JP5768652B2 - Barrier film manufacturing method - Google Patents

Description

The present invention relates to the production how Bas rear film.

  Conventionally, as a packaging material capable of blocking various gases, for example, a film material (aluminum deposited film) having an aluminum thin film formed on the surface has been widely used. Since this aluminum vapor deposition film is basically opaque, there is a problem that the packaged contents cannot be confirmed, and disposal after use may be a problem. Furthermore, it could not be applied at all to applications where transparency of the film material is required.

  Recently, a 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 can block various gases such as water vapor and oxygen. It is used for packaging necessary articles and packaging for preventing alteration of foods, industrial products and pharmaceuticals. Moreover, the barrier film which has a light transmittance is used also for the use which seals electronic devices, such as a liquid crystal display element, a solar cell, and an organic EL element other than a packaging use.

Transparent barrier films, which are being applied to liquid crystal display elements and solar cells, are easy to reduce weight and size, can be produced in roll-to-roll systems, and have improved gas barrier properties. As a result, demand for a transparent base material that is flexible and has a high degree of freedom in shape is increasing instead of a glass base material that is heavy and easily broken.
However, the barrier film mainly composed of a plastic material has a problem that the gas barrier property is inferior to that of a glass substrate. For example, when a barrier film is applied to the substrate of an organic EL element (organic EL panel), if the barrier film has insufficient gas barrier properties, water vapor or air will permeate and the EL material will deteriorate, resulting in performance. There is a problem that decreases with time.

By the way, as a method capable of forming a gas barrier layer by a simple coating process, a gas barrier made of a silica film is formed by modifying a coating film obtained by coating a coating liquid containing a silicon compound such as polysilazane on a substrate. Several methods for forming a layer are known (for example, see Patent Documents 1 to 4).
For example, Patent Document 2 discloses a process for modifying a polysilazane coating film into a silica film by an oxygen plasma discharge treatment under atmospheric pressure, and a gas barrier layer can be formed without requiring a vacuum process. . However, the water vapor permeability of the obtained gas barrier layer is about 0.35 g / (m ² · 24 h), which is a gas barrier property that is insufficient for application to the above-described device sealing. It was. In general, it is said that the water vapor permeability of a gas barrier layer required for sealing a device needs to be significantly lower than 1 × 10 ⁻² g / (m ² · 24 h).
Patent Document 3 and Patent Document 4 disclose a method of irradiating a polysilazane coating film with ultraviolet rays as a method of modifying polysilazane to form a dense silica film. According to this method, since the reaction is considered to proceed by direct oxidation without going through dehydration condensation, it becomes possible to convert silica at a lower temperature, which is very effective in forming a gas barrier layer on a resin film material. Can be said. However, it is in the range of several tens of nm of the surface layer that is modified to a dense silica film by ultraviolet irradiation, and a large amount of silanol is formed in the deep lower layer due to the influence of moisture contained in the coating film, resulting in a dense film structure. The current situation is not.

JP 2000-246830 A JP 2007-237588 A Japanese Patent Laid-Open No. 10-279362 JP 2008-159824 A

  As in the prior art described above, in a gas barrier layer modified by oxygen plasma discharge treatment under atmospheric pressure, or a gas barrier layer modified to a dense silica film only on the surface layer side by ultraviolet irradiation treatment, a desired high It was difficult to obtain a level of gas barrier properties.

The present invention has been made in view of the above problems, and its object is to provide a manufacturing how the barrier fill beam having a high water vapor barrier performance.

In order to solve the above problems, the invention described in claim 1
A method for producing a barrier film in which a gas barrier layer is formed on a substrate,
On the base material, a step of applying a coating liquid containing polysilazane to form a coating film;
The coating film is subjected to a process of irradiating vacuum ultraviolet light, and then the coating film is subjected to a heating process of heating at 100 ° C. or more and 250 ° C. or less under a reduced pressure of 1 Pa or more and 1000 Pa or less, and the coating film is applied to the gas barrier layer. A process of reforming;
It is characterized by providing.

According to the present invention, it is possible to obtain a preparation how the barrier fill beam having a high water vapor barrier performance.

It is explanatory drawing (a) (b) (c) (d) which shows an example of the barrier film which concerns on this invention. It is sectional drawing which shows an example of the organic electroluminescent panel which sealed the organic electroluminescent element using the 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 barrier film (10, 11, 12, 13) according to the present invention comprises at least one gas barrier layer 2 on a gas-permeable base material 1 such as a resin film, and preferably the gas barrier layer. 2 is provided with at least one protective layer 3 laminated so as to cover 2.
The gas barrier layer 2 is a layer formed by applying a coating liquid containing polysilazane, drying it, and irradiating it with vacuum ultraviolet light, followed by heat treatment at 100 ° C. or more and 250 ° C. or less. In particular, it is preferable to form the gas barrier layer 2 by irradiating the coating film with vacuum ultraviolet light and then subjecting the coating film to heat treatment under a reduced pressure of 1 Pa or more and 1000 Pa or less.
The protective layer 3 is a layer formed to protect the gas barrier layer 2.

Moreover, you may provide the smooth layer 4 and an anchor coat layer in the base-material surface as an intermediate | middle layer for improving the smoothness of the base material 1, and the adhesiveness of the gas barrier layer 2 with respect to the base material 1. FIG.
Moreover, in order to prevent the base material 1 from being scratched or soiled, a so-called bleed-out layer is suppressed so that when the base material 1 is heated, low molecular weight components such as monomers and oligomers are deposited from the inside to the surface. For this purpose, a bleed-out prevention layer 5 may be provided on the surface of the substrate.

Specifically, the barrier film 10 according to the present invention includes, for example, as shown in FIG. 1A, a base material 1, a smooth layer 4 formed on one surface of the base material 1, and a smooth layer 4. A gas barrier layer 2 laminated thereon is provided, and a bleed-out prevention layer 5 is further provided on the other surface of the substrate 1.
Moreover, as shown in FIG.1 (b), the barrier film 11 which concerns on this invention is the base material 1, the smooth layer 4 formed in the one surface of the base material 1, and the smooth layer 4, for example. A laminated gas barrier layer 2 and protective layer 3 are provided, and a bleed-out preventing layer 5 is provided on the other surface of the substrate 1.
Moreover, the barrier film 12 according to the present invention includes, for example, a base material 1, a smooth layer 4 formed on one surface of the base material 1, and the smooth layer 4 as shown in FIG. A laminated gas barrier layer 2 is provided, and further, a bleed-out preventing layer 5 formed on the other surface of the substrate 1 and a gas barrier layer 2 laminated on the bleed-out preventing layer 5 are provided.
Moreover, the barrier film 13 according to the present invention includes, for example, a base material 1, a smooth layer 4 formed on one surface of the base material 1, and the smooth layer 4 as shown in FIG. A bleed-out preventing layer 5 formed on the other surface of the substrate 1, and a gas barrier layer 2 and a protective layer laminated on the bleed-out preventing layer 5, each having a laminated gas barrier layer 2 and a protective layer 3. 3 is provided.

  Hereinafter, the structure of the barrier film (10, 11, 12, 13) of this invention is demonstrated in detail.

(Base material)
The substrate 1 in the barrier film (10, 11, 12, 13) of the present embodiment is a foldable film substrate having gas permeability and flexibility. If this base material 1 is a film-form base material which can hold | maintain the gas barrier layer 2 and the protective layer 3, it will not specifically limit.
Here, the base material 1 having gas permeability in the present invention is based on JIS standard K7129 method (temperature 40 ° C., humidity 90% RH) using PERMATRAN-W3 / 33 manufactured by MOCON according to the Mocon method. The measured water vapor transmission rate is defined as 0.5 g / m ² / day or more as measured by the Mocon method.

Examples of the resin base material applicable to the base material 1 include acrylic ester, methacrylic ester, polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polycarbonate (PC), polyarylate, polychlorinated. From resin materials such as vinyl (PVC), polyethylene (PE), polypropylene (PP), polystyrene (PS), nylon (Ny), aromatic polyamide, polyetheretherketone, polysulfone, polyethersulfone, polyimide, and polyetherimide A heat-resistant transparent film (product name: Silplus, manufactured by Nippon Steel Chemical Co., Ltd.) having a basic skeleton of silsesquioxane having an organic / inorganic hybrid structure, and two or more layers of the above film materials are laminated. Tree It can be used films or 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 base material 1 is transparent and various layers formed on the base material 1 are also transparent, a 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 gas barrier layer 2 on the surface of the base material 1 in this embodiment.
Examples of the anchor coating agent used in this anchor coat layer include polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicon resin, and alkyl titanate. One type or two or more types can be used in combination. Conventionally known additives can be added to these anchor coating agents. The anchor coat agent is coated on the substrate by a known method such as roll coat, gravure coat, knife coat, dip coat, spray coat, etc., and the solvent coat, diluent, etc. are removed by drying to remove the anchor coat layer. Can be formed.
The application amount of the anchor coating agent is preferably about 0.1 to 5 g / m ^{2 in} a dry state.

(Smooth layer)
Moreover, you may provide the smooth layer 4 in the surface of the base material 1 in this embodiment. The smooth layer 4 is formed on one surface of the substrate 1, for example.
The smooth layer 4 flattens the rough surface of the substrate 1 on which minute protrusions and the like exist, and forms unevenness and pinholes on the coating film (gas barrier layer 2) formed on the substrate 1 by protrusions on the substrate surface. Is provided to prevent the occurrence of Such a smooth layer 4 is formed, for example, by curing a photosensitive resin.
Examples of the photosensitive resin used to form the smooth layer 4 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 4 on the surface of the substrate 1 is not particularly limited. For example, a dry coating method such as a spin coating method, a spray method, a blade coating method, a wet coating method such as a dip method, or a vapor deposition method is used. It is preferably formed by a coating method.
Moreover, when forming the smooth layer 4, 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 4 and preventing the occurrence of pinholes in the film formed on the smooth layer 4.
In addition, as a solvent used when forming the smooth layer 4 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.

In addition, one of the preferred embodiments as an additive to be added when forming the smooth layer 4 is a reactive silica particle (hereinafter simply referred to as “photosensitive resin group having a photopolymerizable reactivity” introduced in 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 4 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 4 in the present embodiment preferably contains the inorganic particles as described above in a mass ratio of 20% to 60%. Adhesion with the gas barrier layer 2 is improved by adding 20% or more. On the other hand, if it exceeds 60%, the film may be bent, cracks may be generated when heat treatment is performed, and optical properties such as transparency and refractive index of the 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 4 has a thickness of 1 to 10 μm, preferably 2 to 7 μm. By setting the thickness to 1 μm or more, the smoothness of the barrier film having the smooth layer 4 can be easily improved. By setting the thickness to 10 μm or less, the balance of the optical properties of the barrier film can be easily adjusted, and the smooth layer 4 When the film is provided only on one surface of the barrier film, curling of the barrier film can be easily suppressed.

(Bleed-out prevention layer)
Moreover, you may form the bleed out prevention layer 5 in the surface of the lower surface side of the base material 1 in this embodiment.
The bleed-out prevention layer 5 is a smooth layer for the purpose of suppressing a phenomenon in which unreacted oligomers are transferred from the substrate 1 to the surface when the film having the smooth layer 4 is heated to contaminate the film surface. 4 is provided on the opposite surface of the substrate 1 having 4. The bleed-out prevention layer 5 may basically have the same configuration as the smooth layer 4 as long as it has this function.
Examples of the unsaturated organic compound having a polymerizable unsaturated group that can be included in the bleed-out preventing layer 5 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 5 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 5 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 application | coating method, and then irradiating and hardening | curing ionizing radiation. 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 5 in the present embodiment is 1 to 10 μm, preferably 2 to 7 μm. By making it 1 μm or more, it becomes easy to make the heat resistance as a barrier film sufficient, and by making it 10 μm or less, it becomes easy to adjust the balance of the optical properties of the barrier film, and the smooth layer 4 is made one of the barrier films. When it is provided on this surface, curling of the barrier film can be easily suppressed.

(Gas barrier layer)
In the present invention, as a method of forming the gas barrier layer 2 on the substrate 1 or an intermediate layer (for example, the smooth layer 4) formed on the substrate 1, a method of forming a polysilazane modified layer having a water vapor barrier property is used. Can be applied. In this method, a coating solution containing polysilazane is applied onto the substrate 1 or an intermediate layer on the substrate 1 by a wet coating method and dried to form a coating film, and the coating film is irradiated with vacuum ultraviolet light. After that, the gas barrier layer 2 is formed by converting the coating film into a polysilazane modified layer by performing a heat treatment at 100 ° C. or more and 250 ° C. or less.

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

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

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

Perhydropolysilazane is presumed to have a linear structure and a ring structure centered on 6- and 8-membered rings. Its molecular weight is about 600 to 2000 (polystyrene conversion) in terms of number average molecular weight (Mn), and there are liquid or solid substances, and the state varies depending on the molecular weight. These are marketed in a solution state dissolved in an organic solvent, and the commercially available product can be used as it is as a polysilazane-containing coating solution.
As another example of polysilazane which becomes ceramic at low temperature, a silicon alkoxide-added polysilazane obtained by reacting a silicon alkoxide with a polysilazane having a main skeleton composed of a unit represented by the general formula (1) (for example, Japanese Patent Laid-Open No. Hei. No. 5-238827), glycidol-added polysilazane obtained by reacting glycidol (for example, see JP-A-6-122852), and alcohol-added polysilazane obtained by reacting alcohol (for example, JP-A-6-240208). Gazette), metal carboxylate-added polysilazanes obtained by reacting metal carboxylates (for example, see JP-A-6-299118), and acetylacetonate complexes obtained by reacting metal-containing acetylacetonate complexes Additional polysilazanes (for example, See JP -306329), a metal fine metal particles added polysilazane obtained by adding (e.g., JP-see JP 7-196986), and the like.

As the organic solvent for preparing the coating liquid containing polysilazane, it is not preferable to use an alcohol or water-containing one that easily reacts with polysilazane. Therefore, specifically, hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons, halogenated hydrocarbon solvents, ethers such as aliphatic ethers and alicyclic ethers can be used. . Specifically, there are hydrocarbons such as pentane, hexane, cyclohexane, toluene, xylene, solvesso and turben, halogen hydrocarbons such as methylene chloride and trichloroethane, ethers such as dibutyl ether, dioxane and tetrahydrofuran. These organic solvents may be selected according to characteristics such as the solubility of polysilazane and the evaporation rate of the organic solvent, and a plurality of organic solvents may be mixed.
The polysilazane concentration in the polysilazane-containing coating solution varies depending on the film thickness of the target polysilazane modified layer and the pot life of the coating solution, but is preferably about 0.2 to 35% by mass.
In the polysilazane-containing coating solution, an amine or metal catalyst may be added to promote conversion to a silicon oxide compound. Specific examples include Aquamica NAX120-20, NN110, NN310, NN320, NL110A, NL120A, NL150A, NP110, NP140, and SP140 manufactured by AZ Electronic Materials.

In the polysilazane modified layer formed by the polysilazane-containing coating solution used in the present invention, it is preferable that the amount of moisture contained before or during the modification treatment is controlled.
Examples of the supply of moisture that can enter the polysilazane modified 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 base material side into the polysilazane modified layer is to store the base material in a constant temperature and humidity environment before applying the polysilazane-containing coating solution, and control the water content to a desired value. be able to. 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 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 high from the viewpoint of rapid processing. Although it is preferable, it is preferable to appropriately determine the temperature and the processing time in consideration of thermal damage to the substrate 1 that is a resin film. For example, when a polyethylene terephthalate substrate having a glass transition temperature (Tg) of 70 ° C. is used as the substrate 1, the heat treatment temperature can be set to 150 ° C. or less.
The atmosphere in the step of applying and drying the polysilazane-containing coating solution on the substrate is preferably controlled to relatively low humidity, but the humidity in a low-humidity environment varies with temperature, so the relationship between temperature and humidity is the dew point. A preferred form is indicated by the definition of 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 Pa.

(Polysilazane modification treatment / vacuum ultraviolet irradiation treatment)
The polysilazane modification treatment in the present invention refers to a reaction in which part or all of the polysilazane compound is converted into silicon oxide or silicon oxynitride.
For this modification treatment, a known method based on the conversion reaction of polysilazane can be selected. For example, 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, when producing the barrier film of the present invention, it is preferable to use an ultraviolet light irradiation treatment capable of a conversion reaction at a lower temperature 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 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 substrate 1 carrying the polysilazane layer which is the coating film before the irradiation 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, a metal halide lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a xenon arc lamp, a carbon arc lamp, an excimer lamp, and a UV light laser. In addition, when the polysilazane layer before modification is irradiated with the generated ultraviolet light, the polysilazane before modification is reflected after reflecting the ultraviolet light from the generation source with a reflector from the viewpoint of improving efficiency and uniform irradiation. It is desirable to hit the layer.
The ultraviolet irradiation can be adapted to both batch processing and continuous processing, and can be appropriately selected depending on the shape of the substrate 1 to be used. When the base material 1 having the polysilazane modified layer is in the form of a long film, it is converted into ceramics by continuously irradiating ultraviolet rays in the drying zone having the ultraviolet ray generation source as described above while being conveyed. be able to. The time required for ultraviolet irradiation is generally 0.1 seconds to 10 minutes, preferably 0.5 seconds to 3 minutes, although depending on the composition and concentration of the substrate 1 and polysilazane modified layer to be used.
Moreover, it is preferable that oxygen concentration at the time of irradiating with vacuum ultraviolet light (VUV) is 300 ppm to 10000 ppm (1%), and more preferably 500 ppm to 5000 ppm. By adjusting to such an oxygen concentration range, it is possible to prevent the formation of the oxygen-excess gas barrier layer 2 and to prevent the 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 first modification treatment step in the treatment for modifying the polysilazane layer (coating film) in the present invention is a step of irradiating vacuum ultraviolet light. The treatment of irradiation with vacuum ultraviolet light uses light energy with a wavelength of 100 to 200 nm, preferably light energy with a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in the polysilazane compound. This is a modification process that advances the oxidation reaction with active oxygen or ozone while cutting directly by the action of photons, called a process for forming a silicon oxide film at a relatively low temperature by the light energy of vacuum ultraviolet light. Is the method. 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 that it is easy to receive the influence of a heat | fever.

(Polysilazane modification and heat treatment)
In the present invention, the second modification treatment step in the treatment for modifying the polysilazane layer (coating film) is a heat treatment step performed after vacuum ultraviolet light irradiation (after the first modification treatment step).
By performing a heat treatment at 100 ° C. or more and 250 ° C. or less on the polysilazane layer after the vacuum ultraviolet light irradiation treatment, the gas barrier layer 2 having a low moisture permeability and an excellent water vapor barrier property can be formed.

The polysilazane layer that has been subjected to the vacuum ultraviolet light irradiation treatment in the first modification treatment step is modified, and in particular, the surface of the polysilazane layer is modified so as to have a denser structure.
By heating the polysilazane layer whose surface has been modified to a dense structure to 100 ° C. or higher, the water permeability of the polysilazane layer (gas barrier layer 2) is further reduced, and the water vapor barrier property is improved. However, it became clear as a result of earnest research by the inventor.
This is because the polysilazane layer formed on the surface with a dense film having a low moisture permeability by the vacuum ultraviolet light irradiation treatment was heated at 100 ° C. or more, so that the internal moisture contained in the polysilazane layer was expanded. It is presumed that the internal pressure of the layer was increased, the silanol condensation reaction in the polysilazane layer was advanced, and the modification was advanced, so that the inside of the polysilazane layer was modified into a dense structure.
Note that when the polysilazane layer is heated to a temperature higher than 250 ° C., the contained moisture rapidly expands, causing damage such as cracks in the polysilazane layer (gas barrier layer 2), increasing the moisture permeability and increasing the water vapor barrier. Therefore, the heat treatment is preferably performed at 100 ° C. or more and 250 ° C. or less. More preferably, it is 100 degreeC or more and 200 degrees C or less, More preferably, it is 100 degreeC or more and 180 degrees C or less.
The heat treatment time is preferably 10 minutes or more and 5 hours or less, more preferably 30 minutes or more and 2 hours or less.
Further, when the heat treatment at 100 ° C. or higher and 250 ° C. or lower is performed on the polysilazane layer after the vacuum ultraviolet light irradiation treatment, the heat treatment may be performed under atmospheric pressure, but the heat treatment is preferably performed under reduced pressure.
The degree of vacuum and vacuum during the heat treatment is, for example, 1 × 10 ⁻⁴ to 1 × 10 ⁴ Pa, preferably 1 × 10 ⁻² to 1 × 10 ³ Pa, more preferably 1 to 1 × 10 ³ Pa. It is.

  The heat treatment for modifying the polysilazane layer (coating film) may be performed before the formation of the protective layer 3, or after the formation of the protective layer 3, the polysilazane layer (coating film) and the protective layer 3 are both formed. You may make it heat.

(Protective layer)
In the present invention, as a method for forming the protective layer 3 on the gas barrier layer 2, a method for forming a polysiloxane modified layer can be applied. In this method, a polysiloxane-containing coating solution is applied onto the gas barrier layer 2 by a wet coating method and dried, and then the dried coating film is irradiated with vacuum ultraviolet light to form a polysiloxane modified layer. This is a method of forming the protective layer 3.
The coating liquid used for forming the protective layer 3 in the present invention mainly contains polysiloxane and an organic solvent.

The polysiloxane applicable to the formation of the protective layer 3 is not particularly limited, but an organopolysiloxane represented by the following general formula (2) is particularly preferable.
In the present embodiment, an organopolysiloxane represented by the general formula (2) will be described as an example of polysiloxane.

In the general formula (2), R ^{3 to} R ⁸ each represent the same or different organic group having 1 to 8 carbon atoms. R ^{3 to} R ⁸ include either an alkoxy group or a hydroxyl group. m is 1 or more.
Examples of the organic group having 1 to 8 carbon atoms represented by R ^{3 to} R ⁸ include halogenated alkyl groups such as γ-chloropropyl group and 3,3,3-trifluoropropyl group, vinyl group, and phenyl group. , (Meth) acrylic acid ester groups such as γ-methacryloxypropyl group, epoxy-containing alkyl groups such as γ-glycidoxypropyl group, mercapto-containing alkyl groups such as γ-mercaptopropyl group, γ-aminopropyl group, etc. Isocyanate-containing alkyl groups such as aminoalkyl groups and γ-isocyanatopropyl groups, linear or branched alkyl groups such as methyl groups, ethyl groups, n-propyl groups and isopropyl groups, alicyclic alkyl groups such as cyclohexyl groups and cyclopentyl groups Group, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, etc. Group, an acetyl group, a propionyl group, a butyryl group, valeryl group, etc. acyl group such as caproyl group.
Further, in the present invention, in the general formula (2), an organopolysiloxane in which m is 1 or more and the weight average molecular weight in terms of polystyrene is 1,000 to 20,000 is particularly preferable. If the weight average molecular weight in terms of polystyrene of the organopolysiloxane is 1000 or more, the protective layer to be formed is hardly cracked and water vapor barrier properties can be maintained, and if it is 20,000 or less, it is formed. Curing of the protective layer is sufficient, so that sufficient hardness can be obtained as the protective layer obtained.

  Examples of the organic solvent applicable to the formation of the protective layer 3 include alcohol solvents, ketone solvents, amide solvents, ester solvents, aprotic solvents, and the like.

  Here, as alcohol solvents, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, n-pentanol, iso-pentanol, 2-methylbutanol, sec- Pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene Glycol monobutyl ether and the like are preferable.

  Examples of ketone solvents include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl. In addition to ketones, di-iso-butyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone, fenchon, acetylacetone, 2,4-hexanedione, 2 , 4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4-nonanedione, 3,5-nonanedione, 5-methyl-2,4-hexanedione, 2,2,6,6-tetramethyl 3,5-heptanedione, 1,1,1,5,5,5 beta-diketones such as hexafluoro-2,4-heptane dione and the like. These ketone solvents may be used alone or in combination of two or more.

  Examples of amide solvents include formamide, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-ethylacetamide N, N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N-formylpyrrolidine, N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine, etc. Can be mentioned. These amide solvents may be used alone or in combination of two or more.

  Examples of ester solvents include diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, iso-propyl acetate, n-butyl acetate, and iso acetate. -Butyl, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-acetate -Nonyl, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, acetic acid Diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, diacetic acid Glycol, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, iso-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate , Diethyl malonate, dimethyl phthalate, diethyl phthalate and the like. These ester solvents may be used alone or in combination of two or more.

  As aprotic solvents, acetonitrile, dimethyl sulfoxide, N, N, N ′, N′-tetraethylsulfamide, hexamethylphosphoric triamide, N-methylmorpholone, N-methylpyrrole, N-ethylpyrrole, N -Methylpiperidine, N-ethylpiperidine, N, N-dimethylpiperazine, N-methylimidazole, N-methyl-4-piperidone, N-methyl-2-piperidone, N-methyl-2-pyrrolidone, 1,3-dimethyl Examples include 2-imidazolidinone and 1,3-dimethyltetrahydro-2 (1H) -pyrimidinone. The above organic solvents can be used alone or in combination of two or more.

  In the present invention, the organic solvent used for forming the protective layer 3 is preferably an alcohol solvent among the above organic solvents.

  Examples of the method for applying the coating solution for forming the protective layer include spin coating, dipping, roller blades, and spraying methods.

As thickness of the protective layer 3 formed with the coating liquid for protective layer formation, the range of 100 nm-10 micrometers is preferable. When the thickness of the protective layer 3 is 100 nm or more, barrier properties under high humidity can be ensured. Moreover, if the film thickness of the protective layer 3 is 10 micrometers or less, the coating property stable at the time of protective layer formation can be obtained, and high light transmittance can be implement | achieved.
The protective layer 3 has a film density of usually 0.35 to 1.2 g / cm ³ , preferably 0.4 to 1.1 g / cm ³ , more preferably 0.5 to 1.0 g / cm ³ . ³ . If the film density is 0.35 g / cm ³ or more, sufficient mechanical strength of the coating film can be obtained.

In the protective layer 3 of the present invention, a coating solution containing polysiloxane is applied onto the gas barrier layer 2 by a wet coating method and dried, and then the dried coating film (polysiloxane coating film) is irradiated with vacuum ultraviolet light. To form.
As the vacuum ultraviolet light used for the formation of the protective layer 3, vacuum ultraviolet light by the same vacuum ultraviolet light irradiation treatment as described in the formation of the gas barrier layer 2 can be applied.
In the present invention, the integrated light quantity of vacuum ultraviolet light when forming the protective layer 3 by reforming polysiloxane membrane, 500 mJ / cm ² or more, preferably 10,000 / cm ² or less . A sufficient barrier performance can be obtained if the accumulated amount of vacuum ultraviolet light is 500 mJ / cm ² or more, and if it is 10,000 mJ / cm ² or less, a protective layer having high smoothness without deforming the substrate. 3 can be formed.

  Moreover, it is preferable that the protective layer 3 in this invention is formed through the heating process whose heating temperature is 50 degreeC or more and 200 degrees C or less. If the heating temperature is 50 ° C. or higher, sufficient barrier properties can be obtained, and if it is 200 ° C. or lower, the protective layer 3 having high smoothness can be formed without deforming the substrate 1. A heating method using a hot plate, an oven, a furnace, or the like can be applied to this heating step. Further, the heating atmosphere may be any condition such as air, nitrogen atmosphere, argon atmosphere, vacuum, or reduced pressure with controlled oxygen concentration.

The protective layer 3 covers the gas barrier layer 2 and has a function of preventing the gas barrier layer 2 in the barrier film from being damaged, but the gas barrier layer 2 is damaged in the manufacturing process of the barrier film. It can also be prevented.
For example, a polysiloxane coating film is formed on the unmodified polysilazane coating film formed when the gas barrier layer 2 is formed, and the polysilazane coating film and the polysiloxane coating film are simultaneously irradiated with vacuum ultraviolet light, and then heated to 100 ° C. You may make it form the gas barrier layer 2 and the protective layer 3 by performing the heat processing above 250 degreeC. In addition, a polysiloxane coating film is formed on the polysilazane coating film that has been subjected to the vacuum ultraviolet light irradiation treatment, and after the vacuum ultraviolet light irradiation treatment is applied to the polysiloxane coating film, a heat treatment of 100 ° C. or higher and 250 ° C. or lower is performed. And the gas barrier layer 2 and the protective layer 3 may be formed.
As described above, when the heat treatment at 100 ° C. or higher is performed with the polysilazane coating film (gas barrier layer 2) covered with the protective layer 3 (polysiloxane coating film), the gas barrier layer is caused by the thermal stress caused by the heat treatment. It is possible to prevent the occurrence of minute cracks in 2 and to stabilize the water vapor barrier performance of the gas barrier layer 2.

(Organic EL panel as an electronic device)
The barrier film 10 (11, 12, 13) 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 the barrier film 10 as a sealing film is shown in FIG.
As shown in FIG. 2, the organic EL panel 20 includes a barrier film 10, a transparent electrode 6 such as ITO formed on the barrier film 10, and an organic EL formed on the barrier film 10 via the transparent electrode 6. An element 7 and a counter film 9 disposed via an adhesive layer 8 so as to cover the organic EL element 7 are provided. It can be said that the transparent electrode 6 forms part of the organic EL element 7.
The transparent electrode 6 and the organic EL element 7 are formed on the surface of the barrier film 10 (11) on which the gas barrier layer 2 (or the protective layer 3) is formed.
The counter film 9 may be a barrier film according to the present invention in addition to a metal film such as an aluminum foil. When a barrier film is used for the counter film 9, the surface on which the gas barrier layer or the protective layer 3 is 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 barrier film 10 (11, 12, 13) 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 and 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, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used. In addition, inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material.
The hole transport layer can be formed by thinning the hole transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. it can. Although there is no restriction | limiting in particular about the film thickness of a positive hole transport layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5-200 nm. The hole transport layer may have a single layer structure composed of one or more of the above materials.

(Electron transport layer)
The electron transport layer is made of an electron transport material having a function of transporting electrons, and in a broad sense, an electron injection layer and a hole blocking layer are also included in the electron transport layer. The electron transport layer can be provided as a single layer or a plurality of layers.
The electron transport material only needs to have a function of transmitting electrons injected from the cathode to the light emitting layer, and the material can be selected and used from conventionally known compounds. Examples include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, and the like. Furthermore, in the above oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, 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 (11) so as to have a film thickness of 1 μm or less, preferably 10 to 200 nm, such as vapor deposition, sputtering, plasma CVD, etc. The anode is prepared by the method.
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 positive polarity of the anode and the negative polarity of the cathode. Luminescence can be observed by applying. An alternating voltage may be applied. The alternating current waveform to be applied may be arbitrary.

  Hereinafter, although the specific example is given and the 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.

Example 1
In Example 1, a barrier film having the same layer configuration as that of the barrier film 10 shown in FIG. 1 (a) was produced and evaluated.
[Preparation of Barrier Film 1-1]
<Production of base material>
As a heat-resistant substrate, a 200 μm thick transparent polyimide film (manufactured by Mitsubishi Gas Chemical Co., Ltd., Neoprim L) with easy-adhesion processing on both sides is used. As shown below, both sides of the substrate are smooth. What formed the layer was made into the barrier base material.

<< Smooth layer formation and barrier substrate preparation >>
<Preparation of smooth layer coating solution>
8.0 g of trimethylolpropane triglycidyl ether (Epolite 100MF manufactured by Kyoeisha Chemical Co., Ltd.), 5.0 g of ethylene glycol diglycidyl ether (Epolite 40E manufactured by Kyoeisha Chemical Co., Ltd.), silsesquioxane having an oxetanyl group: OX-SQ- 12.0 g of H (manufactured by Toagosei Co., Ltd.), 32.5 g of 3-glycidoxypropyltrimethoxysilane, 2.2 g of Al (III) acetylacetonate, methanol silica sol (manufactured by Nissan Chemical Co., Ltd., solid content concentration 30) (Mass%) is 134.0 g, BYK333 (BIC Chemie Japan Co., Ltd., silicon surfactant) 0.1 g, butyl cellosolve 125.0 g, 0.1 mol / L hydrochloric acid aqueous solution 15.0 g is mixed sufficiently. Was stirred. This was further left standing and deaerated at room temperature to obtain a smooth layer coating solution.

<Formation of first smooth layer>
After applying a corona discharge treatment to one surface side of the heat-resistant substrate by a conventional method, the smooth layer coating solution is applied under the condition that the film thickness after drying is 4.0 μm, and then 3 ° C. at 80 ° C. Dried for minutes. Furthermore, the heat treatment for 10 minutes was performed at 120 degreeC, and the 1st smooth layer was formed.
<Formation of second smooth layer>
A second smooth layer was formed on the surface of the heat resistant substrate opposite to the surface on which the first smooth layer was formed in the same manner as the first smooth layer forming method. In other words, a barrier substrate is formed by forming smooth layers on both sides of a heat-resistant substrate. It can be said that one of the first smooth layer and the second smooth layer is a bleed-out prevention layer.
And as a result of measuring the surface roughness of the formed 1st smooth layer and 2nd smooth layer based on the method prescribed | regulated by JISB0601, it was about 20 nm in Rz. The surface roughness was measured using an AFM (Atomic Force Microscope) SPI3800N DFM manufactured by SII. The measurement range at one time was 80 μm × 80 μm, and the measurement location was changed, and the measurement was performed three times. The average of the Rz values obtained in each measurement was taken as the measurement value.

<Formation of gas barrier layer>
A coating solution containing the following polysilazane compound was applied onto the barrier substrate, formed into a dry film thickness of 150 nm using a spin coater, and dried at 100 ° C. for 2 minutes to form a polysilazane coating film. Then, the process which irradiates a vacuum ultraviolet light to a coating film with the following method was given, and the barrier film 1-1 was obtained.

<Preparation of polysilazane compound-containing coating solution>
Dibutyl ether solution containing 20% by mass of non-catalyzed perhydropolysilazane (Aquamica NN120-20 manufactured by AZ Electronic Materials Co., Ltd.) and 20% by mass of perhydropolysilazane containing 5% by mass of amine catalyst in solid content The solution (Aquamica NAX120-20 manufactured by AZ Electronic Materials Co., Ltd.) was mixed and used to adjust the amine catalyst to a solid content of 1% by mass, and then diluted with dibutyl ether to give a total solid content of 10%. A polysilazane compound-containing coating solution was prepared as a% dibutyl ether solution.

<Vacuum ultraviolet light irradiation treatment>
The polysilazane coating film was modified by subjecting the sample after the coating film was dried to vacuum ultraviolet light irradiation treatment with the following apparatus and conditions.
・ 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: 0.2%
Stage transfer speed during excimer light irradiation: 10 mm / sec Stage transfer count during excimer light irradiation: 6 reciprocations

[Preparation of Barrier Film 1-2]
A barrier substrate similar to the barrier film 1-1 was used.
The above-mentioned polysilazane compound-containing coating solution was applied onto the barrier substrate, formed into a dry film thickness of 150 nm using a spin coater, and dried at 100 ° C. for 2 minutes to form a polysilazane coating film.
Subsequently, the polysilazane coating film was subjected to a heat treatment at 200 ° C. for 1 hour, and then subjected to a vacuum ultraviolet light irradiation treatment by the method described above to obtain a barrier film 1-2.

[Preparation of Barrier Films 1-3 to 1-9]
Similarly to the barrier film 1-1, a polysilazane compound-containing coating solution was applied on the barrier substrate to form a polysilazane coating, and the polysilazane coating was irradiated with vacuum ultraviolet light, and then the temperatures shown in Table 1, Under the conditions of pressure (degree of vacuum), heat treatment using a vacuum oven was performed for 1 hour to obtain barrier films 1-3 to 1-9.

(Evaluation of barrier film)
About the barrier film samples 1-1 to 1-9 produced as described above, performance evaluation as a barrier film was performed.
Regarding the performance evaluation of the barrier film, the moisture permeability of each sample (1-1 to 1-9) was measured as an evaluation of the water vapor barrier property.

In evaluating the water vapor barrier property, the following apparatuses and materials were used.
<Device used>
Vapor deposition apparatus: Vacuum vapor deposition apparatus JEE-400 manufactured by JEOL Ltd.
Constant temperature and humidity oven: Yamato Humidic Chamber IG47M
<Evaluation materials>
Metal that reacts with water and corrodes: Calcium (granular)
Water vapor-impermeable metal: Aluminum (φ3-5mm, granular)
<Preparation of water vapor barrier property sample>
Using a vacuum vapor deposition apparatus (JEE-400), metallic calcium was vapor-deposited with a size of 12 mm × 12 mm through the mask on the surface of the gas barrier layer of the produced barrier film (Samples 1-1 to 1-9).
Thereafter, the mask was removed in a vacuum state, and aluminum was vapor-deposited on the entire surface of one side of the sheet to perform temporary sealing. Next, the vacuum state is released, quickly transferred to a dry nitrogen gas atmosphere, and a quartz glass with a thickness of 0.2 mm is bonded to the aluminum deposition surface via an ultraviolet curing resin for sealing (manufactured by Nagase ChemteX). A sample for water vapor barrier property evaluation was prepared by irradiating ultraviolet rays to cure and adhere the resin to perform main sealing.
Then, using a constant temperature and humidity oven, the obtained sample for evaluation was stored under high temperature and high humidity of 40 ° C. and 90% RH, and based on the method described in JP 2005-283561 A, the corrosion amount of metallic calcium From this, the amount of moisture permeated into the cell was calculated, and the moisture permeability was measured.
In addition, in order to confirm that there is no permeation of water vapor from other than the barrier film surface, instead of the barrier film sample as a comparative sample, a sample obtained by depositing metallic calcium using a quartz glass plate having a thickness of 0.2 mm, Similarly, it was stored under high temperature and high humidity at 40 ° C. and 90% RH, and it was confirmed that no corrosion of metallic calcium occurred even after 10,000 hours.
In this example, based on the moisture permeability of sample 1-1, the ratio of the moisture permeability value of each sample to the reference value was obtained and shown in Table 1.

As is clear from the evaluation results shown in Table 1, compared with a barrier film (sample 1-1) having a gas barrier layer subjected only to vacuum ultraviolet light irradiation treatment, heat treatment was performed before vacuum ultraviolet light irradiation treatment. It can be seen that (sample 1-2) and the sample subjected to low-temperature heat treatment after vacuum ultraviolet light irradiation treatment (sample 1-3) have almost no change in moisture permeability. In addition, in the sample subjected to high-temperature heat treatment after the vacuum ultraviolet light irradiation treatment (Sample 1-4), a significant increase in moisture permeability, which was considered to be caused by damage such as cracks, was observed in the gas barrier layer.
On the other hand, as in the present invention, after the vacuum ultraviolet light irradiation treatment to the polysilazane coating film, the barrier fill beam forming the gas barrier layer is subjected to heat treatment at 100 ° C. or higher 250 ° C. or less, the moisture permeability It can be seen that the water vapor barrier property was improved. In addition, in the case where the heat treatment after the vacuum ultraviolet light irradiation treatment was performed under reduced pressure (Samples 1-7, 1-8, 1-9), the water permeability was further reduced, and the water vapor barrier property was further improved. I understand that.

(Example 2)
In Example 2, a barrier film having the same layer structure as that of the barrier film 12 shown in FIG. 1C was prepared and evaluated.
[Preparation of Barrier Film 2-1]
Using the same barrier substrate as the barrier film 1-1, after forming the gas barrier layer on one surface of the barrier substrate in the same manner as the barrier film 1-1, the other surface of the barrier substrate Similarly, a gas barrier layer was formed to obtain a barrier film 2-1.

[Preparation of barrier films 2-2 to 2-6]
After forming a gas barrier layer on both sides of the barrier substrate in the same manner as the barrier film 2-1, heat treatment using a vacuum oven is performed for 1 hour under the conditions of temperature and pressure (degree of vacuum) shown in Table 2. Barrier films 2-2 to 2-6 were obtained.

(Evaluation of barrier film)
The barrier film samples 2-1 to 2-6 produced as described above were evaluated for performance as a barrier film.
Regarding the performance evaluation of the barrier film, the water permeability of each sample (2-1 to 2-6) was measured by the same method as in Example 1 described above as an evaluation of the water vapor barrier property.
In this example, based on the moisture permeability of the sample 2-1, the ratio of the moisture permeability value of each sample to the reference value was obtained and shown in Table 2.

As is clear from the evaluation results shown in Table 2, even in the case of a barrier film in which a gas barrier layer is provided on both surfaces of a base material, a barrier film having a gas barrier layer subjected only to vacuum ultraviolet light irradiation treatment (Sample 2- Compared to 1), it can be seen that the moisture permeability was hardly changed in the sample subjected to the low-temperature heat treatment after the vacuum ultraviolet light irradiation treatment (sample 2-2). In addition, in the sample subjected to high-temperature heat treatment after the vacuum ultraviolet light irradiation treatment (Sample 2-3), a significant increase in water permeability, which was considered to be caused by damage such as cracks, occurred in the gas barrier layer.
On the other hand, as in the present invention, the after vacuum ultraviolet light irradiation treatment to the polysilazane coating film, barrier film formed of the gas barrier layer is subjected to heat treatment at 100 ° C. or higher 250 ° C. or less (specimen 2 -6) It can be seen that the water permeability is lowered and the water vapor barrier property is improved. In particular, since the rate of reduction in moisture permeability is greater than the results shown in Table 1, the barrier film having gas barrier layers formed on both sides of the base material has even better water vapor barrier performance. I understand.

(Example 3)
In Example 3, a barrier film having the same layer structure as that of the barrier film 13 shown in FIG. 1 (d) was produced and evaluated.
[Preparation of Barrier Film 3-1]
A barrier substrate similar to the barrier film 1-1 was used, and after forming a gas barrier layer on one surface of the barrier substrate by the same method as the barrier film 1-1 described above, a protective layer was formed by the following method. Formed. Subsequently, after the gas barrier layer and the protective layer were similarly laminated on the other surface of the barrier substrate, heat treatment was performed at 200 ° C. and 100 Pa for 1 hour to obtain a barrier film 3-1.
<Formation of protective layer>
On the gas barrier layer, a coating solution containing the following polysiloxane compound is applied using a spin coater under the condition that the dry film thickness is 1 μm, and dried at 120 ° C. for 2 minutes to form a polysiloxane coating film. did. Thereafter, the polysiloxane coating film was irradiated with vacuum ultraviolet light under the following conditions to form a protective layer.
<Preparation of polysiloxane compound-containing coating solution>
“Glaska HPC7003” and “Glaska HPC404H” manufactured by JSR Corporation are mixed at a ratio of 10: 1. The mixed solution was diluted 2-fold with butanol, and a solution obtained by adding 5% of butyl cellosolve to the mixed solution was used as a coating solution (coating solution having a solid content of 10%).
<Vacuum ultraviolet irradiation treatment>
The polysiloxane coating film was subjected to the vacuum ultraviolet irradiation treatment in the same manner except that the number of stage conveyances in the vacuum ultraviolet light irradiation treatment for the polysilazane coating film was changed to 2 reciprocations.

(Evaluation of barrier film)
About the barrier film sample 3-1 produced as mentioned above, the performance evaluation as a barrier film was performed.
Ten samples 3-1 of this barrier film were prepared, and the moisture permeability of sample 3-1 was measured by the same method as in Example 1 described above. As a result, it was confirmed that the 10 samples of Sample 3-1 showed that Ca corrosion progressed uniformly, and the variation in water permeability of each sample was within 5%.
On the other hand, when 10 samples of the barrier film sample 2-6 were prepared and the same measurement was performed, an event in which rapid Ca corrosion progressed from a specific position in 2 samples in 10 samples was confirmed. The variation in water permeability of each sample was as large as 30% or more.
As is clear from these results, a barrier film provided with a protective layer covering the gas barrier layer suppresses variation in moisture permeability more than a barrier film having the gas barrier layer disposed on the outermost surface. It can be seen that the water vapor barrier performance of the barrier film is stable.

Example 4
In Example 4, an organic EL element / organic EL panel using a barrier film having the same layer configuration as that of the barrier film 13 shown in FIG.
In this example, the barrier film 3-1 of Example 3 and the barrier film 3-2 that was not subjected to heat treatment at 200 ° C. and 100 Pa × 1 hour in the production process of the barrier film 3-1, An organic EL element / organic EL panel was produced.

  A transparent conductive film was produced on the barrier layers of the barrier film 3-1 and the barrier film 3-2 by the following methods. In addition, the sample which produced the transparent conductive film on the protective layer of the barrier film 3-1 becomes a sample 4-1, and the sample which produced the transparent conductive film on the protective layer of the barrier film 3-2 becomes a sample 4-2.

-Formation of transparent conductive film As the plasma discharge apparatus, an electrode having a parallel plate type was used. The 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 barrier film is subjected to atmospheric pressure plasma treatment, and a tin-doped indium oxide (ITO) film is formed to a thickness of 100 nm on the protective layer. Samples 4-1 and 4-2 with a transparent conductive film 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 The obtained samples 4-1 and 4-2 with a transparent conductive film were used as a substrate of 100 mm x 100 mm, patterned, and then the barrier film substrate provided with the ITO transparent electrode was isopropyl. It was ultrasonically cleaned with alcohol and dried with dry nitrogen gas. This transparent support substrate is fixed to a substrate holder of a commercially available vacuum deposition apparatus, while 200 mg of α-NPD (the following formula (3)) is put in a molybdenum resistance heating boat, and the host compound is put in another molybdenum resistance heating boat. 200 mg of CBP (the following formula (4)), 200 mg of bathocuproine (BCP (the following formula (5))) in another molybdenum resistance heating boat, and Ir-1 ( 100 mg of the following formula (6) was put, and 200 mg of Alq ₃ (the following formula (7)) was put in another resistance heating boat made of molybdenum, and attached to a vacuum deposition apparatus.

Next, after reducing the vacuum tank to 4 × 10 ⁻⁴ Pa, the heating boat containing α-NPD is heated by heating, vapor-deposited on a transparent support substrate at a vapor deposition rate of 0.1 nm / second, and hole transport A layer was provided.
Further, the heating boat containing CBP and Ir-1 was energized and heated, and co-evaporated on the hole transport layer at a deposition rate of 0.2 nm / second and 0.012 nm / second, respectively, to provide a light emitting layer. . In addition, the substrate temperature at the time of vapor deposition was room temperature.
Further, the heating boat containing BCP was energized and heated, and was deposited on the light emitting layer at a deposition rate of 0.1 nm / second to provide a hole blocking layer having a thickness of 10 nm.
Further, the heating boat containing Alq ₃ is further heated by energization, and is deposited on the hole blocking layer at a deposition rate of 0.1 nm / second to further provide an electron transport layer having a thickness of 40 nm. It was. In addition, the substrate temperature at the time of vapor deposition was room temperature.
Subsequently, lithium fluoride 0.5 nm and aluminum 110 nm were vapor-deposited to form a cathode, and organic EL element samples 4-1 and 4-2 were prepared using samples 4-1 and 4-2 with transparent conductive films, respectively. did.

-Sealing of organic EL element sample In an environment purged with nitrogen gas (inert gas), the aluminum vapor deposition surface of organic EL element samples 4-1 and 4-2 faces an aluminum foil with a thickness of 100 μm. Then, it was sealed using an epoxy adhesive manufactured by Nagase ChemteX Corporation.

-Evaluation of organic EL element sample The encapsulated organic EL element samples 4-1 and 4-2 were energized in an environment of 40 ° C and 90% RH, and the size of the non-light-emitting portion after 120 days was measured.
As a result, the size of the non-light emitting part of the organic EL element sample 4-1 is 1/10 or less than the size of the non-light emitting part of the organic EL element sample 4-2, and the organic EL using the barrier film 3-1. It was confirmed that the element sample 4-1 had light emission characteristics superior in dark spot resistance and luminance unevenness resistance than the organic EL element sample 4-2 using the barrier film 3-2.
That is, even when the barrier film is used in an electronic device, it has been found that there is utility in performing a heat treatment on the gas barrier layer of the barrier film.

  As described above, the barrier film according to the present invention was subjected to a heat treatment of 100 ° C. or more and 250 ° C. or less after irradiating the coating film formed by applying the coating liquid containing polysilazane with vacuum ultraviolet light. Since the gas barrier layer 2 having a reduced water permeability is provided, it can be used as a barrier film having high water vapor barrier performance.

  The application of the present invention is not limited to the above-described embodiment, and can be appropriately changed without departing from the spirit of the present invention.

DESCRIPTION OF SYMBOLS 1 Base material 2 Gas barrier layer 3 Protective layer 4 Smooth layer 5 Bleed-out prevention layer 7 Organic EL element (electronic device)
10-13 Barrier film 20 Organic EL panel (electronic equipment)

Claims (1)

A method for producing a barrier film in which a gas barrier layer is formed on a substrate,
On the base material, a step of applying a coating liquid containing polysilazane to form a coating film;
The coating film is subjected to a process of irradiating vacuum ultraviolet light, and then the coating film is subjected to a heating process of heating at 100 ° C. or more and 250 ° C. or less under a reduced pressure of 1 Pa or more and 1000 Pa or less, and the coating film is applied to the gas barrier layer. A process of reforming;
A method for producing a barrier film, comprising:

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