WO2019203071A1 - Matériau d'encapsulation pour élément d'affichage électroluminescent organique - Google Patents

Matériau d'encapsulation pour élément d'affichage électroluminescent organique Download PDF

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Publication number
WO2019203071A1
WO2019203071A1 PCT/JP2019/015509 JP2019015509W WO2019203071A1 WO 2019203071 A1 WO2019203071 A1 WO 2019203071A1 JP 2019015509 W JP2019015509 W JP 2019015509W WO 2019203071 A1 WO2019203071 A1 WO 2019203071A1
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Prior art keywords
meth
acrylate
organic
organic electroluminescence
electroluminescence display
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PCT/JP2019/015509
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English (en)
Japanese (ja)
Inventor
剛介 中島
麻希子 佐々木
啓之 栗村
仁 仲田
結城　敏尚
憲史 川村
Original Assignee
デンカ株式会社
国立大学法人山形大学
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Application filed by デンカ株式会社, 国立大学法人山形大学 filed Critical デンカ株式会社
Priority to KR1020207032556A priority Critical patent/KR20200143442A/ko
Priority to CN201980025710.0A priority patent/CN111972047A/zh
Priority to JP2020514095A priority patent/JP7360131B2/ja
Publication of WO2019203071A1 publication Critical patent/WO2019203071A1/fr

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/871—Self-supporting sealing arrangements
    • H10K59/8722—Peripheral sealing arrangements, e.g. adhesives, sealants
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F22/10—Esters
    • C08F22/1006—Esters of polyhydric alcohols or polyhydric phenols, e.g. ethylene glycol dimethacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H05B33/04—Sealing arrangements, e.g. against humidity
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/873—Encapsulations

Definitions

  • the present invention relates to an encapsulant for organic electroluminescence display elements.
  • OLED elements Organic electroluminescence (EL) elements (also referred to as OLED elements) are attracting attention as element bodies capable of emitting light with high luminance.
  • the OLED element has a problem in that it deteriorates due to oxygen and moisture, resulting in a decrease in light emission characteristics.
  • An organic electroluminescence display element (see Patent Document 2), wherein the sealing layer is a laminate in which at least a barrier layer, a resin layer, and a barrier layer are sequentially formed, and an inorganic film and an organic film for sealing the organic EL element And a sealing glass substrate disposed in close contact with the uppermost organic material film of the sealing layer so as to cover the entire upper surface of the uppermost organic material film.
  • the sealing layer is a laminate in which at least a barrier layer, a resin layer, and a barrier layer are sequentially formed, and an inorganic film and an organic film for sealing the organic EL element And a sealing glass substrate disposed in close contact with the uppermost organic material film of the sealing layer so as to cover the entire upper surface of the uppermost organic material film.
  • a sealing agent for an organic electroluminescence display element containing a cyclic ether compound, a cationic polymerization initiator, and a polyfunctional vinyl ether compound
  • Patent Document 4 cationic polymerizable A cationically polymerizable resin composition containing a compound and a photocationic polymerization initiator or a thermal cationic polymerization initiator has been proposed (see Patent Document 5).
  • Patent Documents 6 to 14 As a resin composition for sealing an organic EL element, a (meth) acrylic resin composition has been proposed (Patent Documents 6 to 14).
  • Patent Document 1 when mass production is performed, a method is adopted in which an organic EL element is sandwiched between substrates having low moisture permeability, such as glass, and the outer peripheral portion is sealed.
  • this structure is a hollow sealing structure, there is a problem that moisture cannot be prevented from entering the hollow sealing structure, leading to deterioration of the organic EL element.
  • Patent Documents 2 to 3 there is a problem that the thickness of the organic film becomes 3 ⁇ m or less because the organic film is formed by vapor deposition.
  • the thickness of the organic film is 3 ⁇ m or less, not only particles generated during device formation cannot be completely covered, but also there is a problem that it is difficult to apply the film while maintaining flatness on the inorganic film.
  • Patent Document 4 proposes a sealant using an epoxy-based material. However, since such a material requires heating to be cured, the organic EL element is damaged and there is a problem in terms of yield. It was.
  • Patent Document 5 a photo-curing type sealant using an epoxy-based material has been proposed. However, since such a material is cured by UV light, the organic EL element is damaged by UV light and the yield is increased. There was a problem in terms of.
  • Patent Documents 6 to 10 and 12 to 14 there is a description about reducing the water vapor transmission rate as a necessary characteristic of such a sealing material, but the sealing material itself penetrates from the pinhole of the passivation film. There is no description about the problem of reducing the reliability of organic EL elements and the countermeasures.
  • patent document 11 describes use of cyclic monofunctional (meth) acrylate, the unreacted substance becomes outgas and cannot solve the problem that leads to light emission failure of the organic EL element.
  • This invention is made
  • the embodiment of the present invention can provide the following.
  • (C) It further contains (meth) acrylates other than the component (A), and the total amount of the component (A) and the component (C) is 100 parts by mass, and the component (A) is 30 parts by mass or more and less than 100 parts by mass,
  • the component (C) is at least one member of the group consisting of an alkyl (meth) acrylate having 8 or more carbon atoms, a (meth) acrylate having an alicyclic hydrocarbon group, and a (meth) acrylate having an aromatic hydrocarbon group.
  • the sealing agent for organic electroluminescence display elements according to any one of [2] to [9].
  • (C) component is dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and dicyclopentanyloxy
  • the sealing agent for organic electroluminescence display elements according to any one of [2] to [11], which contains one or more members selected from the group consisting of ethyl (meth) acrylate.
  • a display comprising the encapsulant for organic electroluminescence display elements according to any one of [1] to [14].
  • the sealant according to the present invention has an effect of being excellent in dischargeability when using an ink jet and excellent in reliability, applicability, and low moisture permeability of an organic EL element to be obtained.
  • the present embodiment relates to a sealant for organic electroluminescence display elements.
  • This embodiment is related with the (meth) acrylic-type resin composition which can be used for the sealing agent for organic electroluminescent (EL) display elements, for example.
  • (Meth) acrylate represents acrylate or methacrylate, and “(meth) acryloyloxy”, “(meth) acrylamide” and the like have the same meaning.
  • “Monofunctional (meth) acrylate” refers to (meth) acrylate having one (meth) acryl group
  • “bifunctional (meth) acrylate” refers to (meth) acrylate having two (meth) acryl groups.
  • Polyfunctional (meth) acrylate refers to (meth) acrylate having 3 or more (meth) acryl groups, and does not include bifunctional (meth) acrylate.
  • 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, a cathode are sequentially stacked on a substrate, and a laminate of an inorganic film and an organic film covering the entire organic EL element. It has a structure in which a sealing layer made of a film and a sealing substrate provided on the sealing layer are sequentially formed.
  • various substrates such as a glass substrate, a silicon substrate, and a plastic substrate can be used.
  • a glass substrate As the substrate, various substrates such as a glass substrate, a silicon substrate, and a plastic substrate can be used.
  • 1 or more types in the group which consists of a glass substrate and a plastic substrate are preferable, and a glass substrate is more preferable.
  • 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, polycycloolefin, and polyacryl. 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, polyethylene terephthalate are high in the ability to transmit energy rays such as ultraviolet rays or visible rays.
  • One or more members selected from the group consisting of polyethylene naphthalate are more preferable.
  • a conductive metal oxide film or a translucent metal thin film having a relatively large work function is generally used.
  • the material of the anode include indium tin oxide (Indium Tin Oxide, hereinafter referred to as ITO), metal oxide such as tin oxide, gold (Au), platinum (Pt), silver (Ag), copper (Cu), and the like.
  • ITO indium tin oxide
  • metal oxide such as tin oxide
  • silver (Ag), copper (Cu) and the like.
  • an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof, or the like.
  • 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 ⁇ m, more preferably 20 nm to 1 ⁇ m, 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.
  • a reflective film for reflecting light emitted to 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 contains a light emitting material.
  • the luminescent material include organic substances (low molecular compounds or high molecular compounds) that emit fluorescence or phosphorescence.
  • the light emitting layer may further contain a dopant material.
  • the organic material include a dye material, a metal complex material, and a polymer material.
  • the dopant material is doped into the organic material for the purpose of improving the luminous efficiency of the organic material or changing the emission wavelength.
  • the thickness of the light emitting layer composed of these organic substances and a dopant doped as necessary is usually 2 to 200 nm.
  • dye materials include cyclopentamine derivatives, tetraphenylbutadiene derivative compounds, triphenylamine derivatives, oxadiazole derivatives, pyrazoloquinoline derivatives, distyrylbenzene derivatives, distyrylarylene derivatives, pyrrole derivatives, thiophene ring compounds, pyridine
  • dye materials include cyclopentamine derivatives, tetraphenylbutadiene derivative compounds, triphenylamine derivatives, oxadiazole derivatives, pyrazoloquinoline derivatives, distyrylbenzene derivatives, distyrylarylene derivatives, pyrrole derivatives, thiophene ring compounds, pyridine
  • ring compounds include ring compounds, perinone derivatives, perylene derivatives, oligothiophene derivatives, trifumanylamine derivatives, oxadiazole dimers, and pyrazoline dimers.
  • 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. And metal complexes such as porphyrin zinc complex and europium complex.
  • the central metal includes rare earth metals such as terbium (Tb), europium (Eu), and dysprosium (Dy), aluminum (Al), zinc (Zn), beryllium (Be), etc., and a ligand
  • rare earth metals such as terbium (Tb), europium (Eu), and dysprosium (Dy), aluminum (Al), zinc (Zn), beryllium (Be), etc.
  • a ligand examples thereof include metal complexes having oxadiazole, thiadiazole, phenylpyridine, phenylbenzimidazole, quinoline structure, and the like.
  • a metal complex having aluminum (Al) as a central metal and a quinoline structure or the like as a ligand is preferable.
  • metal complexes having aluminum (Al) as a central metal and a quinoline structure as a ligand tris (8-hydroxyquinolinato) aluminum is preferable.
  • Polymer material include polyparaphenylene vinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, polyacetylene derivatives, polyfluorene derivatives, polyvinylcarbazole derivatives, substances obtained by polymerizing the above chromophores and metal complex light emitting materials, etc. Is mentioned.
  • materials that emit blue light include distyrylarylene derivatives, oxadiazole derivatives, polyvinylcarbazole derivatives, polyparaphenylene derivatives, polyfluorene derivatives, and polymers thereof.
  • a polymer material is preferable.
  • the polymer materials one or more members selected from the group consisting of polyvinylcarbazole derivatives, polyparaphenylene derivatives, and polyfluorene derivatives are preferable.
  • Examples of materials that emit green light include quinacridone derivatives, coumarin derivatives, polyparaphenylene vinylene derivatives, polyfluorene derivatives, and polymers thereof.
  • a polymer material is preferable.
  • the polymer materials one or more members selected from the group consisting of polyparaphenylene vinylene derivatives and polyfluorene derivatives are preferable.
  • Examples of materials that emit red light include coumarin derivatives, thiophene ring compounds, polyparaphenylene vinylene derivatives, polythiophene derivatives, polyfluorene derivatives, and polymers thereof.
  • a polymer material is preferable.
  • the polymer materials one or more members selected from the group consisting of polyparaphenylene vinylene derivatives, polythiophene derivatives, and polyfluorene derivatives are preferable.
  • Dopant material examples include perylene derivatives, coumarin derivatives, rubrene derivatives, quinacridone derivatives, squalium derivatives, porphyrin derivatives, styryl dyes, tetracene derivatives, pyrazolone derivatives, decacyclene, phenoxazone, and the like.
  • 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.
  • a hole injection layer for improving the hole injection efficiency from the anode, or holes injected from the anode or the hole injection layer are transported to the light emitting layer.
  • a hole transport layer examples of the layer provided between the light emitting layer and the cathode include an electron injection layer for improving electron injection efficiency from the cathode and an electron transport layer for transporting electrons injected from the cathode or the electron injection layer to the light emitting layer. It is done.
  • Examples of the material for forming the hole injection layer include phenylamines such as 4,4 ′, 4 ′′ -tris ⁇ 2-naphthyl (phenyl) amino ⁇ triphenylamine, starburst amines, phthalocyanines, vanadium oxide, Examples thereof include oxides such as molybdenum oxide, ruthenium oxide, and aluminum oxide, amorphous carbon, polyaniline, and polythiophene derivatives.
  • 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.
  • the benzidine derivative include N, N′-diphenyl-N, N′-dinaphthylbenzidine and the like.
  • 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.
  • Electrode 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, and 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.
  • 8-hydroxyquinoline or a derivative thereof is preferable.
  • tris (8-hydroxyquinolinato) aluminum is preferable because it can be used as an organic substance that emits fluorescence or phosphorescence contained in the light emitting layer.
  • the electron injection layer is an electron injection layer having a single layer structure of a calcium (Ca) layer or a metal belonging to groups IA and IIA of the periodic table and having a work function of 1 depending on the type of the light emitting layer. And an electron injection layer having a laminated structure of a Ca layer and a layer formed of one or more members selected from the group consisting of a metal of 0.5 to 3.0 eV and oxides, halides and carbonates of the metal. .
  • Examples of metals of Group IA of the periodic table having a work function of 1.5 to 3.0 eV or oxides, halides, and carbonates thereof include lithium (Li), lithium fluoride, sodium oxide, lithium oxide, lithium carbonate, etc. Is mentioned.
  • Group IIA metals or oxides, halides, and carbonates thereof having a work function of 1.5 to 3.0 eV include strontium (Sr), magnesium oxide, magnesium fluoride, strontium fluoride, fluoride Barium, strontium oxide, magnesium carbonate and the like can be mentioned.
  • 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.
  • 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.
  • cathode materials include lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), beryllium (Be), magnesium (Mg), calcium (Ca), and strontium (Sr).
  • the cathode may have a laminated structure of two or more layers.
  • the laminated structure of two or more layers include a laminated structure of the metal, metal oxide, fluoride, and alloys thereof and a metal such as Al, Ag, and Cr.
  • the film thickness of the cathode can be appropriately selected in consideration of electric conductivity and durability.
  • the thickness of the cathode is preferably 10 nm to 10 ⁇ m, more preferably 15 nm to 1 ⁇ m, and most preferably 20 nm to 500 nm.
  • 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.
  • the structure of the organic EL element used in the present embodiment can have any of the following layer configurations (i) to (xv).
  • 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 /
  • 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.
  • a gas such as water vapor or oxygen
  • 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 to provide flatness to the surface in order to cover 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.
  • the uppermost organic film formed in the uppermost layer of the entire sealing layer 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 a composition having good adhesion with the above-described inorganic film is used.
  • This embodiment is suitable for, for example, ink jet coating capable of coating with excellent flatness with a film thickness of 3 ⁇ m or more in a short time, and is excellent in ejection property by ink jet and flatness after ink jet coating, and has a barrier property against water vapor (
  • the organic electroluminescence display element that forms the organic film, in which the sealing agent permeates through the pinholes on the inorganic film and the reliability of the organic EL element does not deteriorate is also referred to as “low moisture permeability”.
  • An object of the present invention is to provide a sealing agent. If an application method using an inkjet method is used, an organic film can be formed at high speed and uniformly.
  • the viscosity of the composition of this embodiment it is preferable that the viscosity measured on 25 degreeC and 100 rpm conditions using an E-type viscosity meter is 2 mPa * s or more and 50 mPa * s or less. If it is difficult to eject by inkjet, the inkjet head is heated appropriately. When the viscosity is 2 mPa ⁇ s or more, the coated organic EL display element sealant does not flow out of the organic EL display element before curing, does not flow into the pinhole on the inorganic film, and the reliability of the OLED element Will improve. When the viscosity is 50 mPa ⁇ s or less, application by ink jet becomes easy.
  • the viscosity of the composition is more preferably 5 mPa ⁇ s to 30 mPa ⁇ s.
  • the composition of this embodiment is a (meth) acrylic resin composition containing (A) an alkanediol di (meth) acrylate having 4 to 20 carbon atoms and (B) a photopolymerization initiator.
  • A an alkanediol di (meth) acrylate having 4 to 20 carbon atoms
  • B a photopolymerization initiator.
  • carbon number of a (meth) acrylate part shall not be included.
  • Examples of the alkane of the alkanediol di (meth) acrylate having 4 to 20 carbon atoms include chain compounds and cyclic compounds.
  • a chain compound is preferable.
  • the chain compound may be a linear compound or a branched compound.
  • As the alkane a saturated hydrocarbon is preferable.
  • Alkanediol di (meth) acrylate having 4 to 20 carbon atoms alkane is a chain compound and saturated hydrocarbon
  • Alkanediol di (meth) acrylate having 4 to 20 carbon atoms includes 1,2-cyclohexanediol di (meth) acrylate, 1,3-cyclohexanediol di (meth) acrylate 1,4-cyclohexanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, hydrogenated bisphenol A di (meth) acrylate, and the like.
  • alkanediol di (meth) acrylates having 4 or more and 20 or less carbon atoms, it is better to have a large number of carbon atoms in the main chain from the viewpoint of reliability to the OLED element, but the composition may crystallize during storage, The problem of storage stability that a crystallized product is generated occurs.
  • the carbon number is preferably 6 or more and 18 or less, more preferably 9 or more and 16 or less, still more preferably 12 or more and 16 or less, and most preferably 12.
  • 1,12-dodecanediol di (meth) acrylate is preferable.
  • the component (A) include a trade name “1.9ND-A” manufactured by Kyoeisha Chemical Co., a trade name “SR262” manufactured by Sartomer.
  • a photoinitiator is used in order to accelerate the photocuring of a resin composition by sensitizing with actinic light of visible light or ultraviolet light.
  • a radical photopolymerization initiator is preferable.
  • radical photopolymerization initiators benzophenone and derivatives thereof, benzyl and derivatives thereof, enthraquinone and derivatives thereof, benzoin derivatives such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, Acetophenone derivatives such as diethoxyacetophenone and 4-tert-butyltrichloroacetophenone, 2-dimethylaminoethylbenzoate, p-dimethylaminoethylbenzoate, diphenyldisulfide, thioxanthone and its derivatives, camphorquinone, 7,7-dimethyl-2,3 -Dioxobicyclo [2.2.1] heptane-1-carboxylic acid, 7,7-dimethyl-2,3-dioxobicyclo [2.2.1] Tan-1-carboxylic
  • a photoinitiator can be used combining 1 or more types.
  • acylphosphine oxide derivatives are preferred in that they can be cured using only visible light of 390 nm or more when cured, and can be cured without damaging the organic electroluminescence display element.
  • 2,4,6-trimethylbenzoyl-diphenyl can be cured using only light of 395 nm or more without reducing visible light transmittance when used as a display.
  • -Phosphine oxide is most preferred.
  • Examples of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide include “Irgacure TPO” manufactured by BASF Japan.
  • the content of the (B) photopolymerization initiator is preferably 0.05 to 6 parts by mass with respect to 100 parts by mass in total of the component (A) and the component (C) used as necessary, and 0.5 to More preferred is 4 parts by weight, most preferred is 2 to 3.9 parts by weight, and still more preferred is 2.2 to 3.5 parts by weight. If the content of the component (C) is 0.05 parts by mass or more, the effect of promoting curing is surely obtained, and if it is 6 parts by mass or less, the transmittance with visible light decreases when used for a display. There is nothing to do.
  • the amount of the hydrophilic functional group per (meth) acrylate contained is 4.80 to 7.60 mmol / g.
  • the amount of the hydrophilic functional group of the (meth) acrylic resin composition is calculated by the following formula for the amount of the hydrophilic functional group per (meth) acrylate of the component (A) and, if present, the component (C), and thereafter Calculate the product obtained by multiplying the amount of hydrophilic functional group of each material by the mass fraction of each material shown in the formula below, which is blended in the (meth) acrylic resin composition, and then add the total to (meth) acrylic It was set as the amount of hydrophilic functional groups of the resin composition.
  • the total of (meth) acrylate was 100 parts by mass.
  • the material means each (meth) acrylate component
  • the material means each (meth) acrylate component
  • the amount of the hydrophilic functional group is 4.80 mmol / g or more, since there are many (meth) acryloyl groups that are reactive groups, the reactivity becomes high, and the sealing performance of the organic EL element is satisfactorily expressed. Since it becomes moisture permeable, the reliability of the organic EL element is improved and the flatness is improved.
  • this embodiment contains (meth) acrylates other than (A) component as (C) component.
  • (C) component 1 or more types in the group which consists of monofunctional (meth) acrylate, bifunctional (meth) acrylate, and polyfunctional (meth) acrylate can be used.
  • component (C) it is possible to adjust the amount of the hydrophilic functional group of the composition, and it is also possible to adjust the viscosity, inkjet coating property, and moisture permeability.
  • the hydrophilic functional group means that the maximum value of the difference in electronegativity among atoms constituting the functional group is 0.6 or more.
  • hydrophilic functional groups include (meth) acryloyl group, ester group, aldehyde group, nitro group, hydroxyl group, ethylene oxide group, propylene oxide group, ether group, amide group, cyclic amide group, sulfoxide group, carbonyl group, A group consisting of carboxylic acid (salt) group, sulfonic acid (salt) group, sulfinic acid (salt) group, phosphonic acid (salt) group, phosphoric acid (salt) group, sulfobetaine group, carbobetaine group, phosphobetaine group One or more are preferred.
  • (meth) acrylate of the component (C) As the monofunctional (meth) acrylate of the component (C), (meth) acrylate having a cyclic structure such as a heterocyclic structure containing a cyclic amide group, a tetrahydrofurfuryl group, a piperidinyl group or the like can be used.
  • a cyclic structure such as a heterocyclic structure containing a cyclic amide group, a tetrahydrofurfuryl group, a piperidinyl group or the like can be used.
  • Component bifunctional (meth) acrylates include dicyclopentanyl di (meth) acrylate, 2-ethyl-2-butyl-propanediol (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) Acrylate, stearic acid-modified pentaerythritol di (meth) acrylate, polypropylene glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, 2,2-bis (4- (meth) acryloxydiethoxyphenyl) Propane, 2,2-bis (4- (meth) acryloxypropoxyphenyl) propane, 2,2-bis (4- (meth) acryloxytetraethoxyphenyl) propane, 2- (1,2-cyclohexacarboximide) ) Ethyl (meth) acrylate, bis Phenol A epoxy di (meth) acrylate.
  • an ethoxylated bisphenol A di (meth) acrylate compound represented by the following structural formula a propoxylated bisphenol A di (meth) acrylate, a propoxylated ethoxylated bisphenol A di ( And (meth) acrylate.
  • R in the following formula is each independently a hydrogen atom or a methyl group.
  • m + n 2 to 10 is preferable.
  • trimethylolpropane tri (meth) acrylate tris [(meth) acryloyloxyethyl] isocyanurate, dimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) ) Acrylate, pentaerythritol ethoxytetra (meth) acrylate, dipentaerystol penta (meth) acrylate, dipentaerystol hexa (meth) acrylate, and the like.
  • the amount of the hydrophilic functional group of the component (C) is preferably 3.00 to 15.00 mmol / g.
  • the amount of the hydrophilic functional group of the component (C) is preferably 4.00 to 15.00 mmol / g, more preferably 4.10 to 8.20 mmol / g. Even more preferred is ⁇ 7.60 mmol / g.
  • the component (C) includes an alkyl (meth) acrylate having 8 or more carbon atoms, a (meth) acrylate having an alicyclic hydrocarbon group, and an aromatic hydrocarbon. It is preferable that it is 1 or more types of the group which consists of (meth) acrylate which has group.
  • the alkyl (meth) acrylate having 8 or more carbon atoms is preferably one or more members selected from the group consisting of isooctyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate, and lauryl (meth). Most preferred are acrylates.
  • Examples of (meth) acrylate having an alicyclic hydrocarbon group include cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, di One or more members selected from the group consisting of cyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, and tricyclodecane dimethanol di (meth) acrylate are preferred.
  • Dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl One or more members of the group consisting of (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and dicyclopentanyloxyethyl (meth) acrylate are more preferable.
  • the (meth) acrylate having an aromatic hydrocarbon group ethoxylated-o-phenylphenol (meth) acrylate is preferable.
  • the content of the component (A) is preferably 30 to 100 parts by mass and more preferably 30 parts by mass or more and less than 100 parts by mass with respect to 100 parts by mass in total of the components (A) and (C).
  • the content of (A) is 30 parts by mass or more, inkjet coating properties, low moisture permeability, and reliability of the organic EL element are excellent.
  • ink jet coating property, low moisture permeability, and reliability of the organic EL device 55 to 99 parts by mass is preferable, 60 to 95 parts by mass is more preferable, and 65 to 95 parts by mass is still more preferable.
  • the content of the component (C) is preferably more than 0 parts by mass and 70 parts by mass or less with respect to 100 parts by mass in total of the components (A) and (C).
  • the content of the component (C) is 70 parts by mass or less, the inkjet coating property, low moisture permeability, and the reliability of the organic EL element are excellent.
  • the content of the component (C) is preferably 1 to 45 parts by weight, more preferably 5 to 40 parts by weight, and further preferably 5 to 35 parts by weight from the viewpoints of ink jet coating property, low moisture permeability, and reliability of the organic EL element. preferable.
  • the composition of the present embodiment has a low water content.
  • the water content is preferably 90 ppm or less, more preferably 50 ppm or less, and even more preferably 30 ppm or less.
  • Such moisture content can be measured using a commercially available moisture meter, but a Karl Fischer moisture meter is generally used.
  • the desiccant is not particularly limited as long as the resin composition is not affected, but is not limited to polymer adsorbents (molecular sieve, synthetic zeolite, alumina, silica gel, etc.), inorganic salts (calcium chloride, anhydrous magnesium sulfate, quicklime, anhydrous sodium sulfate) And anhydrous calcium sulfate) and solid alkalis (sodium hydroxide, potassium hydroxide, etc.).
  • polymer adsorbents molecular sieve, synthetic zeolite, alumina, silica gel, etc.
  • inorganic salts calcium chloride, anhydrous magnesium sulfate, quicklime, anhydrous sodium sulfate
  • anhydrous calcium sulfate solid alkalis
  • the water content may be reduced by reducing the moisture for each component before mixing, or by reducing the moisture after mixing each component.
  • One or more kinds of water content reduction steps may be used. In order to prevent re-mixing of the water after the water content reduction step, it is preferable to handle in an inert gas atmosphere.
  • the dissolved oxygen amount is small in the composition of the present embodiment.
  • the amount of dissolved oxygen is preferably 20 ppm or less, and more preferably 10 ppm or less.
  • dissolved oxygen reacts with active radicals generated from the composition to produce inactive peroxide radicals, thereby suppressing the thickening associated with the polymerization of the composition. From the viewpoint, 1 ppm or more is preferable, and 2 ppm or more is more preferable.
  • Such a dissolved oxygen amount can be measured by a titration method using a reagent, a diaphragm electrode method using a diaphragm, a fluorescence method using a fluorescent substance, or the like.
  • the measuring method is not particularly limited, but the diaphragm electrode method is simple and preferable.
  • the amount of dissolved oxygen may be reduced for each component before mixing, or may be reduced after mixing each component.
  • One or more kinds of steps for reducing the amount of dissolved oxygen may be used. In order to prevent re-mixing of oxygen after the step of reducing the amount of dissolved oxygen, it is preferable to handle in an inert gas atmosphere.
  • the (meth) acrylate is preferably a monomer from the viewpoint of inkjet dischargeability.
  • the component (A) or the component (C) is preferably a monomer.
  • the molecular weight of the monomer is preferably 1000 or less.
  • the bifunctional (meth) acrylate oligomer / polymer and the polyfunctional (meth) acrylate oligomer / polymer are 3 parts in 100 parts by weight of (meth) acrylate containing the component (A) or the component (C).
  • the content is preferably not more than 1 part by mass, more preferably not more than 1 part by mass, and most preferably not.
  • Oligomer / polymer refers to one or more of the group consisting of oligomers and polymers.
  • the molecular weight of the oligomer / polymer preferably exceeds 1000.
  • composition of this embodiment can use (D) antioxidant for the improvement of storage stability.
  • Antioxidants include methylhydroquinone, hydroquinone, octadecyl 3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionate, 2,2-methylene-bis (4-methyl-6-tert-butylphenol) ), Catechol, hydroquinone monomethyl ether, mono tert-butyl hydroquinone, 2,5-di tert-butyl hydroquinone, p-benzoquinone, 2,5-diphenyl-p-benzoquinone, 2,5-di tert-butyl-p-benzoquinone , Picric acid, citric acid, phenothiazine, tert-butylcatechol, 2-butyl-4-hydroxyanisole, and 2,6-ditert-butyl-p-cresol.
  • a phenolic antioxidant is preferable at the point with big effects, such as transparency and storage stability.
  • hindered phenolic antioxidants are preferable.
  • the hindered phenol antioxidants include octadecyl 3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionate, 2,2-methylene-bis (4-methyl-6-tert-butylphenol).
  • one or more members of the group consisting of: octadecyl 3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionate and 2,2-methylene-bis (4-methyl-6-tert- (Butylphenol) is more preferable.
  • octadecyl 3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionate include “Irganox 1076” manufactured by BASF Japan.
  • 2,2-methylene-bis (4-methyl-6-tert-butylphenol) include “SUMILIZER MDP-S” manufactured by Sumitomo Chemical Co., Ltd.
  • the content of the antioxidant is preferably 0.001 to 3 parts by mass and more preferably 0.01 to 2 parts by mass with respect to 100 parts by mass in total of the components (A) and (C). If it is 0.001 mass part or more, storage stability will be ensured, and if it is 3 mass parts or less, favorable adhesiveness will be obtained and it will not become uncured.
  • the composition of this embodiment can be used as a resin composition.
  • the composition of this embodiment can be used as a photocurable resin composition.
  • the composition of this embodiment can be used as a sealing agent for organic EL display elements.
  • Examples of the method of curing the composition by irradiation with visible light or ultraviolet light include a method of curing the composition by irradiation with at least one of visible light or ultraviolet light.
  • Examples of energy irradiation sources for irradiating visible light or ultraviolet light include deuterium lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, low-pressure mercury lamps, xenon lamps, xenon-mercury hybrid lamps, halogen lamps, excimer lamps,
  • Examples of the energy irradiation source include an indium lamp, a thallium lamp, an LED lamp, and an electrodeless discharge lamp.
  • the composition of the present embodiment is preferably cured at a wavelength of 380 nm or more, more preferably cured at a wavelength of 395 nm or more, and is cured at a wavelength of 395 nm because it is difficult to damage the organic EL element.
  • the wavelength of the energy irradiation source is preferably 500 nm or less because the temperature of the irradiated part is increased by emitting infrared light and may damage the organic EL element.
  • an LED lamp having a single emission wavelength is preferable.
  • curing composition By irradiating visible or ultraviolet light, when curing composition is preferably cured by irradiating the composition with an energy ray of 100 ⁇ 8000mJ / cm 2 at a wavelength of 395 nm. If it is 100 to 8000 mJ / cm 2 , the composition is cured and sufficient adhesive strength can be obtained. 100 mJ / cm 2 or more value, if the composition is sufficiently cured, does not damage the organic EL element if 8000 mJ / cm 2 or less. The amount of energy for curing the composition is more preferably 300 to 2000 mJ / cm 2 .
  • the transparency of the composition of this embodiment is as follows.
  • the spectral transmittance in the ultraviolet-visible light region of 360 nm or more and 800 nm or less is preferably 95% or more, more preferably 97% or more, and most preferably 99% or more. If it is 95% or more, an organic EL device excellent in luminance and contrast can be provided.
  • the sealing layer made of the composition of the present embodiment is preferably 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 of the inorganic / organic laminate is preferably 50 nm to 1 ⁇ m.
  • the thickness of the organic film of the inorganic / organic laminate is preferably 1 to 15 ⁇ m, and more preferably 3 to 10 ⁇ m. When the thickness of the organic film is 1 ⁇ m or more, the particles generated at the time of element formation are completely covered, and the film can be applied on the inorganic film while ensuring flatness. When the thickness of the organic film is 15 ⁇ m or less, moisture does not enter from the side surface of the organic film, and the reliability of the organic EL element is improved.
  • 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 include the aforementioned substrates. Among these, a substrate transparent to visible light is preferable. Among substrates transparent to visible light (transparent sealing substrate), one or more members selected from the group consisting of glass substrates and plastic substrates are preferable, and glass substrates are more preferable.
  • the thickness of the transparent sealing substrate is preferably from 1 ⁇ m to 1 mm, more preferably from 10 ⁇ m to 800 ⁇ m, and most preferably from 50 ⁇ m to 300 ⁇ m.
  • 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.
  • 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.
  • a predetermined thickness is formed on the substrate on which the organic EL element is formed by a film formation 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.
  • the composition of the present embodiment is deposited on the first inorganic film by using a coating film forming method such as a solution coating method or a spray coating method, a flash vapor deposition method, an ink jet method, or the like.
  • the inkjet method is preferable in terms of productivity.
  • the composition is cured by irradiation with energy rays such as ultraviolet rays, electron beams, and plasmas, and a first organic film is formed.
  • energy rays such as ultraviolet rays, electron beams, and plasmas
  • a first organic film is formed.
  • the curing rate of the composition is not particularly limited as long as the effect of the present embodiment is exhibited, but for example, 90% or more is preferable and 95% or more is more preferable as a value obtained according to a measurement method described later.
  • the formation process of the inorganic / organic laminated body shown above is repeated a predetermined number of times.
  • the composition is adhered to the upper surface of the inorganic film by a coating method, a flash vapor deposition method, an ink jet method or the like so that the upper surface is flattened. Also good.
  • a transparent sealing substrate is bonded to the surface on which the composition on the substrate is attached. Alignment is performed during pasting. Thereafter, the composition of the present embodiment existing between the uppermost inorganic film and the transparent sealing substrate is cured by irradiating energy rays from the transparent sealing substrate side. Accordingly, the 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.
  • the composition After the 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
  • 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.
  • the top emission type organic EL device has been described as an example.
  • the present embodiment can also be applied to a bottom emission type organic EL device that emits light generated in the organic EL layer from the substrate side.
  • the organic EL element of this embodiment can be used as a planar light source, a segment display device, and a dot matrix display device.
  • the organic EL element formed on the first substrate is formed with a sealing layer for blocking the outside air, and the transparent sealing substrate is further disposed on the sealing layer.
  • a sealing structure having a sufficient water vapor and oxygen barrier property for the EL element can be obtained.
  • the sealing structure which has sufficient adhesive strength between a transparent sealing substrate and a sealing layer can be obtained.
  • the transparent sealing substrate is placed without curing the composition, and then the composition Since the product is cured, 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.
  • the present embodiment 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.
  • the composition of this embodiment has a moisture permeability value at a thickness of 100 ⁇ m measured by exposing the cured body to an environment of 85 ° C. and 85% RH for 24 hours.
  • m is preferably 2 or less.
  • the moisture permeability is 350 g / m 2 or less, moisture does not reach the organic light emitting material layer and dark spots are unlikely to occur.
  • the sealing agent for organic EL display elements which can be easily apply
  • the manufacturing method of the organic EL display element using the sealing agent for organic EL display elements can be provided.
  • the ink jet method is a method in which fine droplets are ejected from a nozzle and applied to a target without contact.
  • E-type viscosity The viscosity of the composition was measured using an E-type viscometer (cone plate type: cone angle 1 ° 34 ′, cone rotor radius 24 mm) at a temperature of 25 ° C. and a rotation speed of 100 rpm.
  • the water content of the composition was measured with a trace moisture analyzer CA-06 (manufactured by Mitsubishi Chemical Corporation) using Aquamicron AX (manufactured by Mitsubishi Chemical Corporation) as a Karl Fischer solution.
  • the dissolved oxygen amount of the composition was measured using a dissolved oxygen meter (trade name “DO meter B-506 (diaphragm type galvanic cell type)” manufactured by Iijima Electronics Co., Ltd.).
  • the composition was cured under the following light irradiation conditions.
  • the composition is photocured and cured under the condition of an integrated light amount of 1,500 mJ / cm 2 at a wavelength of 395 nm by an LED lamp (UV-LED LIGHT SOURCE H-4MLH200-V1 manufactured by HOYA) that emits a wavelength of 395 nm.
  • UV-LED LIGHT SOURCE H-4MLH200-V1 manufactured by HOYA UV-LED LIGHT SOURCE H-4MLH200-V1 manufactured by HOYA
  • An infrared spectrometer (Nicolet is5, DTGS detector, resolution 4 cm ⁇ 1 , manufactured by Thermo Scientific Co.) is used for the composition after curing and the composition before curing, and infrared light is applied to the measurement sample. The incident infrared spectrum was measured. In the obtained infrared spectrum, the peak of the stretching vibration of the carbon-hydrogen bond of the methylene group observed near 2950 cm ⁇ 1 that does not cause a peak change before and after curing is taken as an internal standard, and before and after curing of this internal standard.
  • Curing rate (%) [1 ⁇ (Ax / Bx) / (Ao / Bo)] ⁇ 100 here, Ao: represents a peak area before curing near 810 cm ⁇ 1 . Ax: represents the peak area after curing near 810 cm ⁇ 1 . Bo: represents the peak area before curing in the vicinity of 2950 cm ⁇ 1 . Bx: it represents the peak area after curing in the vicinity of 2950 cm -1.
  • the composition obtained in each experimental example was formed to a thickness of 10 ⁇ m between two glass plates (non-alkali glass, Corning Eagle XG) each having a size of 25 mm ⁇ 25 mm ⁇ 1 mmt (mm thickness), and an LED lamp was used.
  • irradiation amount of ultraviolet rays of wavelength 395nm Te to obtain a cured product is cured by irradiation so that the 1500 mJ / cm 2.
  • the obtained cured product was measured for its spectral transmittance at 380 nm, 412 nm, and 800 nm with an ultraviolet-visible spectrophotometer (“UV-2550” manufactured by Shimadzu Corporation) to make it transparent.
  • Anode ITO anode film thickness 150nm Hole injection layer 4,4 ′, 4 ′′ -tris ⁇ 2-naphthyl (phenyl) amino ⁇ triphenylamine (2-TNATA) -Hole transport layer N, N'-diphenyl-N, N'-dinaphthylbenzidine ( ⁇ -NPD) -Light emitting layer Tris (8-hydroxyquinolinato) aluminum (metal complex material), the light emitting layer has a thickness of 1000 mm, and the light emitting layer also functions as an electron transport layer.
  • Electron injection layer Lithium fluoride ⁇ Cathode Aluminum Thickness 150nm
  • the thickness of the formed SiN was about 1 ⁇ m. Then, using a transparent substrate-less double-sided tape of 30 mm ⁇ 30 mm ⁇ 25 ⁇ mt, it was bonded to 30 mm ⁇ 30 mm ⁇ 0.7 mmt non-alkali glass (Corning's Eagle XG) to produce an organic EL element (organic EL evaluation) ).
  • the diameter of the dark spot can be regarded as an index for evaluating the degree of penetration of the sealing agent into the pinhole of the passivation film and the degree to which the moisture in the sealing agent is discharged as outgas.
  • the diameter of the dark spot was preferably 300 ⁇ m or less, more preferably 50 ⁇ m or less, and it was evaluated that it was most preferable that no dark spot existed.
  • the composition according to the present embodiment can provide a composition excellent in the reliability of the organic EL device, the discharge property by high-precision ink jet, the shape maintaining property after ink jet coating, and the low moisture permeability.
  • the composition of this embodiment is excellent in the discharge property by highly accurate inkjet, and the flatness after inkjet application
  • inkjet coating can be performed in a short time.
  • the composition of the present embodiment is suitably applied to bonding of electronic products, particularly display components such as organic EL, electronic components such as image sensors such as CCD and CMOS, and device packages used for semiconductor components. it can. In particular, it is optimal for adhesion for organic EL sealing, and satisfies characteristics required for an adhesive for element packages such as organic EL elements.
  • composition is one aspect of the present embodiment, and a sealing agent for organic EL elements, a cured body, a covering, a bonded body, an organic EL device, a display, and production thereof using the composition according to the present embodiment.
  • the method and the like have the same configuration and effect.

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Abstract

La présente invention concerne un matériau d'encapsulation pour des éléments d'affichage électroluminescents organiques qui comprend (A) un alcanediol(C4-20) di(méth)acrylate et (B) un initiateur de photopolymérisation et présente une teneur en groupes fonctionnels hydrophiles comprise dans la plage de 4,80 à 7,60 mmol par gramme du (méth)acrylate.
PCT/JP2019/015509 2018-04-16 2019-04-09 Matériau d'encapsulation pour élément d'affichage électroluminescent organique WO2019203071A1 (fr)

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KR1020207032556A KR20200143442A (ko) 2018-04-16 2019-04-09 유기 일렉트로루미네센스 표시 소자용 봉지제
CN201980025710.0A CN111972047A (zh) 2018-04-16 2019-04-09 有机电致发光显示元件用密封剂
JP2020514095A JP7360131B2 (ja) 2018-04-16 2019-04-09 有機エレクトロルミネッセンス表示素子用封止剤

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020105483A (ja) * 2018-12-27 2020-07-09 パナソニックＩｐマネジメント株式会社 紫外線硬化性樹脂組成物、発光装置の製造方法及び発光装置
JP2020105482A (ja) * 2018-12-27 2020-07-09 パナソニックＩｐマネジメント株式会社 紫外線硬化性樹脂組成物、発光装置の製造方法及び発光装置
JP2021123692A (ja) * 2020-02-07 2021-08-30 パナソニックＩｐマネジメント株式会社 紫外線硬化性樹脂組成物、光学部品、光学部品の製造方法、発光装置、及び発光装置の製造方法
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CN115298226A (zh) * 2020-03-31 2022-11-04 电化株式会社 感光性组合物、固化物、有机电致发光显示装置和感光性组合物的制造方法
KR20230019072A (ko) 2020-05-29 2023-02-07 덴카 주식회사 감광성 조성물, 그 경화물, 유기 전계발광 표시장치 및 감광성 조성물의 제조 방법
WO2023182281A1 (fr) * 2022-03-25 2023-09-28 デンカ株式会社 Agent d'encapsulation pour élément électroluminescent organique, matériau d'encapsulation et dispositif d'affichage électroluminescent organique

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CN114555661A (zh) * 2019-11-18 2022-05-27 电化株式会社 组合物、固化物、有机电致发光显示元件用密封材料及有机电致发光显示装置
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CN115298226A (zh) * 2020-03-31 2022-11-04 电化株式会社 感光性组合物、固化物、有机电致发光显示装置和感光性组合物的制造方法
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KR20230019072A (ko) 2020-05-29 2023-02-07 덴카 주식회사 감광성 조성물, 그 경화물, 유기 전계발광 표시장치 및 감광성 조성물의 제조 방법
WO2023182281A1 (fr) * 2022-03-25 2023-09-28 デンカ株式会社 Agent d'encapsulation pour élément électroluminescent organique, matériau d'encapsulation et dispositif d'affichage électroluminescent organique

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