JP2003118030A - Gas-barrier organic base material and electroluminescent element using the base material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic base material having a gas-barrier coat excellent in gas-barrier properties to various gases such as oxygen and water vapor and an EL element using the base material. SOLUTION: A gas-barrier later (A) is formed at least on one surface of the organic base material, and a cured substance layer (B) of a cured coating composition (b) containing polysilazane is formed on the surface of the layer (A) by a wet method to obtain the gas-barrier organic base material. The base material is used for the substrate and/or the protective layer of the EL element.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic base material having a gas barrier film having excellent barrier properties against various gases such as oxygen or water vapor, and an electroluminescence device using the same.

[0002]

2. Description of the Related Art Electroluminescent devices (hereinafter referred to as
Electroluminescence is called EL. In order to protect the EL layer from moisture and oxidation, a glass excellent in gas barrier property is generally used for), but since glass is weak against impact and heavy, an organic substrate having gas barrier property is used as a substitute for it. (In the present invention, a gas barrier organic base material) is used.

As the gas-barrier organic base material used for a display device such as an EL device, a physical method such as a vacuum deposition method or a sputtering method or a CV is used on the surface of the organic base material.
A gas barrier film (for example, a metal oxide film) formed by a vapor phase method such as a chemical method such as D is widely used.

[0004]

However, although the gas barrier coating formed by the dry method as described above has a high gas barrier property of the coating itself, microscopic cracks and pinholes are easily generated in the coating, There is a problem that the gas barrier property is deteriorated.

It is an object of the present invention to provide an organic base material having a gas barrier coating excellent in barrier properties against various gases such as oxygen or water vapor, and an EL element using the organic base material with little deterioration in light emission characteristics. .

[0006]

To achieve the above object, one of the present inventions is to provide a gas barrier layer (A) formed on at least one surface of an organic base material in order from the base material side by a dry method. And a cured product layer (B) made of a cured product of the coating composition (b) containing a polysilazane formed by a wet method, and a gas barrier organic substrate.

In this gas barrier organic substrate, a cured product layer (B) made of a cured product of the coating composition (b) containing polysilazane is formed on the surface of the gas barrier layer (A) formed by the dry method. Therefore, defects such as pinholes generated in the gas barrier layer (A) are filled with the coating composition (b), and the gas barrier property can be improved. Further, since the coating composition (b) is cured at a low temperature, has a low curing shrinkage rate, and has a high density of the cured product, cracks and the like hardly occur even if the film thickness is increased, and a cured product layer ( B) shows an excellent gas barrier property, and due to the synergistic effect with the gas barrier layer (A), a further excellent gas barrier property can be expressed.

In the above invention, it is preferable that the coating composition (b) contains a compound having at least one active energy ray-curable polymerizable functional group. According to this aspect, since the flexibility of the cured product layer (B) is increased, even if the thickness of the cured product layer (B) is increased, the flexibility of the organic base material is not impaired, and the bending resistance is improved. Can be improved.

Another aspect of the present invention is to cover an EL layer, electrodes provided on both sides of the EL layer, a substrate arranged to cover one electrode, and another electrode. An EL element having a laminated structure including a disposed protective layer, wherein the substrate and / or the protective layer is the gas barrier organic base material.

Since this EL element uses the above gas barrier organic base material for the substrate and / or the protective layer, it is less susceptible to moisture or oxygen, so that the light emitting characteristics are less deteriorated.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The gas barrier organic substrate of the present invention comprises a gas barrier layer (A) formed by a dry method on at least one surface of an organic substrate in order from the substrate side.
And a cured product layer (B) made of a cured product of the coating composition (b) containing polysilazane formed by a wet method.

The substrate and each layer will be described in more detail below. The organic base material used in the present invention is not particularly limited, but since it is transparent and easily available,
A base material made of one selected from a thermoplastic norbornene-based resin, an aromatic polycarbonate resin, a polymethylmethacrylate resin or a polyethylene terephthalate resin is preferable. Further, it is also possible to use two or more kinds of base materials made of one kind selected from each of the above resins, and use a base material obtained by laminating them. In the present invention, a base material made of a thermoplastic norbornene resin is particularly preferable because it has a low birefringence and a low water absorption.

The thickness of the above-mentioned organic base material can be appropriately selected depending on the application, but is preferably 0.1 to 2 mm when it is used as a substrate of an EL element, and is 0.1 mm when used as a protective layer.
05-1 mm is preferable.

Next, the gas barrier layer (A) will be described. In the present invention, the type of the gas barrier layer (A) formed by the dry method is not particularly limited, but from the viewpoint of transparency and gas barrier property, a silicon oxynitride film, a silica film, an alumina film, a silica-alumina composite film or diamond-like carbon. It is preferable to include one or more films selected from the film.

For example, the silicon oxynitride film is preferably oxygen-rich from the viewpoint of transparency, but is preferably nitrogen-rich from the viewpoint of gas barrier property. Therefore, the ratio of oxygen (oxygen atom / (oxygen atom + nitrogen atom)) is preferably 100/0 to 40/60, particularly 50/50.
-80/20 is preferable. The thickness of the silicon oxynitride film is preferably 400 nm or less from the viewpoint of gas barrier properties and cracks,
Particularly, 100 to 250 nm is more preferable.

The silica film is a silicon oxide film, and the preferable film thickness is the same as that of the above-mentioned silicon oxynitride film.

The alumina film is dense and has a high gas barrier property, but cracks easily occur.
100 nm is preferable, and 20 to 50 nm is particularly preferable.

A silica-alumina composite film combining the fineness of alumina and the flexibility of silica is more preferable because it has high transparency, gas barrier property and flexibility. The ratio of alumina (silica / alumina) is 70/30 to 90 by mass ratio.
/ 10 is preferable. The film thickness is preferably 50 to 300 nm, and particularly preferably 100 to 200 nm.

The diamond-like carbon film has an excellent gas barrier property, but since the color absorption is strong, the film thickness is preferably 20 to 200 nm, particularly preferably 20 to 100 nm.

The dry method for forming the gas barrier layer (A) is not particularly limited, and a vapor deposition method, a CVD method, a sputtering method or the like can be adopted. In the present invention, a CVD method or a sputtering method that can obtain a denser film at a low temperature is preferably adopted.

Next, the coating composition (b) will be described. In the following description, the acryloyl group and the methacryloyl group are collectively referred to as a (meth) acryloyl group, and the expressions (meth) acryloyloxy group, (meth) acrylic acid, (meth) acrylate and the like are also the same.

The polysilazane contained in the coating composition (b) is preferably the polysilazane described in paragraph Nos. 0097 to 0104 of JP-A No. 11-240103. In the present invention, perhydropolysilazane is preferable, and its molecular weight is preferably 200 to 50,000 in terms of number average molecular weight. If the number average molecular weight is less than 200, it is difficult to obtain a uniform cured product even after firing, and if it exceeds 50,000, it is difficult to dissolve in a solvent, which is not preferable.

The coating composition (b) preferably contains a compound having one or more active energy ray-curable polymerizable functional groups (hereinafter referred to as active energy ray-curable component). Of the active energy ray-curable components, the compound having one polymerizable functional group capable of being polymerized by active energy rays (hereinafter, simply referred to as a monofunctional compound) is preferably a compound having a (meth) acryloyl group, A compound having an acryloyl group is particularly preferable. In addition, it may have a functional group such as a hydroxyl group and an epoxy group. Preferred examples of the monofunctional compound include the following.

Alkyl (meth) acrylate (wherein the alkyl group has 1 to 13 carbon atoms), allyl (meth) acrylate, benzyl (meth) acrylate, butoxyethyl (meth) acrylate, butanediol (meth) acrylate, butoxytriethylene glycol. Mono (Meta)
Acrylate, t-butylaminoethyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth)
Acrylate, 2-cyanoethyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 2,3-dibromopropyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl ( (Meth) acrylate,

N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2 (2-ethoxyethoxy) ethyl (meth) acrylate, 2- Ethylhexyl (meth) acrylate, glycerol (meth) acrylate, glycidyl (meth)
Acrylate, heptadecafluorodecyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyltrimethylammonium chloride, 2-hydroxypropyl (meth) acrylate, isobornyl (meth) acrylate , 3- (meth) acryloyloxypropyltrimethoxysilane, 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, methoxydipropylene Glycol (meth) acrylate, methoxylated cyclodecatriene (meth) acrylate,

Morpholine (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, nonylphenoxy polypropylene glycol (meth) acrylate, octafluoropentyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, phenoxyethyl (meth) acrylate,
Phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxy (meth) acrylate,
Polypropylene glycol (meth) acrylate, sodium sulfonate (meth) acrylate sulfonate, tetrafluoropropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, trifluoroethyl (meth) acrylate, vinyl acetate, N-vinylcaprolactam, N- Vinylpyrrolidone, N-vinylformamide, morpholino (meth) acrylate, 2-morpholinoethyl (meth) acrylate.

Among the active energy ray-curable components,
The compound having two or more active energy ray-curable polymerizable functional groups (hereinafter, simply referred to as a polyfunctional compound) is described, for example, in paragraphs 0016 to 0020 and 0023 to 0047 of JP-A No. 11-240103. The compound mentioned above is included. Preferred polyfunctional compounds include compounds having two or more (2 to 50 are preferable, and 3 to 30 are preferable) one or more kinds of polymerizable functional groups selected from (meth) acryloyl groups. Among them, a compound having two or more (meth) acryloyloxy groups, that is, a polyester of (meth) acrylic acid and a compound having two or more hydroxyl groups such as polyhydric alcohol is preferable. Further, it may be a compound having various functional groups or bonds other than the above-mentioned polymerizable functional groups. In particular, a (meth) acryloyl group-containing compound having a urethane bond (hereinafter referred to as acrylic urethane) and a (meth) acrylic acid ester compound having no urethane bond are preferable.

The above-mentioned acrylic urethane is an acrylic urethane which is a reaction product of pentaerythritol or polypentaerythritol which is a multimer thereof, polyisocyanate and hydroxyalkyl (meth) acrylate, and which is active energy ray-curable and polymerizable. 3 functional groups
A polyfunctional compound having one or more (more preferably 4 to 20) or a hydroxyl group-containing poly (meth) acrylate of pentaerythritol or polypentaerythritol,
A polyfunctional compound which is an acrylic urethane which is a reaction product with a polyisocyanate and which has 3 or more (more preferably 4 to 20) active energy ray-curable polymerizable functional groups can be mentioned.

Examples of the (meth) acrylic acid ester compound having no urethane bond include pentaerythritol type poly (meth) acrylate and isocyanurate type poly (meth) acrylate. The pentaerythritol-based poly (meth) acrylate is a polyester of pentaerythritol or polypentaerythritol and (meth) acrylic acid (preferably having 4 to 20 active energy ray-curable polymerizable functional groups). Say. In addition, isocyanurate poly (meta)
Acrylate is a polyester of (meth) acrylic acid and a compound obtained by adding 1 to 6 mol of caprolactone or alkylene oxide to 1 mol of tris (hydroxyalkyl) isocyanurate or tris (hydroxyalkyl) isocyanurate. (Preferably having 2 to 3 active energy ray-curable polymerizable functional groups).

In the present invention, the above-mentioned preferred polyfunctional compounds and polyfunctional compounds having two or more other active energy ray-curable polymerizable functional groups (particularly poly (meth) acrylate of polyhydric alcohol). You may use together with.

The proportion of the monofunctional compound or the polyfunctional compound in the active energy ray-curable component is not particularly limited.

The proportion of the active energy ray-curable component in the coating composition (b) is preferably 60% by mass or less in order to improve the gas barrier property.

The coating composition (b) may contain a solvent and various functional compounding agents in addition to the above basic components.

Examples of the solvent include hydrocarbons, hydrogen halides, ethers, esters and ketones, with xylene or dibutyl ether being particularly preferred. As the solvent, a plurality of kinds of solvents may be mixed and used in order to adjust the solubility of polysilazane and the evaporation rate of the solvent. The amount of the solvent used varies depending on the coating method used, the structure of polysilazane, the average molecular weight, and the like, but it is preferable to prepare the solvent so that the solid content concentration is 0.5 to 80% by mass.

The functional compounding agents include photopolymerization initiators, adhesion promoters, ultraviolet absorbers, light stabilizers, antioxidants, thermal polymerization inhibitors, leveling agents, defoamers, thickeners, At least one selected from an anti-settling agent, a dispersant and a curing catalyst can be used.

Examples of the photopolymerization initiator include arylketone photopolymerization initiators (for example, acetophenones, benzophenones, alkylaminobenzophenones, benzyls, benzoins, benzoin ethers, benzyldimethylketals, benzoylbenzoates, α). -Acyloxime esters, etc.), sulfur-containing photopolymerization initiators (for example, sulfides, thioxanthones, etc.), acylphosphine oxide photopolymerization initiators, diacylphosphine oxide photopolymerization initiators, and other photopolymerization initiators. Can be mentioned. Specifically, JP-A-11-240103
The compounds described in paragraph Nos. 0081 to 0085 of the publication are listed. In the present invention, an acylphosphine oxide photopolymerization initiator is particularly preferable. A plurality of types of photopolymerization initiators may be used in combination, and a photosensitizer such as amines may be used in combination.

The amount of the photopolymerization initiator used is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the total amount of the polysilazane and the active energy ray-curable component.

Examples of the adhesion-imparting agent include silane coupling agents. As the ultraviolet absorber, a benzotriazole-based ultraviolet absorber, which is used as a synthetic resin ultraviolet absorber, a benzophenone-based ultraviolet absorber,
Salicylic acid-based UV absorbers, phenyltriazine-based UV absorbers and the like are preferable. Specifically, JP-A-11-2
The compound described in paragraph No. 0093 of 40103 is mentioned. In the present invention, 2- {2-hydroxy-5- (2-acryloyloxyethyl) phenyl} benzotriazole, 2-hydroxy-3-methacryloyloxypropyl-3- {3- (benzotriazol-2-yl)- Particularly preferred are those having a polymerizable functional group in the molecule, such as 4-hydroxy-5-t-butylphenyl} propionate.

The light stabilizer is preferably a hindered amine light stabilizer used as a light stabilizer for synthetic resins. Specific examples thereof include the compounds described in paragraph No. 0094 of JP-A No. 11-240103. In the present invention, 1,2,2,6,6-pentamethyl-
A compound having a polymerizable functional group in the molecule, such as 4-piperidyl methacrylate, is particularly preferable.

Examples of the antioxidant include hindered phenolic antioxidants such as 2,6-di-t-butyl-p-cresol and phosphorus antioxidants such as triphenylphosphite. Examples of the leveling agent include silicone resin-based leveling agents and acrylic resin-based leveling agents.

Examples of the defoaming agent include silicone resin defoaming agents such as polydimethylsiloxane. Examples of the thickener include polymethylmethacrylate-based polymers, hydrogenated castor oil-based compounds, and fatty acid amide-based compounds.

The thickness of the cured product layer (B) comprising the cured product of the coating composition (b) is preferably 0.005 to 2 μm, and particularly preferably 0.5 to 1 μm. If the thickness of the cured product layer (B) is less than 0.005 μm, sufficient gas barrier properties cannot be obtained, and if it exceeds 2 μm, a coating film with good appearance without cracks cannot be obtained, which is not preferable.

The coating composition (b) is added to the gas barrier layer (A).
There is no particular limitation on the method of coating the surface of the above, and a known wet method can be adopted. For example, dip method, float coating method, spraying method, bar coating method, gravure coating method, roll coating method, blade coating method, air knife coating method, spin coating method, die coating method, slit coating method, micro gravure coating method, etc. Various methods can be adopted. In the present invention, the spin coating method or the spraying method is preferable in the case of the sheet method from the viewpoint of productivity and the surface appearance, and the die coating method or the gravure coating method is preferably used in the case of continuous coating.

The polysilazane contained in the coating composition (b) may be cured by irradiating with active energy rays after coating, heating, leaving at room temperature, or exposing to the vapor of a curing catalyst solution of polysilazane. Can be adopted. In the present invention, from the viewpoint of heat resistance of the base material, the temperature is 120 ° C.
It is preferable that the polysilazane is cured by firing below. In order to cure the polysilazane at a low temperature, it is preferable to add a catalyst to the coating composition (b), and it is preferable to use a catalyst that can be cured at a lower temperature. Depending on the type and amount of the catalyst, it can be fired at a lower temperature, and in some cases, can be cured at room temperature. Examples of such a catalyst include gold and silver described in JP-A-7-196986.
Examples thereof include fine particles of metals such as palladium, platinum and nickel, carboxylic acid complexes of the metals described in JP-A-5-93275, and amines and acids described in JP-A-9-31333.

The particle size of the fine metal particles is preferably smaller than 0.1 μm, and more preferably smaller than 0.05 μm to ensure the transparency of the cured product. Further, the smaller the particle size, the larger the specific surface area and the higher the catalytic activity. Therefore, it is preferable to use a catalyst having a smaller particle size from the viewpoint of improving the catalytic performance.

Examples of the above amines include monoalkylamine, dialkylamine, trialkylamine,
Examples include monoarylamine, diarylamine, cyclic amine and the like. Examples of the acids include organic acids such as acetic acid and inorganic acids such as hydrochloric acid.

When the fine particles of the above-mentioned metal are added to the coating composition (b) in advance as a catalyst, the addition amount thereof is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass based on 100 parts by mass of polysilazane. Parts by mass are preferred. If the amount added is less than 0.01 parts by mass, a sufficient catalytic effect cannot be expected, and if it exceeds 10 parts by mass, the catalysts tend to agglomerate and the transparency may be impaired.

The amines and acids may be added to the coating composition (b) in advance, and the coating composition (b) may be used.
After coating, it may be brought into contact with a solution of amines or acids (including an aqueous solution) or a vapor thereof (including a vapor from an aqueous solution).

The atmosphere in which oxygen is present, such as air, is preferable as the atmosphere for curing. By firing, nitrogen atoms of polysilazane are replaced with oxygen atoms to generate silica, so that a dense silica layer can be formed by firing in an atmosphere in which sufficient oxygen exists.

JP-A-11-181290 describes that curing of polysilazane is accelerated by irradiation with an active energy ray in the presence of a photoradical generator. By optimizing the irradiation conditions of the rays, even when the above catalyst is not included, curing can be performed with active energy rays.

The active energy ray for curing the active energy ray-curable component contained in the coating composition (b) is not particularly limited, and ultraviolet rays, electron rays and other active energy rays can be used. In the present invention, ultraviolet rays are preferred. As the ultraviolet ray source, a xenon lamp, a pulse xenon lamp, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a carbon arc lamp, a tungsten lamp, etc. can be used.

The gas barrier organic base material of the present invention can be produced, for example, as follows. That is, after forming the gas barrier layer (A) on at least one surface of the organic substrate by a dry method, the coating composition (b) is applied on the surface by a wet method to cure the coating composition (b). Let In addition, when the coating composition (b) contains a solvent, it is preferable to cure after removing the solvent after coating.

The gas-barrier organic base material of the present invention can be used in various applications requiring gas barrier properties, and is preferably used, for example, as a substrate and / or protective layer of an EL device. When used as a substrate of an EL device, the gas barrier organic base material is preferably transparent.

Next, the EL device of the present invention will be described. The EL device of the present invention comprises an EL layer, electrodes provided on both sides of the EL layer, a substrate arranged to cover one electrode, and a protective layer arranged to cover the other electrode. In the EL element having a laminated structure including the above, the gas barrier organic base material is used for the substrate and / or the protective layer.

1 and 2 show an embodiment E of the present invention.
A schematic view of a cross section of the L element is shown. As shown in FIG. 1, in the organic EL element 1, a laminated structure 7 composed of a transparent electrode 3 (anode), an organic light emitting material layer 4 and a cathode 5 is formed on one surface of a substrate 2 composed of the gas barrier organic base material. Has been done. Then, the protective layer 6 made of the gas barrier organic base material is laminated by a method such as thermocompression bonding or thermal fusion so as to cover the laminated structure 7. As shown in FIG. 2, the laminated structure 7 has a gas barrier layer (A) 2b and a cured product layer (B) 2c formed on the surface of the organic base material 2a.
Is formed on the gas barrier film. In addition, the protective layer 6 is laminated such that a gas barrier coating composed of a gas barrier layer (A) 6b and a cured product layer (B) 6c formed on the surface of the organic base material 6a is in contact with the laminated structure 7. .

In the present invention, known materials can be used for the transparent electrode 3, the organic light emitting material layer 4 and the cathode 5, respectively, and a known method can be adopted for forming them. The laminated structure 7 may further include a hole injection layer and an electron injection layer.

[0057]

EXAMPLES The present invention will be described below based on Examples 1 to 7, but the present invention is not limited to these. As examples of the organic base material, in Examples 1 and 5, a thermoplastic saturated norbornene-based resin film (thickness 100 μm, trade name “ZEONOR 142” was used.
0R ", manufactured by Zeon Corporation), and in Example 2, a polycarbonate film (thickness 100 μm) manufactured by a casting method.
m), a PET film (thickness 12 μm, trade name “Ecosiar” manufactured by Toyobo Co., Ltd.) on which a composite vapor-deposited film of alumina silica is formed in Example 3, and PET films (thickness 100 μm, trade name in Examples 4 and 6). “A4300”, manufactured by Toyobo Co., Ltd.) was used. Further, the gas permeability and the like of the samples obtained in each example were measured by the following methods, and the results are shown in Table 1.

[Oxygen permeability] Oxygen permeability (cc / m ² ·
24 hr.atm) at 25 ° C. and 100 RH% atmosphere for measuring oxygen permeability (model “MOCON OXTRAN”).
10 / 40A ", manufactured by Modern Control Co., Ltd.).

[Water vapor permeability] Water vapor permeability (g / m ²
・ 24 hr) was measured at 40 ° C. in an atmosphere of 90 RH% using a water vapor permeability measuring device (model “PERMATRAN W6”, manufactured by Modern Control Co., Ltd.).

[Measurement of transmittance] Luminous transmittance (light wavelength 400
The average reflectance at 800 nm) was measured.

[Example 1] In order to improve adhesion, the surface of the organic base material was oxygen-sputtered, and then silicon carbide was formed as a primer layer. After that, silicon nitride was used as a sputtering target, and argon and oxygen were introduced as a deposition gas to form a silicon oxynitride film with a thickness of 100 nm, whereby a base material A was obtained.

A solution of perhydropolysilazane in dibutyl ether (solid content: 20%) was formed on the surface of the silicon oxynitride film of the substrate A.
Mass%, trade name "L120", manufactured by Clariant Japan Co., Ltd.) was applied by a spin coating method, and was held in a hot air circulation oven at 80 ° C. for 10 minutes to remove the solvent.
It was kept in a hot air circulation oven at 0 ° C. for 120 minutes to be sufficiently cured, and thus a base material B on which a film having a film thickness of 0.4 μm was formed was obtained.

[Example 2] In order to improve adhesion, the surface of the organic base material was oxygen-sputtered, and then silicon carbide was formed as a primer layer. After that, silicon oxide was used as a sputtering target, and argon and oxygen were introduced as a film forming gas to form a silicon dioxide film with a thickness of 200 nm, whereby a base material C was obtained.

On the surface of the silicon dioxide film of the base material C, a solution of perhydropolysilazane in dibutyl ether (solid content: 20
Mass%, trade name "L120", manufactured by Clariant Japan Co., Ltd.) was applied by a spin coating method, and was held in a hot air circulation oven at 80 ° C. for 10 minutes to remove the solvent.
The substrate was held in a hot air circulation oven at 0 ° C. for 120 minutes to be sufficiently cured to obtain a substrate D having a film having a thickness of 0.3 μm formed thereon.

[Example 3] Organic substrate (hereinafter referred to as substrate E)
Was coated with a solution of perhydropolysilazane in dibutyl ether (solid content: 20% by mass, trade name "D120", manufactured by Clariant Japan Co., Ltd.) by a spin coating method in a hot air circulating oven at 50 ° C. 1
After holding it for 0 minutes to remove the solvent, it was held in a humid heat oven at 60 ° C. and 90 RH% for 120 minutes to be sufficiently cured to obtain a substrate F on which a film having a thickness of 0.1 μm was formed.

[Example 4] 2 equipped with a stirrer and a cooling pipe
In a 00 mL four-necked flask, 15 g of xylene, dipentaerythritol hexaacrylate, 2-methyl-1.
1-g of-(4-methylthiophenyl) -2-morpholino-propan-1-one and 4 g of dipentaerythritol hexaacrylate were added and dissolved. Subsequently, 80 g of a xylene solution of perhydropolysilazane (solid content 20% by mass, manufactured by Clariant Japan Co., Ltd., trade name "V110") was added, and stirred at room temperature for 1 hour under a nitrogen atmosphere to obtain a coating liquid 1.

On the other hand, a diamond-like carbon film having a thickness of 30 nm was formed on the surface of the organic base material by a plasma CVD method to obtain a base material G. The conditions of the plasma CVD method are as follows.
Using methane gas and argon gas as raw material gas,
RF power 250W, chamber pressure 0.9 Tor
It was performed as r.

The coating liquid 1 is applied to the surface of the diamond-like carbon film of the base material G by spin coating,
After being kept in a hot air circulation oven at 60 ° C. for 10 minutes to remove the solvent, it was irradiated with ultraviolet rays of 500 mJ / cm ² using a high pressure mercury lamp and sufficiently cured to form a film having a film thickness of 2 μm. Material H was obtained.

Example 5 A solution of perhydropolysilazane in dibutyl ether (solid content 20% by mass, manufactured by Clariant Japan, trade name "L120") is provided on one side of an organic substrate.
Was applied by a spin coating method and kept in a hot air circulation oven at 80 ° C. for 10 minutes to remove the solvent, and then 120 ° C.
It was held in the hot-air circulation oven for 120 minutes to be sufficiently cured to obtain a substrate I having a coating film with a thickness of 0.4 μm.

[Example 6] Coating liquid 1 was applied to one surface of an organic substrate by spin coating, kept in a hot air circulation oven at 60 ° C for 10 minutes to remove the solvent, and then a high pressure mercury lamp was used. Then, it was sufficiently cured by irradiating it with ultraviolet rays of 500 mJ / cm ² to obtain a base material J on which a film having a film thickness of 2 μm was formed.

[0071]

[Table 1]

Example 7 On the surface of the substrate B obtained in Example 1 on which the gas barrier film was formed, an anode made of translucent ITO was vapor-deposited so as to form an electrode pattern. On its surface, a hole injection layer made of copper phthalocyanine, TP
A hole transport layer composed of D (triphenylamine derivative),
Light emitting layer made of Alq ₃ (aluminum chelate complex), Li ₂
An electron injection layer made of O (lithium oxide) was deposited. Further, a cathode made of Al was vapor-deposited on this surface and patterned so as to face the electrode pattern of the anode.

Without exposing the laminated structure on the surface of the base material B thus obtained to the atmosphere, another base material B
The gas barrier coating was laminated so as to be in contact with the laminated structure and thermocompression bonded at 120 ° C. to produce an organic EL device.

A direct current voltage was applied between both electrodes of the obtained organic EL device, and the initial emission brightness measured by a brightness meter was 200
The emission luminance was measured after 35 hours and 70 hours, respectively, by continuously emitting light in an atmosphere of 20 ° C. and 80 RH% at cd / m ² . As a result, it was confirmed that stable light emission characteristics were maintained even in the high humidity atmosphere as described above, and the reliability was extremely high.

[0075]

The gas-barrier organic substrate of the present invention comprises a cured product layer (B) made of a cured product of the coating composition (b) containing polysilazane on the surface of the gas barrier layer (A) formed by the dry method. ) Is formed, defects such as pinholes in the gas barrier layer (A) are filled with the coating composition (b), and the gas barrier property can be improved. Further, since the coating composition (b) is cured at a low temperature, has a low curing shrinkage rate, and has a high density of the cured product, cracks and the like hardly occur even if the film thickness is increased, and a cured product layer ( B) exhibits excellent gas barrier properties, and the synergistic effect with the gas barrier layer (A) allows the gas barrier organic base material of the present invention to exhibit gas barrier properties equivalent to those of glass.

In addition, the EL device of the present invention is not affected by moisture or oxygen by using the above gas-barrier organic base material, and the light emitting characteristics are not deteriorated.

[Brief description of drawings]

FIG. 1 is a schematic view showing a cross section of an EL device which is an embodiment of the present invention.

FIG. 2 is an enlarged schematic view of a cross section of the EL element shown in FIG.

[Explanation of symbols]

1 Organic EL element 2 substrates 2a, 6a Organic base material 2b, 6b Gas barrier layer (A) 2c, 6c cured product layer (B) 3 transparent electrodes 4 Organic light emitting material layer 5 cathode 6 protective layer 7 Laminated structure

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Hiroshi Yamamoto             1150 Hazawa-machi, Kanagawa-ku, Yokohama-shi, Kanagawa             Asahi Glass Co., Ltd. (72) Inventor Hirokazu Wakabayashi             1150 Hazawa-machi, Kanagawa-ku, Yokohama-shi, Kanagawa             Asahi Glass Co., Ltd. F-term (reference) 2K009 CC24 CC42 DD02 EE00                 3K007 AB11 AB13 AB17 BA07 BB00                       CA06 CB01 DB03 EB00 FA02                 4F100 AK01A AK02 AK42 AK45                       AK52C AK52E AK79C AK79E                       AR00B AR00D AT00A BA03                       BA05 BA06 BA07 BA10C                       BA10E EH46 EH462 EH66                       EH662 EJ42 EJ422 EJ86                       EJ862 GB41 JD02 JD02B                       JD02D

Claims (3)

[Claims] 1. A coating composition (b) containing, on at least one surface of an organic substrate, a gas barrier layer (A) formed by a dry method and a polysilazane formed by a wet method in order from the substrate side. And a cured product layer (B) composed of the cured product. 2. The gas barrier organic substrate according to claim 1, wherein the coating composition (b) contains a compound having at least one active energy ray-curable polymerizable functional group. 3. An electroluminescent layer, electrodes provided on both sides of the electroluminescent layer, a substrate provided so as to cover one electrode, and a protective layer provided so as to cover the other electrode. In the electroluminescent element having a laminated structure consisting of, the substrate and / or the protective layer is the gas barrier organic base material according to claim 1 or 2.