and light emission spots of the organic EL element caused by the water vapor 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 water vapor 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)
-Production of cell for evaluating water vapor barrier property Using a vacuum vapor deposition apparatus (vacuum vapor deposition apparatus JEE-400 manufactured by JEOL Ltd.), metallic calcium was deposited on the surface of the protective layer 5 of the water vapor barrier film samples 1-19. 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 water vapor barrier film surface, a sample obtained by depositing metallic calcium using a quartz glass plate having a thickness of 0.2 mm instead of the water vapor barrier film sample as a comparative sample Was stored under the same high temperature and high humidity conditions of 40 ° C. and 90% RH, and it was confirmed that no corrosion of metallic calcium occurred even after 10000 hours.
The water vapor transmission rate of the water vapor barrier film of each sample thus measured was evaluated.
Here, the water vapor transmission rate W1 of the central region Rc was measured by the above method for a 5 mm square area centered at a distance of 40 mm from the edge of each sample. Further, the water vapor transmission rate W2 of the low transmission region Rb was measured by the above method for a 5 mm square area centered at a distance of 5 mm from the edge of each sample. Each measurement was performed 10 times by sampling moving in parallel from the edge, and the average value was taken as the WVTR value.
Along with the measurement results of the water vapor transmission rates W1 and W2, the ratio of (water vapor transmission rate W1 of the central region Rc) / (water vapor transmission rate W2 of the low transmission region Rb) obtained from this measurement value is shown in Tables 1-3.

(Evaluation of organic EL elements)
The organic EL element samples using the produced water vapor barrier films of Samples 1 to 19 were evaluated for light emission spots of the organic EL elements caused by the water vapor barrier film.
First, a transparent conductive film was produced on the protective layer 5 of the produced samples 1 to 19 by the following method.
-Formation of transparent conductive film As the plasma discharge apparatus, an electrode having a parallel plate type was used, the water vapor 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 above-described water vapor 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 protective layer 5. Films 1 to 19 with transparent conductive films were obtained.
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 After 100 mm x 80 mm of the obtained samples 1-19 with a transparent conductive film was used as a barrier film substrate, and this was patterned, the barrier film substrate provided with this ITO transparent electrode was made of isopropyl alcohol. Ultrasonic cleaning and drying with dry nitrogen gas. This barrier film substrate is fixed to a substrate holder of a commercially available vacuum evaporation apparatus, while 200 mg of α-NPD (the following formula (9)) is placed in a molybdenum resistance heating boat, and the host compound is placed in another molybdenum resistance heating boat. 200 mg of CBP (the following formula (10)), 200 mg of bathocuproine (BCP (the following formula (11))) in another molybdenum resistance heating boat, and Ir-1 ( 100 mg of the following formula (12) was added, and 200 mg of Alq ₃ (the following formula (13)) was put in another molybdenum resistance heating boat, and attached to a vacuum deposition apparatus.

Next, after reducing the pressure of the vacuum chamber to 4 × 10 ⁻⁴ Pa, the heating boat containing α-NPD was energized and heated, and the deposition rate was 0.1 nm / sec. The film was vapor-deposited in an area of 80 mm × 60 mm to provide a hole transport layer. 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 1-19 using the samples 1-19 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 19 and an aluminum foil with a thickness of 100 μm face each other. Sealing was performed by adhering the four sides of the base material with a width of 10 mm through an epoxy adhesive manufactured by Chemtex.
・ Evaluation of organic EL device samples (dark spots, uneven brightness)
The encapsulated organic EL element samples 1 to 19 were energized in an environment of 40 ° C. and 90% RH, and changes in the state of light emission unevenness such as generation of dark spots from the 0th day to the 120th day were observed.
The emission unevenness of each sample observed in this way was classified into the following five stages and evaluated.
“5”: No reduction in emission area or uneven brightness is observed on the 0th day. 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 had a size (0.1 mm or less) that could not be easily observed visually.
“4”: All dark spots generated on the 0th day have a size (0.1 mm or less) that cannot be easily observed visually, and no luminance unevenness is observed. After 120 days, the non-light-emitting region was 0.5% or less of the total light-emitting area, and the generated dark spot maintained a size (0.1 mm or less) that could not be easily observed with the naked eye.
“3”: Brightness unevenness that can be visually discerned on day 0 was not observed, and all the generated dark spots had a size (0.1 mm or less) that could not be easily visually observed. After 120 days, the non-light emitting region was 1% or less of the total light emitting area.
“2”: Luminance unevenness and dark spots that were visually distinguishable were observed on the 0th day, and after 60 days, the non-light-emitting area in the peripheral area exceeded 10% of the initial total light-emitting area.
“1”: On day 0, dark spots and non-luminous areas with uneven brightness that are visually identifiable are observed to exceed 1% of the total luminous area, and within 30 days, the non-luminous area accounts for 30% of the total luminous area. Beyond.

(Durability test of water vapor barrier film)
Using each of the water vapor barrier film samples 1 to 19 which were bent 100 times at an angle of 180 degrees so as to have a radius of curvature of 10 mm, an organic EL element sample similar to the above was prepared, and its light emission By evaluating the unevenness, the durability of the water vapor barrier film (deterioration of the water vapor barrier property) was evaluated.
That is, the light emission unevenness of the organic EL element by the above-described water vapor barrier film samples 1 to 19 (before bending) and the organic EL element sample using the samples 1 to 19 repeatedly bent (after bending). Was evaluated.

  Regarding the above organic EL element evaluation results (five-step evaluation), the evaluation of samples 1 to 10 in the first embodiment is shown in Table 1, the evaluation of samples 11 to 16 in the second embodiment is shown in Table 2, and the third implementation. The evaluation of Samples 6 and 17-19 in the examples is shown in Table 3.

As shown in Table 1, this is a water vapor barrier film 10 in which a protective layer 5 is laminated on a water vapor barrier layer 4, and has a low transmission region Rb formed with a low water vapor transmission rate over the entire periphery of the peripheral portion. Even if the water vapor barrier film of the invention (samples 3 to 10) is a water vapor barrier film immediately after production (before folding) or a film obtained by repeatedly bending each water vapor barrier film sample (after folding), it is good. It can be seen that the water vapor barrier property is obtained, and the emission spots of the organic EL element are reduced as compared with the comparative examples (Samples 1 and 2).
Further, as shown in Table 2, regarding the water vapor transmission rate of the water vapor barrier film 10, the ratio of (water vapor transmission rate W1 of the central region Rc) / (water vapor transmission rate W2 of the low transmission region Rb) is 3 times or more. The water vapor barrier properties of samples (samples 12 to 15) that are less than or equal to 2 times are good, and each water vapor barrier film sample is bent repeatedly (after folding) even if it is a water vapor barrier film (before folding) just after production. Even so, it can be seen that the emission spots of the organic EL elements are reduced as compared with the comparative example (sample 11). For sample 16, the evaluation of the organic EL element after bending is slightly deteriorated. This is presumably because the hardness of the low transmission region Rb was increased due to excessive additional modification treatment, and the flexibility of the water vapor barrier film was lowered.
Furthermore, as shown in Table 3, as the low-permeation region Rb of the water vapor barrier film 10 is provided over the entire periphery (sample 6), the water vapor barrier property is better, and immediately after the production. It can be seen that even if the water vapor barrier film (before bending) or the water vapor barrier film sample repeatedly bent (after bending), the emission spots of the organic EL element are reduced. Then, after all the four sides of the water vapor barrier film sample were modified (sample 6), the water vapor barrier of the water vapor barrier film sample that was modified on three sides (sample 17). The water vapor barrier property of the water vapor barrier film sample (sample 18) that has been subjected to the modification treatment (sample 18) is also good. On the other hand, the water vapor barrier property of the sample subjected to the modification treatment only on one side of the water vapor barrier film sample (sample 19) is slightly inferior to that of the comparative water vapor barrier film having no low transmission region Rb. It can be said that the water vapor barrier property is excellent.

As mentioned above, the water vapor | steam barrier film 10 to which the additional modification process which forms the low permeable area | region Rb whose water vapor transmission rate is lower than the center side of a water vapor | steam barrier film was given to at least one part of the peripheral part of a water vapor | steam barrier film. In addition to suppressing water vapor penetration from the front surface (film surface) of the water vapor barrier film 10, water vapor permeation from the side surface (end surface) of the water vapor barrier film 10, particularly water vapor permeation in the protective layer 5 film is suppressed. Can do.
And when this water vapor | steam barrier film 10 is used for sealing of the organic EL element 7 in the organic EL panel 20, the organic EL element 7 is hardly exposed to water vapor, and the organic EL element 7 is hardly deteriorated. The organic EL panel 20 can be used for a long time, and the durability of the organic EL panel 20 can be improved.
Thus, according to this invention, the manufacturing method of the water vapor | steam barrier film 10 which has high durability and favorable water vapor | steam barrier performance is realizable, and the water vapor | steam barrier film 10 which has such outstanding performance can be obtained. Furthermore, by using the water vapor barrier film 10, an electronic device (for example, the organic EL panel 20) having excellent water vapor barrier properties can be obtained.

DESCRIPTION OF SYMBOLS 1 Base material 2 Bleed-out prevention layer 3 Smooth layer 4 Water vapor | steam barrier layer 5 Protective layer 10 (11-14) Water vapor | steam barrier film 7 Organic EL element (electronic device)
20 Organic EL panel (electronic equipment)
40 1st coating unit 50 1st drying unit 60 1st excimer processing unit 70 2nd coating unit 80 2nd drying unit 90 2nd excimer processing unit 100 Water vapor | steam barrier film manufacturing apparatus Rb Low-permeability area | region Rc Center side area | region

Claims (10)

A water vapor barrier film in which a water vapor barrier layer and a protective layer are laminated on a substrate,
A water vapor barrier film characterized by having a low-permeability region having a water vapor transmission rate lower than that at the center of the water vapor barrier film at least at a part of the peripheral edge of the water vapor barrier film.   The water vapor barrier film according to claim 1, wherein the low-permeability region is formed in at least one of the water vapor barrier layer and the protective layer.   The water vapor barrier film according to claim 1 or 2, wherein the water vapor transmission rate in the central region of the water vapor barrier film is 3 to 20 times the water vapor transmission rate in the low transmission region.   The said water vapor | steam barrier layer is a layer formed by apply | coating the coating liquid containing at least polysilazane on the said base material, and giving a predetermined modification | reformation to the dried layer. The water vapor barrier film according to claim 1.   The water vapor barrier film according to any one of claims 1 to 4, wherein the protective layer contains a metal compound containing at least one of Si, Ti, and Zr.   The said low permeable area | region is provided over the whole peripheral part of the said water vapor | steam barrier film, The water vapor | steam barrier film as described in any one of Claims 1-5 characterized by the above-mentioned.   A coating solution containing at least polysilazane is coated on the substrate and dried, and then subjected to a predetermined modification treatment to form a water vapor barrier layer. Next, at least one of Si, Ti, and Zr is formed on the water vapor barrier layer. After applying and drying a coating solution containing a metal compound containing two, a predetermined reforming treatment is performed to form a protective layer, and the water vapor barrier layer and the protection in a portion corresponding to the edge of the substrate A method for producing a water vapor barrier film, characterized in that at least one of the layers is subjected to additional modification treatment to form a low-permeability region having a lower water vapor transmission rate than other regions.   The method for producing a water vapor barrier film according to claim 7, wherein the modification treatment is heat treatment or ultraviolet irradiation treatment.   The water vapor barrier film according to any one of claims 1 to 6, or the water vapor barrier film obtained by the method for producing a water vapor barrier film according to claim 7 or 8, and an electron sealed by the water vapor barrier film. An electronic device comprising a device.   The electronic device according to claim 9, wherein the electronic device is arranged closer to a center side of the water vapor barrier film than the low transmission region of the water vapor barrier film.

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