WO2008032526A1 - processus de PRODUCtion d'UN film d'étanchéité flexible et dispositifs électroluminescents organiques réalisés à l'aide du film - Google Patents

processus de PRODUCtion d'UN film d'étanchéité flexible et dispositifs électroluminescents organiques réalisés à l'aide du film Download PDF

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Publication number
WO2008032526A1
WO2008032526A1 PCT/JP2007/066021 JP2007066021W WO2008032526A1 WO 2008032526 A1 WO2008032526 A1 WO 2008032526A1 JP 2007066021 W JP2007066021 W JP 2007066021W WO 2008032526 A1 WO2008032526 A1 WO 2008032526A1
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WIPO (PCT)
Prior art keywords
film
gas barrier
substrate
barrier layer
organic
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PCT/JP2007/066021
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English (en)
Japanese (ja)
Inventor
Shigeru Kojima
Keiichi Furukawa
Original Assignee
Konica Minolta Holdings, Inc.
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Publication date
Application filed by Konica Minolta Holdings, Inc. filed Critical Konica Minolta Holdings, Inc.
Priority to JP2008534275A priority Critical patent/JPWO2008032526A1/ja
Publication of WO2008032526A1 publication Critical patent/WO2008032526A1/fr

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Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/841—Self-supporting sealing arrangements
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/844—Encapsulations
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs
    • H10K2102/311—Flexible OLED

Definitions

  • the present invention relates to a method for producing a flexible sealing film having a gas barrier layer that provides a new bonding method, and an organic material excellent in adhesion using the same and long-term storage in a high-temperature and high-humidity environment.
  • the present invention relates to an electo-luminescence element. Background art
  • ELD electoluminescence display
  • the components of ELD include inorganic electorium luminescence elements (inorganic EL elements) and organic electoric luminescence elements.
  • Inorganic electoric luminescence elements have been used as planar light sources, but an alternating high voltage is required to drive the light emitting elements.
  • An organic electoluminescence device has a configuration in which a light-emitting layer containing an organic light-emitting material that emits light is sandwiched between a cathode and an anode, and recombines by injecting electrons and holes into the light-emitting layer.
  • fluorescence / phosphorescence the emission of light
  • it since it is a self-luminous type, it has a wide viewing angle and is a thin-film type completely solid element with high visibility, so it has been attracting attention from the viewpoints of space saving and portability.
  • the organic-electric-luminescence element itself is designed to be extremely thin, it has the thickness of the sealing member and the space for placing the hygroscopic material. It is a mouth luminescence element.
  • a close-contact type sealing method for example, a method is known in which a metal oxide thin film is formed on a film substrate to form a film sealing substrate to which gas barrier properties are imparted.
  • Japanese Laid-Open Patent Publication No. 53-12953 discloses a film in which silicon oxide is deposited on a plastic film, and Japanese Laid-Open Patent Publication No. 58-217344, in which aluminum oxide is deposited, both of which have a water vapor transmission rate of lg / m 2. Has a water vapor barrier of about / day.
  • the adhesion between the base material and the sealing member deteriorates,
  • the gas barrier layer made of ceramic is particularly susceptible to the residual stress caused by the difference in thermal expansion coefficient.
  • the gas barrier layer was easily cracked, and peeling occurred between the base material and the gas barrier layer, or between the sealing film base material and the gas barrier layer.
  • the outside air containing oxygen and moisture enters the organic electroluminescence device from the location where the gas layer is peeled off, causing serious damage to the organic layer composed of organic light emitting materials. As a result!
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2003-45652
  • Patent Document 2 JP 2004-95503 A
  • the present invention has been made in view of the above-mentioned problems, and the object thereof is adhesion between an organic electoluminescence device excellent in adhesion and long-term storage under a high-temperature and high-humidity environment, and a substrate used therefor.
  • the object is to provide a method for producing a flexible sealing film having a gas barrier layer having excellent properties.
  • a flexible seal having a gas barrier layer on the flexible film on the organic electroluminescence device member.
  • a stop film is provided, the substrate is a glass substrate, and the flexible sealing film has a gas barrier layer on at least the organic electroluminescence port luminescence side so as to surround the periphery of the organic electroluminescence device element.
  • the flexible sealing film in the inner peripheral area of the close contact area with the substrate is a gas.
  • the gas barrier layer of the flexible sealing film and the substrate are bonded to each other, and the gas sealing layer is provided on the flexible sealing film in the outer peripheral region of the close contact region with the substrate.
  • an organic electoluminescence device having an organic electoluminescence device on a substrate, a flexible seal having a gas barrier layer on the flexible film on the organic electroluminescence device.
  • a stop film is provided, the substrate is a flexible film substrate having a gas barrier layer, and the flexible sealing film and the substrate have a gas barrier layer at least on the organic electroluminescence port luminescence side;
  • Organic Electrum Luminescence Adhesive so as to surround the element member, and the flexible sealing film in the inner peripheral area of the contact area with the substrate is provided with a gas barrier layer.
  • the gas barrier layer and the substrate are bonded together, and the outer peripheral area of the contact area between the flexible sealing film and the substrate is the gas barrier layer.
  • Organic elect port Ruminessen scan element and the flexible film substrate and the flexible film not layer is provided is characterized in that it is bonded.
  • a method for producing a flexible sealing film comprising: arranging a plurality of mask members, and applying a gas barrier film forming material to form a plurality of gas barrier layers having gas noriality.
  • a gas containing a discharge gas and a gas barrier film-forming gas is supplied to a discharge space formed between the counter electrodes under atmospheric pressure or a pressure in the vicinity thereof.
  • the high-frequency voltage is applied to the discharge space from at least one of the electrodes to excite the gas, and the mask member having a plurality of flexible films and openings is exposed to the excited gas.
  • a method for producing a flexible sealing film having a gas barrier layer having excellent adhesion to a substrate, adhesion using the same, and excellent long-term storage in a high-temperature and high-humidity environment are provided.
  • An organic electoluminescence device could be provided.
  • FIG. 1 is a schematic cross-sectional view showing an example of the configuration of an organic-electric-luminescence panel constructed by a conventional sealing method.
  • FIG. 2 is a schematic cross-sectional view showing another example of a contact-type organic electricular luminescence panel configuration configured by a conventional sealing method.
  • FIG. 3 is a schematic view of an organic electoric luminescence element in a state in which a flexible sealing film having a gas barrier layer provided on the entire surface is superimposed on the organic electrifying luminescence element shown in FIG. .
  • FIG. 4 is a schematic view showing an example of a comparison composed of an organic electoluminescence device, a base material, and a flexible sealing film having a gas barrier layer.
  • FIG. 5 is a schematic cross-sectional view showing an example of the configuration of a flexible sealing film applied to the present invention.
  • FIG. 6 is a schematic view showing an example of the present invention composed of an organic electoluminescence device, a base material, and a flexible sealing film having a gas barrier layer according to the present invention.
  • FIG. 7 is a schematic cross-sectional view showing an example in which a gas barrier layer is continuously formed on a flexible film using an atmospheric pressure plasma discharge treatment apparatus and a mask member.
  • FIG. 8 is a schematic view showing an example of a mask member having a plurality of predetermined openings.
  • FIG. 9 is a schematic view showing an example of a flexible sealing film sheet in which a plurality of gas noble layers are formed on a flexible film.
  • FIG. 10 is a schematic cross-sectional view showing another example of continuously forming a gas barrier layer on a flexible film using an atmospheric pressure plasma discharge treatment apparatus and a mask member.
  • FIG. 11 is a schematic view showing an example of a bonding process between the flexible sealing film of the present invention and an organic electoluminescence device.
  • the inventor of the present invention has an organic electroluminescent element having an organic electroluminescent element on a glass substrate.
  • a flexible sealing film having a gas barrier layer is provided on the flexible film, and the flexible sealing film has a gas barrier layer at least on the organic-elect luminescence side, and is an organic-elect luminescence device
  • the adhesion portion which is an area where the flexible sealing film and the substrate are bonded
  • the flexible sealing film is provided with a gas barrier layer.
  • the flexible sealing film is not provided with a gas barrier layer, and it is possible to directly bond the flexible film and the board.
  • a gas barrier layer By further improving the adhesion between the flexible sealing film and the substrate, it was found that an organic electoluminescence device excellent in adhesion and long-term storage under high-temperature and high-humidity environments could be realized. It depends on you.
  • the flexible film is formed on the organic electroluminescence device member.
  • a flexible sealing film having a gas barrier layer is provided on the substrate.
  • the flexible sealing film and the substrate have a gas barrier layer on at least the organic electroluminescence port luminescence side, and surround the organic electroluminescence device member.
  • the flexible sealing film By adhering so as to surround, it prevents the ingress of moisture and oxygen into the organic-elect mouth luminescence element member, and furthermore, the inner peripheral area of the close contact area, which is the area where the flexible sealing film and the substrate are bonded
  • the flexible sealing film is provided with a gas barrier layer, and the flexible barrier film gas barrier layer and the substrate As for the outer peripheral area of the close contact area, neither the flexible sealing film nor the substrate is provided with a gas barrier layer.
  • FIG. 1 is a schematic cross-sectional view showing an example of the configuration of an organic electoluminescence panel (hereinafter also referred to as an organic EL panel) configured by a conventional sealing method.
  • reference numeral 100 denotes an organic electoluminescence element member (hereinafter also referred to as an organic EL element member).
  • the organic EL element member 100 includes a first electrode 102, a hole transport layer (hole injection layer) 103, an organic compound layer (light emitting layer) 104, an electron injection layer 105,
  • the second electrode 106, the adhesive 107, and the sealing member 108 having a gas barrier layer on the surface facing the adhesive 107 are provided in this order.
  • 102a represents an external extraction electrode of the first electrode 102
  • 106a represents an external extraction electrode of the second electrode 106.
  • the organic electroluminescence device 1 shown in the figure is sealed through an adhesive layer 107 except for the tip of the external extraction electrode 102a of the first electrode 102 and the external extraction electrode 106a of the second electrode 106.
  • the structure is tightly sealed with member 108.
  • a glass substrate is mainly used as the substrate.
  • a hole injection layer (not shown) may be provided between the first electrode 102 and the hole transport layer 103. Further, an electron transport layer (not shown) may be provided between the second electrode 106, the organic compound layer (light emitting layer) 104, and the electron injection layer 105.
  • the layer configuration of the organic electroluminescence device shown in this figure is an example, and the following configuration can be given as the layer configuration of force S, and another typical organic electroluminescence device.
  • transparent electrode materials IT 2 O (a mixture of tin oxide and indium oxide), IZO (a mixture of zinc oxide and indium oxide), Zn 0, SnO, In 2 O and the like are known.
  • ITO electrodes can be used as transparent electrodes for liquid crystal displays and solar cells because they have a high light transmittance of 90% or more and a low sheet resistance of 10 ⁇ / mouth.
  • the IZO electrode has the advantages that a predetermined low resistance and resistance value can be obtained without heating the substrate during formation, and that the film surface is smoother than the ITO electrode.
  • an electrode such as aluminum or silver having a thickness of several to several tens of nm is provided on the organic layer, and the above-mentioned transparent electrode is further provided.
  • FIG. 2 is a schematic cross-sectional view showing another example of the structure of a contact type organic EL panel configured by a conventional sealing method.
  • reference numeral 109 denotes a light emitting portion where the first electrode 102 and the second electrode 106 overlap
  • 110 denotes a state in which the leading ends of the external extraction electrode 102a and the external extraction electrode 106a are exposed.
  • the light emitting part including the external extraction electrode 102a and a part of the external extraction electrode 106a An outer peripheral surface (portion indicated by hatching in the figure) is shown. The other symbols have the same meaning as in FIG.
  • FIG. 3 is a schematic view of an organic electoluminescence device in a state where a flexible sealing film having a gas noble layer provided on the entire surface is superimposed on the organic EL device member shown in FIG. It is.
  • FIG. 3 (a) is a schematic plan view of the organic electoluminescence device in which a flexible sealing film having a gas barrier layer is superimposed on the entire surface of the organic EL device member shown in FIG. Fig. 3 (b) is a schematic cross-sectional view along A-A 'in Fig. 3 (a).
  • FIG. 3 shows a state where a flexible sealing film 108 having a gas barrier layer 108a on the entire surface on which the adhesive 107 is disposed is overlaid on the organic EL element member.
  • the adhesive 107 disposed on the flexible sealing film 108 includes the light emitting portion 109 and the outer peripheral surface 110 in a state where the leading ends of the external extraction electrode 102a and the external extraction electrode 106a of the organic EL element member are exposed. It arrange
  • Reference numeral 107 a denotes an adhesive disposed on the flexible sealing film corresponding to the outer peripheral surface 110 of the light emitting unit 109.
  • the adhesive 107 a on the outer peripheral surface 110 is pressure-bonded via the flexible sealing film 108.
  • the organic electoluminescence device as described above.
  • the adhesive 107 and the gas barrier layer 108a or the adhesive layer is extremely thin when stored for a long time under high temperature and high humidity, cracking or peeling occurs between the film substrate 101 and the gas noble layer 108a. As a result, non-light emitting points called dark spots are generated.
  • FIG. 4 is a schematic view showing an example of comparison composed of an organic EL element member, a base material, and a flexible sealing film having a gas barrier layer.
  • FIG. 4 shows a first electrode, a hole transport layer (hole injection layer), an organic compound layer (light emitting layer), and a glass substrate 101 ′.
  • An organic EL layer group 110 composed of an electron injection layer, a second electrode, and the like is provided, and only a top surface thereof is sealed with a flexible sealing film 108 having a gas barrier layer 108a.
  • FIG. 4B shows a form in which the organic EL layer group 110 is sealed with a flexible sealing film 108 having a gas barrier layer 108a on the entire surface, as shown in FIG. ing.
  • FIGS. 4C and 4D show an organic EL layer group 110 provided on a flexible film substrate 101 having a gas barrier layer 108b on the entire surface. In this case, a configuration is shown in which the film is sealed with a flexible sealing film 108 having a gas barrier layer 108a on a part or the entire surface.
  • the gas prevention layer is provided only in the upper part of the organic EL layer group 110 in FIG. 4 (a), so that the gas prevention effect is not sufficient.
  • the gas barrier layer sufficient to cover the organic EL layer group 110 is provided.
  • the gas barrier layer Since the gas barrier layer is in contact with the outside at the edge of the substrate, the gas barrier layer deteriorates when stored for a long period of time under high temperature and high humidity by such a configuration, and the generation of cracks and the Peeling from the material and the flexible film occurs, and as a result, a desired gas barrier property cannot be obtained.
  • the gas barrier layer is not present in the area A having the gas barrier layer having a gas barrier property on the flexible film and around the gas barrier layer.
  • a flexible sealing film having region B is used and sealed with the substrate.
  • the close contact region E where the substrate and the flexible sealing film are in contact with each other includes a region having a gas barrier layer (inner peripheral region) and a region in which no gas barrier layer is present in the outer peripheral portion of the region (outer periphery). Region) at the same time.
  • the flexible sealing film according to the present invention includes a region A having a gas barrier layer having gas barrier properties on the flexible film, and a region B (where no gas barrier layer is present around the gas barrier layer). Specifically, it is composed of only a flexible film.
  • FIG. 5 is a schematic cross-sectional view showing an example of the configuration of the flexible sealing film applied to the present invention.
  • a flexible sealing film 108 according to the present invention has a region A in which a gas barrier layer 108a is provided inside the flexible film, and a region B that is a peripheral part of the gas barrier layer 108a. Is a configuration in which no gas noria layer is provided.
  • the gas barrier layer according to the present invention is a ceramic composed of an inorganic compound. It is preferable that the gas barrier layer is a single layer or a stack of layers with different properties (for example, carbon content, density, elastic modulus, etc.). It may be a body.
  • FIG. 6 is a schematic view showing an example of the present invention including an organic EL element member, a base material, and a flexible sealing film having a gas noble layer according to the present invention.
  • (a) in FIG. 6 is composed of a first electrode, a hole transport layer (hole injection layer), an organic compound layer (light emitting layer), an electron injection layer, a second electrode, and the like on a glass substrate lO.
  • the organic EL layer group 110 to be formed is provided, and the upper surface portion thereof is sealed with a flexible sealing film 108 composed of a region A and a region B having a gas barrier layer 108a as shown in FIG. Shows the form.
  • the gas barrier layer is present on the upper surface portion and both side surface portions of the organic EL layer group 110, and in the contact portion region E, the gas barrier layer is not present in all regions.
  • the substrate and the gas noble layer are in direct contact with each other or via an adhesive (not shown), and the outer peripheral region of the contact region E including the end of the base material is flexible with the base material. The film comes into contact with the adhesive film directly or via an adhesive (not shown).
  • the flexible film substrate has a vinylem substrate 101 force S and a gas noble layer 108b, and the flexible film substrate has a gas barrier layer force.
  • a ceramic layer composed of an inorganic compound is preferred.
  • FIGS. 6B and 6C show an organic EL layer group 110 provided on a flexible film substrate 101 having a gas barrier layer, and a gas barrier layer 108a as shown in FIG. The form sealed with the flexible sealing film 108 comprised from the area
  • the gas barrier layer is present on the upper surface portion and both side surface portions of the organic EL layer group 110, and in the adhesion portion region E, the gas barrier layer is not present in all regions. At least a part of the film including the edge is directly Alternatively, it is brought into contact with an adhesive (not shown).
  • the resin film constituting the flexible sealing film according to the present invention is not particularly limited, for example, a homopolymer such as ethylene, polypropylene, or butene or a copolymer or a copolymer.
  • PO Polyolefin resins
  • APO amorphous polyolefin resins
  • PET polyethylene terephthalate
  • PEEK Polyetheretherketone
  • PC polycarbonate
  • PVB polyvinyl butyrate
  • PAR polyarylate
  • EFE ethylene tetrafluoroethylene copolymer
  • PFA ethylene trifluoride chloride
  • FEP Tetrafluorinated styrene perfluorinated alkyl butyl ether copolymer
  • PVDF vinylidene fluoride
  • PVF vinylene fluoride
  • Fluorine resin such as coalescence (EPA) can be used.
  • a resin composition comprising an acrylate compound having a radical-reactive unsaturated compound, or a resin composition comprising a mercapto compound having an acrylate compound and a thiol group.
  • a photocurable resin such as a resin composition obtained by dissolving an oligomer, an epoxy acrylate, a urethane acrylate, a polyester acrylate, a polyether acrylate, etc. in a polyfunctional acrylate monomer, and a mixture thereof. is there.
  • a resin film obtained by laminating one or more of these resins by means of lamination, coating, or the like.
  • ZE NEX and ZEONOR manufactured by ZEON CORPORATION
  • ARTON manufactured by GIRL
  • amorphous cyclopolyolefin resin film Pureace of polycarbonate film (manufactured by Teijin Limited)
  • cellulose triacetate film Konica Minolta Tack KC4UX, KC8UX
  • Commercially available products such as (manufactured by Konica Minoltaput Co., Ltd.) can be preferably used.
  • the resin film is preferably transparent. Since the resin film is transparent and the gas barrier layer formed on the resin film is also transparent, a transparent gas-nore film can be obtained. It can also be applied as a substrate (abbreviated as an element).
  • the resin film according to the present invention can be produced by a conventionally known general method.
  • the unstretched base material is subjected to a known method such as -axial stretching, tenter-type sequential biaxial stretching, tenter-type simultaneous biaxial stretching, and tubular-type simultaneous biaxial stretching in the direction of base material flow (vertical axis).
  • a stretched substrate can be produced by stretching in a direction perpendicular to the flow direction of the substrate (horizontal axis).
  • the draw ratio is a force that can be appropriately selected according to the resin that is the raw material of the base material.
  • the resin film according to the present invention before forming the gas barrier film, the polymer film or the like, corona treatment, flame treatment, plasma treatment, glow discharge treatment, roughening treatment, chemical treatment, etc.
  • the surface treatment may be performed.
  • the resin film is conveniently a long product wound up in a roll.
  • the thickness of the resin film differs depending on the intended use of the resulting gas barrier film, and cannot be specified unconditionally.However, when the gas barrier film is used for packaging, it is not particularly restricted and suitable as a packaging material. Therefore, it is preferable to be in the range of 3 to 400 111, especially 6 to 30 111.
  • the film thickness of the resin film used in the present invention is preferably 10 to 200 ⁇ m force S, more preferably 50 to 100 ⁇ m.
  • the composition and the like of the gas noble layer formed on the flexible sealing film according to the present invention is not particularly limited as long as it is a layer that blocks permeation of oxygen and water vapor.
  • the material constituting the gas barrier layer according to the present invention silicon oxide, aluminum oxide, silicon oxynitride, aluminum oxynitride, magnesium oxide, which are preferably inorganic oxides, Examples thereof include zinc oxide, indium oxide, and tin oxide.
  • the thickness of the gas barrier layer in the present invention is appropriately selected depending on the type and configuration of the material used, and is suitably selected, but is preferably in the range of 5 to 2000 nm. This is because when the thickness of the gas noble layer is smaller than the above range, a uniform film cannot be obtained, and it is difficult to obtain a barrier property against the gas. In addition, when the thickness of the gas barrier layer is larger than the above range, it is difficult to maintain flexibility in the gas nootropic film, and it is difficult to maintain the gas barrier film due to external factors such as bending and pulling after film formation. This is because cracks may occur.
  • the gas barrier layer according to the present invention uses the raw materials described later as a spray method, a spin coat method, a sputtering method, an ion assist method, a plasma CVD method described later, and a plasma CVD under atmospheric pressure or a pressure close to atmospheric pressure described later. It can be formed by applying a law or the like.
  • the film is formed by a plasma CVD method or the like.
  • the atmospheric pressure plasma CVD method does not require a decompression chamber and the like, and high-speed film formation can be achieved.
  • it is a film forming method. This is because by forming the gas barrier layer by the atmospheric pressure plasma CVD method, it is possible to relatively easily form a film having a uniform and smooth surface.
  • Plasma CVD method plasma CVD method under atmospheric pressure or pressure near atmospheric pressure
  • 1S Particularly preferably, it is formed using a plasma CVD method under atmospheric pressure or a pressure near atmospheric pressure. The details of the layer formation conditions of the plasma CVD method will be described later.
  • the gas barrier layer obtained by the plasma CVD method, or the plasma CVD method under atmospheric pressure or a pressure near atmospheric pressure is made up of raw materials (also referred to as raw materials) such as organometallic compounds, decomposition gas, decomposition temperature, and input power.
  • raw materials also referred to as raw materials
  • metal carbides, metal nitrides, metal oxides, metal sulfides, metal halides, and mixtures thereof metal oxynitrides, metal oxides, rogenides, metal nitride carbides, etc. are also created. This is preferable.
  • silicon An oxide is formed.
  • zinc compound is used as a raw material compound and carbon disulfide is used as cracking gas, zinc sulfide is generated. This is because highly active charged particles and active radicals are present in the plasma space at a high density, so that multistage chemical reactions are accelerated very rapidly in the plasma space, and the elements present in the plasma space are heated. This is because it is converted into a mechanically stable compound in a very short time.
  • a raw material of such an inorganic substance may be in a gas, liquid, or solid state at normal temperature and pressure as long as it contains a typical or transition metal element.
  • gas it can be introduced into the discharge space as it is, but in the case of liquid or solid, it is vaporized by means such as heating, publishing, decompression or ultrasonic irradiation.
  • organic solvents such as methanol, ethanol, and n-hexane, and mixed solvents thereof may be used as a solvent that may be diluted with a solvent. Since these diluted solvents are decomposed into molecular and atomic forms during the plasma discharge treatment, the influence can be almost ignored.
  • organometallic compounds include silicon compounds such as silane, tetramethoxysilane, tetraethoxysilane, tetra n propoxy silane, tetraisopropoxy silane, tetra n butoxy silane, tetra t butoxy silane, dimethylenoresi methoxy silane, Dimethinoresietic silane, etyltrimethoxysilane, phenyltriethoxysilane, (3, 3, 3-trifluoropropyl) trimethoxysilane, hexamethyldisiloxane, bis (dimethylamino) dimethylsilane, bis (dimethylamino) methylvinylsilane, bis (Ethylamino) dimethylsilane, tinoleaminotrimethylenosilane, dimethinoreaminodimethylenosilane, hexamethinoresilazane, hexamethinoresil
  • titanium compound examples include titanium methoxide, titanium ethoxide, and titanium isopropyl.
  • Lucacetoacetate titanium di-n-butoxide (bis 2,4-pentanedionate), titanium acetylacetonate, butyl titanate dimer, and the like.
  • Zirconium compounds include zirconium n-propoxide, zirconium n butoxide, zirconium t-butoxide, zirconium tree n-butoxide acetylacetonate, zirconium di-n-butoxide bisacetylacetonate, zirconium acetyl. Examples include acetonate, dinoleconium acetate, dinolecoum hexahexoleolone pentanedionate, and the like.
  • Examples of the aluminum compound include aluminum ethoxide, aluminum triisopropoxide, aluminum isopropoxide, aluminum n butoxide, aluminum s butoxide, aluminum tert butoxide, aluminum acetyl cetateate, triethyl dialmine mini s-butoxide and the like. Can be mentioned.
  • Examples of the boron compound include diborane, tetraborane, boron fluoride, boron chloride, boron bromide, borane-jetyl ether complex, borane THF complex, borane dimethylsulfide complex, boron trifluoride jetyl ether complex. , Trietylborane, trimethoxyborane, triethoxyborane, tri (isopropoxy) borane, borazole, trimethylpolarazole, triethylpolarazole, triisopropylborazole, and the like.
  • tin compound examples include tetraethyltin, tetramethyltin, dibutyltin diacetate, tetrabutyltin, tetraoctyltin, tetraethoxytin, methyltriethoxytin, jetyljettin, triisopropylethoxytin, and jetyltin.
  • Tin halides include tin dichloride, tin tetrachloride, etc. Can be mentioned.
  • organometallic compounds include, for example, antimony ethoxide, arsenic triethoxide, norlium 2, 2, 6, 6 tetramethylheptanedionate, beryllium acetylacetonate, bismuth hexafluoro.
  • a decomposition gas for decomposing a raw material gas containing these metals to obtain an inorganic compound hydrogen gas, methane gas, acetylene gas, carbon monoxide gas, carbon dioxide gas, nitrogen gas, ammonia Gas, Nitrous oxide gas, Nitrogen oxide gas, Nitrogen dioxide gas, Oxygen gas, Water vapor, Fluorine gas, Hydrogen fluoride, Trifnoreolo anocorone, Trifluorotoluene, Hydrogen sulfide, Sulfur dioxide, Carbon disulfide, Chlorine Gas etc. are mentioned.
  • metal carbides, metal nitrides, metal oxides, metal halides, and metal sulfides can be obtained by appropriately selecting a source gas containing a metal element and a decomposition gas.
  • a discharge gas that tends to be in a plasma state is mixed with these reactive gases, and the gas is sent to the plasma discharge generator.
  • discharge gases include nitrogen gas and / or group 18 atoms of the periodic table, specifically helium, neon, argon, krypton, Xenon, radon, etc. are used. Of these, nitrogen, helium, and argon are particularly preferably used.
  • the discharge gas and the reactive gas are mixed and supplied to a plasma discharge generator (plasma generator) as a mixed gas to form a film.
  • a plasma discharge generator plasma generator
  • the ratio of the discharge gas to the reactive gas varies depending on the properties of the film to be obtained.
  • the water vapor permeability of the flexible sealing film according to the present invention is such that the water vapor permeability measured according to the JIS K7129 B method is 0 for use in an organic EL display that requires a high water vapor barrier property. 01 g / m and a 2 / day or less, and more preferably not more than 1 X 10- 3 g / m 2 / day, further, even slight poles, dark spot to grow is generated, the display of the de Isupurei because in some cases life is extremely short, the water vapor permeability, it is preferably less than 1 X 10- 5 g / m 2 / day! / ,.
  • a mask member having a plurality of predetermined openings is disposed on a flexible film, and a gas barrier film forming material is applied to provide a plurality of gas barrier properties.
  • a method of forming the gas noble layer in the discharge space formed between the counter electrodes under atmospheric pressure or a pressure in the vicinity thereof.
  • a gas containing a gas for forming a barrier film is supplied, a high-frequency voltage is applied to the discharge space from at least one electrode to excite the gas, and the mask member having a plurality of the flexible film and the opening is excited.
  • the atmospheric pressure plasma treatment is preferred in which the treatment is carried out by exposure to a gas.
  • the atmospheric pressure plasma method is, for example, a force described in JP-A-10-154598, JP-A-2003-49272, WO02 / 048428, or the like.
  • the method for forming a thin film described in the publication No. 1 is preferable for forming a dense ceramic layer having a high gas barrier property.
  • a gas-like base layer can be continuously formed by feeding a web-like base material from a roll-shaped original winding.
  • the atmospheric pressure plasma method according to the present invention is performed under atmospheric pressure or a pressure in the vicinity thereof.
  • 93 kPa to 104 kPa is preferable.
  • the discharge condition in the present invention is to apply the electric field by superimposing the first high-frequency electric field and the second high-frequency electric field, which is preferably applied to two or more electric fields having different frequencies in the discharge space.
  • the frequency ⁇ 2 of the second high-frequency electric field is higher than the frequency ⁇ 1 of the first high-frequency electric field, and the strength VI of the first high-frequency electric field VI and the strength of the second high-frequency electric field With V2
  • the output density of the second high frequency electric field is lW / cm 2 or more.
  • a high frequency refers to one having a frequency of at least 0.5 kHz.
  • the strength of the discharge starting electric field refers to the discharge in the discharge space (electrode configuration, etc.) and reaction conditions (gas conditions, etc.) used in the actual thin film formation method.
  • the discharge starting electric field strength is governed by the discharge starting electric field strength of the discharge gas in the same discharge space, which varies somewhat depending on the gas type supplied to the discharge space, the dielectric type of the electrode, or the distance between the electrodes.
  • a first electrode having a frequency ⁇ 1 and an electric field strength VI is applied to the first electrode constituting the counter electrode.
  • An atmospheric pressure plasma discharge treatment apparatus is used in which a first power source for applying a high-frequency electric field is connected, and a second power source for applying a second high-frequency electric field having a frequency ⁇ 2 and an electric field strength V2 is connected to the second electrode.
  • the atmospheric pressure plasma discharge treatment apparatus includes gas supply means for supplying a discharge gas and a thin film forming gas between the counter electrodes. Furthermore, it is preferable to have an electrode temperature control means for controlling the temperature of the electrode.
  • the first filter is connected to the first electrode, the first power source, or any of them
  • the second filter is connected to the second electrode, the second power source, or any of them.
  • the first filter facilitates the passage of the current of the first high-frequency electric field from the first power source to the first electrode, grounds the current of the second high-frequency electric field, and the first power source from the second power source It is difficult to pass the current of the second high-frequency electric field to.
  • the second filter makes it easy to pass the current of the second high-frequency electric field from the second power source to the second electrode, grounds the current of the first high-frequency electric field, Use a power supply with a function that makes it difficult to pass the current of the first high-frequency electric field to the power supply.
  • the phrase “difficult to pass” preferably means that only 20% or less, more preferably 10% or less of the current can pass.
  • being easy to pass means preferably passing 80% or more, more preferably 90% or more of the current.
  • a capacitor of several tens of pF to several tens of thousands of pF or a coil of about several H can be used depending on the frequency of the second power supply.
  • the second filter can be used as a filter by using a coil of 10 H or higher according to the frequency of the first power supply and grounding it through these coils or capacitors.
  • the first power source of the atmospheric pressure plasma discharge treatment apparatus of the present invention has the ability to apply a higher electric field strength than the second power source!
  • the applied electric field strength and the discharge starting electric field strength referred to in the present invention were measured by the following methods. It means what was done.
  • a high-frequency voltage probe (P6015A) is installed at each electrode, and the output signal of the high-frequency voltage probe is connected to an oscilloscope (Tektronix, TDS3012B), and the electric field strength at a predetermined time is measured.
  • an oscilloscope Tektronix, TDS3012B
  • the discharge gas is supplied between the electrodes, the electric field strength between the electrodes is increased, and the electric field strength at which the discharge starts is defined as the discharge starting electric field strength IV.
  • the measuring instrument is the same as the applied electric field strength measurement.
  • High performance thin film formation can be performed.
  • the frequency of the first power supply is preferably 200 kHz or less.
  • the electric field waveform may be a continuous wave or a pulse wave.
  • the lower limit is preferably about 1kHz.
  • the frequency of the second power source is preferably 800 kHz or more.
  • the upper limit is about 200MHz! /.
  • the application of a high-frequency electric field from such two power sources is necessary for initiating discharge of a discharge gas having a high discharge starting electric field strength by the first high-frequency electric field, and the second high-frequency electric field. It is an important point of the present invention to form a dense and high-quality thin film by increasing the plasma density by high frequency and high power density. [0110] Further, by increasing the output density of the first high-frequency electric field, the output density of the second high-frequency electric field can be improved while maintaining the uniformity of discharge. Thereby, a further uniform high-density plasma can be generated, and a further improvement in film forming speed and an improvement in film quality can be achieved.
  • the atmospheric pressure plasma discharge treatment apparatus used in the present invention discharges between the counter electrodes, puts the gas introduced between the counter electrodes into a plasma state, and leaves the gas between the counter electrodes or A thin film is formed on the base material by exposing the base material transferred between the electrodes to the plasma state gas.
  • the atmospheric plasma discharge treatment apparatus discharges between the counter electrodes similar to the above, excites the gas introduced between the counter electrodes, or puts it in a plasma state, and jets the gas outside the counter electrode. Jet system that forms a thin film on the substrate by blowing out excited or plasma state gas and exposing the substrate in the vicinity of the counter electrode (which may be stationary or transported) There is a device.
  • FIG. 7 is a schematic cross-sectional view showing an example in which a gas barrier layer is continuously formed on a flexible film using an atmospheric pressure plasma discharge treatment apparatus and a mask member.
  • the jet type atmospheric pressure plasma discharge processing apparatus has a gas supply means and an electrode temperature adjusting means, which are not shown in FIG. It's a device!
  • the plasma discharge treatment apparatus 10 has a counter electrode composed of a first electrode 11 and a second electrode 12, and the first electrode 11 is connected to the first power source 21 between the counter electrodes.
  • the first high-frequency electric field of frequency ⁇ 1, electric field strength VI, and current II is applied, and the second high-frequency electric wave from the second power source 22 from the second electrode 12, ⁇ 2, electric field strength V2, and the second high-frequency electric current 12 An electric field is applied.
  • the first power supply 21 applies a higher frequency electric field strength (VI> V2) than the second power supply 22, and the first frequency ⁇ 1 of the first power supply 21 is lower than the second frequency ⁇ 2 of the second power supply 22. Apply wavenumber.
  • a first filter 23 is installed between the first electrode 11 and the first power supply 21 to facilitate the passage of current from the first power supply 21 to the first electrode 11, and the second power supply. It is designed so that the current from the second power source 22 to the first power source 21 is less likely to pass through by grounding the current from the second power source 22.
  • a second filter 24 is installed between the second electrode 12 and the second power source 22, 2 Designed to facilitate the passage of current from the power source 22 to the second electrode, ground the current from the first power source 21 and make it difficult to pass current from the first power source 21 to the second power source .
  • a thin film forming gas G is introduced from a gas supply means (not shown) between the opposing electrodes of the first electrode 11 and the second electrode 12 (discharge space) 13 by a first power source 21 and a second power source 22.
  • the above-described high-frequency electric field is applied between the first electrode 11 and the second electrode 12 to generate a discharge, and the thin film forming gas G described above is in a plasma state while being jetted on the lower side of the counter electrode (lower side of the paper).
  • the treatment space created by the lower surface of the counter electrode and the flexible film F is filled with the gas G ° in the plasma state, not shown!
  • FIG. 7 shows the measuring instruments and measurement positions used to measure the applied electric field strength and the discharge starting electric field strength.
  • 25 and 26 are high-frequency voltage probes, and 27 and 28 are oscilloscopes.
  • the gas barrier layer having the gas barrier property according to the present invention as shown in FIG. 5 is provided.
  • a predetermined opening is formed in the state where the flexible film F is accompanied at the lower part of the counter electrode.
  • a mask member having a plurality of layers is disposed.
  • FIG. 8 is a schematic diagram showing an example of a mask member having a plurality of predetermined openings.
  • the mask member 38 is formed with an opening 42 for forming a region A having a gas barrier layer having a gas barrier property, and a region B where no gas barrier layer is present around the gas barrier layer. And a shielding portion 41 for preventing plasma processing.
  • a member that does not affect the plasma discharge treatment is preferably selected as appropriate.
  • FIG. 9 is a schematic diagram showing an example of a flexible sealing fine sheet in which a plurality of gas barrier layers are formed on a flexible film.
  • a flexible sealing film sheet 2 in which a plurality of layers is formed is prepared.
  • a plurality of jet-type atmospheric pressure plasma discharge treatment devices are arranged in parallel with the conveyance direction of the flexible film F, and simultaneously discharge gases of the same plasma state, thereby forming a plurality of thin films at the same position. Therefore, a desired film thickness can be formed in a short time. Also, multiple thin films with different layers can be formed by arranging multiple units parallel to the transport direction of the flexible film F, supplying different thin film forming gases to each device, and jetting different plasma states. You can also.
  • FIG. 10 is a schematic cross-sectional view showing another example of continuously forming a gas noble layer on a flexible film using an atmospheric pressure plasma discharge treatment apparatus and a mask member.
  • the atmospheric pressure plasma discharge device 30 is disposed at a position where the first electrode 33 and the second electrode 34 face each other, and a high frequency power source 37 is connected to each of them.
  • a discharge space is formed between the first electrode 33 and the second electrode 34, and a flexible film F and a cylindrical shape accompanied by the discharge film are formed in the discharge space.
  • the gas barrier layer 39 is continuously formed on the flexible film F.
  • the flexible film F drawn out from the former winding part 31 is associated with a cylindrical mask member 38 as shown in Fig. 8 and is moved to the discharge space.
  • the gas noble layer 39 is continuously formed at a predetermined position.
  • the flexible film F on which the gas barrier layer 39 is formed and separated from the mask member 38 at the position of the support roll 32 is laminated on the take-up roll 40.
  • FIG. 11 is a schematic view showing an example of a bonding step between the flexible sealing film of the present invention and the organic electoluminescence device.
  • the flexible sealing film laminating step 500 is performed in the alignment detecting the alignment mark 3011 arranged in alignment with the position of the organic EL element unit 301il formed on the strip-shaped flexible film substrate 301i. Align the mark detector 505 and the organic EL element unit 301il.
  • a sealant coating part 502 for coating a laminating sealant, a supply part 503 for a roll-shaped flexible sealing member 503a, and a bonding part 504 for bonding a strip-shaped flexible sealing member 503b. Have! /,
  • the alignment mark detection unit 505 includes an alignment mark detection device 505a and a casing 505b in which the alignment mark detection device 505a is disposed.
  • the alignment mark detection device 500a is arranged in accordance with the position of the alignment mark 3011 previously disposed on the belt-like flexible support C301i.
  • the information detected by the alignment mark detection device 505a is input to a control unit (not shown) to control the sealant coating device 502a of the sealant coating unit 502.
  • the alignment mark detection device 505 is not particularly limited. For example, image recognition using a CCD camera can be used.
  • the sealant coating unit 5 02 is provided with a sealant coating device 502a and a sealant coating device 502a that apply a sealant to the organic-elect luminescence element in accordance with information from the alignment mark detection unit 505. And a housing 502b to be installed!
  • the number of the sealant coating apparatus 502a to be disposed is not particularly limited. However, the sealant coating apparatus 502a may be disposed in accordance with the number of organic electroluminescence elements disposed in the width direction of the strip-shaped flexible film substrate 301i. preferable. This figure shows a case where three sealant coating devices 502a are provided in accordance with the number of organic electoluminescence elements arranged in the width direction.
  • the housing 502b can be moved in the xy direction (arrow direction in the figure) by a driving device (not shown).
  • the laminating portion 504 has a roll 504b that comes into contact with the main body 504c and the strip-shaped flexible film substrate, a strip-shaped flexible ten-year-sealed rod material 503b, and a ronole 504a that contacts the hornworm.
  • a strip-shaped flexible film substrate having an organic-electto-luminescence element formed of 504b and Ronole 504a 3 Oli and a strip-shaped flexible sealing film 503b are pressed and sandwiched to form a strip-shaped flexible fine substrate. It has become like pasting.
  • the function of the curing treatment is adjusted according to the properties of the sealing agent used for the bonding part 504 (for example, the ultraviolet irradiation device is provided when the sealing agent is an ultraviolet curing type, and the roll is provided with a heating function when the sealing agent is a thermosetting type. ) Is preferred!
  • the width of the flexible sealing film 503b is preferably detectable by the alignment mark 3011 attached to the strip-shaped flexible film substrate 301i.
  • the supply system of the sealant to the sealant coating apparatus 502a is omitted.
  • the method for applying the sealant is not particularly limited, and examples thereof include methods used for usual adhesive application, such as a spray method, an extrusion nozzle method, and a screen printing method.
  • the viscosity of the sealant used is preferably 40 Pa • s to 400 Pa ⁇ s in consideration of application uniformity, spread prevention, etc.!
  • the liquid sealant includes photocuring and thermosetting sealants having a reactive bur group of acrylic acid-based oligomers and methacrylic acid-based oligomers, moisture-curing types such as 2-cyanacrylic acid esters, etc. And a sealing agent such as an epoxy-based heat and chemical curing type (two-component mixture), a cationic curing type ultraviolet curing epoxy resin sealing agent, and the like. It is preferable to add a filler to the liquid sealant as necessary. The amount of filler added is preferably 5 to 70% by volume in consideration of adhesive strength.
  • the size of the filler to be added is preferably 1 to 111 to 100 to 111 in consideration of the adhesive strength, the thickness of the sealant after bonding and bonding.
  • the type of filler to be added is not particularly limited, and examples thereof include soda glass, alkali-free glass or silica, metal oxides such as titanium dioxide, antimony oxide, titania, alumina, zirconia, and tungsten oxide.
  • the bonding unit 504 is a band-shaped flexible sealing film 503b fed from the roll-shaped band-shaped flexible sealing member 503a supplied to the supply unit 503, and a band-shaped acceptable coating coated with a sealing agent.
  • the flexible film substrate 301i the belt-shaped flexible sealing film 503b side pressure inlet 504a, the belt-shaped flexible film substrate 301i side pressure roll 504b, and these pressure rolls And a main body 504c.
  • bonding unit 504 bonding stability, bubbly prevention to lamination portion, considering a flat surface of the holding and the like of the flexible sealing member, vacuum conditions 10-1 X 10- 5 Pa It is preferable to carry out with.
  • a sealant layer may be provided in advance on the side of the flexible sealing film to be bonded to the organic EL element member, and examples thereof include a sheet-like sealant and a thermoplastic resin.
  • the organic-electric-luminescence element includes a substrate, a first pixel electrode provided on the substrate, It is composed of an organic electoluminescence layer composed of one or more layers including a light emitting layer, a second pixel electrode, a flexible sealing film, and the like.
  • Examples of the substrate according to the present invention include a single-wafer sheet-like substrate and a strip-like flexible substrate.
  • Examples of the sheet-like substrate include a transparent glass plate and a sheet-like transparent resin film.
  • resin films include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate (CAP).
  • cellulose ester such as cell mouth sulphonate or derivatives thereof, polyvinylidene chloride, polyvinylinoleo alcohole, polyethylene vinylenoreo alcohole, syndiotactic polystyrene, polycarbonate, norbornene resin , Polymethylpentene, Polyetherketone, Polyimide, Polyethersulfone (PES), Polyphenylene sulfide, Polysulfones, Polyether Luimide, polyether ketone imide, polyamide, fluororesin, nylon, polymethyl methacrylate, acrylic or polyarylates, Arton (trade name, manufactured by JSR) or Vapelle (trade name, manufactured by Mitsui Chemicals) Examples include cycloolefin resins. Examples of the belt-like flexible substrate include a transparent resin film, and the same resin film as that of the single-wafer sheet-like substrate can be used.
  • the substrate is preferably a flexible film substrate composed of a transparent resin film or the like, more preferably a flexible film substrate having a gas barrier layer, and further, a gas barrier layer.
  • the ceramic layer is preferably composed of an inorganic compound.
  • gas barrier layer examples include those similar to the gas barrier layer formed of the flexible sealing film described above.
  • an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used.
  • electrode materials include metals such as Au, and conductive transparent materials such as Cul, indium tinoxide (ITO), SnO, and ZnO.
  • ITO indium tinoxide
  • ZnO ZnO
  • IDIXO In O ⁇ ⁇
  • the anode may form a thin film by depositing these electrode materials by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method, or the pattern accuracy is not so required!
  • a pattern may be formed through a mask having a desired shape when the electrode material is deposited or sputtered.
  • the transmittance be greater than 10%
  • the sheet resistance as the anode is preferably several hundred ⁇ / mouth or less.
  • the film thickness is a force depending on the material. Usually 10 to 1000 nm, preferably 10 to 200 nm.
  • a hole injection layer (anode buffer layer) may be present.
  • the hole injection layer is a layer provided between the electrode and the organic layer in order to lower the driving voltage and improve the luminance of the light emission. “Organic electoluminescence device and its forefront of industrialization (November 30, 1998) The details are described in Volume 2, Chapter 2, “Electrode Materials” (pages 123–166). Examples of the material used for the anode buffer layer (hole injection layer) include materials described in JP-A No. 2000-160328.
  • the hole transport layer is made of a hole transport material having a function of transporting holes, and in a broad sense, a hole injection layer and an electron blocking layer are also included in the hole transport layer.
  • the hole transport layer can be provided as a single layer or a plurality of layers.
  • the hole transport material has any of hole injection or transport and electron barrier properties, and may be either organic or inorganic.
  • triazole derivatives for example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylenerealkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, Examples thereof include hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.
  • aromatic tertiary amine compounds and styrylamine compounds include N, N, N ', N' — Tetraphenolinore 4, 4 '— Diaminophenol; N, N' Diphenylenole N, N ' Bis (3-methinolephenol) 1 [1, 1'-biphenenole] 4, A'-diamin (TPD); 2, 2-bis (4-di-triarylaminophenole) propane; 1, 1-bis (4-di-p-triaminophenenyl) cyclohexane; N, N, N ', N' —tetra-p-trinole 4, 4'-diaminobiphenyl; 1,1--bis (4-di-p-triol)
  • No. 5,061,569 For example, 4, 4'-bis [N- (1-naphthyl) N phenylamino] biphenyl (NPD), three triphenylamine units described in JP-A-4-308688 4, 4 ', A "—Tris [N— (3-methylphenyl) N phenylamino] triphenylamine (MTDATA) and the like.
  • a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.
  • Inorganic compounds such as p-type Si and p-type SiC can also be used as a hole injection material and a hole transport material.
  • a so-called p-type hole transport material as described in Letters 80 (2002), p. 139) can also be used.
  • the thickness of the hole transport layer is not particularly limited, but is usually about 51 111 to 5 111, preferably 5 to 200 nm.
  • This hole transport layer is one or more of the above materials. It may be a layered structure. It is also possible to use a hole transport layer having a high P property doped with impurities. Examples thereof include those described in JP-A-4-297076, JP-A-2000-196140, JP-A-2001-102175, J. Appl. Phys., 95, 5773 (2004), and the like. . It is preferable to use such a hole transport layer having a high ⁇ property because an organic electroluminescence element with lower power consumption can be produced.
  • the light emitting layer refers to a blue light emitting layer, a green light emitting layer, and a red light emitting layer.
  • the order of stacking the light emitting layers is not particularly limited, and a non-light emitting intermediate layer may be provided between the light emitting layers.
  • the total film thickness of the light emitting layer is not particularly limited, but is usually selected in the range of 21 111 to 5 111, preferably 2 to 200 nm in consideration of the homogeneity of the film and the voltage required for light emission. Further, it is preferably in the range of 10 to 20 nm. A film thickness of 20 nm or less is preferable because it has the effect of improving the stability of the emission color with respect to the driving current as well as the voltage aspect.
  • the thickness of each light emitting layer is preferably selected in the range of 2 to 100 nm, and more preferably in the range of 2 to 20 nm. There are no particular restrictions on the relationship between the blue, green, and red light-emitting layer thicknesses, but among the three light-emitting layers, the blue light-emitting layer (the sum of multiple layers) is the thickest! / ,.
  • the light-emitting layer includes at least three layers having different emission spectra in the range of 430 to 480, 510 to 550, and 600 to 640, respectively. If there are three or more layers, there is no particular limitation. When there are more than four layers, there may be a plurality of layers having the same emission spectrum.
  • a layer having an emission maximum wavelength in the range of 430 to 480 nm is referred to as a blue light emitting layer
  • a layer in the range of 510 to 550 nm is referred to as a green light emitting layer
  • a layer in the range of 600 to 640 nm is referred to as a red light emitting layer.
  • a plurality of light emitting compounds may be mixed in each light emitting layer within the range in which the maximum wavelength is maintained.
  • a blue light emitting compound having a maximum wavelength of 430 to 480 nm and a green light emitting compound having the same wavelength of 10 to 550 nm may be mixed and used in the blue light emitting layer.
  • the organic light-emitting material used as the material of the light-emitting layer is (a) a charge injection function, that is, holes can be injected from the anode or hole injection layer when an electric field is applied, and from the cathode or electron injection layer.
  • a function capable of injecting electrons (b) a transport function, ie, a function of moving injected holes and electrons by the force of an electric field, and (c) a light emission function, ie, an electric power.
  • fluorescent brighteners such as benzothiazole, benzimidazole, and benzoxazole, and styrylbenzene compounds can be used.
  • Specific examples of the above-mentioned optical brightener include 2,5 bis (5,7 di-t-pentyl-2-benzoxazolyl) 1,3,4 thiodia zonole, 4,4 'bis (5 , 7— t-pentyl-2 benzoxazolyl) stilbene, 4, ′ bis [5,7 di (2 methyl-2 butyl) -2 benzoxazolyl] stinoleben, 2, 5 bis (5, 7 di-t-pentyl) 2 Benzoxazolyl) thiophene, 2, 5 Bis [5 ⁇ , a-dimethylbenzyl-2 Benzoxazolyl] thiophene, 2, 5 Bis [5, 7 Di (2 methyl-2-butyl) -2 Benzoxazolyl] —3, 4 -Diphenylthiophene
  • styrylbenzene compounds include 1,4 bis (2-methylstyryl) benzene, 1,4 bis (3-methylstyryl) benzene, 1,4 bis (4-methylenostyryl).
  • optical brightener and styrylbenzene compound for example, 12-lid perinone, 1,4-diphenolino 1,3-butadiene, 1,1,4,4- Tetraphenyl-1,3-butadiene, naphthalimide derivatives, perylene derivatives, oxadiazole derivatives , Aldazine derivatives, pyrazirine derivatives, cyclopentagen derivatives, pyrophloropyrrole derivatives, styrylamine derivatives, coumarin compounds, international publications WO90 / 1314 8 and Appl. Phys.
  • aromatic dimethylidin-based compounds include 1, 4 phenylene dimethylidene, 4, 4 'phenylene dibibidimethylidene, 1, 4 ⁇
  • aromatic dimethylidin-based compounds include 1, 4 phenylene dimethylidene, 4, 4 'phenylene dibibidimethylidene, 1, 4 ⁇
  • examples thereof include bis (2,2 di-tert-butylphenylbinole) biphenyl, 4, A′-bis (2,2 diphenylbinyl) biphenyl, and the like, and derivatives thereof.
  • Specific examples of the compound represented by the general formula (I) include bis (2 methyl-8 quinolinolato) (p-phenolphenolate) aluminum (111), bis (2 methyl-8 quinolinolato) (1 naphtholato) aluminum. (III) etc. are mentioned.
  • a compound in which the above-described organic light-emitting material is used as a host and the host is doped with a strong fluorescent dye from blue to green, for example, a coumarin group or a fluorescent dye similar to the host is also suitable as the organic light-emitting material.
  • a strong fluorescent dye from blue to green for example, a coumarin group or a fluorescent dye similar to the host
  • the organic light-emitting material it is possible to obtain blue to green light emission (the emission color varies depending on the type of dopant) with high efficiency.
  • the host that is the material of the compound include organic light-emitting materials having a distyrylarylene skeleton (particularly preferably, for example, 4,4′bis (2,2diphenylvinyl) biphenyl).
  • the dopant are diphenylaminovinylarylene (particularly preferably, for example, N, N diphenylaminobiphenylbenzene and 4, A'-bis [2- [4- (N, N di-p-tolyl), phen-yl, bur, biphenyl).
  • the light emitting layer preferably contains a known host compound and a known phosphorescent compound (also referred to as a phosphorescent compound) in order to increase the luminous efficiency of the light emitting layer!
  • the host compound is a compound contained in the light-emitting layer, the mass ratio of which is 20% or more, and the phosphorescence quantum yield power of phosphorescence emission at room temperature (25 ° C) 0. defined as less than 1 compound.
  • the phosphorescence quantum yield is preferably less than 0.01.
  • a plurality of host compounds may be used in combination. Use multiple host compounds to transfer charges It can be adjusted, and the efficiency of the organic-electric-luminescence element can be improved.
  • by using a plurality of phosphorescent compounds it is possible to mix different light emission, thereby obtaining any light emission color.
  • White light emission is possible by adjusting the type of phosphorescent compound and the amount of doping, and it can also be applied to lighting and knocklights.
  • Known host compounds include, for example, Japanese Patent Application Laid-Open No. 2001-257076 No. I 2002-308855, No. 2001-313179, No. 2002-319491, No. 2001-357977.
  • Gazette 2002-334786, 2002-8860, 2002-334787, 2002-15871, 2002-334788, 2002-43056, 2002-334789 2002-75645, 2002-33857 9, 2002-105445, 2002-343568, 2002-141 173, 2002-352957, 2002-203683 Gazette, 2002-3 63227 Gazette, 2002-231453 Gazette, 2003-3165 Gazette, 2002-2 34888 Gazette, 2003-27048 Gazette, 2002-255934 Gazette, 2002- 260861 Publication No. 2002-280183 Publication No. 2002-299060 Publication No. 2002-302516 Publication No. 2002-305083 Publication No. 2002-305084 Publication No. 2 And compounds described in JP 02-308837.
  • the host compound in each layer is the same compound, since it is easy to obtain a uniform film property over the entire organic layer, and further, the host
  • the ability of the phosphorescent energy of the compound to be 2.9 eV or more is more preferable because it is advantageous for efficiently suppressing energy transfer from the dopant and obtaining high brightness.
  • Phosphorescence emission energy refers to the peak energy of the 0-0 band of phosphorescence emission measured by measuring the photoluminescence of a deposited film of lOOnm on a substrate with a host compound.
  • the host compound has a phosphorescence emission energy of 2.9 eV or more and a Tg of 90 considering the deterioration of the organic electroluminescence device over time (decrease in brightness, deterioration of film properties) and market needs as a light source. It is preferable that the temperature is higher than ° C. That is, both brightness and durability In order to satisfy the above, it is preferable that the phosphorescence emission energy is 2.9 eV or more and the Tg is 90 ° C. or more. Tg is more preferably 100 ° C or higher.
  • a phosphorescent compound is a compound in which light emission from an excited triplet is observed, and is a compound that emits phosphorescence at room temperature (25 ° C). A compound having a rate of 0.01 or more at 25 ° C. By using it together with the host compound described above, an organic electoluminescence device with higher luminous efficiency can be obtained.
  • the phosphorescent compound according to the present invention preferably has a phosphorescence quantum yield of 0.1 or more.
  • the above phosphorescence quantum yield can be measured by the method described on page 398 (1992 edition, Maruzen) of Spectroscopic II, 4th edition, Experimental Chemistry Course 7. Although the phosphorescence quantum yield in a solution can be measured using various solvents, the phosphorescence quantum yield used in the present invention is only required to achieve the phosphorescence quantum yield in any solvent.
  • the light emission of a phosphorescent compound can be described in two types in principle.
  • One is the recombination of carriers on the host compound to which carriers are transported, generating an excited state of the host compound, and this energy is generated.
  • An energy transfer type in which light emission from the phosphorescent compound is obtained by transferring it to the phosphorescent compound, and the other is that the phosphorescent compound becomes a carrier trap, and recombination of the carriers on the phosphorescent compound occurs. It is a carrier trap type force S that allows light emission from the phosphorescent compound to occur. In either case, the excited state energy of the phosphorescent compound must be lower than the excited state energy of the host compound. It is.
  • the phosphorescent compound can be appropriately selected from known materials used for the light-emitting layer of the organic electoluminescence device.
  • the phosphorescent compound is preferably a complex compound containing a group 8 or group 10 metal in the periodic table of elements, more preferably an iridium compound, an osmium compound, or a platinum compound (platinum complex compound), a rare earth complex. Of these, iridium compounds are most preferred.
  • the phosphorescent compound maximum wavelength of the phosphorescent compound is not particularly limited. In principle, by selecting a central metal, a ligand, a substituent of the ligand, and the like. The emission wavelength obtained can be changed.
  • the light-emitting layer is white by combining two or more light-emitting materials that emit blue, green, yellow, red, and the like.
  • a luminescent compound having a near emission wavelength is contained in the same layer. This increases the energy transition to the long wave luminescent compound and improves the luminous efficiency.
  • the same layer in the case of blue, green, and red, at least one of blue, green, and green and red is contained in the same layer.
  • it is composed of blue, green, yellow, and red
  • a luminescent color that contains a longer-wave luminescent compound is contained in the same layer.
  • it is yellow red, green one yellow.
  • the electron injection layer is made of a material having a function of transporting electrons and is included in the electron transport layer in a broad sense.
  • the electron injection layer is a layer that is provided between the electrode and the organic layer in order to lower the driving voltage and improve the luminance of the light emission.
  • Organic electorium luminescence element and its industrialization front line June 30, 1998) The details are described in Volume 2, Chapter 2, “Electrode Materials” (pp. 123-166) of Volume 2 of TS Co., Ltd.).
  • the details of the electron injection layer (one cathode buffer layer) are described in JP-A-6 325871, JP-A-9 17574, JP-A-10-74586, and the like, and specifically, strontium, aluminum, etc.
  • the buffer layer should be a very thin film. S Desirably, depending on the material, the film thickness is preferably in the range of 0.1111 to 5 ⁇ 111.
  • an electron transport material also serving as a hole blocking material
  • any of the conventionally known compounds can be selected and used.
  • nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiobilanoxide derivatives, carpositimide, fluorenylidenemethane derivatives, anthraquinodimethane and Anthrone derivatives, oxadiazole derivatives and the like can be mentioned.
  • thiadiazole derivatives in which the oxygen atom of the oxaziazole ring is replaced with a sulfur atom, and quinoxaline derivatives having a quinoxaline ring known as an electron withdrawing group can also be used as the electron transport material.
  • quinoxaline derivatives having a quinoxaline ring known as an electron withdrawing group can also be used as the electron transport material.
  • a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.
  • metal complexes of 8 quinolinol derivatives such as tris (8 quinolinol) aluminum (Alq), tris (5,7-dichloro-l-quinolinol) aluminum, tris (5,7-dive mouth) Mo 8 quinolinol ) Aluminum, Tris (2methyl-8quinolinol) aluminum, Tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq) etc., and the central metals of these metal complexes are In, Mg, Cu, Metal complexes replacing Ca, Sn, Ga or Pb can also be used as electron transport materials.
  • metal-free or metal phthalocyanine or those having an end substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transport material.
  • Distyrubirazine derivatives can also be used as electron transport materials, and inorganic semiconductors such as n-type Si and n-type SiC can be used as electron transport materials as well as hole injection layers and hole transport layers. I can do it.
  • the thickness of the electron transport layer is not particularly limited, but is usually 51 111 to 5 About m, preferably 5 to 200 nm.
  • the electron transport layer may have a single layer structure that can be one or more of the above materials.
  • an electron transport layer having a high n property doped with impurities can be used.
  • examples thereof include JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, JP-A-2001-102175, J. Appl. Phys., 95, 5773 (2004). ) And the like. It is preferable to use such an electron transport layer having a high ⁇ property because a device with lower power consumption can be manufactured.
  • the second electrode a material having a small work function! /, (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof is used.
  • an electron injecting metal a material having a small work function! /, (4 eV or less) metal
  • an alloy a material having a small work function! /, (4 eV or less) metal
  • an alloy an electrically conductive compound
  • a mixture thereof is used as the second electrode.
  • Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide. (Al 2 O 3) mixture, indium, lithium / aluminum mixture, rare earth metal, and the like.
  • a mixture of an electron injectable metal and a second metal which is a stable metal having a larger work function value than this for example, a magnesium / silver mixture.
  • a magnesium / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al 2 O 3) mixture, a lithium / aluminum mixture, aluminum and the like are suitable.
  • the cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. Further, the sheet resistance as the cathode is preferably several hundred ⁇ / mouth or less, and the preferred film thickness is usually 101 111 to 5 111, preferably 50 to 200 nm.
  • the first electrode (anode) or the second electrode (cathode) of the organic electoric luminescence element is transparent or translucent, it is convenient to improve the light emission luminance. .
  • the transparent conductive material described in the description of the first electrode is formed thereon, thereby forming a transparent or translucent first electrode.
  • Two electrodes (cathode) can be produced, and by applying this, an element in which both the first electrode (anode) and the second electrode (cathode) are transmissive can be produced.
  • the external extraction efficiency at room temperature of light emission of the organic electoluminescence device of the present invention is preferably 1% or more, more preferably 5% or more.
  • the external extraction quantum efficiency (%) the number of photons emitted to the outside of the organic electoluminescence device / the number of electrons X 100 flowing through the organic electroluminescence device.
  • a hue improving filter such as a color filter or the like
  • a color conversion filter that converts the emission color from the organic electroluminescence device to multiple colors using a phosphor is also used. Also good.
  • the maximum light emission of the organic-electric-luminescence element is preferably 480 nm or less! /.
  • the organic electoluminescence device of the present invention preferably uses the following method in combination.
  • Organic-electric-luminescence elements emit light inside a layer that has a higher refractive index than air (refractive index is about 1.7 to 2.1), and about 15% to 20% of the light generated in the light emitting layer. It is generally said that only light can be extracted. This is because light incident on the interface (interface between the transparent substrate and air) at an angle ⁇ greater than the critical angle causes total reflection and cannot be taken out of the device, or the transparent electrode or light emitting layer is transparent. This is because light is totally reflected between the substrate and the light, and the light is guided through the transparent electrode or the light emitting layer, and as a result, the light escapes in the side direction of the element.
  • a method for improving the light extraction efficiency for example, a method of forming irregularities on the surface of the transparent substrate to prevent total reflection at the interface between the transparent substrate and the air (US Pat. No. 4,774,435).
  • a method for improving efficiency by providing a substrate with a light condensing property Japanese Patent Laid-Open No. 63-314795.
  • a method of forming a reflective surface on the side surface of an element Japanese Patent Laid-Open No. 1 220394.
  • a method of forming an antireflection film by introducing a flat layer having an intermediate refractive index between a substrate and a light emitter Japanese Patent Laid-Open No. 62-172691.
  • Japanese Patent Laid-Open No. 2001-202827 A method of introducing a flat layer having a lower refractive index than the substrate between the substrate and the light emitter. There is a method of forming a diffraction grating between any one of the substrate, the transparent electrode layer and the light emitting layer (including between the substrate and the outside) (Japanese Patent Laid-Open No. 1 283 751).
  • these methods can be used in combination with an organic electoluminescence device, but a flat layer having a lower refractive index than the substrate is provided between the substrate and the light emitter.
  • a method of forming a diffraction grating between any layers of the substrate, the transparent electrode layer and the light emitting layer (including between the substrate and the outside) can be suitably used.
  • by combining these means it is possible to obtain an element having higher luminance or durability.
  • the low refractive index layer include air mouth gel, porous silica, magnesium fluoride, and fluorine-based polymer. Since the refractive index of the transparent substrate is generally about 1.5 to about 1.7, the low refractive index layer preferably has a refractive index of about 1.5 or less. Further, it is preferably 1.35 or less. The thickness of the low refractive index medium should be at least twice the wavelength in the medium.
  • the method of introducing a diffraction grating into an interface or any medium that causes total reflection is characterized by a high effect of improving light extraction efficiency.
  • This method is generated from the light-emitting layer by utilizing the property that the diffraction grating can change the direction of light to a specific direction different from refraction by so-called Bragg diffraction such as first-order diffraction and second-order diffraction.
  • the light that cannot go out due to total reflection between layers is introduced by introducing a diffraction grating into any layer or medium (in a transparent substrate or transparent electrode).
  • the light is diffracted and light is taken out.
  • the diffraction grating to be introduced has a two-dimensional periodic refractive index. This is because light emitted from the light-emitting layer is randomly generated in all directions, so in a general one-dimensional diffraction grating having a periodic refractive index distribution only in one direction, light traveling in a specific direction It is only diffracted and the light extraction efficiency does not increase so much. However, by making the refractive index distribution a two-dimensional distribution, the light traveling in all directions is diffracted, and the light extraction efficiency increases.
  • the position where the diffraction grating is introduced may be in any one of the layers or in the medium (in the transparent substrate or the transparent electrode), but in the vicinity of the organic light emitting layer where light is generated. desirable.
  • the period of the diffraction grating is preferably about 1/2 to 3 times the wavelength of light in the medium.
  • the diffraction grating is arranged in a square lattice shape, a triangular lattice shape, or a honeycomb lattice. It is preferable that the arrangement is repeated two-dimensionally.
  • the organic electoluminescence device of the present invention is processed so that a structure on a microlens array, for example, is provided on the light extraction side of the substrate in order to efficiently extract light generated in the light emitting layer.
  • the light in the specific direction can be increased by condensing light in a specific direction, for example, in the front direction with respect to the light emitting surface of the element.
  • a microlens array square pyramids are arranged two-dimensionally on the light extraction side of the substrate so that one side is 30 mm and the apex angle is 90 degrees.
  • One side is preferably 10 111 to 100 m. If it is smaller than this, the effect of diffraction is generated, and if the color is too large, the thickness becomes undesirably high.
  • the light condensing sheet for example, an LED backlight of a liquid crystal display device that is put into practical use can be used.
  • a brightness enhancement film (BEF) manufactured by Sumitomo 3EM may be used.
  • BEF brightness enhancement film
  • the shape of the prism sheet for example, an octagonal stripe having a vertex angle of 90 degrees and a pitch of 50 ⁇ 111 may be formed on the substrate, or the vertex angle may be rounded and the pitch may be changed randomly. Other shapes may be used.
  • a diffusion film (light-up) manufactured by Kimoto Co., Ltd. can be used.
  • Manufactured by: NA-45 is cut into a size of 55mm x 45mm, patterned so that the light emitting part is a 45mm x 34mm rectangle, and then a transparent substrate with this ITO transparent electrode
  • the sample was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to ultraviolet ozone cleaning for 5 minutes.
  • This transparent substrate was fixed to a substrate holder of a commercially available vacuum deposition apparatus, and a stainless steel rectangular perforated mask was attached.
  • the mask was attached so as to satisfy the conditions for covering ITO with an organic layer strength of 6 mm X 35 mm.
  • a-NPD, CBP, Ir-1, BCP, and Alq were loaded into five tantalum resistance heating boats, respectively.
  • Lithium fluoride was placed in a resistance heating boat made of tantalum and aluminum was placed in a resistance heating boat made of tungsten, and each was attached to the second vacuum chamber of the vacuum evaporation system.
  • the heating boat containing CBP and the heating boat containing Ir 1 are independently energized, so that the deposition rate of CBP as the luminescent host and Ir-1 as the luminescent dopant becomes 100: 7.
  • the light emitting layer was provided by vapor deposition so as to have a thickness of 30 nm.
  • a heating boat containing BCP was energized and heated to provide a 10-nm-thick hole blocking layer electron transport layer at a deposition rate of 0.15 nm / sec. Furthermore, a heating boat containing Alq was energized and heated, and an electron transport layer electron injection layer having a film thickness of 40 nm was provided at a deposition rate of 0.15 nm / second.
  • the organic EL element unit 101 was transferred to a glove box (a glove box substituted with high-purity nitrogen gas with a purity of 99.999% or more) in a nitrogen atmosphere without being exposed to the air.
  • a glove box a glove box substituted with high-purity nitrogen gas with a purity of 99.999% or more
  • a polyethylene terephthalate film film made by Teijin's DuPont, hereinafter abbreviated as PET
  • PET polyethylene terephthalate film
  • An inorganic gas noble film with SiO force is formed on a flexible film and has an oxygen permeability of 0.01 ml / m 2 / day or less and a water vapor permeability of 0. Olg / m 2 / day or less.
  • a flexible sealing film was prepared.
  • the flexible sealing film having the gas barrier layer formed on the entire surface was cut into a size of 55 mm x 45 mm, and this was used as the flexible sealing film 1 ⁇ Applying adhesive>
  • the organic EL element unit surface formed on the glass so as to face the flexible sealing film having the bus barrier layer to which the adhesive has been applied is directed toward the flexible sealing film, and FIG. Alignment was performed so that the configuration described in (1) was achieved, and the ambient environment was reduced to lOPa.
  • a flexible sealing film having gas barrier properties was pressure bonded by a flat plate press at a pressure of 0.05 MPa.
  • the adhesive was irradiated from the cathode side under an irradiation energy condition of 6000 mj / cm 2 to harden the adhesive. Thereafter, the organic element taken out from the glove box and made in this manner was designated as an organic electoluminescence element 101.
  • a flexible sealing film 2 produced by the following method was used in place of the flexible sealing film 1, and sealed with the configuration shown in FIG.
  • the organic electroluminescent mouth luminescence element 102 was made in the same manner except that
  • a polyethylene terephthalate film film made by Teijin's DuPont, hereinafter abbreviated as PET
  • an atmospheric pressure plasma discharge treatment apparatus having the configuration shown in FIG. 7, and the configuration shown in FIG.
  • an inorganic gas barrier film made of SiO, etc. is continuously formed on a flexible film with an oxygen permeability of 0.01 ml. / m 2 / day or less, to produce a flexible sealing film of the following gas barrier vapor permeability 0. 01G / m 2 / day.
  • the above-prepared flexible sealing film having a gas barrier layer was cut so that the total area was 55 mm x 45 mm and the gas barrier layer area was 51 mm x 40 mm. Two.
  • the organic electroluminescent mouth luminescence element 101 instead of the flexible sealing film 1, a flexible sealing film 3 prepared by the following method was used and sealed with the configuration shown in FIG. In the same manner as described above, the organic electroluminescent mouth luminescence element 103 was manufactured.
  • a polyethylene terephthalate film film made by Teijin's DuPont, hereinafter abbreviated as PET
  • an atmospheric pressure plasma discharge treatment apparatus having the configuration shown in FIG. 7, and the configuration shown in FIG.
  • an inorganic gas barrier film of SiO force, etc. is continuously formed on a flexible film, and oxygen permeability is 0.01ml / m 2 / day or less, to produce a flexible sealing film of the following gas barrier vapor permeability 0. 01G / m 2 / day.
  • the flexible sealing film having the gas barrier layer formed on the entire surface was cut so that the total area was 55 mm x 45 mm and the gas barrier layer area was 46 mm x 35 mm.
  • the stop film was 3.
  • each organic-elect mouth luminescence device When each organic-elect mouth luminescence device is stored for 250 hours in an environment at 85 ° C and 5% relative humidity, it is dark when driven to a constant current of 10 mA / cm 2 for each organic-elect-mouth luminescence device.
  • the presence / absence of spot generation, reduction of light emission area, and change in light emission luminance were measured, and compared with each characteristic of each untreated organic electoluminescence device, high temperature storage stability was evaluated according to the following criteria.
  • the emission luminance was measured using CS-1000 manufactured by Konica Minolta Sensing.
  • the reduction ratio of the light emitting area including dark spots is 10% or more, or the luminance fluctuation at a constant current density is 10% or more.
  • each organic-elect mouth luminescence element After storing each organic-elect mouth luminescence element in an environment of 45 ° C and relative humidity 90% for 250 hours, the darkness when driving each organic-elect-mouth luminescence element with a constant current of 10 mA / cm— The presence / absence of sbots, reduction of light emission area, and change in light emission luminance were measured and compared with the characteristics of each untreated organic-electrical luminescence element, and high-humidity storage stability was evaluated according to the following criteria. The emission luminance was measured using CS-1000 manufactured by Konica Minolta Sensing.
  • the reduction ratio of the light emitting area including dark spots is 5% or more and less than 10% of the untreated product, and the luminance fluctuation at a constant current density is 5% or more and less than 10%.
  • the reduction ratio of the light emitting area including dark spots is 10% or more, or the luminance fluctuation at a constant current density is 10% or more.
  • Table 1 shows the results obtained as described above.
  • Example 2 As is clear from the results shown in Table 1, using a flexible sealing film having the configuration defined in the present invention, a region having a gas barrier layer in a close contact region and a region where no gas barrier layer is present.
  • the organic electoluminescence device of the present invention sealed so as to have at the same time does not break the sealed portion even when stored for a long time at high temperature or high humidity. It turns out that it has preservability. [0217]
  • Example 2 Example 2
  • an inorganic gas noble film having SiO force is formed on the entire surface of a polyethylene terephthalate film (film made by Teijin's DuPont, hereinafter abbreviated as PET) using the atmospheric pressure plasma discharge treatment apparatus shown in FIG.
  • PET polyethylene terephthalate film
  • This flexible film substrate 1 was cut into a size of 55 mm x 45 mm, and on top of this, an example
  • the organic EL element unit was formed by patterning so that the light-emitting portion had a rectangular shape of 45 mm x 34 mm.
  • An organic electoluminescence device 202 was produced in the same manner as in the production of the organic electroluminescence device 201 except that the flexible sealing film 2 was used instead of the flexible encapsulation film 1.
  • the organic electoluminescence device 202 For the production of the organic electoluminescence device 202, the organic electophoresis was produced in the same manner except that the flexible film substrate 2 produced by the following method was used instead of the flexible film substrate 1. A luminescence element 203 was manufactured.
  • a polyethylene terephthalate film (a film made by Teijin's DuPont, hereinafter abbreviated as PET) is used as the substrate, and an atmospheric pressure plasma discharge treatment apparatus having the configuration shown in FIG.
  • PET polyethylene terephthalate film
  • an atmospheric pressure plasma discharge treatment apparatus having the configuration shown in FIG.
  • an inorganic gas barrier film with SiO force is continuously formed on the substrate to allow oxygen permeation.
  • the flexible film substrate having the gas barrier layer produced above was cut so that the total area was 55 mm x 45 mm and the gas barrier layer area was 51 mm x 40 mm. did.
  • the flexible sealing film having the configuration defined in the present invention is used, and the region having the gas barrier layer in the close contact region and the gas barrier layer do not exist.
  • the organic electoluminescence device of the present invention sealed so as to have a region at the same time does not break the sealed portion even when stored for a long time at high temperature or high humidity. It can also be seen that it has a high humidity storage property.
  • the base sheet having a gas barrier layer having a plurality of organic-electrical-luminescence elements unit (organic-illuminating-luminescence element 301il shown in FIG. 11) described in FIG. 11) described in FIG. 11 the bonding process and cutting process shown in FIG.
  • a plurality of organic electroluminescent elements having the same structure as the organic electroluminescent element 102 described in Example 1 and the organic electroluminescent element described in Example 2 were formed and described in Example 1.

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Abstract

L'invention concerne un dispositif électroluminescent (EL) organique excellent en matière d'adhérence étroite et de stabilité au stockage à long terme à haute température et dans une atmosphère d'humidité et un processus de production d'un film d'étanchéité flexible à utiliser dans le dispositif, ledit film comportant une couche de protection contre le gaz et étant excellent en matière d'adhérence étroite avec un substrat. Le dispositif EL organique comprend un substrat, un élément EL organique reposant sur le substrat, et un film d'étanchéité flexible disposé sur l'élément EL, ledit film étant composé d'un film flexible et d'une couche de protection contre le gaz reposant sur le film flexible, et est caractérisé en ce que le substrat est en verre et le film d'étanchéité flexible présente la couche de protection contre le gaz côté élément EL organique et ainsi adhère au substrat pour recouvrir la périphérie de l'élément EL organique sous réserve que dans la zone de périmètre interne dans la région adhérant étroitement au substrat, le film d'étanchéité flexible soit pourvu d'une couche de protection contre le gaz et la couche de protection contre le gaz du film adhère étroitement au substrat, tandis que dans la zone de périmètre externe dans la région adhérant étroitement au substrat, le film d'étanchéité flexible n'est pas pourvu d'une couche de protection contre le gaz et le film flexible adhère directement au substrat.
PCT/JP2007/066021 2006-09-15 2007-08-17 processus de PRODUCtion d'UN film d'étanchéité flexible et dispositifs électroluminescents organiques réalisés à l'aide du film WO2008032526A1 (fr)

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