JP6095978B2 - Resin composition for organic EL device and organic EL device - Google Patents

Description

The present invention relates to a resin composition for an organic EL device used for an organic electroluminescence (hereinafter referred to as EL) device. The present invention relates to an organic EL device.

The organic EL element has a structure in which an organic EL layer including a light emitting layer made of an organic light emitting material is sandwiched between a pair of transparent or translucent electrodes. When a voltage is applied between the pair of electrodes of the organic EL element having such a structure, electrons are injected into the light emitting layer from the cathode, holes are injected from the anode, and these are recombined in the light emitting layer. The light emitting material in the light emitting layer is excited by the energy generated at this time, and light is emitted from the light emitting layer. A device in which the organic EL element is formed on a substrate is referred to as an organic EL device in this specification. For example, an organic EL device in which an organic EL element is formed on a flat substrate can be used for a planar light source, a segment display device, a dot matrix display device, and the like.

The organic EL element deteriorates when exposed to water vapor or oxygen. Therefore, after forming an organic EL element by sequentially stacking an anode, an organic EL layer including a light emitting layer, and a cathode on a substrate such as a glass substrate, an inorganic passivation film made of silicon oxide, silicon nitride, or the like; An organic film made of a resin is laminated on the surface of the inorganic passivation film to cover the entire organic EL element (see, for example, Patent Document 1). Here, when there is no defect in the inorganic passivation film, a sufficiently high barrier property can be obtained with only the inorganic passivation film. Here, the barrier property refers to a barrier property to a gas such as water vapor or oxygen. However, defects such as pinholes are present in the normally produced inorganic passivation film. Therefore, an organic film is formed on the upper surface of the inorganic passivation film and the defects on the inorganic passivation film are covered, thereby blocking the permeation path of gas such as water vapor and oxygen, and improving the overall barrier property. Prevents deterioration.

However, in the organic EL device having a sealing structure in which the inorganic passivation film and the organic film described in Patent Document 1 are stacked, the organic film is exposed to the atmosphere, and the deterioration of the organic film layer is large. Gases such as water vapor and oxygen gradually enter from the organic film layer, and this gas diffuses through the interface between the organic film layer and the inorganic passivation film and the defects of the inorganic passivation film, and reaches the organic EL element. There was a problem.

As a method for solving such a problem, by laminating an inorganic passivation film and an organic film made of a (meth) acrylic compound, and further providing a sealing substrate such as glass or plastic on the outermost layer, An organic EL device and a manufacturing method for preventing oxygen intrusion have been proposed (see, for example, Patent Document 2 and Patent Document 3).

However, as described in Patent Document 2 and Patent Document 3, when the organic film is made of a (meth) acrylic compound, outgas is generated from the (meth) acrylic compound in a moisture resistance test or the like, causing a pinhole. End up. There has been a problem that water vapor or oxygen enters from these pinholes, thereby reducing the lifetime of the organic EL device.

As a resin composition for organic EL devices, a polyene / polythiol resin composition is disclosed (for example, see Patent Documents 4 to 6). However, when the polyene / polythiol resin composition described in Patent Documents 4 to 6 is used as an organic material film of an organic EL device which is the object of the present invention, the viscosity is too high and the storage stability is not excellent. As a result, there was a problem that coating property was poor, and thinning and flattening were impossible. In addition, the glass transition temperature of the polymer is too high, the flexibility is not excellent, and there is a problem that when bent at a certain curvature or more, cracks or cracks occur and water vapor and oxygen leak.

Conventionally, when a polymerization inhibitor is contained, the viscosity cannot be kept low and becomes high, so that only the periphery of the element can be used. Conventional sealing agents need to have a high viscosity, and the example of Patent Document 4 was 300,000 mPa · s.

JP 2000-223264 A JP 2009-37812 A JP 2008-173838 A JP 2004-107450 A Special table 2008-536968 gazette JP 2007-70417 A

The present invention has been made in view of the above problems. By selecting a polymerization inhibitor, the present invention has a low viscosity (at 25 ° C., 1 mPa · s or more and 200 mPa · s or less) and is excellent in storage stability. It became so.

The present invention is as follows.
(1) (a) a polyene compound which is an allyl compound , (b) a polythiol compound having an alkylene oxide group, (c) a polymerization inhibitor which is one or more members selected from the group consisting of a quinone compound and a nitrosamine compound, ( contains d) a photopolymerization initiator, (c) the content of polymerization inhibitor per 100 parts by weight of the polyene compound and a polythiol compound, 0.00001 to 1.0 parts by mass der Ru organic EL device Resin composition.
(2) (b) The polythiol compound having an alkylene oxide group is 1,8-dimercapto-3,6-dioxaoctane, and the quinone compound (c) is selected from the group consisting of hydroquinone monomethyl ether and hydroquinone. Ri der 1 or more, is one or more of the group consisting of (c) nitrosamine-based compounds and N- nitrosophenylhydroxylamine ammonium salt N- nitrosophenylhydroxylamine aluminum salt, (d) a photopolymerization initiator but acylphosphine oxide derivative, one or more der Rukoto of the group consisting of oxime ester compound.
(3) The allyl compound is at least one member selected from the group consisting of diallyl phthalate, diallyl maleate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, tetraallyloxyethane, (a) polyene The mass ratio of the compound and the polythiol compound having (b) an alkylene oxide group is 90:10 to 10:90, and the content of the photopolymerization initiator (d) is 100 parts by mass in total of the polyene compound and the polythiol compound. Te, 0.001 to 10 parts by mass der Rukoto are preferred.
(4) The use is preferably for a flexible organic EL device.
(5) The viscosity at 25 ° C. is preferably 1 mPa · s or more and 200 mPa · s or less, and the glass transition temperature of the film obtained by polymerization with energy rays is preferably −40 ° C. or more and 40 ° C. or less.
( 6) The resin composition for an organic EL device is preferably an energy ray-curable resin composition for full-surface coating used for the purpose of covering the entire surface of the sealing substrate.
(7) An organic EL element configured by sandwiching an organic EL layer including a light emitting layer between a pair of electrodes, at least one of which is transparent or translucent, on the substrate, and an inorganic material that seals the organic EL element A sealing layer in which films and organic films are alternately stacked, and a sealing substrate disposed in close contact with the uppermost organic film of the sealing layer so as to cover the entire upper surface of the uppermost organic film; An organic EL device in which the organic film is a resin composition.
(8) It is preferable that the sealing layer is formed by alternately laminating the inorganic film and the organic film.
(9) The substrate is preferably a plastic substrate.
(10) The plastic substrate is preferably one or more members selected from the group consisting of polyimide, polyetherimide, polyethylene terephthalate, and polyethylene naphthalate.
(11) A flexible organic EL device is preferable.
(12) A display comprising an organic EL device is preferred .

The present invention has effects such as low viscosity and good storage stability.

Hereinafter, preferred embodiments of an organic EL device and a method for manufacturing the same according to the present invention will be described in detail. In addition, this invention is not limited by this embodiment.

Hereinafter, a top emission type organic EL device that irradiates light from the opposite side of the organic EL element formed on the substrate will be described as an example. The top emission type organic EL device includes an organic EL element in which an anode, an organic EL layer including a light emitting layer, and a cathode are sequentially stacked on a substrate, and an inorganic film and an organic film covering the entire organic EL element. The sealing layer which consists of this laminated body, and the sealing substrate provided on a sealing layer have the structure formed in order.

Here, various substrates such as a glass substrate, a silicon substrate, and a plastic substrate can be used as the substrate. Among these, a plastic substrate is preferable in terms of flexibility.

Plastics used for plastic substrates include polyimide, polyetherimide, polyethylene terephthalate, polyethylene naphthalate, polyoxadiazole, aromatic polyamide, polybenzimidazole, polybenzobisthiazole, polybenzoxazole, polythiazole, polyparaphenylene. Examples include vinylene, polymethyl methacrylate, polystyrene, polycarbonate, and polycycloolefin. Among these, polyimide, polyetherimide, polyethylene terephthalate, polyethylene naphthalate, polyoxadiazole, aromatic polyamide, polybenzimidazole, and polybenzoic acid are excellent in low moisture permeability, low oxygen permeability, and heat resistance. One or more members selected from the group consisting of bisthiazole, polybenzoxazole, polythiazole, and polyparaphenylene vinylene are preferable, and polyimide, polyetherimide, One or more members selected from the group consisting of polyethylene terephthalate and polyethylene naphthalate are more preferable.

As the anode, a conductive metal oxide film or a translucent metal thin film having a relatively large work function (preferably one having a work function larger than 4.0 eV) is generally used. For example, indium tin oxide (hereinafter referred to as ITO), metal oxide such as tin oxide, metal such as gold (Au), platinum (Pt), silver (Ag), copper (Cu), or these An alloy containing at least one of them, an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof, or the like can be used. If necessary, the anode can be formed with a layer structure of two or more layers. The film thickness of the anode can be appropriately selected in consideration of electric conductivity (in the case of a bottom emission type, light transmittance is also taken into consideration). The thickness of the anode is preferably 10 nm to 10 μm, more preferably 20 nm to 1 μm, and most preferably 50 nm to 500 nm. Examples of a method for producing the anode include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method. In the case of the top emission type, a reflective film for reflecting light irradiated on the substrate side may be provided under the anode.

The organic EL layer includes at least a light emitting layer made of an organic material. This light emitting layer has an organic substance (low molecular compound or high molecular compound) that emits fluorescence or phosphorescence. The light emitting layer may further contain a dopant material. Examples of the organic substance include a dye material, a metal complex material, and a polymer material. The dopant material is doped into the organic material as necessary for the purpose of improving the luminous efficiency of the organic material and changing the emission wavelength. The thickness of the light emitting layer composed of these organic substances and a dopant doped as necessary is usually 20 to 2,000 mm.

(Dye material)
Examples of dye-based materials include cyclopentamine derivatives, tetraphenylbutadiene derivative compounds, triphenylamine derivatives, oxadiazole derivatives, pyrazoloquinoline derivatives, distyrylbenzene derivatives, distyrylarylene derivatives, pyrrole derivatives, thiophene ring compounds, pyridine Examples thereof include ring compounds, perinone derivatives, perylene derivatives, oligothiophene derivatives, trifumanylamine derivatives, oxadiazole dimers, and pyrazoline dimers.

(Metal complex materials)
Metal complex materials include metal complexes that emit light from triplet excited states such as iridium complexes and platinum complexes, aluminum quinolinol complexes, benzoquinolinol beryllium complexes, benzoxazolyl zinc complexes, benzothiazole zinc complexes, azomethyl zinc complexes. , Porphyrin zinc complex, europium complex, etc., the central metal has rare earth metals such as terbium (Tb), europium (Eu), dysprosium (Dy), aluminum (Al), zinc (Zn), beryllium (Be), etc. Examples of the ligand include metal complexes having oxadiazole, thiadiazole, phenylpyridine, phenylbenzimidazole, quinoline structure and the like.

(Polymer material)
Polymeric materials include polyparaphenylene vinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, polyacetylene derivatives, polyfluorene derivatives, polyvinylcarbazole derivatives, and polymerized chromophores and metal complex light emitting materials. Etc.

Among the above light emitting materials, materials emitting blue light include distyrylarylene derivatives, oxadiazole derivatives, and polymers thereof, polyvinylcarbazole derivatives, polyparaphenylene derivatives, polyfluorene derivatives, and the like. Among these, one or more members selected from the group consisting of polyvinylcarbazole derivatives, polyparaphenylene derivatives, and polyfluorene derivatives as polymer materials are preferable.

Examples of materials that emit green light include quinacridone derivatives, coumarin derivatives, and polymers thereof, polyparaphenylene vinylene derivatives, polyfluorene derivatives, and the like. Among these, one or more members selected from the group consisting of polyparaphenylene vinylene derivatives and polyfluorene derivatives as polymer materials are preferable.

Examples of materials that emit red light include coumarin derivatives, thiophene ring compounds, and polymers thereof, polyparaphenylene vinylene derivatives, polythiophene derivatives, and polyfluorene derivatives. Among these, one or more members selected from the group consisting of polyparaphenylene vinylene derivatives, polythiophene derivatives, and polyfluorene derivatives as polymer materials are preferable.

(Dopant material)
Examples of the dopant material include perylene derivatives, coumarin derivatives, rubrene derivatives, quinacridone derivatives, squalium derivatives, porphyrin derivatives, styryl dyes, tetracene derivatives, pyrazolone derivatives, decacyclene, phenoxazone, and the like.

In addition to the light emitting layer, the organic EL layer can be appropriately provided with a layer provided between the light emitting layer and the anode and a layer provided between the light emitting layer and the cathode. First, as a layer provided between the light emitting layer and the anode, the hole injection layer for improving the hole injection efficiency from the anode, the hole, the hole injection layer or the hole transport layer closer to the anode to the light emitting layer. And a hole transport layer for improving the hole injection. The layer provided between the light emitting layer and the cathode has a function of improving electron injection from the cathode, the electron injection layer, or an electron transport layer closer to the cathode. Examples thereof include an electron transport layer.

(Hole injection layer)
Materials for forming the hole injection layer include phenylamine, starburst amine, phthalocyanine, vanadium oxide, molybdenum oxide, ruthenium oxide, aluminum oxide and other oxides, amorphous carbon, polyaniline, polythiophene derivatives, etc. It is done.

(Hole transport layer)
Materials constituting the hole transport layer include polyvinyl carbazole or derivatives thereof, polysilane or derivatives thereof, polysiloxane derivatives having aromatic amines in the side chain or main chain, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine. Derivatives, polyaniline or derivatives thereof, polythiophene or derivatives thereof, polyarylamine or derivatives thereof, polypyrrole or derivatives thereof, poly (p-phenylene vinylene) or derivatives thereof, or poly (2,5-thienylene vinylene) or derivatives thereof, etc. Is mentioned.

When these hole injection layers or hole transport layers have a function of blocking electron transport, these hole transport layers and hole injection layers are sometimes referred to as electron blocking layers.

(Electron transport layer)
Materials constituting the electron transport layer include oxadiazole derivatives, anthraquinodimethane or derivatives thereof, benzoquinone or derivatives thereof, naphthoquinone or derivatives thereof, anthraquinones or derivatives thereof, tetracyanoanthraquinodimethane or derivatives thereof, fluorenone derivatives. , Diphenyldicyanoethylene or a derivative thereof, diphenoquinone derivative, 8-hydroxyquinoline or a derivative thereof, polyquinoline or a derivative thereof, polyquinoxaline or a derivative thereof, polyfluorene or a derivative thereof, and the like. Examples of the derivatives include metal complexes.

(Electron injection layer)
The electron injection layer is an electron injection layer having a single layer structure of a calcium (Ca) layer or a metal of group IA and IIA of the periodic table excluding Ca and a work function depending on the type of the light emitting layer. An electron injection layer having a layered structure of a Ca layer and a layer formed of one or more members selected from the group consisting of metals of 1.5 to 3.0 eV and oxides, halides and carbonates of the metals Can be mentioned. As a metal of group IA of the periodic table having a work function of 1.5 to 3.0 eV, or an oxide, halide or carbonate thereof, lithium (Li), lithium fluoride, sodium oxide, lithium oxide, lithium carbonate, etc. Is mentioned. The metal of group IIA of the periodic table excluding Ca having a work function of 1.5 to 3.0 eV, or oxides, halides and carbonates thereof include strontium (Sr), magnesium oxide, magnesium fluoride, fluoride Examples include strontium, barium fluoride, strontium oxide, and magnesium carbonate.

When these electron transport layers or electron injection layers have a function of blocking hole transport, these electron transport layers and electron injection layers are sometimes referred to as hole blocking layers.

As the cathode, a transparent or translucent material having a relatively small work function (preferably one having a work function smaller than 4.0 eV) and easy electron injection into the light emitting layer is preferable. As a cathode, lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), Be, magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba) , Al, scandium (Sc), vanadium (V), Zn, yttrium (Y), indium (In), cerium (Ce), samarium (Sm), Eu, Tb, ytterbium (Yb) and other metals, or the above metals Two or more alloys, or one or more of them, Au, Ag, Pt, Cu, manganese (Mn), titanium (Ti), cobalt (Co), nickel (Ni), tungsten (W), Alloy with one or more of tin (Sn), graphite or graphite intercalation compound, or metal such as ITO or tin oxide Product, and the like.

The cathode may have a laminated structure of two or more layers. Examples of this include a laminated structure of the above metals, metal oxides, fluorides, and alloys thereof and metals such as Al, Ag, and chromium (Cr). The thickness of the cathode can be appropriately selected in consideration of electric conductivity and durability, but the thickness of the cathode is preferably 10 nm to 10 μm, more preferably 20 nm to 1 μm, and most preferably 50 nm to 500 nm. . Examples of the method for producing the cathode include a vacuum deposition method, a sputtering method, and a laminating method in which a metal thin film is thermocompression bonded.

The layers provided between the light emitting layer and the anode and between the light emitting layer and the cathode can be appropriately selected according to the performance required for the organic EL device to be produced. For example, the structure of the organic EL element used in the present invention may have any of the following layer configurations (i) to (xv).

(I) Anode / hole transport layer / light emitting layer / cathode (ii) anode / light emitting layer / electron transport layer / cathode (iii) anode / hole transport layer / light emitting layer / electron transport layer / cathode (iv) anode / Hole injection layer / light emitting layer / cathode (v) anode / light emitting layer / electron injection layer / cathode (vi) anode / hole injection layer / light emitting layer / electron injection layer / cathode (vii) anode / hole injection layer / Hole transport layer / light emitting layer / cathode (viii) anode / hole transport layer / light emitting layer / electron injection layer / cathode (ix) anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode (X) Anode / hole injection layer / light emitting layer / electron transport layer / cathode (xi) anode / light emitting layer / electron transport layer / electron injection layer / cathode (xii) anode / hole injection layer / light emitting layer / electron transport Layer / electron injection layer / cathode (xviii) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode (xiv) anode / positive Transport layer / light-emitting layer / electron transport layer / electron injection layer / cathode (xv) anode / hole injection layer / hole transport layer / light-emitting layer / electron transport layer / electron injection layer / cathode (where “/” is (Indicates that each layer is laminated adjacently. The same applies hereinafter.)

The sealing layer is provided to seal the organic EL element with a layer having a high barrier property against the gas in order to prevent a gas such as water vapor or oxygen from coming into contact with the organic EL element. In this sealing layer, inorganic films and organic films are alternately formed from below. The inorganic / organic laminate may be formed repeatedly twice or more.

The inorganic film of the inorganic / organic laminate is a film provided to prevent the organic EL element from being exposed to a gas such as water vapor or oxygen existing in an environment where the organic EL device is placed. The inorganic film of the inorganic / organic laminate is preferably a continuous dense film with few defects such as pinholes. Examples of the inorganic film include a single film such as a SiN film, a SiO film, a SiON film, an Al ₂ O ₃ film, and an AlN film, and a laminated film thereof.

The organic film of the inorganic / organic laminate is provided in order to provide flatness to the surface in order to satisfy defects such as pinholes formed on the inorganic film. The organic film is formed in a region narrower than a region where the inorganic film is formed. This is because if the organic film is formed to be the same as or wider than the formation area of the inorganic film, the organic film is deteriorated in the exposed area. However, the organic film formed in the uppermost layer of the entire sealing layer (hereinafter referred to as the uppermost organic film) is formed in substantially the same region as the formation region of the inorganic film. And it forms so that the upper surface of a sealing layer may be planarized. As the organic film, there is used a film obtained by reacting (a) a polyene compound and (b) a polythiol compound, which has an adhesion function with good adhesion performance to the above-described inorganic film.

The (a) polyene compound used in the present invention is an alkene having two or more carbon-carbon unsaturated bonds per molecule. (A) As polyene compounds, vinyl compounds such as divinylbenzene and divinyltoluene, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate , Trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tetraethylene glycol di (meth) ) (Meth) acrylates such as acrylate, diallyl phthalate, diallyl maleate, triallyl cyanurate, triallyl isocyanurate, Li triallyl trimellitate, allyl compounds such as tetraallyloxyethane, allyl ethers such as polyoxypropylene diallyl ether compounds, and the like. In these, an allyl compound is preferable at the point which the reactivity with (b) polythiol compound is excellent.

The present invention contains (b) a polythiol compound having an alkylene oxide group for the purpose of ensuring low viscosity and lowering the glass transition temperature of the organic film after polymerization. (B) The polythiol compound having an alkylene oxide group is a compound having two or more thiol groups per molecule and an alkylene oxide group represented by the following formula (1).

Formula (1)
_{- (- C n H 2n O} -) m -
(In the formula, m represents an integer of 1 to 12, and n represents an integer of 2 to 30. The alkyl chain in the formula may be linear or branched.)

(B) As polythiol compounds having an alkylene oxide group, 1,8-dimercapto-3,6-dioxaoctane, 1,11-dimercapto 3,6,9-trioxadodecane, diethylene glycol bisthioglycolate, triethylene Glycol bisthioglycolate, tetraethylene glycol bisthioglycolate, pentaethylene glycol bisthioglycolate, hexaethylene glycol bisthioglycolate, octaethylene glycol bisthioglycolate, dodecane ethylene glycol bisthioglycolate, diethylene glycol bis (3 -Mercaptopropionate), triethylene glycol bis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), Taethylene glycol bis (3-mercaptopropionate), hexaethylene glycol bis (3-mercaptopropionate), octaethylene glycol bis (3-mercaptopropionate), dodecane ethylene glycol bis (3-mercaptopropionate) ), Diethylene glycol bis (3-mercaptobutyrate), triethylene glycol bis (3-mercaptobutyrate), tetraethylene glycol bis (3-mercaptobutyrate), pentaethylene glycol bis (3-mercaptobutyrate), hexaethylene Glycol bis (3-mercaptobutyrate), octaethylene glycol bis (3-mercaptobutyrate), dodecane ethylene glycol bis (3-mercaptobutyrate), polyethylene glycol Bisthioglycolate, polyethylene glycol bis (3-mercaptopropionate), polyethylene glycol bis (3-mercaptobutyrate), polypropylene glycol bisthioglycolate, polypropylene glycol bis (3-mercaptopropionate), polypropylene glycol Ethylene oxide adduct of bis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, trimethylolpropane-tris- (3-mercaptopropinate), tris-[(3-mercapto Propionyloxy) -ethyl] -isocyanurate ethylene oxide adduct, pentaerythritol tetrakis (3-mercaptopropionate) ethylene oxide adduct, pentaerythritol tet Ethylene oxide adduct of lakis (3-mercaptobutyrate), ethylene oxide adduct of trimethylolethanetris (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1, Examples include 3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, ethylene oxide adduct of dipentaerythritol hexakis (3-mercaptopropionate), and the like. Among these, 1,8-dimercapto-3,6-dioxaoctane is preferable from the viewpoint of low viscosity and glass transition temperature.

As long as the object of the embodiment is not impaired, the resin composition of the present invention may contain a polythiol compound having no alkylene oxide group.

The mass ratio of (a) polyene compound and (b) polythiol compound having an alkylene oxide group is preferably 90:10 to 10:90, more preferably 80:20 to 20:80, and most preferably 70:30 to 30:70. preferable.

The resin composition of the present invention contains (c) a polymerization inhibitor for the purpose of imparting low viscosity and viscosity stability. (C) As a polymerization inhibitor, 1 or more types in the group which consists of a quinone type compound and a nitrosamine type compound are mentioned. As quinone compounds, β-naphthoquinone, 2-methoxy-1,4-naphthoquinone, 4-methoxy-1-naphthol, methylhydroquinone, hydroquinone, hydroquinone monomethyl ether, mono-tert-butylhydroquinone, 2,5-di- Examples include tert-butyl hydroquinone, p-benzoquinone, 2,5-diphenyl-p-benzoquinone, 2,5-di-tert-butyl-p-benzoquinone, and the like. Examples of the nitrosamine compound include N-nitrosophenylhydroxylamine ammonium salt (cuperon), N-nitrosophenylhydroxylamine aluminum salt, and the like. Among the quinone compounds, one or more members selected from the group consisting of hydroquinone and hydroquinone monomethyl ether are preferable. Among the nitrosamine compounds, one or more members selected from the group consisting of cuperone and N-nitrosophenylhydroxylamine aluminum salt are preferable.

(C) The content of the polymerization inhibitor is preferably 0.00001 to 1.0 parts by mass, more preferably 0.0005 to 0.1 parts by mass, with respect to 100 parts by mass in total of the polyene compound and the polythiol compound. 0.001-0.01 mass part is the most preferable.

A polymerization inhibitor other than the polymerization inhibitor (c) of the present invention may be used as long as the object of the embodiment is not impaired.

As the photopolymerization initiator (d) of the present invention, benzoin derivatives such as benzyl, benzoin, benzoin benzoic acid, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzophenone derivatives such as benzophenone and 4-phenylbenzophenone, 2, Alkylacetophenone derivatives such as 2-diethoxyacetophenone, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 1- (4-isopropylphenyl) 2-hydroxy-2-methylpropan-1-one, 1- (4- (2 -Hydroxyethoxy) -phenyl) -2-hydroxy-2-methyl-1-propan-1-one, α-hydroxyacetophenone derivatives such as 2-hydroxy-2-methyl-1-phenylpropan-1-one Bisdiethylaminobenzophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1- Α-Aminoalkylacetophenone derivatives such as butanone-1, isobutyryl-methylphosphinic acid methyl ester, isobutyryl-phenylphosphinic acid methyl ester, pivaloyl-phenylphosphinic acid methyl ester, 2-ethylhexanoyl-phenylphosphinic acid methyl ester Ester, pivaloyl-phenylphosphinic acid isopropyl ester, p-toluyl-phenylphosphinic acid methyl ester, o-toluyl-phenylphosphinic acid methyl ester, 2,4-dimethylbenzoyl-phenylphosphite Acid methyl ester, p-3 tertiary butylbenzoyl-phenylphosphinic acid isopropyl ester, bivaloyl- (4-methylphenyl) -phosphinic acid methyl ester, pivaloyl-phenylphosphinic acid vinyl ester, acryloyl-phenylphosphinic acid methyl ester, Isobutyryl-diphenylphosphine oxide, pivaloyl-diphenylphosphine oxide, 1-methyl-1-cyclohexanoyl-diphenylphosphine oxide, 2-ethylhexanoyl-diphenylphosphine oxide, p-toluyl-diphenylphosphine oxide, o -Toluyl-diphenylphosphine oxide, p-tert-butylbenzoyl-diphenylphosphine oxide, acryloyldiphenylphosphine Oxide, benzoyl-diphenylphosphine oxide, 2,2-dimethyl-heptanoyl-diphenylphosphine oxide, terephthaloyl-bis-diphenylphosphine oxide, adipoyl-bis-diphenylphosphine oxide, 2,6-dimethylbenzoyl-diphenylphosphine Fin oxide, 2,6-dimethoxybenzoyl-phenylphosphinic acid methyl ester, 2,6-dimethylbenzoyl-diphenylphosphine oxide, 2,6-dimethoxybenzoyl-diphosphine oxide, 2,4,6-trimethylbenzoyl- Phenylphosphinic acid methyl ester, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,3,6-trimethylbenzoyl-diphenyl Phosphine oxide, 2,4,6-trimethylbenzoyl-triphosphinic acid methyl ester, 2,4,6-trimethoxybenzoyl-diphenylphosphine oxide, 2,6-dichlorobenzoyl-phenylphosphinic acid ester, 2, 6-dichlorobenzoyl-diphenylphosphine oxide, 2,3,4,6-tetramethylbenzoyl-diphenylphosphine oxide, 2,6-dibromobenzoyl-diphenylphosphine oxide, 2,6-dimethylbenzoyldiphenylphosphine Oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyl-phenylphosphinic acid methyl ester, 2,6-dichlorobenzoyl- or 2,6-dimethyl Acyl such as xylbenzoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide Phosphine oxide derivative, 1,2-octanedione, 1-[-4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone 1- [9-ethyl-6- (2-methylbenzoyl)- And oxime ester compounds such as 9H-carbazol-3-yl] -1- (O-acetyloxime).

When the substrate of the organic EL device of the present invention is a plastic substrate, the acylphosphine oxide derivative can be cured with light of 380 nm to 430 nm, and the organic film after curing is highly transparent. One or more members selected from the group consisting of oxime ester compounds are preferred.

(D) 0.001-10 mass parts is preferable with respect to a total of 100 mass parts of a polyene compound and a polythiol compound, and, as for content of a photoinitiator, 0.05-5 mass parts is more preferable.

Silane coupling agents, photosensitizers, light stabilizers, solvents, fillers, reinforcing materials, plasticizers, thickeners, dyes, pigments, flame retardants, and surfactants, as long as the purpose of the present embodiment is not impaired. Etc. You may contain additives, such as.

In the present invention, (a) a polyene compound, (c) a polymerization inhibitor, and (d) a photopolymerization initiator are mixed in advance, and then (b) a polythiol compound having an alkylene oxide group is mixed to form an energy ray curable resin. It is preferred to produce the composition. When mixing (a) polyene compound, (c) polymerization inhibitor, and (d) photopolymerization initiator in advance, the mixing temperature is preferably 10 to 150 ° C, more preferably 30 to 80 ° C. Subsequently, (b) the mixing temperature when mixing the polythiol compound having an alkylene oxide group is preferably 10 to 40 ° C, and more preferably 20 to 30 ° C.

The viscosity of the resin composition of the present invention can be measured with a known viscometer such as a B-type viscometer or an E-type viscometer, but is preferably 1 mPa · s or more and 200 mPa · s or less at 25 ° C. More preferably, it is s or more and 150 mPa · s or less. Within this range, the viscosity is too low, the organic film thickness is not too thin, the viscosity is too high, the organic film thickness is not too thick, Flatness can be obtained.

The glass transition temperature of the resin composition of the present invention is preferably −40 ° C. or higher and 40 ° C. or lower, and more preferably −20 ° C. or higher and 10 ° C. or lower. If it is -40 degreeC or more, an organic substance film will not become sticky after hardening, and if it is 40 degrees C or less, an organic substance film will become hard too much, a crack and a crack will not generate | occur | produce, and organic EL excellent in flexibility An apparatus can be provided.

The glass transition temperature is measured by a known dynamic viscoelasticity spectrometer (for example, DMS series manufactured by SI Nanotechnology, RSA series manufactured by TA Instruments), differential calorimeter (DSC), etc. Can be used.

Regarding the transparency of the resin composition of the present invention, when the thickness of the organic film is 1 μm or more and 10 μm or less, the spectral transmittance in the ultraviolet-visible light region of 360 nm or more and 800 nm or less is preferably 97% or more, more preferably 99% or more. preferable. If it is 97% or more, an organic EL device excellent in luminance and contrast can be provided.

The sealing layer of the present invention is preferably about 1 to 5 sets when the inorganic / organic laminate is counted as one set. This is because when the inorganic / organic laminate is 6 sets or more, the sealing effect on the organic EL element is almost the same as that of 5 sets. The thickness of the inorganic film is preferably 50 nm to 1 μm, and the thickness of the organic film is preferably 1 to 3 μm.

The sealing substrate is formed in close contact so as to cover the entire top surface of the uppermost organic film of the sealing layer. The sealing substrate is preferably a substrate that is transparent to visible light. Examples of the substrate transparent to visible light include glass and plastic substrates such as acrylic, polycarbonate, polycycloolefin, and polyester. Among these, a plastic substrate is more preferable in terms of flexibility.

The thickness of the transparent sealing substrate is preferably 50 μm or more and 300 μm or less. By providing the transparent sealing substrate in an upper layer of the sealing layer, deterioration that proceeds when the surface of the uppermost organic film is exposed to gas can be suppressed, and the barrier property of the organic EL device can be improved.

Next, a method for manufacturing an organic EL device having such a configuration will be described. First, an organic EL element is formed by sequentially forming an anode patterned in a predetermined shape, an organic EL layer including a light emitting layer, and a cathode on a first substrate by a conventionally known method. For example, when an organic EL device is used as a dot matrix display device, a bank is formed to divide the light emitting region into a matrix, and an organic EL layer including a light emitting layer is formed in a region surrounded by the bank.

Next, a predetermined thickness is formed on the substrate on which the organic EL element is formed by a film forming method such as a PVD (Physical Vapor Deposition) method such as a sputtering method or a CVD method such as a plasma CVD (Chemical Vapor Deposition) method. A first inorganic film is formed. Thereafter, the resin composition of the present invention is deposited on the first inorganic film using a known coating film forming method such as a solution coating method or a spray coating method, a flash vapor deposition method, or the like. Thereafter, the resin composition is cured by irradiation with energy rays such as ultraviolet rays, electron beams, and plasmas, and a first organic film is formed. Through the above steps, one set of inorganic / organic laminate is formed.

The formation process of the inorganic / organic laminated body shown above is repeated a predetermined number of times. However, for the last set, that is, the uppermost inorganic / organic laminate, the resin composition may be attached to the upper surface of the inorganic film by a coating method, a flash vapor deposition method, or the like so that the upper surface is flattened.

Next, a transparent sealing substrate is bonded to the surface on which the resin composition is attached on the substrate. Alignment is performed during pasting. Thereafter, the resin composition of the present invention present between the uppermost inorganic film and the transparent sealing substrate is cured by irradiating energy rays from the transparent sealing substrate side. Thereby, the resin composition is cured to form the uppermost organic film, and the uppermost organic film and the transparent sealing substrate are bonded to each other. Thus, the method for manufacturing the organic EL device is completed.

After the resin composition is deposited on the inorganic film, it may be polymerized by partially irradiating energy rays. By doing in this way, when the transparent sealing board | substrate is mounted, collapse of the shape of the resin composition used as the uppermost organic substance film can be prevented. The thickness of the inorganic film and the organic film may be the same for each inorganic / organic laminate, or may be different for each inorganic / organic laminate.

In the above description, the top emission type organic EL device has been described as an example. The present invention can also be applied to a bottom emission type organic EL device that irradiates light generated in the organic EL layer from the substrate side.

The organic EL element of the present invention can be used as a planar light source, a segment display device, and a dot matrix display device.

According to the embodiment of the present invention, the sealing layer for blocking the organic EL element formed on the first plastic substrate from the outside air is formed, and the transparent sealing substrate is further disposed on the sealing layer. Therefore, a sealing structure having a sufficient water vapor and oxygen barrier property for the organic EL element can be obtained. According to the embodiment of the present invention, it is possible to obtain a sealing structure having sufficient adhesive strength between the transparent sealing substrate and the sealing layer.

According to the present embodiment, after attaching the resin composition of the present invention constituting the uppermost organic film of the sealing layer, the transparent sealing substrate is placed without curing the resin composition, and then Since the resin composition is cured, the adhesion between the sealing layer and the transparent sealing substrate can be performed simultaneously with the formation of the uppermost organic film constituting the sealing layer. As a result, the present invention has an effect that the process can be simplified as compared with the case where the sealing layer and the transparent sealing substrate are bonded with an adhesive.

Hereinafter, the present invention will be described by way of examples. The present invention is not limited to the examples.

(Adjustment of resin composition (A))
In a flask equipped with a stirrer, 50 parts by mass of triallyl isocyanurate (“TAIC” manufactured by Nippon Kasei Co., Ltd.) as a polyene compound, and bis (2,4,6-trimethylbenzoyl) -phenylphosphine as a photopolymerization initiator 0.1 parts by mass of oxide ("Irgacure-819" manufactured by BASF), and 0.002 parts by mass of N-nitrosophenylhydroxylamine aluminum salt ("Q-1301" manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization inhibitor And stirred at 60 ° C. for 1 hour. After stirring, cool to 30 ° C. or less, add 50 parts by mass of 1,8-dimercapto-3,6-dioxaoctane (“DMDO” manufactured by Maruzen Petrochemical Co., Ltd.) as a polythiol compound, and continue stirring for 1 hour. A resin composition (A) was obtained.

(Adjustment of resin composition (B))
In a flask equipped with a stirrer, 40 parts by mass of tetraethylene glycol diacrylate (“A-200” manufactured by Shin-Nakamura Chemical Co., Ltd.) as a polyene compound, and bis (2,4,6-trimethylbenzoyl) as a photopolymerization initiator -Phenylphosphine oxide ("Irgacure-819" manufactured by BASF) 0.1 parts by mass, N-nitrosophenylhydroxylamine aluminum salt ("Q-1301" manufactured by Wako Pure Chemical Industries, Ltd.) 0.002 as a polymerization inhibitor A mass part was charged and stirred at 60 ° C. for 1 hour. After stirring, cool to 30 ° C. or less, add 60 parts by mass of 1,8-dimercapto-3,6-dioxaoctane (“DMDO” manufactured by Maruzen Petrochemical Co., Ltd.) as a polythiol compound, and continue stirring for 1 hour. A resin composition (B) was obtained.

(Adjustment of resin composition (C))
In a flask equipped with a stirrer, 35 parts by mass of diallyl maleate (“DAM” manufactured by Kurokin Kasei Co., Ltd.) as a polyene compound, and bis (2,4,6-trimethylbenzoyl) -phenylphosphine as a photopolymerization initiator 0.1 parts by mass of oxide (“Irgacure-819” manufactured by BASF) and 0.002 parts by mass of cuperone (“Q-1300” manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization inhibitor were charged and stirred at 60 ° C. for 1 hour. did. After stirring, the mixture was cooled to 30 ° C. or less, and 10 parts by mass of 1,8-dimercapto-3,6-dioxaoctane (“DMDO” manufactured by Maruzen Petrochemical Co., Ltd.), trimethylolpropane-tris- (3- 55 parts by mass of mercaptopropinate) (“TMMP-20P” manufactured by SC ORGANIC CO., LTD.) Was added, and stirring was continued for 1 hour to obtain a resin composition (C).

(Adjustment of resin composition (D))
In a flask equipped with a stirrer, 30 parts by mass of diallyl maleate (“DAM” manufactured by Kurokin Kasei Co., Ltd.) as a polyene compound, and bis (2,4,6-trimethylbenzoyl) -phenylphosphine as a photopolymerization initiator 0.1 parts by mass of oxide (“Irgacure-819” manufactured by BASF) and 0.002 parts by mass of cuperone (“Q-1300” manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization inhibitor were charged and stirred at 60 ° C. for 1 hour. did. After stirring, the mixture is cooled to 30 ° C. or less, and 30 parts by mass of 1,8-dimercapto-3,6-dioxaoctane (“DMDO” manufactured by Maruzen Petrochemical Co., Ltd.), pentaerythritol tetrakis (3-mercaptobutyrate) as a polythiol compound. ) (“Karenz MT-PE1” manufactured by Showa Denko KK) was added in an amount of 40 parts by mass, and stirring was further continued for 1 hour to obtain a resin composition (D).

(Adjustment of resin composition (E))
In a flask equipped with a stirrer, 40 parts by mass of triallyl isocyanurate (“TAIC” manufactured by Nippon Kasei Co., Ltd.) as a polyene compound, and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (as photopolymerization initiator) 0.1 parts by mass of BASF “LUCIRIN-TPO” and 0.1 parts by mass of hydroquinone (“Hydroquinone” manufactured by Seiko Chemical Co., Ltd.) were charged as a polymerization inhibitor and stirred at 60 ° C. for 1 hour. After stirring, cool to 30 ° C. or less, add 60 parts by mass of 1,8-dimercapto-3,6-dioxaoctane (“DMDO” manufactured by Maruzen Petrochemical Co., Ltd.) as a polythiol compound, and continue stirring for 1 hour. A resin composition (E) was obtained.

(Adjustment of resin composition (F))
In a flask equipped with a stirrer, 30 parts by mass of triallyl isocyanurate (“TAIC” manufactured by Nippon Kasei Co., Ltd.) as a polyene compound, and 1,2-octanedione, 1-[-4- (phenylthio) as a photopolymerization initiator )-, 2- (O-benzoyloxime)] ("Irgacure-OXE01" manufactured by BASF) 0.1 parts by mass, as a polymerization inhibitor, hydroquinone monomethyl ether ("MEHQ" manufactured by Wako Pure Chemical Industries, Ltd.) 0.001 A mass part was charged and stirred at 60 ° C. for 1 hour. After stirring, cool to 30 ° C. or less, add 70 parts by mass of 1,8-dimercapto-3,6-dioxaoctane (“DMDO” manufactured by Maruzen Petrochemical Co., Ltd.) as a polythiol compound, and continue stirring for 1 hour. A resin composition (F) was obtained.

(Adjustment of resin composition (G))
In a flask equipped with a stirrer, 40 parts by mass of triallyl isocyanurate (“TAIC” manufactured by Nippon Kasei Co., Ltd.) as a polyene compound, and bis (2,4,6-trimethylbenzoyl) -phenylphosphine as a photopolymerization initiator 0.1 parts by mass of oxide ("Irgacure-819" manufactured by BASF), and 0.002 parts by mass of N-nitrosophenylhydroxylamine aluminum salt ("Q-1301" manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization inhibitor And stirred at 60 ° C. for 1 hour. After stirring, the mixture is cooled to 30 ° C. or less, 60 parts by mass of trimethylolpropane-tris- (β-thiopropinate) (“SCMP Organic Co., Ltd.“ TMMP-20P ”) is added, and the stirring is continued for another hour to obtain a resin composition. A product (G) was obtained. As the resin composition (G), a polythiol compound having no alkylene oxide group was used.

(Adjustment of resin composition (H))
In a flask equipped with a stirrer, 50 parts by mass of triallyl isocyanurate (“TAIC” manufactured by Nippon Kasei Co., Ltd.) as a polyene compound, and bis (2,4,6-trimethylbenzoyl) -phenylphosphine as a photopolymerization initiator 0.1 parts by mass of oxide (“Irgacure-819” manufactured by BASF) was charged and stirred at 60 ° C. for 1 hour. After stirring, cool to 30 ° C. or less, add 50 parts by mass of 1,8-dimercapto-3,6-dioxaoctane (“DMDO” manufactured by Maruzen Petrochemical Co., Ltd.) as a polythiol compound, and continue stirring for 1 hour. A resin composition (H) was obtained. The resin composition (H) did not use a polymerization inhibitor.

(Adjustment of resin composition (I))
In a flask equipped with a stirrer, isocyanuric acid EO (ethylene oxide) -modified triacrylate (“Aronix M-315” manufactured by Toa Gosei Co., Ltd.), 50 parts by mass, tetraethylene glycol diacrylate (“A-200” manufactured by Shin-Nakamura Chemical Co., Ltd.) 50 parts by mass, 0.1 parts by mass of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (“Irgacure-819” manufactured by BASF) as a photopolymerization initiator, and 2,6 as a polymerization inhibitor -Resin composition (I) was obtained by charging 0.1 part by weight of di-tert-butyl-p-cresol (“Sumilyzer BHT” manufactured by Sumitomo Chemical Co., Ltd.) and stirring at 60 ° C. for 1 hour. Resin composition (I) did not use a polythiol compound.

(Adjustment of resin composition (J))
In a flask equipped with a stirrer, 100 parts by mass of tetraethylene glycol diacrylate (“A-200” manufactured by Shin-Nakamura Chemical Co., Ltd.), and bis (2,4,6-trimethylbenzoyl) -phenylphosphine as a photopolymerization initiator 0.1 part by mass of oxide (“Irgacure-819” manufactured by BASF), 0.1 part by mass of 2,6-di-tert-butyl-p-cresol (“Sumilyzer BHT” manufactured by Sumitomo Chemical Co., Ltd.) as a polymerization inhibitor Was stirred at 60 ° C. for 1 hour to obtain a resin composition (J). For the resin composition (J), a polymerization inhibitor other than the present invention was used.

Table 1 shows the physical properties of each resin composition prepared as described above. Each physical property was measured by the following method.

(Viscosity measurement)
Using an E-type viscometer, the viscosity at a temperature of 25 ° C. and a rotation speed of 20 rpm was measured (immediately after production).
As an evaluation of storage stability, the viscosity of the obtained resin composition after standing for 24 hours in a 40 ° C. atmosphere was also measured (after standing for 40 ° C. × 24 h).

(Spectral transmittance measurement)
After coating the resin composition on 0.7 mm thick glass (Corning “Eagle 2000”) with a film thickness of 10 μm, the illuminance is applied by an irradiator equipped with an ultra-high pressure mercury lamp (“UL-750” manufactured by HOYA). 100 mW / cm ² (405 nm) of light was irradiated for 30 seconds to produce a cured test piece. Spectral transmittances of 360 nm, 500 nm, and 800 nm were measured with an ultraviolet-visible spectrophotometer (“UV-2550” manufactured by Shimadzu Corporation).

(Glass-transition temperature)
The resin composition is poured into a 5 mm × 50 mm × 1 mm mold, and light with an illuminance of 100 mW / cm ² (405 nm) is irradiated by an irradiator equipped with an ultrahigh pressure mercury lamp (“UL-750” manufactured by HOYA). Irradiated for 2 seconds to produce a cured specimen. The prepared test piece was set with a dynamic viscoelasticity spectrometer (DMS-210, manufactured by SI Nanotechnology Co., Ltd.) with a distance between chucks of 20 mm, a frequency of 1 Hz, a heating rate of 2 ° C./min, and a tensile mode. The temperature at which tan δ (loss tangent) shows the maximum value was read and used as the glass transition temperature.

Example 1
(Manufacture of flexible organic EL devices)
An ITO film having a thickness of about 150 nm is formed by sputtering on a 125 μm-thick polyimide substrate (“Kapton 500H / V” manufactured by DuPont) that has been subjected to a drying treatment and a corona treatment at 200 ° C. for 2 hours as a pretreatment. Then, the anode was formed by patterning into a predetermined shape using a photolithography technique and an etching technique. Next, the polyimide substrate on which the anode was formed was washed with an organic solvent, an alkaline detergent and ultrapure water and dried, and then an ultraviolet / ozone cleaning treatment was performed with an ultraviolet / ozone cleaning apparatus.

Next, a suspension of poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid (HC Starckvitech “Vitron P TP AI 4083 (trade name)”) was filtered through a 0.5 μm filter, and filtered. The resulting suspension was formed into a film with a thickness of 70 nm on a polyimide substrate on which an anode was formed by spin coating. Thereafter, the polyimide substrate was placed on a hot plate and dried at 200 ° C. for 10 minutes in an air atmosphere to form a hole injection layer.

Next, using a solvent in which xylene and anisole were mixed at a ratio of 1: 1, a solution of 1.5% by mass of a polymer organic light-emitting material (“Lumation GP1300” manufactured by Summation) was prepared. This solution was formed into a film having a thickness of 80 nm on the polyimide substrate on which the hole injection layer was formed by spin coating to form a light emitting layer. Thereafter, the light emitting layer in the extraction electrode portion and the sealing area portion on the polyimide substrate was removed, and the polyimide substrate was introduced into the vacuum chamber and transferred to the heating chamber. In the subsequent processes, since the processing is performed in a vacuum or a nitrogen atmosphere, the organic EL device being processed is not exposed to the air.

After transferring the polyimide substrate to the heating chamber, the heating chamber in the vacuum chamber was heated to 100 ° C. for 60 minutes under a vacuum degree of 1 × 10 ⁻⁴ Pa or less. Next, the polyimide substrate is moved to the vapor deposition chamber, the cathode mask is aligned with the polyimide substrate, and the cathode is formed on the light emitting portion where the light emission is performed in the organic EL device and the extraction electrode portion. Vapor deposited. Here, the cathode is formed by heating the metal Ba so that the deposition rate is about 2 mm / sec by resistance heating method, and depositing the Ba film until the film thickness becomes 50 mm, and about 2 cm / sec by electron beam deposition method. It formed with the Al film | membrane vapor-deposited until it became a film thickness of 100 tons with the vapor deposition rate. Thereafter, the glass substrate was transferred to a vacuum chamber having a counter target type sputtering apparatus, argon gas and oxygen gas were introduced into the vacuum chamber, and an ITO film having a thickness of 1500 mm was formed by a counter target type sputtering method. Thus, an organic EL element was formed on the polyimide substrate.

Thereafter, the polyimide substrate on which the organic EL element was produced was transferred to a film sealing apparatus without being exposed to the atmosphere, and the mask was aligned with the polyimide substrate and set. Next, the polyimide substrate was moved to the inorganic film formation chamber, and an aluminum oxide film as a first inorganic film was formed by a sputtering method. Here, using an Al metal target with a purity of 5N, argon gas and oxygen gas were introduced into the inorganic film formation chamber, and a transparent and flat aluminum oxide film having a thickness of about 60 nm was formed on the polyimide substrate.

Next, the mask was replaced, and the polyimide substrate was transferred to the organic film formation chamber. Thereafter, the resin composition (A) was introduced into a vaporizer, vaporized, and vapor was ejected from the slit nozzle, and the polyimide substrate was controlled to pass at a predetermined speed. Thereby, the resin composition (A) having a uniform thickness adhered to the polyimide substrate. Thereafter, light having an illuminance of 100 mW / cm ² (405 nm) was irradiated on the polyimide substrate on which the resin composition (A) was adhered for 30 seconds with an irradiator equipped with an ultra-high pressure mercury lamp (“UL-750” manufactured by HOYA). Irradiation was performed to cure the film of the resin composition (A) to form a first organic film. As a result, a first organic film having a transparent and flat film thickness of about 1.3 μm was obtained.

Next, the polyimide substrate was transferred again to the inorganic film formation chamber, and argon gas and oxygen gas were introduced into the inorganic film formation chamber, and aluminum oxide as the second inorganic film was formed by sputtering. At this time, a transparent and flat aluminum oxide film having a thickness of about 40 nm was formed on the polyimide substrate.

Thereafter, the second organic film is formed on the second inorganic film in the same manner as the first organic film, and the third inorganic film is formed on the second organic film in the same manner as the second inorganic film. did.

Next, in the same manner as the first organic film, after the resin composition (A) is attached on the third inorganic film, the organic film forming chamber is not irradiated with light or exposed to the atmosphere. The polyimide substrate was transferred to a glove box (sealing chamber) under a vacuum atmosphere. Here, a 125 μm thick polyester substrate (“Cosmo Shine A4100” manufactured by Toyobo Co., Ltd.) prepared in advance was applied to the surface on which the resin composition (A) on the polyimide substrate on which the sealing layer was formed was adhered. Combined. In this state, the vacuum is maintained, and then the pressure is returned to atmospheric pressure. With an irradiator equipped with an ultrahigh pressure mercury lamp (“UL-750” manufactured by HOYA), light of 100 mW / cm ² (405 nm) is applied for 30 seconds to a polyester substrate. Irradiated from the side, the polyester substrate was fixed. Thus, an organic EL device having the sealing structure of this embodiment was produced. The organic EL device produced as described above is excellent in flexibility and has a sufficient barrier property and adhesion strength against water vapor and oxygen, so that the organic EL device is excellent in moisture resistance.

(Examples 2-6, Comparative Examples 1-4)
An organic EL device was produced in the same manner as in Example 1 except that the resin composition (A) was changed to the resin compositions (B) to (J) in Example 1.

Table 2 shows the characteristics of each organic EL device manufactured as described above. Each characteristic was evaluated by the following method.

(Flexibility evaluation)
Using an MIT tester (manufactured by Toyo Seiki Co., Ltd.), a bending test of the organic EL device is performed according to JIS P 8115, and the presence or absence of a change in appearance is confirmed every 100 times. The number of times was measured. Evaluation was made with the maximum number of bendings being 500 times.

(Moisture resistance evaluation)
The organic EL device was exposed to an atmosphere at a temperature of 85 ° C. and a humidity of 85% RH, and the presence or absence of an appearance change was confirmed every 50 hours, and the time when black spots (dark spots) were generated was measured. The maximum exposure time was 300 hours.

Since the present invention has a low viscosity and good storage stability, it is excellent in coating properties, thinning and flattening. INDUSTRIAL APPLICABILITY Since the glass transition temperature after polymerization is low, the present invention can provide an energy curable resin composition for an organic material film of an organic EL device excellent in flexibility. The present invention comprises an organic film made of the resin composition, has a structure with an improved barrier property against gas such as water vapor and oxygen entering the organic EL element formed on the substrate, and has excellent moisture resistance. An organic EL device and a manufacturing method thereof can be provided.

As described above, since the organic EL device according to the present invention is an organic EL device having excellent flexibility and moisture resistance, displays such as televisions, notebook computers, smartphones, tablets, car navigation systems, and electronic papers. It can also be applied to lighting devices and the like, and is very useful industrially.

Claims (12)

(A) a polyene compound which is an allyl compound , (b) a polythiol compound having an alkylene oxide group, (c) a polymerization inhibitor which is one or more members selected from the group consisting of a quinone compound and a nitrosamine compound, (d) light contain a polymerization initiator, (c) the content of polymerization inhibitor per 100 parts by weight of the polyene compound and a polythiol compound, a resin composition for an organic EL device Ru 0.00001 to 1.0 parts by der object. (B) The polythiol compound having an alkylene oxide group is 1,8-dimercapto-3,6-dioxaoctane, and (c) one or more members selected from the group consisting of hydroquinone monomethyl ether and hydroquinone der is, is at least one of the group consisting of (c) and nitrosamine compound is N- nitrosophenylhydroxylamine ammonium salt N- nitrosophenylhydroxylamine aluminum salt, is (d) a photopolymerization initiator, an acyl phosphine oxide derivative, an oxime ester a compound der Ru claim 1 for the organic EL device resin composition according one or more of the group. The allyl compound is at least one member selected from the group consisting of diallyl phthalate, diallyl maleate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, tetraallyloxyethane, (a) a polyene compound and ( b) The mass ratio of the polythiol compound having an alkylene oxide group is 90:10 to 10:90, and (d) the content of the photopolymerization initiator is 0 with respect to 100 parts by mass in total of the polyene compound and the polythiol compound. .001～10 parts by der Ru claim 1 or 2 for the organic EL device resin composition. The resin composition for an organic EL device according to claim 1, wherein the use is for a flexible organic EL device. 25 viscosity when ° C. is not more than 1 mPa · s or higher 200 mPa · s, and the film obtained by being polymerized by energy ray glass transition temperature of claims 1-4 is -40 ℃ than 40 ° C. or less Item 1. A resin composition for an organic EL device according to item 1. Entirely covering the energy ray-curable resin composition for the organic EL device resin composition according paragraph 1 is used in applications where the entire surface covering the sealing substrate surface of claim 1-5. A substrate, an organic EL element including an organic EL layer including a light emitting layer between a pair of electrodes, at least one of which is transparent or translucent, on the substrate; an inorganic film that seals the organic EL element; and an organic substance A sealing layer in which films are alternately stacked, and a sealing substrate disposed in close contact with the uppermost organic film of the sealing layer so as to cover the entire upper surface of the uppermost organic film, the organic layer is an organic EL device is a resin composition according one of claims 1 to 5. The organic EL device according to claim 7, wherein the sealing layer is configured by alternately laminating a plurality of the inorganic films and the organic films. The organic EL device according to claim 7 or 8, wherein the substrate is a plastic substrate. An organic EL device, wherein the plastic substrate according to claim 9 is at least one member selected from the group consisting of polyimide, polyetherimide, polyethylene terephthalate, and polyethylene naphthalate. The organic EL device according to claim 7, which is a flexible organic EL device. Display comprising an organic EL device according one of the claims 7-11.