JP2003118029A - 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 which is excellent in adhesion to the base material and in gas-barrier properties to various gases such as oxygen and steam and an EL element using the base material. SOLUTION: A cured substance layer (A) of a cured coating composition (a) containing polysilazane is formed at least on one surface of the organic base material, and a gas-barrier layer (C) is formed on the surface of the layer (A) by a dry 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 substrate having a gas barrier coating which has excellent adhesion to an organic substrate and excellent barrier properties against various gases such as oxygen or water vapor, and an electro substrate using the same. It relates to a luminescence element.

[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, the gas barrier film formed by the dry method as described above has a high gas barrier property of the film itself, but the gas barrier property is not sufficient because the adhesiveness to the organic substrate is not sufficient. There was a problem that lowers. Further, when the organic base material is bent, there is a problem that the gas barrier coating is easily peeled off from the organic base material.

The present invention has an organic base material having a gas barrier coating excellent in adhesion to an organic base material and excellent in barrier properties against various gases such as oxygen or water vapor, and deterioration of light emission characteristics using the same. An object is to provide a small number of EL elements.

[0006]

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

The above gas barrier organic substrate is a gas barrier formed by a dry method on the surface of the organic substrate through a cured product layer (A) made of a cured product of a coating composition (a) containing polysilazane. Since it has the layer (C), the cured product layer (A) functions as a base film of the gas barrier layer (C), and the adhesiveness between the organic base material and the gas barrier layer (C) is excellent. Further, since the coating composition (a) is cured at a low temperature, has a low curing shrinkage rate, and has a high density of the cured product, the cured product layer (A) formed of the cured product exhibits excellent gas barrier properties, and the gas barrier layer ( An excellent gas barrier property is exhibited by the synergistic effect with C).

The gas barrier organic substrate of the present invention is a coating containing a compound having at least one active energy ray-curable polymerizable functional group between the organic substrate and the cured product layer (A). It is preferable to have an underlayer (B) made of a cured product of the composition (b). According to this aspect, the underlayer (B)
Since the cured product layer (A) is formed through the adhesive, the adhesiveness between the organic base material and the cured product layer (A) can be further enhanced. Therefore, the adhesiveness between the organic base material and the gas barrier layer (C) Can be further improved.

Further, the coating composition (a) preferably contains a compound having at least one active energy ray-curable polymerizable functional group. According to this aspect, the adhesion of the cured product layer (A) to the organic base material and the gas barrier layer (C) can be further improved. Further, since the flexibility of the cured product layer (A) is increased, even if the cured product layer (A) is thickened, the flexibility of the organic base material is not impaired, and the bending resistance 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 the EL element uses the gas-barrier organic base material for the substrate and / or the protective layer, it is not easily affected by moisture or oxygen, so that the light emitting characteristics are less deteriorated.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The gas barrier organic substrate of the present invention is a cured product of a cured product of a coating composition (a) containing polysilazane on at least one surface of the organic substrate in order from the substrate side. It has a layer (A) and a gas barrier layer (C) formed by a dry method.

The gas barrier organic substrate is a coating composition containing a compound having at least one active energy ray-curable polymerizable functional group between the organic substrate and the cured product layer (A). It is preferable to have an underlayer (B) made of the cured product of (b).

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 it is used as a protective layer.
05-1 mm is preferable.

Next, the coating composition (a) 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.

Preferred examples of the polysilazane contained in the coating composition (a) include the polysilazanes 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 (a) 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 compound and a polyfunctional compound 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 ratio of the monofunctional compound or the polyfunctional compound in the active energy ray-curable component is not particularly limited.

The proportion of polysilazane (polysilazane / (polysilazane + active energy ray-curable component)) in the coating composition (a) is set so as to improve the gas barrier property.
It is preferably 40% by mass or more.

The coating composition (a) 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 type photopolymerization initiators (for example, acetophenones, benzophenones, alkylaminobenzophenones, benzyls, benzoins, benzoin ethers, benzyl dimethyl ketals, benzoyl benzoates, 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, and particularly 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 and the like. 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 antioxidants 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 (A) composed of the cured product of the coating composition (a) is preferably 0.005 to 2 μm, and particularly preferably 0.5 to 1 μm. If the thickness of the cured product layer (A) 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.

Next, the coating composition (b) will be described. As the active energy ray-curable component contained in the coating composition (b), the same compounds as those described in the coating composition (a) are preferably used.

Further, the coating composition (b) may contain, in addition to the above-mentioned basic components, the same solvent as that described in the coating composition (a) and various functional compounding agents.

In the present invention, it is preferable to include a photopolymerization initiator in order to efficiently cure the active energy ray-curable component.

The thickness of the underlayer (B) formed of the cured product of the coating composition (b) is preferably 0.5 to 20 μm, and particularly 2 to
10 μm is preferable. The thickness of the underlayer (B) is 0.5 μ
If it is less than m, sufficient adhesion to the organic base material and the cured product layer (A) cannot be obtained, and if it exceeds 20 μm, the flexibility is lowered, which is not preferable.

The method for applying the coating compositions (a) and (b) onto the surface of the organic base material is not particularly limited, and known methods 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.

As a method for curing the polysilazane contained in the coating composition (a), after coating, irradiation with active energy rays, heating, leaving at room temperature, or exposure to vapor of a curing catalyst solution of polysilazane is carried out. 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 (a), 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 in order 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 (a) as a catalyst in advance, the addition amount thereof is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass with respect to 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 above amines and acids may be added to the coating composition (a) in advance and 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 promoted 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 rays for curing the active energy ray-curable components contained in the coating compositions (a) and (b) are not particularly limited, and ultraviolet rays, electron beams or other active energy rays are used. it can. 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.

Next, the gas barrier layer (C) will be described. In the present invention, the type of the gas barrier layer (C) 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. These coatings have excellent adhesion to the cured product layer (A).

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 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 denseness 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 (C) 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.

The gas barrier organic base material of the present invention can be produced, for example, as follows. That is, the coating composition (a) is applied to at least one surface of the organic base material, the coating composition (a) is cured, and then the gas barrier layer (C) is formed on the surface by a dry method. When the coating composition (b) is applied, the coating composition (b) is applied to the surface of the organic base material and irradiated with active energy rays to cure or partially cure the coating composition (b). After that, the coating composition (a) may be applied to the surface and cured. When each coating composition contains a solvent, it is preferable to cure the coating composition after removing the solvent.

In the present invention, in order to develop a higher gas barrier property, after forming the gas barrier layer (C), a layer of the cured product of the coating composition (a) may be further formed on the surface thereof.

The gas-barrier organic base material of the present invention can be used in various applications where gas barrier properties are required, and is preferably used, for example, as a substrate and / or a 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 cured product layer (A) 2b and a gas barrier layer (C) 2c formed on the surface of the organic base material 2a.
Is formed on the gas barrier film. Further, the protective layer 6 is laminated such that a gas barrier coating film composed of a cured product layer (A) 6b and a gas barrier layer (C) 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.

[0064]

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), in Examples 3 and 6, PET film (thickness 100 μm,
The product name "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 ·
Oxygen permeability measuring device (model “OCON OXTRAN 1
0 / 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 “ERMATRAN 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 2 parts by mass of a hydrogenated product of a maleic anhydride-modified styrene / ethylene / butadiene / styrene / block copolymer (trade name "Tuftec M1943", manufactured by Asahi Kasei Co., Ltd.) was dissolved in 48 parts by mass of cyclohexane. A coating liquid 1 was obtained.

The coating liquid 1 was applied to one surface of the organic base material by the spin coating method, and the coating liquid 1 was applied in a hot air circulating oven at 80 ° C.
It was held for curing for a minute to form a film having a thickness of 0.2 μm.

Next, a low temperature-curable perhydropolysilazane dibutyl ether solution (solid content 20% by mass, trade name "D120", manufactured by Clariant Japan) was applied to this surface.
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.
The substrate was held in the hot air circulation oven for 120 minutes to be sufficiently cured to obtain a substrate A on which a coating having a total film thickness of 0.6 μm was formed.

To improve adhesion, the surface of the base material A was first oxygen sputtered, then silicon nitride was used as a sputtering target, and argon and oxygen were introduced as a film forming gas to form a silicon oxynitride film with a thickness of 100 nm. The film was formed into a base material B.

[Example 2] 2 equipped with a stirrer and a cooling pipe
In a 00 mL four-necked flask, 20.5 g of isopropyl alcohol, 20.5 g of butyl acetate, 1-methoxy-2
-Propanol 10.3 g, 2,4,6-trimethylbenzoyldiphenylphosphine oxide 0.33
g, 2- [4- (2-hydroxy-3-dodecyloxypropyloxy) -2-hydroxyphenyl] -4,6
0.66 g of -bis (2,4-dimethylphenyl) -1,3,5-triazine, 2.0 g of PMMA resin, and N-methyl-4-methacryloyloxy-2,2,6,
0.44 g of 6-tetramethylpiperidine was added and dissolved.

Subsequently, 10.0 g of urethane acrylate (containing an average of 15 acryloyl groups per molecule), which is a reaction product of dipentaerythritol polyacrylate having a hydroxyl group and partially nurated hexamethylene diisocyanate, and caprolactone-modified tris ( 10.0 g of acryloyloxyethyl) isocyanurate (trade name "Aronix M-325", manufactured by Toagosei Co., Ltd.) was added and stirred at room temperature for 1 hour to obtain a coating liquid 2.

The coating liquid 2 was applied to one surface of the organic base material by the spin coating method, and the coating liquid 10 was applied in a hot air circulating oven at 80 ° C.
After holding for a minute to remove the solvent, it is irradiated with ultraviolet rays of 150 mJ / cm ² using a high pressure mercury lamp in an air atmosphere,
A partially cured product layer having a film thickness of 3 μm was formed.

Then, a low temperature-curable xylene solution of perhydropolysilazane (solid content 20% by mass, trade name "L110", manufactured by Clariant Japan Co., Ltd.) was applied to this surface by spin coating, and hot air at 80 ° C was applied. After removing the solvent by holding it in the circulation oven for 10 minutes, irradiate it with 1500 mJ / cm ² of ultraviolet light using a high pressure mercury lamp in an air atmosphere, and then keep it for 120 minutes in a hot air circulation oven at 100 ° C. To obtain a substrate C on which a coating having a total film thickness of 3.6 μm was formed.

To improve the adhesion, the surface of the organic base material C is first oxygen sputtered, then silicon oxide is used as a sputtering target, and argon and oxygen are introduced as a film forming gas to form a silicon oxynitride film with a thickness of 200 nm. A film was formed to obtain a base material D.

[Example 3] 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, trade name "V110", manufactured by Clariant Japan Co., Ltd.) was added, and the mixture was stirred at room temperature for 1 hour under a nitrogen atmosphere to obtain a coating liquid 3.

The coating liquid 3 was applied to one surface of the organic base material by the spin coating method, and the coating liquid 3 was applied in a hot air circulating oven at 90 ° C. for 10 hours.
After removing the solvent by holding for 5 minutes, use a high pressure mercury lamp to
It was irradiated with ultraviolet rays of 00 mJ / cm ² and sufficiently cured to obtain a substrate E on which a film having a film thickness of 2 μm was formed.

A diamond-like carbon film having a thickness of 30 nm was formed on the surface of the base material E by a plasma CVD method to obtain a base material F. 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.

Example 4 On the surface of the substrate D obtained in Example 2,
Furthermore, a low-temperature curable dibutyl ether solution of perhydropolysilazane (solid content 20% by mass, manufactured by Clariant Japan Co., Ltd., product name "L120") was applied by spin coating and kept in a hot air circulation oven at 80 ° C for 10 minutes. After removing the solvent, the product is kept in a hot air circulation oven at 100 ° C. for 120 minutes for sufficient curing, and the total film thickness is 3.9 μm.
A base material G on which the film of No. 1 was formed was obtained.

Example 5 A substrate H was obtained by depositing a 100 nm thick silicon oxynitride film on one surface of an organic substrate in the same manner as in Example 1.

Example 6 A substrate I was obtained by forming a diamond-like carbon film with a thickness of 30 nm on one surface of an organic substrate in the same manner as in Example 3.

[0083]

[Table 1]

Example 7 On the surface of the base material B obtained in Example 1 on which the gas barrier coating 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.

[0087]

The gas-barrier organic substrate of the present invention is produced by a dry method on the surface of an organic substrate through a cured product layer (A) made of a cured product of a coating composition (a) containing polysilazane. Since it has the formed gas barrier layer (C), the cured product layer (A) functions as a base film of the gas barrier layer (C), and the adhesiveness between the organic base material and the gas barrier layer (C) is excellent. Further, the coating composition (a) is cured at a low temperature, has a low curing shrinkage, and has a high density of the cured product, so that the cured product layer (A) made of the cured product exhibits excellent gas barrier properties. Therefore, the gas barrier organic base material of the present invention exhibits a gas barrier property equivalent to that of glass due to a synergistic effect with the gas barrier layer (C).

In addition, the EL device of the present invention is not affected by moisture or oxygen and does not deteriorate the light emitting property by using the gas barrier organic base material.

[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 cured product layer (A) 2c, 6c Gas barrier layer (C) 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) 4F100 AK01A AK02 AK04 AK42                       AK45 AK52B AK52D AK73                       AK79B AK79D AL02 AL05B                       AL05D AT00A BA03 BA05                       BA06 BA07 BA10A BA10C                       BA10E EH46 EH462 EH66                       EH662 EJ42 EJ422 EJ86                       EJ862 GB41 JB12B JB12D                       JD02 JD02C JD02E

Claims (4)

[Claims] 1. A cured product layer (A) made of a cured product of a coating composition (a) containing polysilazane, and a dry layer formed on at least one surface of an organic substrate in order from the substrate side. A gas-barrier organic base material having a gas barrier layer (C). 2. A cured product of a coating composition (b) containing a compound having one or more active energy ray-curable polymerizable functional groups between the organic base material and the cured product layer (A). The gas-barrier organic substrate according to claim 1, which has a base layer (B) consisting of. 3. The gas barrier organic substrate according to claim 1, wherein the coating composition (a) contains a compound having one or more active energy ray-curable polymerizable functional groups. . 4. 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 electroluminescence element having a laminated structure consisting of, the substrate and / or the protective layer is the gas barrier organic base material according to any one of claims 1 to 3. element.