JP2007073332A - Organic electroluminescent panel and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thin and light-weighted organic EL panel dispensing with complicated control accompanied by sealing layer setting, restrained from occurrence of dark spot, having a light emission layer with a long life, and a method of manufacturing the same. <P>SOLUTION: The electroluminescent layer has an anode layer at least including a first electrode, an organic compound layer including a light emitting layer, a cathode layer including a second electrode, and a sealing layer. The sealing layer is constituted by at least one layer of resin base material and at least one layer of barrier layer. A water absorption rate of the flexible sealing member at sealing measured in conformity with ASTM D570 is 1.0% or less. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an organic electroluminescence panel (hereinafter also referred to as an organic EL panel) and a method for producing an organic electroluminescence panel.

  In recent years, organic EL elements using organic substances have been promising for use as solid light-emitting inexpensive, large-area full-color display elements and writing light source arrays, and active research and development have been promoted. The organic EL element includes a first electrode (anode or cathode) formed on a substrate, an organic compound layer (single layer portion or multilayer portion) containing an organic light emitting material laminated thereon, that is, a light emitting layer, It is a thin film type element having a second electrode (cathode or anode) laminated on the light emitting layer. When a voltage is applied to such an organic EL element, electrons are injected from the cathode and holes are injected from the anode into the organic compound layer. It is known that light is obtained by releasing energy as light when the electrons and holes recombine in the light emitting layer and the energy level returns from the conduction band to the valence band.

  As described above, since the organic EL element is a thin film type element, when an organic EL panel in which one or a plurality of organic EL elements are formed on a substrate is used as a surface light source such as a backlight, a surface light source. It is possible to easily make a device equipped with In addition, when a display device is configured using an organic EL panel in which a predetermined number of organic EL elements as pixels are formed on a substrate as a display panel, the liquid crystal display device has high visibility and no viewing angle dependency. There are benefits that cannot be obtained.

  Usually, an organic EL panel has a first electrode (anode), a hole transport layer (hole injection layer), an organic compound layer (light emitting layer), an electron injection layer, and a second electrode (on the substrate). Cathode), adhesive layer, and flexible sealing member in this order. In the organic EL panel having such a configuration, an electron transport layer may be provided between the cathode, the organic compound layer (light emitting layer), and the electron injection layer. A gas barrier film may be provided between the anode and the substrate.

In the case of an organic EL panel, the first electrode (anode) side is usually the observation side, and the first electrode (anode) includes ITO (mixture of tin oxide and indium oxide), IZO (mixture of zinc oxide and indium oxide), ZnO. SnO ₂ , In ₂ O _{3 and the} like are known. Among them, the ITO electrode has a high light transmittance of 90% or more and a low sheet resistance value of 10Ω / □ or less, and is also used as a transparent electrode for liquid crystal displays and solar cells. Further, the IZO electrode has an advantage that a predetermined low resistance value can be obtained without heating the substrate at the time of formation, and the film surface is smoother than the ITO electrode.

  In applying the organic EL panel as described above to a display device, stable light emission of the three primary colors of RGB is an indispensable condition. However, in an organic EL panel, a non-light emitting point called a dark spot is generated by long-time driving, and the growth of the dark spot is one of the causes for shortening the lifetime of the organic EL panel. It is known that a dark spot is generally generated in a size that cannot be seen with the naked eye immediately after driving, and grows by continuous driving using this as a core. Further, it is known that dark spots are generated even in a storage state where driving is not performed and grows with time.

  There are various causes of dark spots, but external factors include crystallization of the organic layer due to the penetration of moisture and oxygen into the organic electroluminescent element, peeling of the second electrode, and the like. As internal factors, short spots due to crystal growth of the metal constituting the second electrode, crystallization and deterioration of the organic layer due to heat generation due to light emission, and the like are considered as factors of dark spots.

  As countermeasures for preventing the occurrence of these dark spots, for example, JP-A-5-182759, JP-A-5-36475, and JP-A-2002-43055 disclose an EL element in a dry nitrogen atmosphere using a metal or glass sealing can. Is described. However, since a glass or metal sealing can is used, there is a limit to reducing the thickness and weight of the organic EL panel. In addition, in the manufacturing process, a step of encapsulating a desiccant inside the airtight case, a step of applying a photocurable resin to the airtight case, a step of bonding the light transmissive substrate and the airtight case, a step of curing the photocurable resin Therefore, there was a problem in terms of productivity and manufacturing cost.

  Furthermore, as a countermeasure for reducing the thickness and weight by preventing the generation of dark spots, sealing with a film having a high barrier property such as a metal foil provides a thin and light organic EL panel with excellent moisture resistance. Methods have been studied.

  For example, a phosphor cell including a light emitting layer, an insulating layer laminated on the back surface of the light emitting layer, a back electrode laminated on the back surface of the insulating layer, and a transparent electrode layer laminated on the front surface of the light emitting layer is made of sulfuric acid. Sealed with a sealing film having a thermoplastic resin layer containing at least one substance of magnesium, aluminum oxide, barium oxide, calcium oxide and silicon oxide, and a moisture-proof film layer laminated on the surface of the thermoplastic resin layer. A stopped organic EL panel is known (for example, see Patent Document 1).

  At least a transparent anode layer, a light emitting medium layer, and a cathode layer are sequentially laminated on a light-transmitting substrate, and an aluminum foil and a desiccant selected from magnesium sulfate, calcium phosphate, magnesium carbonate, calcium oxide, barium oxide, and strontium oxide are formed thereon. An organic EL panel sealed with a sealing film having a resin film in which is dispersed is known (see, for example, Patent Document 2).

  However, the techniques described in Patent Document 1 and Patent Document 2 have the following drawbacks. 1) Since the sealing member is a resin film, moisture from the outside air permeates. 2) The moisture in the outside air is absorbed more than necessary by the desiccant, and there is an increased concern about moisture permeation into the organic electroluminescence element (hereinafter also referred to as organic EL element). 3) Although it is possible to slow down the water | moisture content arrival to the inside of an organic EL element, it is not a fundamental measure.

A light emitting laminate obtained by laminating a transparent electrode, an organic compound layer including at least a light emitting layer, and a back electrode on a support substrate has a water vapor permeability of 0.01 g / m ² · day or less and an oxygen permeability of 0.01 ml / With a flexible sealing cover of m ² · day · atm or less, the support substrate and the periphery of the light emitting laminate are sealed with an adhesive, and moisture or oxygen is interposed between the sealing cover and the light emitting laminate. A light-emitting element (organic EL panel) in which an inert gas in which an adsorbent that adsorbs adsorbed is enclosed is known (see, for example, Patent Document 3).
However, the technique described in Patent Document 3 requires fairly complicated management in order to maintain constant deposition of the space between the sealing cover and the light emitting laminate, and the performance is not stable with changes in the deposition of the space. Is concerned.

Under these circumstances, thin and lightweight organic EL panels and organic EL panels that do not require complicated management associated with providing a sealing layer, suppress the occurrence of dark spots, and extend the life of the light emitting layer. Development of a manufacturing method is desired.
JP-A-7-153570 JP 2004-335208 A JP 2003-282243 A

  The present invention has been made in view of the above situation, and its purpose is not to require complicated management associated with providing a sealing layer, suppress the occurrence of dark spots, and can extend the life of the light emitting layer. To provide a thin and lightweight organic EL panel and a method for manufacturing the organic EL panel.

  The above object of the present invention has been achieved by the following constitution.

  (1) In an organic electroluminescence panel having an anode layer including at least a first electrode, an organic compound layer including a light emitting layer, a cathode layer including a second electrode, and a sealing layer on a substrate, the sealing The layer is composed of a flexible sealing member having at least one resin base material and at least one barrier layer, and the water absorption measured according to ASTM D570 at the time of sealing of the flexible sealing member is An organic electroluminescence panel characterized by being 1.0% or less.

  (2) The organic electroluminescence panel according to (1) above, wherein an equilibrium water absorption rate of the flexible sealing member in the atmosphere (20 ° C., 65% RH) is 2.0% or less.

  (3) The substrate is a flexible multilayer resin member having at least one resin base material and at least one barrier layer, and the flexible multilayer resin member at the time of sealing the flexible sealing member The organic electroluminescence panel according to (1) or (2) above, wherein the water absorption is 1.0% or less as measured in accordance with ASTM D570.

  (4) The organic electroluminescence panel according to (3), wherein the flexible multilayer resin member has an equilibrium water absorption rate of 2.0% or less in the atmosphere (20 ° C., 65% RH).

  (5) The organic electroluminescence according to any one of (1) to (4), wherein the barrier layer includes at least one metal or non-metal oxide layer. panel.

  (6) A step of sequentially forming an anode layer including at least a first electrode, an organic electroluminescence layer including an organic compound layer including a light emitting layer, a cathode layer including a second electrode, and a sealing layer on a substrate. And forming the sealing layer in the organic electroluminescence panel manufacturing method of manufacturing an organic electroluminescence panel by arranging a flexible sealing member on a light emitting region and a periphery via a sealing agent, The flexible sealing member is a multi-layered resin base material having a barrier layer, and the water absorption measured in accordance with ASTM D570 at the time of sealing the flexible sealing member is 1.0% or less. The manufacturing method of the organic electroluminescent panel characterized by these.

  (7) The organic electroluminescence panel according to (6), wherein the flexible sealing member has an equilibrium water absorption rate of 2.0% or less in the atmosphere (20 ° C., 65% RH). Production method.

  (8) The substrate is a flexible multilayer resin member having at least one resin base material and at least one barrier layer, and the flexible multilayer resin member at the time of sealing the flexible sealing member The water absorption of the organic electroluminescence panel as described in (6) or (7) above is 1.0% or less as measured in accordance with ASTM D570.

  (9) The organic multilayer panel according to (8), wherein the flexible multilayer resin member has an equilibrium water absorption rate of 2.0% or less in the atmosphere (20 ° C., 65% RH). Production method.

  (10) The organic electroluminescence according to any one of (6) to (9), wherein the barrier layer includes at least one metal or non-metal oxide layer. Panel manufacturing method.

  Provided are a thin and lightweight organic EL panel and a method for manufacturing the organic EL panel that do not require complicated management associated with providing a sealing layer, suppress the generation of dark spots, and extend the life of the light emitting layer. As a result, it was possible to improve the quality and production efficiency of organic EL panels.

  Embodiments of the present invention will be described with reference to FIGS. 1 to 7, but the present invention is not limited thereto.

  FIG. 1 is a schematic cross-sectional view showing an example of a layer structure of an organic EL panel.

  In the figure, 1 indicates an organic EL panel. The organic EL panel 1 includes an anode layer 102 including a first electrode, a hole transport layer (hole injection layer) 103, an organic compound layer (light emitting layer) 104, an electron injection layer 105, and a substrate 101. The cathode layer 106 including the second electrode, the sealing agent layer 107, and the sealing layer 108 are provided in this order. In the organic EL panel shown in this figure, a hole injection layer (not shown) may be provided between the anode layer 102 including the first electrode and the hole transport layer 103. An electron transport layer (not shown) may be provided between the cathode layer 106 including the second electrode, the organic compound layer (light emitting layer) 104, and the electron injection layer 105. In the organic EL element 1, a gas barrier film (not shown) may be provided between the anode layer 102 including the first electrode and the substrate 101.

  The layer configuration of the organic EL panel shown in this figure shows an example, but the following configurations can be cited as the layer configuration of another typical organic EL panel.

(1) Substrate / anode (first electrode) / light emitting layer / electron transport layer / cathode (second electrode) / sealing layer (2) substrate / anode (first electrode) / hole transport layer / light emitting layer / positive Hole blocking layer / electron transport layer / cathode (second electrode) / sealing layer (3) substrate / anode (first electrode) / hole transport layer (hole injection layer) / light emitting layer / hole blocking layer / electron Transport layer / cathode buffer layer (electron injection layer) / cathode (second electrode) / sealing layer (4) substrate / anode (first electrode) / anode buffer layer (hole injection layer) / hole transport layer / light emission Layer / hole blocking layer / electron transport layer / cathode buffer layer (electron injection layer) / cathode (second electrode) / sealing layer In the present invention, an organic compound comprising at least a first electrode layer and a light emitting layer on a substrate The state in which the layers and the second electrode layer are sequentially laminated is referred to as an organic EL element, and the state covered with the sealing layer is referred to as an organic EL panel.

In the case of an organic EL panel, the anode (first electrode) 102 side is usually the observation side, and the anode (first electrode) 102 has ITO (mixture of tin oxide and indium oxide) and IZO (mixture of zinc oxide and indium oxide). ZnO, SnO ₂ , In ₂ O _{3 and the} like are known. Among them, the ITO electrode has a high light transmittance of 90% or more and a low sheet resistance value of 10Ω / □ or less, and is also used as a transparent electrode for liquid crystal displays and solar cells. Further, the IZO electrode has an advantage that a predetermined low resistance value can be obtained without heating the substrate at the time of formation, and the film surface is smoother than the ITO electrode.

  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 single-wafer sheet-like substrate include a transparent glass plate and a sheet-like transparent resin film. Examples of the resin film 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 esters such as cellulose acetate phthalate (TAC) and cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide , Polyethersulfone (PES), polyphenylene sulfide, polysulfones, poly Cycloolefin resins such as ether imide, polyether ketone imide, polyamide, fluororesin, nylon, polymethyl methacrylate, acrylic or polyarylate, Arton (trade name, manufactured by JSR) or Apel (trade name, manufactured by Mitsui Chemicals) Can be mentioned. Examples of the strip-shaped flexible substrate include a transparent resin film, and a flexible multilayer resin member having at least one resin base material and at least one barrier layer. As the transparent resin film, the same resin film as the single-wafer sheet-like substrate can be used.

When a transparent resin film is used as the substrate, a gas barrier film is preferably formed on the surface of the resin film as necessary. Examples of the gas barrier film include an inorganic film, an organic film, or a hybrid film of both. As a characteristic of the gas barrier film, the water vapor permeability is preferably 0.01 g / m ² · day · atm or less. Furthermore, a high barrier film having an oxygen permeability of 10 ⁻³ ml / m ² / day or less and a water vapor permeability of 10 ⁻⁵ g / m ² / day or less is preferable.

  As a material for forming the gas barrier film, any material may be used as long as it has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride, or the like can be used. Further, in order to improve the brittleness of the film, it is more preferable to have a laminated structure of these inorganic layers and layers made of organic materials. Although there is no restriction | limiting in particular about the lamination | stacking order of an inorganic layer and an organic layer, It is preferable to laminate | stack both alternately several times. The method for forming the barrier film is not particularly limited, and for example, vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam, ion plating, plasma polymerization, atmospheric pressure plasma polymerization A plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used, but an atmospheric pressure plasma polymerization method as described in JP-A-2004-68143 is particularly preferable.

  When a flexible multilayer resin member having at least one resin base material and at least one barrier layer is used as the substrate, the layer configuration of the flexible multilayer resin member is the same as the flexible sealing member described later. In addition, the equilibrium water absorption rate in the atmosphere (20 ° C., 65% RH) is preferably 2.0% or less in consideration of the water absorption, moisture permeability, etc. of the flexible multilayer resin member. The equilibrium water absorption is a value of water absorption measured according to ASTM D570 after being left in the atmosphere (20 ° C., 65% RH) for 100 hours. The thickness of the resin base material 108a is preferably 10 μm to 500 μm in consideration of handling at the time of manufacture, tensile strength, stress cracking resistance of the barrier layer, and the like. The water absorption measured in accordance with ASTM D570 at the time of sealing the flexible multilayer resin member takes into account the crystallization of the organic layer, the generation of dark spots, the extension of the lifetime of the organic EL element, etc. due to the brought-in moisture. 0% or less is preferable. As the barrier layer, the same material as the flexible sealing member can be used.

  FIG. 2 is an enlarged schematic sectional view of a portion indicated by T in FIG.

  The sealing layer 108 is composed of a flexible sealing member 108 'having a resin base material 108a and a barrier layer 108b. Note that a protective layer (not shown) may be provided on the barrier layer 108b (in the drawing, between the barrier layer 108b and the sealant layer 107). The resin base material 108a may be a single body or a laminate, and can be appropriately selected as necessary. The barrier layer 108b may be a single body or a laminate, and can be appropriately selected as necessary. The sealing layer 108 is formed by bonding a flexible sealing member 108 ′ onto the anode layer including the first electrode through a sealing agent.

  The water absorption measured according to ASTM D570 when sealing the flexible sealing member is 1.0% or less. When the water absorption rate exceeds 1.0%, the organic layer is crystallized by the moisture brought in by the flexible sealing member, the generation of dark spots can be achieved by peeling the second electrode, and the life of the organic EL element can be extended. Since it disappears, it is not preferable.

  In addition, the equilibrium water absorption rate of the flexible sealing member in the atmosphere (20 ° C., 65% RH) at 23 ° C. and 50% RH takes into consideration the water absorption and moisture permeability of the flexible sealing member. It is preferably 0% or less. The equilibrium water absorption is a value of water absorption measured according to ASTM D570 after being left in the atmosphere (20 ° C., 65% RH) for 100 hours.

  The thickness of the resin base material 108a is preferably 10 μm to 500 μm in consideration of handling at the time of manufacture, tensile strength, stress cracking resistance of the barrier layer, and the like. The thickness of the barrier layer 108b is preferably 5 nm to 200 μm in consideration of the barrier performance, the stress cracking resistance of the barrier layer, and the like.

  The other physical properties (water vapor permeability, oxygen permeability, rigidity) of the flexible sealing member according to the present invention preferably have the following values.

The water vapor transmission rate is preferably 0.01 g / m ² · day or less in consideration of gas barrier properties required for producing an organic EL panel as a product. The water vapor transmission rate is a value measured mainly by the MOCON method by a method based on the JIS K7129B method (1992).

The oxygen permeability is preferably 0.01 ml / m ² · day · atm or less. The oxygen permeability is a value measured mainly by the MOCON method by a method based on JIS K7126B method (1987).

Rigidity (Young's modulus) is preferably 1 × 10 ⁻³ GPa to 80 GPa in consideration of handling at the time of manufacture, tensile strength, stress cracking resistance of the barrier layer, and the like.

  The resin base material 108a constituting the flexible sealing member used in the present invention is not particularly limited. For example, ethylene tetrafluoroethyl copolymer (ETFE), high density polyethylene (HDPE), stretched polypropylene (0PP) ), Polystyrene (PS), polymethyl methacrylate (PMMA), stretched nylon (ONy), polyethylene terephthalate (PET), polycarbonate (PC), polyimide, polyether styrene (PES), etc. A thermoplastic resin film material can be used. As these thermoplastic resin films, a multilayer film produced by coextrusion with a different film, a multilayer film produced by bonding with different stretching angles, etc. can be used as required. Further, it is naturally possible to combine the density and molecular weight distribution of the film used to obtain the required physical properties.

Examples of the barrier layer include an inorganic vapor deposition film and a metal foil. As inorganic vapor deposition films, thin film handbooks p879-p901 (Japan Society for the Promotion of Science), vacuum technology handbooks p502-p509, p612, p810 (Nikkan Kogyo Shimbun), vacuum handbook revised editions p132-p134 (ULVAC Japan Vacuum Technology KK) Inorganic films as described in (1). For example, In, Sn, Pb, Au , Cu, Ag, Al, Ti, a metal such as _{Ni, MgO, SiO, SiO 2,} Al 2 O 3, GeO, NiO, CaO, BaO, Fe 2 O 3, Y 2 O ₃ , TiO ₂ , Cr ₂ O ₃ , Si _x O _y (x = 1, y = 1.5 to 2.0), Ta ₂ O ₃ , ZrN, SiC, TiC, PSG, Si ₃ N ₄ , single Crystalline Si, amorphous Si, W, etc. are used.

  Moreover, as a material of the metal foil, for example, a metal material such as aluminum, copper, or nickel, or an alloy material such as stainless steel or an aluminum alloy can be used, but aluminum is preferable in terms of workability and cost. The film thickness is about 1 to 100 μm, preferably about 10 to 50 μm.

  Further, a protective layer may be provided on the barrier layer. The thickness of the protective layer is preferably 100 nm to 200 μm in consideration of stress cracking resistance, electrical insulation resistance of the barrier layer, adhesiveness (adhesive force, step following ability), etc. when used as a sealing agent layer. As the protective layer, a thermoplastic resin film having a JIS K 7210 standard melt flow rate of 5 to 20 g / 10 min is preferable, and a thermoplastic resin film of 6 to 15 g / 10 min or less is more preferably used. This is because if a resin having a melt flow rate of 5 (g / 10 min) or less is used, the gap caused by the step of the lead electrode of each electrode cannot be completely filled, and a resin of 20 (g / 10 min) or more cannot be filled. This is because if used, the tensile strength, stress cracking resistance, workability and the like are lowered. The thermoplastic resin film is not particularly limited as long as it satisfies the above numerical values. For example, low-density polyethylene (LDPE), which is a polymer film described in Toray Research Center, Inc., a new development of functional packaging materials, HDPE, linear low density polyethylene (LLDPE), medium density polyethylene, unstretched polypropylene (CPP), OPP, ONy, PET, cellophane, polyvinyl alcohol (PVA), stretched vinylon (OV), ethylene-vinyl acetate copolymer ( EVOH), ethylene-propylene copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, vinylidene chloride (PVDC), and the like can be used. Among these thermoplastic resin films, it is particularly preferable to use LDPE, LLDPE produced by using LDPE, LLDPE and a metallocene catalyst, or a film using a mixture of these films and HDPE films.

  The flexible sealing member used to form the sealing layer is a laminated film in which a barrier layer (a protective layer as required) is formed on the resin base material in order to facilitate handling during production. It is preferable to use it in the state. As a method for producing a laminated film, various methods generally known on the inorganic layer of a thermoplastic resin film on which an inorganic material is deposited and a thermoplastic resin film on which an aluminum foil is laminated, such as a wet laminating method and a dry laminating method. It can be made by using a method, a hot melt laminating method, an extrusion laminating method, or a thermal laminating method.

  When using a flexible sealing member for formation of a sealing layer, it is preferable that the side which contacts a sealing agent is a barrier layer (a protective layer when there is a protective layer).

  FIG. 3 is a schematic view showing an example of a process for producing an organic EL panel when a belt-like flexible support is used as a base material. This figure shows a case in which a strip-like film in which a gas barrier film and an anode layer including a first electrode are formed on a base material in advance is used. Further, as the flexible sealing member, a strip-shaped flexible sealing member having the configuration shown in FIG. 2 is used.

  In the figure, reference numeral 2 denotes a manufacturing apparatus for producing an organic EL panel. The manufacturing apparatus 2 includes an organic compound layer forming step 3, a cathode layer forming step 4, a flexible sealing member bonding step 5, a punching and cutting step 6, and a recovery step 7.

  The organic compound layer forming step 3 includes a strip-shaped flexible support supply section 301, a strip-shaped flexible support cleaning surface modification processing section 302, a first coating / drying section 303, and a first heat processing section. 304, a second charge removal processing unit 305, and a second application / drying unit 306.

  In the supply unit 301, a strip-shaped flexible support 301b in which a gas barrier film and an anode layer including a first electrode are already formed in this order is wound around a winding core and supplied as a roll-shaped flexible support 301a. It has become like that.

  The cleaning surface modification processing unit 302 performs cleaning to modify the surface of the anode layer (not shown) of the strip-shaped flexible support 301b sent from the supply unit 301 before applying the organic compound layer forming coating solution. It has surface modification processing means 302a and first charge removal processing means 302b.

  The first coating / drying unit 303 includes a backup roll 303a that holds the strip-shaped flexible support 301b, and a coating liquid for forming the first organic compound layer on the strip-shaped flexible support 301b that is held by the backup roll 303a. The solvent of the first organic compound layer 301c formed on the anode layer (not shown) on the first wet coater 303b and the strip-like flexible support 301b to be coated except for a part serving as the extraction electrode is removed. And a first drying device 303c. Reference numeral 304 denotes a first heat treatment unit.

  Reference numeral 305 denotes a second charge removal processing means for removing charge from the formed first organic compound layer 301c. In this figure, the first organic compound layer forming coating liquid refers to a hole transport layer forming coating liquid, and the first organic compound layer 301c refers to a hole transport layer.

  The second application / drying unit 306 includes a first accumulator unit 306a, a pattern application unit 306b, a drying unit 306c, a heat processing unit 306d, a charge removal processing unit 306e, a second accumulator unit 306f, and a recovery unit 306g. have.

  The first accumulator unit 306a adjusts the difference in transport speed between the first coating / drying unit 303 and the second coating / drying unit 306 by moving the roll 306a1a in the vertical direction (the arrow direction in the drawing). The roll 306a1a can be added according to the speed difference.

  The pattern coating unit 306b includes a belt-like flexible support holding base 306b2 on which a hole transport layer 301c is formed, and a light emitting layer forming coating solution on the hole transport layer 301c in accordance with the pattern of the first electrode under atmospheric pressure conditions. And a wet pattern formation coating device 306b1 for pattern coating below. The light emitting layer drying unit 306c has a function of removing the solvent in the light emitting layer under atmospheric pressure conditions, and has the same configuration as that of the first drying device 303c. The holding base 306b2 is not particularly limited as long as the belt-like flexible support can be fixed while maintaining flatness. For example, the holding base 306b2 is preferably fixed by an adsorption method.

  When coating is performed by the wet pattern formation coating apparatus 306b1 in the pattern coating unit 306b, the alignment mark 10c (provided on the strip-shaped flexible support A on which the hole transport layer transported from the previous step is formed). 5) is detected by the detector of the alignment detecting means disposed in the pattern application unit 306b, and the belt-like flexible support A on which the hole transport layer is formed is adsorbed and fixed on the holding table, and the alignment is performed. The wet pattern forming and coating apparatus 306b1 is aligned according to the mark, and the light emitting layer forming coating liquid is applied to the pattern of the first electrode except for a part of the end portion of the patterned first electrode. It is applied on the electrode.

  The neutralization processing unit 306e has a function of performing static neutralization on the belt-like flexible support on which the light emitting layer is formed and preventing a failure due to static electricity in the next process, and can be disposed as necessary. ing. The neutralization processing unit 306e preferably uses the same neutralization processing unit as the neutralization processing unit used in the first application / drying unit 303.

  The second accumulator unit 306f is arranged to adjust the difference in transport speed between the pattern application / drying unit 306 and the collection unit 306g by moving the roll 306f1 in the vertical direction (the arrow direction in the figure). Thus, the roll 306f1a can be added according to the speed difference. The second accumulator unit 306f has the same configuration as the first accumulator unit 306a. In the recovery part 306g, it is preferable to wind the belt-shaped flexible support 301f on which the light emitting layer is formed after cooling it to room temperature with a cooling device (not shown).

  The cathode layer formation step 4 includes a material supply unit 401, a first cathode layer formation unit 402, a second cathode layer formation unit 403, and a second winding unit 404, and is collected from the supply unit 401. Up to the portion 404 is continuously performed under reduced pressure conditions.

  In the supply unit 401, an anode, a hole transport layer, and an organic compound layer (light emitting layer) are formed on the band-shaped flexible support prepared in the organic compound layer forming step 3, and wound around a winding core. The roll-shaped strip-shaped flexible support body 301f thus taken is supplied.

  An electron injection layer 301g is formed by the first cathode layer forming unit 402 on the organic compound layer (light emitting layer) of the strip-shaped flexible support 301f having the organic compound layer (light emitting layer) unwound from the supply unit 401. . Reference numeral 402a denotes a vapor deposition apparatus, and 402b denotes an evaporation source container.

  In the second cathode layer forming unit 403, the cathode layer 301h of the second electrode is formed on the electron injection layer 301g formed in the first cathode layer forming unit 402. Reference numeral 403a denotes a vapor deposition apparatus, and reference numeral 403b denotes an evaporation source container. The strip-shaped flexible support 301i formed by the second cathode layer forming unit 403 in a state where the cathode layer 301h of the second electrode is orthogonal to the first electrode is wound around the winding core by the collecting unit 404 and can be rolled into a strip. It becomes the flexible support body C301j.

  The flexible sealing member bonding step 5 includes a roll-like strip-like flexible support C301j formed up to the cathode layer 301h of the second electrode, a sealant placement part (sealant coating part) ) 502, a flexible sealing member supply portion 503, and a flexible sealing member bonding portion 504, and preferably a sealing agent curing processing portion (not shown). If necessary, it is preferable to dispose a curing treatment part (not shown) before the cutting step or after the cutting step. The curing method of the curing treatment unit can be appropriately selected according to the type of sealant used (for example, a thermosetting sealant, an ultraviolet curable sealant, etc.). A flexible strip having a plurality of organic EL panels by bonding the flexible sealing member to each organic EL element formed on the flexible strip C301j in the flexible sealing member bonding step 5. A flexible support 301k is produced. The flexible sealing member bonding step 5 will be described with reference to FIG.

  The punching and cutting step 6 is performed in accordance with the position of the alignment mark detection unit 602 that detects the alignment mark disposed on the strip-shaped flexible support 301k, and the position of the organic EL element formed on the strip-shaped flexible support, It has a punching and cutting device 601 that punches and cuts unnecessary portions of the bonded flexible sealing member. The punching and cutting process 6 will be described with reference to FIGS.

  Although this figure shows the case where the flexible sealing member bonding step 5 and the punching and cutting step 6 are continuously performed, after the flexible sealing member is bonded, every certain unit. After cutting and making it into a sheet shape, a method of supplying to the punching and cutting step 6 may be employed.

  In the collection step 7, a winding device (not shown) is provided in which a strip-shaped flexible support having a plurality of organic EL panels in a state where unnecessary flexible sealing members are removed is wound around a winding core. ing. Reference numeral 701 denotes an unnecessary flexible sealing member which is left in a bonded state and is recovered in a roll shape. Reference numeral 702 denotes a strip-shaped flexible support that is removed from an unnecessary strip-shaped flexible support that is not involved in bonding, and the strip-shaped flexible support having at least one organic EL panel is wound into a winding roll. Showing the body. The belt-like flexible support having the organic EL panel collected in a roll form is cut and collected in units of organic EL panels in a separate process. In addition, although this figure shows the case where it winds up once, you may cut | disconnect and collect | recover continuously for an organic EL panel unit. In addition, this figure has shown the case of what is called a roll-to-roll production system which winds up and collect | recovers in the shape of a roll in the state which stamped and removed the excess location of the bonded flexible sealing member.

  FIG. 4 is a schematic view of a method for producing an organic EL panel using a sheet-like substrate. In addition, as a flexible sealing member, the sheet-like flexible sealing member of the structure shown by FIG. 2 is used.

  In the figure, 8 indicates a manufacturing apparatus. The manufacturing apparatus 8 includes a supply process 8a for supplying a single-wafer sheet-like substrate a to the process, a first electrode formation process 8b, a hole transport layer formation process 8c for forming a hole transport layer on the first electrode, A light emitting layer forming step 8d for forming a light emitting layer on the hole transport layer; an electron injection layer forming step 8e for forming an electron injection layer on the light emitting layer; and a second electrode for forming a second electrode on the electron injection layer. Flexible in the forming step 8f, the sealing agent coating step 8g for placing (coating) the sealing agent on the single-wafer sheet-like substrate on which the second electrode is formed, and the region where the sealing agent is placed (coating) It has a flexible sealing member bonding step 8h for bonding the sealing member, a punching cutting step 8i for punching and removing unnecessary portions of the bonded flexible sealing member, and a recovery step 8j. ing.

  The supply process 8a includes a supply device (not shown) for supplying the single-wafer sheet-like substrate a to the next process, and before the first electrode is deposited on the surface of the single-wafer sheet-like substrate a supplied from the supply process 8a. A substrate cleaning apparatus 8a1 for cleaning the surface of the single-wafer sheet-like substrate a in order to improve the deposition property.

  The first electrode forming step 8b includes a vapor deposition device 8b1 having an evaporation source container 8b2, and forms the first electrode on the single-wafer sheet-like substrate a under reduced pressure conditions.

  The hole transport layer forming step 8c includes a vapor deposition device 8c1 having an evaporation source container 8c2, and a part to be an external electrode of the first electrode of the single-wafer sheet substrate b on which the first electrode is formed under reduced pressure conditions A hole transport layer is formed in the region of the first electrode except for.

  The light emitting layer forming step 8d includes a vapor deposition device 8d1 having an evaporation source container 8d2, and forms a light emitting layer on the hole transporting layer of the single wafer sheet substrate c on which the hole transporting layer is formed under reduced pressure. It is like that.

  The electron injection layer forming step 8e includes a vapor deposition apparatus 8e1 having an evaporation source container 8e2, and forms an electron injection layer on the light emitting layer of the single wafer sheet substrate d on which the light emitting layer is formed under reduced pressure. It has become.

  The second electrode forming step 8f includes a vapor deposition device 8f1 having an evaporation source container 8f2, and is orthogonal to the first electrode on the electron injection layer of the single wafer sheet substrate e on which the electron injection layer is formed under reduced pressure conditions. In this manner, the second electrode is formed.

  The sealant coating step 8g includes an alignment mark detection unit 8g1 (see FIG. 8) that detects the alignment mark a1 (see FIG. 9) attached on the belt-like flexible support, and a belt-like flexible support f. A sealing agent coating portion 8g for coating a sealing agent around the light emitting region or the light emitting region of the organic EL element f1 (see FIG. 9) formed by sequentially laminating the first electrode to the second electrode; And a mounting table 8g23 on which the single-wafer sheet-like substrate f is mounted. 8g21 shows a sealing agent coating apparatus.

  The flexible sealing member bonding step 8h includes a flexible sealing member bonding apparatus 8h1 that stacks and bonds the sheet-fed sheet-like substrate g coated with a sealing agent and the flexible sealing member 9; And a flexible sealing member supply device 8h2 (see FIG. 9) for supplying the flexible sealing member 9 onto the single-wafer sheet-like substrate g. Moreover, it is preferable to have a curing processing apparatus (not shown) for curing the sealant, and it is preferable to arrange a curing processing unit (not shown) before the cutting process or after the cutting process as necessary. The curing method of the curing treatment unit can be appropriately selected according to the type of sealant used (for example, a thermosetting sealant, an ultraviolet curable sealant, etc.).

  The punching and cutting step 8i has a punching and cutting device 8i1 for removing unnecessary portions of the bonded flexible sealing members. The sealant coating step 8g and the flexible sealing member bonding step 8h will be described with reference to FIG.

The cleaning surface modification process performed before applying the organic compound layer forming coating liquid in the step of manufacturing the organic EL element shown in FIGS. 1 and 2 includes a low-pressure mercury lamp, an excimer lamp, a plasma cleaning apparatus, and the like. Can be mentioned. As conditions for the cleaning surface modification treatment using a low-pressure mercury lamp, for example, a cleaning surface modification treatment is performed by irradiating a low-pressure mercury lamp with a wavelength of 184.2 nm at an irradiation intensity of 5 to ²⁰ mW / cm ² and a distance of 5 to 15 mm. Conditions are mentioned. For example, atmospheric pressure plasma is preferably used as the condition for the cleaning surface modification treatment by the plasma cleaning apparatus. Examples of the cleaning conditions include conditions in which a gas containing oxygen of 1 to 5% by volume is used for argon gas, and the cleaning surface modification treatment is performed at a frequency of 100 KHz to 150 MHz, a voltage of 10 V to 10 KV, and an irradiation distance of 5 to 20 mm.

  Examples of the charge removal processing means performed in the process of manufacturing the organic EL panel shown in FIG. 1 include a light irradiation method and a corona discharge method, and these can be appropriately selected and used as necessary. . The light irradiation type generates weak ions, and the corona discharge type generates air ions by corona discharge. The air ions are attracted to the charged object to compensate for the opposite polarity charge and neutralize static electricity. A static eliminator using corona discharge or a static eliminator using soft X-rays can be used. Since the first charge removal processing means removes the charge of the base material, adhesion of dust and dielectric breakdown are prevented, so that the yield of the elements can be improved.

  The vapor deposition apparatus shown in FIG. 1 and FIG. 2 is not particularly limited. For example, sputtering method, reactive sputtering method, molecular beam epitaxy method, cluster ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma weight A legal method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used, and it can be selected and used as necessary.

  FIG. 5 is a schematic diagram showing a state of the organic EL element formed on the substrate. FIG. 5A is a schematic view showing a state of the organic EL element formed on the belt-like flexible support manufactured by the manufacturing apparatus shown in FIG. FIG. 5B is a schematic view showing a state of the organic EL element formed on the single-wafer sheet-like substrate manufactured by the manufacturing apparatus shown in FIG.

  The state of the organic EL element formed on the belt-like flexible support shown in FIG. 5A will be described. In the figure, reference numeral 10 denotes a belt-like flexible support having a plurality of organic EL elements 10b formed up to the second electrode on the belt-like flexible support 10a (second cathode layer forming portion shown in FIG. 3). 403 corresponds to the strip-shaped flexible support 301i formed with the cathode layer 301h of the second electrode orthogonal to the first electrode). In this figure, the case where the organic EL element 10b is formed continuously is shown. Reference numeral 10c denotes an alignment mark aligned with the position of the organic EL element 10b on the strip-like flexible support 10a. The arrangement position of the alignment mark 10c is not particularly limited, and can be changed as necessary. For example, it may be provided for each block of the organic EL element 10b or for each stage of the organic EL element 10b. This figure has shown the case where it attaches for every step | level of the organic EL element 10b.

  The state of the organic EL element formed on the single wafer sheet substrate shown in FIG. 5B will be described. In the figure, reference numeral 11 denotes a single-wafer sheet-like substrate having a single organic EL element 11b formed up to the second electrode on the single-wafer sheet-like substrate 11a (the second electrode forming portion 8f shown in FIG. This corresponds to a single-wafer sheet-like substrate f having a second electrode formed in a state orthogonal to one electrode.) The organic EL element 10b and the organic EL element 11b have the same configuration. Reference numeral 11c denotes an alignment mark attached to the position of the organic EL element 11b on the sheet-like substrate 11a. The arrangement position of the alignment mark 11c is not particularly limited, and can be appropriately changed as necessary. For example, there may be four corners with respect to the organic EL element 11b. Further, when a plurality of organic EL elements are formed on the sheet-like substrate 11a, it can be appropriately changed according to the position of the organic EL elements as in FIG.

  FIG. 6 is a schematic view showing a state in which a sealing agent is applied in order to bond a flexible sealing member having no sealant layer (sealing agent) on the organic EL element. FIG. 6A is an enlarged schematic view of a portion indicated by P in FIG. FIG. 6B is an enlarged schematic view showing a state in which a sealing agent is applied to the light emitting region of the organic EL element in the portion indicated by P in FIG. FIG. 6C is a schematic view showing a state in which a sealing agent is applied around the light emitting region of the portion of the organic EL element indicated by P in FIG.

In the figure, 10c represents a first electrode formed on the single-wafer sheet-like substrate 10a, and 10d represents a second electrode formed on an organic compound layer (not shown) including a light emitting layer. 10e shows the light emission area | region (the range enclosed with the thick line in the figure) of the organic EL element 10b. 10f shows the sealing agent applied to the light emission area 10e. Reference numeral 10g denotes a sealant coated around the light emitting region except for a portion to be an external extraction electrode of the first electrode and a portion to be an external extraction electrode of the second electrode. The coating (arrangement) of the sealing agent shown in (b) and (c) of this figure is applicable to all the organic EL elements shown in (a) and (b) of FIG.

  FIG. 7 is an enlarged schematic view of a portion indicated by Q in FIG. FIG. 7A is an enlarged schematic perspective view of a portion indicated by Q in FIG. FIG. 7B is a schematic cross-sectional view of FIG.

  The flexible sealing member bonding step 5 includes an alignment mark detection unit 505 that detects an alignment mark 301l arranged in alignment with the position of the organic EL element 301i1 formed on the belt-like flexible support 301i, and an organic EL. Bonding for bonding the sealant coating portion 502 for applying a sealant to the position of the element 301i1, the supply portion 503 of the strip-shaped flexible sealing member 503a, and the strip-shaped flexible sealing member 503a Part 504.

  The alignment mark detection unit 505 includes an alignment mark detection device and a housing 505b in which the alignment mark detection device 505 is disposed. The alignment mark detection device is arranged in advance in accordance with the position of the alignment mark arranged on the belt-like flexible support 301i. Information detected by the alignment mark detection device 505 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, and for example, image recognition using a CCD camera can be used. A sealing agent coating unit 502a applies a sealing agent to the organic EL element in accordance with information from the alignment mark detection unit 505, as shown in FIG. 6B or 6C. And a casing 502b in which the sealant coating device 502a is disposed. The number of sealant coating apparatuses 502a to be disposed is not particularly limited, but it is preferable to dispose them in accordance with the number of organic EL elements disposed in the width direction of the strip-shaped flexible support 301i. This figure shows a case where three sealant coating devices 502a are arranged in accordance with the number of organic EL elements. The housing 502b can be moved in the xy directions (arrow directions in the drawing) by a driving device (not shown).

The bonding unit 504 includes a roll 504b that comes into contact with the main body 504c and the flexible support, and a roll 504a that comes into contact with the flexible sealing member 503b, and an organic EL element is formed by the roll 504b and the roll 504a. The flexible sealing member is bonded by pressing and sandwiching the belt-like flexible support 301k and the flexible sealing member 503b. The width of the flexible sealing member 503b is preferably the same as the width of the belt-like flexible support 301k. In the drawing, the supply system of the sealant to the sealant coating apparatus 502a is omitted. The flexible sealing member 503b is bonded to the cathode layer including the second electrode through a sealing agent in consideration of exclusion of oxygen and moisture, mixing of bubbles into the bonding portion, and the like. It is preferably carried out under reduced pressure conditions of ^-5 Pa and in an environment with an oxygen concentration of 10 ppm or less and a water concentration of 10 ppm or less.

  The method for applying the sealing agent is not particularly limited, and examples thereof include methods used for applying an ordinary adhesive such as a spray method, an extrusion nozzle method, a screen printing method, and a silk method. The viscosity of the sealant to be used is preferably 40 Pa · s to 400 Pa · s in consideration of coating uniformity, spread prevention, and the like.

  Examples of the liquid sealing agent according to the present invention include acrylic curing oligomers, photocuring and thermosetting sealing agents having reactive vinyl groups of methacrylic acid oligomers, and moisture curing sealing agents such as 2-cyanoacrylate. And epoxy-based heat and chemical curing type (two-component mixed) sealing agents, cationic curing type ultraviolet curing epoxy resin sealing agents, and the like. It is preferable to add a filler to the liquid sealant as necessary. The addition amount of the filler is preferably 5 to 70% by volume in consideration of adhesive strength. In addition, the size of the filler to be added is preferably 1 μm to 100 μm in consideration of the adhesive strength, the thickness of the sealant after bonding and bonding, and the like. The kind of filler to be added is not particularly limited, and examples thereof include soda glass, alkali-free glass, or metal oxides such as silica, titanium dioxide, antimony oxide, titania, alumina, zirconia, and tungsten oxide.

  In addition, although the case where the flexible sealing member (strip | belt-shaped flexible sealing member) which does not have a sealing agent was used was shown in this figure, a sealant layer (sealing agent) is previously provided in the side bonded with an organic EL element. It is also possible to use a flexible sealing member (a strip-like flexible sealing member, a single-wafer sheet-like flexible sealing member) provided with the above. However, the sealant layer (sealant) provided on the side to be bonded to the organic EL element is only bonded to the light emitting area of the organic EL element or the periphery of the light emitting area when being bonded to the organic EL element. And after bonding, the flexible sealing member which is not concerned in bonding is removed as an unnecessary part.

  Examples of the sealant layer (sealant) provided in advance on the side of the flexible sealing member to be bonded to the organic EL element include a sheet-like sealant and a thermoplastic resin. The sheet-like sealant refers to a sealant that is non-flowable at room temperature (about 25 ° C.) and exhibits fluidity in the range of 50 ° C. to 100 ° C. when heated and is formed into a sheet shape. Examples of the sealant to be used include a photocurable resin mainly composed of a compound having an ethylenic double bond at the molecular end or side chain and a photopolymerization initiator. In use, for example, it is bonded to a flexible sealing member (strip-shaped flexible sealing member, single-sheet flexible sealing member) in advance and used at a room temperature (about 25 ° C.) or lower. It is preferable.

  As the thermoplastic resin, a thermoplastic resin having a melt flow rate of JIS K 7210 specified in a range of 5 to 20 g / 10 min is preferable, and a thermoplastic resin of 6 to 15 g / 10 min or less is more preferably used. This is because if a resin having a melt flow rate of 5 (g / 10 min) or less is used, the gap caused by the step of the lead electrode of each electrode cannot be completely filled, and a resin of 20 (g / 10 min) or more cannot be filled. This is because if used, the tensile strength, stress cracking resistance, workability and the like are lowered. These thermoplastic resins are preferably formed into a film and bonded to a flexible sealing member (a strip-shaped flexible sealing member or a single-sheet flexible sealing member). The laminating method can be made by using various generally known methods such as a wet laminating method, a dry laminating method, a hot melt laminating method, an extrusion laminating method, and a thermal laminating method.

  The thermoplastic resin is not particularly limited as long as it satisfies the above numerical values. For example, low-density polyethylene (LDPE), HDPE, which is a polymer film described in Toray Research Center, Inc., a new development of functional packaging materials. , Linear low density polyethylene (LLDPE), medium density polyethylene, unstretched polypropylene (CPP), OPP, ONy, PET, cellophane, polyvinyl alcohol (PVA), stretched vinylon (OV), ethylene-vinyl acetate copolymer (EVOH) ), Ethylene-propylene copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, vinylidene chloride (PVDC), and the like can be used. Among these thermoplastic resins, LDPE, LLDPE produced using LDPE, LLDPE and a metallocene catalyst, or a thermoplastic resin using a mixture of LDPE, LLDPE and HDPE films is preferably used.

  FIG. 8 is an enlarged schematic perspective view of a portion indicated by R in FIG.

  In the figure, reference numeral 602a denotes an alignment mark detection device for detecting an alignment mark previously disposed on the belt-like flexible support 301k. The alignment mark detection device 602a is not particularly limited, and for example, image recognition using a CCD camera can be used. Reference numeral 602b denotes a housing in which the alignment mark detection device 602a is disposed. Information detected by the alignment mark detection device 602a is input to a control unit (not shown) to control the punching and cutting device 601. The punching and cutting device 601 includes an upper die 601b provided with a punching blade 601a for punching an unnecessary portion of the flexible sealing member 503b bonded on the belt-like flexible support 301k, and an upper die 601b in the vertical direction. It has four guide posts 601c that enable operation in the direction of the arrow in the figure, and a mounting surface 601e (also serving as a receiving portion of the punching blade 601a) on which the belt-like flexible support 301k is mounted. A lower mold 601d.

  The number of punching blades 601a can be appropriately selected from the number of organic EL elements formed on the belt-like flexible support 301k, the number of punching at a time, the size of the punching cutting device 601, and the like. This figure has shown the case where the number punched at once is six. The punching and cutting device 601 is a half-cut method because it punches only unnecessary portions of the flexible sealing member 503b.

  The half-cut method is a method of cutting while leaving the thickness direction of the material to be cut, and can be achieved by adjusting the minimum distance (bottom dead center) between the punching blade and the receiving portion of the punching blade. A block (not shown) is installed in the upper mold or the lower mold or both, and when the upper mold is lowered, the lowered position is limited by the block. The bottom dead center can be adjusted by adjusting the height of the block. Thereby, it is possible to punch out only the unnecessary flexible sealing member 503b that is not bonded with the sealant except the light emitting region of the organic EL element or the periphery of the light emitting region.

  301m shows the strip | belt-shaped flexible support body E which removed the unnecessary flexible sealing member and formed the some organic EL panel. The punched flexible sealing member is wound up and removed. Thereafter, the strip-shaped flexible support E301m in which a plurality of organic EL panels are formed is cut for each organic EL panel, thereby completing one organic EL panel.

  Note that the punching / cutting device 8i1 used in the punching / cutting step 8i shown in FIG. 4 can be dealt with by changing the transport system of the belt-like flexible support shown in this figure to a single-sheet flexible support. It is possible. Further, when one organic EL element is formed on the single-wafer sheet-like support shown in FIG. 5 (b), the punching blade is made into a size and shape of an unnecessary flexible sealing member. Correspondence is possible by arranging in the upper die.

  FIG. 9 is an enlarged schematic view of a portion indicated by S in FIG. FIG. 9A is an enlarged schematic perspective view of a portion indicated by S in FIG. FIG. 9B is a schematic cross-sectional view of FIG.

  The sealing agent coating step 8g includes an alignment mark detection unit 8g1 for detecting the alignment mark a1 formed on the single-wafer sheet-like substrate a, and a sealing agent coating unit for coating the sealing agent in accordance with the position of the organic EL element f1. 8g2.

  The alignment mark detection unit 8g1 includes an alignment mark detection device 8g11 and a housing 8g12 in which the alignment mark detection device 8g11 is disposed. The alignment mark detection device is arranged in advance in accordance with the position of the alignment mark a1 arranged on the sheet-like substrate a. Information detected by the alignment mark detection device 8g11 is input to a control unit (not shown), and the sealant coating device 8g21 of the sealant coating unit 8g2 is controlled. The alignment mark detection device 505 is not particularly limited, and for example, image recognition using a CCD camera can be used.

  The sealant coating portion 8g2 includes a sealant coating device 8g21, a housing 8g22, and a mounting table 8g23 (see FIG. 2). The sealant application unit 8g2 and the sealant application device 8g21 for applying the sealant to the device as shown in FIG. 4 (b) or (c) according to the information from the alignment mark detection unit 8g1 and the sealant And a casing 8g22 in which the coating device 8g21 is disposed. The number of sealant coating devices 8g21 disposed is not particularly limited, but it is preferable to dispose the sealant coating devices 8g21 according to the number of organic EL elements f1 disposed in the width direction of the sheet-like substrate f. This figure has shown the case where the two sealing agent coating apparatuses 8g21 are arrange | positioned according to the number of organic EL elements. The housing 8g22 can be moved in the xy directions (arrow directions in the drawing) by a driving device (not shown). In this drawing, the supply system of the sealant to the sealant coating device 8g21 is omitted.

  The method of applying the sealing agent is the same as that of the sealing agent application apparatus shown in FIG. 5, and the same sealing agent is used. Moreover, you may add the same filler similarly to the sealing agent used for a sealing agent coating apparatus.

  The flexible sealing member bonding step 8h includes a flexible sealing member supply device 8h2 that supplies the flexible sealing member f on the flexible support f on which the sealing agent is applied (arranged) and the flexible support f. It has the flexible sealing member bonding apparatus 8h1 which bonds the flexible sealing member supplied on the top. The flexible sealing member supply device 8h2 includes a mounting table 8h21 for mounting the flexible sealing member 9, and a robot arm 8h23 having a holding means 8g22 for sucking and holding the flexible sealing members 9 one by one. Have. The robot arm 8h23 rotates so as to be rotatable (in the direction of the arrow in the drawing), and the flexible sealing member 9 can be supplied onto the single-wafer sheet-like substrate f. The size of the flexible sealing member 9 is preferably the same size as the single-wafer sheet-like substrate f.

  The flexible sealing member laminating apparatus 8h1 is a flexible sealing member 9 on the light emitting region of the organic EL element f1 formed on the flexible support f or on the sealant coated around the light emitting region. The upper die 8h13 to which the first crimping member 8h11, the second crimping member 8h12, the first crimping member 8h11 and the second crimping member 8h12 are attached, and the upper die 8h13 in the vertical direction (in the drawing) And a lower die 8h15 having four guide posts 8h14 that enable operation in the direction of the arrow).

  The first crimping member 8h11 is attached to the four linear guides 8h16 attached to the upper mold 8h13. 8h17 indicates a spring of an elastic member that is pressure-bonded and held in order to prevent the first pressure-bonding member 8h11 from spreading to a portion where the sealant is not necessary when the flexible sealing member 9 is bonded.

  The lower die 8h15 has a plurality of suction holes (not shown) for sucking and fixing the single-wafer sheet-like substrate f and a suction tube connected to a suction pump (not shown) when the flexible sealing member 9 is bonded. (Not shown).

  8h18 indicates a drive source for operating the upper die 8h13 in the vertical direction (arrow direction in the figure) along the guide post 8h14, and 8h19 indicates a drive shaft.

  When a sealing agent is applied as shown in FIG. 4B, the flexible sealing member laminating device 8h1 is pressure-bonded around the light emitting region with the first pressure-bonding member 8h11, and then second pressure-bonded. It is preferable to bond the flexible sealing member by pressing the light emitting region with the member 8h12. Further, when a sealing agent is applied as shown in FIG. 4C, after the light emitting region is pressure-bonded by the first pressure bonding member 8h11, the periphery of the light emitting region is pressure bonded by the second pressure bonding member 8h12. It is preferable to bond a flexible sealing member. In this figure, the supply system of the sealant to the sealant coating apparatus 502a is omitted.

  In addition, although the case where the flexible sealing member (strip | belt-shaped flexible sealing member) which does not have a sealant layer (sealing agent) was used was shown in this figure, an organic electroluminescent element and a sticking are carried out similarly to the case of FIG. It is also possible to use a flexible sealing member (a strip-like flexible sealing member or a sheet-like flexible sealing member) in which a sealant layer (sealant) is provided in advance on the mating side.

Bonding of the flexible sealing member by the flexible sealing member bonding apparatus shown in FIGS. 7 and 9 is 10 Pa to 1 in consideration of exclusion of oxygen, moisture, mixing of bubbles into the bonding portion, and the like. It is preferably performed under a reduced pressure condition of × 10 ⁻⁵ Pa and an environment having an oxygen concentration of 10 ppm or less and a water concentration of 10 ppm or less.

The following effects can be obtained by using the flexible sealing member shown in FIG. 2 and using the manufacturing apparatus shown in FIGS. 3 to 9 to manufacture the organic EL panel.
1) Intrusion of moisture and oxygen into the organic EL panel is suppressed, and generation of dark spots can be suppressed.
2) A thin and lightweight organic EL panel excellent in moisture resistance can be obtained.
3) A desiccant, a hygroscopic agent, etc. are no longer required, the production process can be simplified, productivity can be improved, and manufacturing costs can be reduced.

  Hereinafter, the gas barrier layer, the first electrode, the hole transport layer, the light emitting layer, the electron transport layer, and the second electrode constituting the organic EL panel according to the present invention will be described.

  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 single-wafer sheet-like substrate include a transparent glass plate and a sheet-like transparent resin film. Examples of the resin film 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 esters such as cellulose acetate phthalate (TAC) and cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide , Polyethersulfone (PES), polyphenylene sulfide, polysulfones, poly Cycloolefin resins such as ether imide, polyether ketone imide, polyamide, fluororesin, nylon, polymethyl methacrylate, acrylic or polyarylate, Arton (trade name, manufactured by JSR) or Apel (trade name, manufactured by Mitsui Chemicals) Can be mentioned. A transparent resin film is mentioned as a strip | belt-shaped flexible board | substrate, The same resin film as a sheet | seat sheet-like board | substrate can be used.

When a transparent resin film is used as the substrate, a gas barrier film is preferably formed on the surface of the resin film as necessary. Examples of the gas barrier film include an inorganic film, an organic film, or a hybrid film of both. As a characteristic of the gas barrier film, the water vapor permeability is preferably 0.01 g / m ² · day · atm or less. Furthermore, a high barrier film having an oxygen permeability of 10 ⁻³ ml / m ² / day or less and a water vapor permeability of 10 ⁻⁵ g / m ² / day or less is preferable.

  As a material for forming the barrier film, any material may be used as long as it has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride, or the like can be used. Further, in order to improve the brittleness of the film, it is more preferable to have a laminated structure of these inorganic layers and layers made of organic materials. Although there is no restriction | limiting in particular about the lamination | stacking order of an inorganic layer and an organic layer, It is preferable to laminate | stack both alternately several times. The method for forming the barrier film is not particularly limited, and for example, vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster ion beam, ion plating, plasma polymerization, atmospheric pressure plasma polymerization A plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used, but an atmospheric pressure plasma polymerization method as described in JP-A-2004-68143 is particularly preferable.

As the first electrode, 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. Specific examples of such an electrode substance include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO ₂ , and ZnO. Alternatively, an amorphous material such as IDIXO (In ₂ O ₃ .ZnO) capable of forming a transparent conductive film may be used. For the anode, these electrode materials may be formed into a thin film by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method, or when the pattern accuracy is not required (about 100 μm or more) ), A pattern may be formed through a mask having a desired shape when the electrode material is deposited or sputtered. When light emission is extracted from the anode, the transmittance is desirably greater than 10%, and the sheet resistance as the anode is preferably several hundred Ω / □ or less. Further, although the film thickness depends on the material, it is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.

  A hole injection layer (anode buffer layer) may be present between the first electrode and the light emitting layer or the hole transport layer. 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 light emission. “The organic EL element and the forefront of industrialization (November 30, 1998, NTS) The details are described in the second volume, Chapter 2, “Electrode Materials” (pages 123 to 166) of “The Company”. 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 one of hole injection or transport and electron barrier properties, and may be either organic or inorganic. For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, Examples include stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.

  The above-mentioned materials can be used as the hole transport material, but it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound. Representative examples of aromatic tertiary amine compounds and styrylamine compounds include N, N, N ', N'-tetraphenyl-4,4'-diaminophenyl; N, N'-diphenyl-N, N'- Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (TPD); 2,2-bis (4-di-p-tolylaminophenyl) propane; 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl; 1,1-bis (4-di-p-tolyl) Aminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminophenyl) phenylmethane; N, N'-diphenyl-N, N ' − (4-methoxyphenyl) -4,4'-diaminobiphenyl; N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether; 4,4'-bis (diphenylamino) quadriphenyl; N, N, N-tri (p-tolyl) amine; 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene; 4-N, N-diphenylamino- (2-diphenylvinyl) benzene; 3-methoxy-4′-N, N-diphenylaminostilbenzene; N-phenylcarbazole, and also two of those described in US Pat. No. 5,061,569. Having a condensed aromatic ring in the molecule, for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), JP-A-4-3086 4,4 ', 4 "-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine in which three triphenylamine units described in Japanese Patent No. 8 are linked in a starburst type ( MTDATA) and the like.

  Furthermore, 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. In addition, inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material.

  JP-A-11-251067, J. Org. Huang et. al. A so-called p-type hole transport material described in a book (Applied Physics Letters 80 (2002), p. 139) can also be used. In the present invention, it is preferable to use these materials because a light-emitting element with higher efficiency can be obtained.

  Although there is no restriction | limiting in particular about the film thickness of a positive hole transport layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5-200 nm. This hole transport layer may have a single layer structure composed of one or more of the above materials. A hole transport layer having a high p property doped with impurities can also be used. Examples thereof include JP-A-4-297076, JP-A-2000-196140, JP-A-2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like. It is preferable to use such a hole transport layer having a high p property because an organic EL element with lower power consumption can be produced.

  In the present invention, the light emitting layer refers to a blue light emitting layer, a green light emitting layer, and a red light emitting layer. There is no restriction | limiting in particular as a lamination order in the case of laminating | stacking a light emitting layer, You may have a nonluminous intermediate | middle layer between each light emitting layer. In the present invention, it is preferable that at least one blue light emitting layer is provided at a position closest to the anode among all the light emitting layers. Also, when four or more light emitting layers are provided, for example, blue light emitting layer / green light emitting layer / red light emitting layer / blue light emitting layer, blue light emitting layer / green light emitting layer / red light emitting layer / blue light emitting from the order close to the anode. Layered / green light emitting layer, blue light emitting layer / green light emitting layer / red light emitting layer / blue light emitting layer / green light emitting layer / red light emitting layer, etc. It is preferable for improving luminance stability. A white element can be manufactured by forming a light emitting layer in multiple layers.

  The total thickness of the light emitting layer is not particularly limited, but is usually selected in the range of 2 nm to 5 μm, preferably 2 to 200 nm in consideration of the uniformity of the film and the voltage required for light emission. Furthermore, it is preferable that it exists in the range of 10-20 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 surface. The film 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. Although there is no restriction | limiting in particular about the film thickness relationship of each light emitting layer of blue, green, and red, It is preferable that the blue light emitting layer (the sum total when there are two or more layers) is the thickest among three light emitting layers.

  The light emitting layer includes at least three layers having different emission spectra, each having an emission maximum wavelength in the range of 430 to 480 nm, 510 to 550 nm, and 600 to 640 nm. If it is three or more layers, there will be no restriction | limiting in particular. 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, and a layer in the range of 600 to 640 nm is referred to as a red light emitting layer. Moreover, in the range which maintains the said maximum wavelength, you may mix a several luminescent compound in each light emitting layer. For example, the blue light emitting layer may be used by mixing 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 510 to 550 nm.

  The organic light emitting material used as the material of the light emitting layer is (a) charge injection function, that is, holes can be injected from the anode or hole injection layer when an electric field is applied, and electrons are injected from the cathode or electron injection layer. (B) a transport function, that is, a function that moves injected holes and electrons by the force of an electric field, and (c) a light emission function, that is, a recombination field of electrons and holes. However, there is no particular limitation as long as it has the three functions of connecting these to light emission. For example, fluorescent whitening agents 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-thiadiazole in the benzoxazole series, 4 , 4′-bis (5,7-t-pentyl-2-benzoxazolyl) stilbene, 4,4′-bis [5,7-di- (2-methyl-2-butyl) -2-benzoxa Zoolyl] stilbene, 2,5-bis (5,7-di-t-pentyl-2-benzoxazolyl) thiophene, 2,5-bis [5-α, α-dimethylbenzyl-2-benzoxazoli Ru] thiophene, 2,5-bis [5,7-di- (2-methyl-2-butyl) -2-benzoxazolyl] -3,4-diphenylthiophene, 2,5-bis (5-methyl) -2-benzoxazolyl) thiophene, 4,4′-bis (2 -Benzoxazolyl) biphenyl, 5-methyl-2- [2- [4- (5-methyl-2-benzoxazolyl) phenyl] vinyl] benzoxazole, 2- [2- (4-chlorophenyl) vinyl Naphtho [1,2-d] oxazole and the like. Examples of the benzothiazole type include 2,2 ′-(p-phenylenedivinylene) -bisbenzothiazole, and examples of the benzimidazole type include 2- [2- [4- (2-benzimidazolyl) phenyl] vinyl] benzimidazole. 2- [2- (4-carboxyphenyl) vinyl] benzimidazole and the like. In addition, other useful compounds are listed in Chemistry of Synthetic Soybean (1971), pages 628-637 and 640.

  Specific examples of the styrylbenzene compound include 1,4-bis (2-methylstyryl) benzene, 1,4-bis (3-methylstyryl) benzene, 1,4-bis (4-methylstyryl). ) Benzene, distyrylbenzene, 1,4-bis (2-ethylstyryl) benzene, 1,4-bis (3-methylstyryl) benzene, 1,4-bis (2-methylstyryl) -2-methylbenzene, 1,4-bis (2-methylstyryl) -2-ethylbenzene and the like can be mentioned.

  Further, in addition to the above-described optical brightener and styrylbenzene compound, for example, 12-phthaloperinone, 1,4-diphenyl-1,3-butadiene, 1,1,4,4-tetraphenyl-1,3- Butadiene, naphthalimide derivatives, perylene derivatives, oxadiazole derivatives, aldazine derivatives, pyrazirine derivatives, cyclopentadiene derivatives, pyrrolopyrrole derivatives, styrylamine derivatives, coumarin compounds, international publications WO 90/13148 and Appl. Phys. Lett. , Vol 58, 18, P1982 (1991), and aromatic dimethylidin compounds. Specific examples of the aromatic dimethylidin compounds include 1,4-phenylene dimethylidin, 4,4′-phenylene dimethylidin, 2,5-xylylene dimethylidin, 2,6-naphthylene dimethylidin, 1,4-biphenylenedimethylidin, 1,4-p-terephenylenedimethylidin, 4,4′-bis (2,2-di-t-butylphenylvinyl) biphenyl, 4,4′-bis (2 , 2-diphenylvinyl) 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-phenylphenolate) aluminum (III), bis (2-methyl-8-quinolinolato). ) (1-naphtholate) aluminum (III) and the like.

In addition, 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, coumarin-based or the same fluorescent dye as the host, is also suitable as the organic light-emitting material. When the above-described compound is used as the organic light-emitting material, blue to green light emission (the emission color varies depending on the type of dopant) can be obtained with high efficiency. Specific examples of the host that is the material of the compound include organic light-emitting materials having a distyrylarylene skeleton (particularly preferably, 4,4′-bis (2,2-diphenylvinyl) biphenyl). Specific examples of the dopant of the material are diphenylaminovinylarylene (particularly preferably, for example, N, N-diphenylaminobiphenylbenzene and 4,4′-bis [2- [4- (N, N-di- -P-tolyl) phenyl] vinyl] 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 light emission efficiency of the light emitting layer.

  The host compound is a compound contained in the light-emitting layer, the mass ratio in the layer is 20% or more, and the phosphorescence quantum yield of phosphorescence emission is 0.1 at room temperature (25 ° C.). Is defined as less than a compound. The phosphorescence quantum yield is preferably less than 0.01. A plurality of host compounds may be used in combination. By using a plurality of types of host compounds, it is possible to adjust the movement of charges, and the organic EL element can be made highly efficient. In addition, by using a plurality of phosphorescent compounds, it is possible to mix different light emission, thereby obtaining an arbitrary emission color. White light emission is possible by adjusting the kind of phosphorescent compound and the amount of doping, and can also be applied to illumination and backlight.

  As these host compounds, compounds having a hole transporting ability and an electron transporting ability, preventing emission light from being increased in wavelength, and having a high Tg (glass transition temperature) are preferable. Known host compounds include, for example, JP-A Nos. 2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, and 2002-334786. Gazette, 2002-8860, 2002-334787, 2002-15871, 2002-334788, 2002-43056, 2002-334789, 2002-75645 2002-338579, 2002-105445, 2002-343568, 2002-141173, 2002-352957, 2002-203683, 2002-363227 2002-231453, 2003-3165, 2002-234888, 2003-27048, 2002-255934, 2002-260861, 2002-280183, Examples thereof include compounds described in 2002-299060, 2002-302516, 2002-305083, 2002-305084, 2002-308837 and the like.

  In the case of having a plurality of light emitting layers, it is preferable that 50% by mass or more of the host compound in each layer is the same compound because it is easy to obtain a uniform film property over the entire organic layer. It is more preferable that the light emission energy is 2.9 eV or more because it is advantageous in efficiently suppressing energy transfer from the dopant and obtaining high luminance. Phosphorescence emission energy means the peak energy of the 0-0 band of phosphorescence emission when the photoluminescence of a deposited film of 100 nm is measured 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 ° C. or more in consideration of deterioration of the organic EL device over time (decrease in luminance and film properties), market needs as a light source, and the like. Preferably there is. That is, in order to satisfy both luminance and durability, it is preferable that phosphorescence emission energy is 2.9 eV or more and Tg is 90 ° C. or more. Tg is more preferably 100 ° C. or higher.

  A phosphorescent compound (phosphorescent compound) is a compound in which light emission from an excited triplet is observed, is a compound that emits phosphorescence at room temperature (25 ° C.), and has a phosphorescence quantum yield of 25. The compound is 0.01 or more at ° C. When used in combination with the host compound described above, an organic EL 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 phosphorescent quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 version, Maruzen) of Experimental Chemistry Course 4 of the 4th edition. Although the phosphorescence quantum yield in a solution can be measured using various solvents, the phosphorescence quantum yield used in the present invention only needs to achieve the phosphorescence quantum yield in any solvent.

  There are two types of light emission of the phosphorescent compound in principle. One is the recombination of the carrier on the host compound to which the carrier is transported to generate an excited state of the host compound, and this energy is transferred to the phosphorescent compound. The energy transfer type, in which light emission from the phosphorescent compound is obtained by moving to the phosphorescent compound, and the other is that the phosphorescent compound becomes a carrier trap, resulting in recombination of the carriers on the phosphorescent compound and from the phosphorescent compound. Although it is a carrier trap type in which light emission can be obtained, in any case, it is a condition that the excited state energy of the phosphorescent compound is lower than the excited state energy of the host compound.

  The phosphorescent compound can be appropriately selected from known compounds used for the light emitting layer of the organic EL device. The phosphorescent compound is preferably a complex compound containing a group 8-10 metal in the periodic table of elements, more preferably an iridium compound, an osmium compound, or a platinum compound (platinum complex compound), rare earth Of these, iridium compounds are the most preferred.

  In the present invention, the phosphorescence emission maximum wavelength of the phosphorescent compound is not particularly limited, and can be obtained in principle by selecting a central metal, a ligand, a ligand substituent, and the like. The emission wavelength can be changed.

  The light emission color of the organic EL device of the present invention and the compound according to the present invention is shown in FIG. 4.16 on page 108 of “New Color Science Handbook” (edited by the Japan Color Society, University of Tokyo Press, 1985). It is determined by the color when the result measured with the total CS-1000 (manufactured by Konica Minolta Sensing) is applied to the CIE chromaticity coordinates.

The white element referred to in the present invention means that the chromaticity in the CIE1931 color system at 1000 cd / m ² is X = 0.33 ± 0.07 when the front luminance at 2 ° C. viewing angle is measured by the above method. It is in the region of Y = 0.33 ± 0.07.

  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 provided between the electrode and the organic layer for lowering the driving voltage and improving the luminance of the light emission. “Organic EL element and its forefront of industrialization (NST 30, November 30, 1998) Issue) ”, Chapter 2, Chapter 2,“ Electrode Materials ”(pages 123-166). The details of the electron injection layer (cathode buffer layer) are also described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specifically, strontium, aluminum, etc. Metal buffer layer typified by lithium, alkali metal compound buffer layer typified by lithium fluoride, alkaline earth metal compound buffer layer typified by magnesium fluoride, oxide buffer layer typified by aluminum oxide, etc. . The buffer layer (injection layer) is preferably a very thin film, and the film thickness is preferably in the range of 0.1 nm to 5 μm although it depends on the material.

  In addition, as an electron transport material (also serving as a hole blocking material) used for the electron transport layer adjacent to the light emitting layer side, it is sufficient if it has a function of transmitting electrons injected from the cathode to the light emitting layer. As a material, any one of conventionally known compounds can be selected and used. For example, nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodisides. Examples include methane and anthrone derivatives, oxadiazole derivatives and the like. Furthermore, in the above oxadiazole derivatives, thiadiazole derivatives in which the oxygen atom of the oxadiazole ring is substituted 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. Furthermore, 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.

  Also, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) aluminum. Tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), and the like, and the central metals of these metal complexes are In, Mg, Metal complexes replaced with Cu, Ca, Sn, Ga or Pb can also be used as the electron transport material. In addition, metal-free or metal phthalocyanine, or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transporting material. Distyrylpyrazine derivatives can also be used as electron transport materials, and inorganic semiconductors such as n-type-Si and n-type-SiC are also used as electron transport materials in the same manner as the hole injection layer and hole transport layer. I can do it. Although there is no restriction | limiting in particular about the film thickness of an electron carrying layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5-200 nm. The electron transport layer may have a single layer structure composed of one or more of the above materials.

  An electron transport layer having a high n property doped with impurities can also be used. Examples thereof include JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, JP-A-2001-102175, J. Pat. Appl. Phys. 95, 5773 (2004), and the like. It is preferable to use such an electron transport layer having a high n property because an element with lower power consumption can be manufactured.

As the second electrode, a material having a work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used. 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 ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, from the point of durability against electron injection and oxidation, etc., a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this, for example, a magnesium / silver mixture, Suitable are 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. The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet resistance as the cathode is preferably several hundred Ω / □ or less, and the film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 to 200 nm. In order to transmit the emitted light, if either one of the first electrode (anode) or the second electrode (cathode) of the organic EL element is transparent or translucent, the emission luminance is advantageously improved.

  Moreover, after producing the metal with a thickness of 1 to 20 nm on the second electrode, the conductive transparent material mentioned in the description of the first electrode is produced thereon, so that a transparent or translucent second electrode ( A cathode) can be manufactured, and by applying this, an element in which both the first electrode (anode) and the second electrode (cathode) are transmissive can be manufactured.

  The external extraction efficiency at room temperature of light emission of the organic EL device of the present invention is preferably 1% or more, more preferably 5% or more. Here, the external extraction quantum efficiency (%) = the number of photons emitted to the outside of the organic EL element / the number of electrons sent to the organic EL element × 100.

  In addition, a hue improvement filter such as a color filter may be used in combination, or a color conversion filter that converts the emission color from the organic EL element into multiple colors using a phosphor may be used in combination. In the case of using a color conversion filter, the λmax of light emission of the organic EL element is preferably 480 nm or less.

  The organic EL device of the present invention preferably uses the following method in combination in order to efficiently extract light generated in the light emitting layer. The organic EL element emits light inside a layer having a refractive index higher than that of air (refractive index is about 1.7 to 2.1), and only about 15% to 20% of the light generated in the light emitting layer can be extracted. It is generally said that there is no. This is because the light incident on the interface (interface between the transparent substrate and air) at an angle θ greater than the critical angle causes total reflection and cannot be taken out of the element, or the transparent electrode or light emitting layer and the transparent substrate This is because the light undergoes total reflection between them, the light is guided through the transparent electrode or the light emitting layer, and as a result, the light escapes in the direction of the side of the device.

  As 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 (JP-A-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). A method of introducing a flat layer having a lower refractive index than the substrate between the substrate and the light emitter (Japanese Patent Laid-Open No. 2001-202827). 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. 11-283951).

  In the present invention, these methods can be used in combination with an organic EL element. However, a method of introducing a flat layer having a lower refractive index than the substrate between the substrate and the light emitter, or a substrate, a transparent electrode layer, A method of forming a diffraction grating between any layers of the light emitting layer (including between the substrate and the outside) can be suitably used. In the present invention, by combining these means, it is possible to obtain an element having higher luminance or durability.

  When a low refractive index medium is formed between the transparent electrode and the transparent substrate with a thickness longer than the wavelength of light, the light extracted from the transparent electrode has a higher extraction efficiency to the outside as the refractive index of the medium is lower. . Examples of the low refractive index layer include aerogel, porous silica, magnesium fluoride, and a fluorine-based polymer. Since the refractive index of the transparent substrate is generally about 1.5 to 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 is preferably at least twice the wavelength in the medium. This is because the effect of the low refractive index layer is diminished when the thickness of the low refractive index medium is about the wavelength of light and the electromagnetic wave that has exuded by evanescent enters the substrate. 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. Of the light, the light that cannot go out due to total reflection between layers, etc. is diffracted by introducing a diffraction grating into any layer or medium (inside a transparent substrate or transparent electrode) , Trying to extract light out. The introduced diffraction grating desirably 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 a certain direction, only light traveling in a specific direction is diffracted. The light extraction efficiency does not increase so much. However, by making the refractive index distribution a two-dimensional distribution, light traveling in all directions is diffracted, and light extraction efficiency is increased.

  As described above, the position where the diffraction grating is introduced may be in any of the layers or in the medium (in the transparent substrate or the transparent electrode), but is preferably in the vicinity of the organic light emitting layer where light is generated. At this time, the period of the diffraction grating is preferably about 1/2 to 3 times the wavelength of light in the medium. The arrangement of the diffraction grating is preferably two-dimensionally repeated, such as a square lattice, a triangular lattice, or a honeycomb lattice.

  Furthermore, the organic EL device of the present invention is processed so as to provide, for example, a structure on the microlens array on the light extraction side of the substrate in order to efficiently extract light generated in the light emitting layer, or so-called condensing. By combining with the sheet, the luminance in the specific direction can be increased by collecting light in a specific direction, for example, in the front direction with respect to the element light emitting surface. As an example of the microlens array, quadrangular pyramids having a side of 30 μm and an apex angle of 90 degrees are two-dimensionally arranged on the light extraction side of the substrate. One side is preferably 10 μm to 100 μm. If it becomes smaller than this, the effect of diffraction will generate | occur | produce and color, and if too large, thickness will become thick and is not preferable.

  As the condensing sheet, for example, a sheet that is put into practical use in an LED backlight of a liquid crystal display device can be used. As such a sheet, for example, a brightness enhancement film (BEF) manufactured by Sumitomo 3M Limited can be used. As the shape of the prism sheet, for example, the substrate may be formed with a triangle stripe having a vertex angle of 90 degrees and a pitch of 50 μm, or the vertex angle is rounded, and the pitch is randomly changed. The shape may be other shapes. Moreover, in order to control the light emission angle from a light emitting element, you may use a light-diffusion plate and a film together with a condensing sheet. For example, a diffusion film (light-up) manufactured by Kimoto Co., Ltd. can be used.

  Hereinafter, although an example is given and the concrete effect of the present invention is shown, the mode of the present invention is not limited to this.

Example 1
(Production of organic EL element)
<Preparation of strip-shaped flexible support having gas barrier layer and first electrode layer in this order>
A gas barrier layer and a first electrode layer are formed by the following method using a polyethylene naphthalate film having a thickness of 100 μm (a film made by Teijin-Dyupon Co., Ltd., hereinafter abbreviated as PEN). A belt-like flexible support having the gas barrier layer and the first electrode layer in this order was prepared.

(Formation of a transparent gas barrier layer)
A transparent gas barrier layer having a thickness of about 90 nm was formed on the prepared PEN by an atmospheric pressure plasma discharge treatment method. As a result of measuring the water vapor transmission rate by a method based on JIS K-7129B, it was 10 ⁻³ g / m ² / day or less. As a result of measuring the oxygen transmission rate by a method based on JIS K-7126B, it was 10 ⁻³ g / m ² / day or less.

(Formation of first electrode layer)
On the transparent gas barrier layer thus formed, ITO (indium tin oxide) having a thickness of 120 nm was patterned by a vapor deposition method to continuously form a plurality of first electrode layers as shown in FIG.

<Formation of hole transport layer and light emitting layer>
Using the manufacturing apparatus shown in FIG. 3, holes are formed on the first electrode layer of the strip-shaped flexible support having the gas barrier layer and the first electrode layer in this order on the prepared winding core in the form of a winding roll. A transport layer and a light-emitting layer were formed, heat-treated, neutralized, cooled to the same temperature as room temperature, and then wound around a winding core. The cleanliness was measured in accordance with JISB 9920, and was measured in class 5.

  The hole transport layer was formed by applying and drying the following coating liquid for forming a hole transport layer by a wet coating method using an extrusion coating machine, followed by heat treatment. The light emitting layer is aligned with the wet pattern coating apparatus in accordance with the alignment mark, and the light emitting layer forming coating solution is aligned with the pattern of the first electrode formed as shown in FIG. 4 while being held by the holding means. It formed with the wet pattern coating device. The electron transport layer was formed by applying and drying the following electron transport layer forming coating solution by a wet coating method using an extrusion coating machine, followed by heat treatment.

Before applying the coating liquid for forming the hole transport layer, the surface of the belt-like flexible support is subjected to a cleaning surface modification treatment using a low-pressure mercury lamp with a wavelength of 184.9 nm at an irradiation intensity of 15 mW / cm ² and a distance of 10 mm. Carried out. The charge removal treatment was performed using a static eliminator with weak X-rays.

  The coating liquid for forming the hole transport layer was applied so that the thickness after drying was 50 nm. The light emitting layer forming coating solution was applied so that the thickness after drying was 100 nm.

  The coating solution for forming an electron transport layer was applied so that the thickness after drying was 30 nm. The conveyance speed was 2 m / min.

(Application conditions)
The coating temperature of the hole transport layer forming coating solution, the light emitting layer forming coating solution, and the electron transport layer forming coating solution is 25 ° C., and the ambient temperature is 25 ° C. except for the drying device and the heat treatment device. I went there.

(Drying and heat treatment conditions)
After applying the hole transport layer forming coating solution, the height of the drying part from the slit nozzle type discharge port to the film forming surface is 100 mm, discharge air velocity is 1 m / s, width air velocity distribution is 5%, and temperature is 100 ° C. After removing the solvent, the back surface heat transfer type heat treatment was subsequently performed at a temperature of 200 ° C. with a heat treatment apparatus to form a hole transport layer.

  After applying the light emitting layer forming coating solution, the drying unit removes the solvent from the slit nozzle type discharge port toward the film forming surface at a height of 100 mm and at a temperature of 60 ° C., and then at the heat treatment unit at a temperature of 220 ° C. Heat treatment was performed to form a light emitting layer.

(Preparation of coating solution for hole transport layer formation)
A solution prepared by diluting polyethylene dioxythiophene / polystyrene sulfonate (PEDOT / PSS, Baytron P AI 4083 manufactured by Bayer) with pure water at 65% and methanol at 5% was prepared as a coating solution for forming a hole transport layer.

(Preparation of light emitting layer forming coating solution)
Preparation of a coating solution for forming a blue light emitting layer A coating material for forming an organic compound layer by dissolving 5% by mass of a dopant material Fir (pic) 3 in 1,2-dichloroethane in polyvinyl carbazole (PVK) as a host material. Prepared as.

Preparation of coating solution for green light emitting layer formation Coating material solution for forming organic compound layer by dissolving 5% by mass of dopant material Ir (ppy) 3 in 1,2-dichloroethane in polyvinylcarbazole (PVK) as a host material Prepared as.

Preparation of coating solution for forming red light-emitting layer 5% by mass of dopant material Btc ₂ Ir (acac) 3 is dissolved in 1,2-dichloroethane in polyvinyl carbazole (PVK) as a host material to form a 1% solution for forming an organic compound layer Prepared as a coating solution.

(Formation of electron transport layer)
Using the manufacturing apparatus shown in FIG. 3, a band-like flexible support having the light emitting layer formed thereon is used, and in the region where the hole transport layer including the light emitting layer is formed, LiF is used as the electron transport layer forming material. LiF was vapor-deposited with an electron transport layer forming vapor deposition apparatus under a vacuum of 5 × 10 ⁻⁴ Pa.

(Formation of second electrode)
Using the manufacturing apparatus shown in FIG. 3, using a belt-like flexible support formed up to the electron transport layer, as a second electrode forming material in a direction perpendicular to the first electrode on the electron transport layer Al was vapor-deposited with a second electrode forming vapor deposition apparatus under a vacuum of 5 × 10 ⁻⁴ Pa using Al.

(Coating with sealant)
Using the manufacturing apparatus shown in FIG. 3, an ultraviolet curable liquid sealant (manufactured by ThreeBond 3124C, manufactured by Three Bond Co., Ltd.) is used as the sealant, and the first electrode, the hole transport layer, and the light emission on the belt-like flexible support. A device in which the layer, the electron transport layer and the second electrode are laminated and formed is coated with a sealant in the light emitting region as shown in FIG. 6B by a sealant coating device shown in FIG. As shown in FIG. 6C, the organic EL element A was coated with a sealant around the light emitting region to obtain an organic EL element B. The viscosity of the sealing agent was 270 Pa · s. The sealant was applied to the light emitting region so as to have a thickness of 60 μm and around the light emitting region so as to have a thickness of 300 μm and a width of 500 μm.
(Preparation of flexible sealing member)
As shown in Table 1, flexible sealing members having different water absorption rates at the time of sealing were prepared. 1-1 to 1-7. The prepared flexible sealing member has a two-layer structure using PEN as a resin base material and silica as a barrier layer. The change in water absorption was adjusted by drying the flexible sealing member and changing the heating temperature and heating time in an oven. The water absorption was measured according to ASTM D570. The thickness of the resin substrate was 100 μm, and the thickness of the barrier layer was 300 nm. The water vapor permeability measured by the MOCON method by a method based on the JIS K-7129B method (1992) was 0.01 g / m ² · day. The oxygen permeability measured mainly by the MOCON method by a method based on the JIS K-7126B method (1987) was 0.01 ml / m ² · day · atm.

(Production of organic EL panel)
Using the organic EL element A and the organic EL element B formed up to the second electrode coated with the sealing agent, as shown in Table 1, each flexible sealing member No. After laminating 1-1 to 1-7 at the laminating portion shown in FIG. 7, while detecting the alignment mark attached on the belt-like flexible supporter for unnecessary portions of the flexible sealing member, FIG. An organic EL panel (a state in which a plurality of organic EL panels are formed on a strip-shaped flexible support (see FIG. 8)) is produced by punching and removing with a punching and cutting apparatus shown in FIG. 101-114.

Evaluation Each sample No. 101-114 (a state in which a plurality of organic EL panels are formed on a strip-shaped flexible support (see FIG. 8)) is cut to produce a single organic EL panel having a temperature of 60 ° C. and a humidity of 90% RH. After storing for 300 hours under the conditions, the presence or absence of the occurrence of dark spots (light emission unevenness) was tested by the test method shown below, and the results of evaluation according to the evaluation rank shown below are shown in Table 2.

Test method of dark spot (light emission unevenness) Using a source measure unit 2400 made by KEITHLEY, a direct current voltage was applied to the organic EL element to emit light. With respect to the light emitting element that emits light at 200 cd, it was observed whether a dark spot (light emission unevenness) occurred with a 50 × microscope.

Evaluation rank of dark spot (light emission unevenness) ◎: 90% or more emits uniformly ○: 80% or more emits uniformly △: 70% or more emits uniformly ×: Less than 70% Only emits light uniformly

  The effectiveness of the present invention was confirmed.

Example 2
With the manufacturing apparatus shown in FIG. 4, an organic EL element in which a first electrode, a hole transport layer, a light emitting layer, an electron transport layer, a second electrode, and a sealing member were formed in this order on a substrate was produced.

(Production of organic EL element)
(Preparation of substrate)
A soda-lime glass having a thickness of 1.1 mm, a width of 40 mm, and a length of 60 mm was prepared as a substrate. In addition, the surface of the soda-lime glass used was a silica-coated glass for protection from acid and alkali.

(Formation of the first electrode)
The prepared glass substrate was cleaned by irradiation at a distance of 12 mm with an irradiation intensity of 15 mW / cm ² using a low-pressure mercury lamp having a wavelength of 184.2 nm. Thereafter, using the first electrode forming vapor deposition apparatus shown in FIG. 4 and using indium tin oxide (ITO) under a vacuum of 5 × 10 ⁻⁴ Pa, the deposited film forming region ( In order to form one organic EL element as shown in FIG. 5B in the first electrode formation region), as shown in FIG. 6, the width is 2 mm, the length is 50 mm, the interval is 2 mm, the thickness is 150 nm, and the seven rows. The patterned first electrode was formed.

(Formation of hole transport layer)
Using a glass substrate on which the first electrode is formed, N, N′-diphenyl-N, as a hole transport layer forming material in a hole transport layer forming vapor deposition apparatus under a vacuum of 5 × 10 ⁻⁴ Pa, Using N′-m-tolyl 4,4′-diamino-1,1′-biphenyl, vapor deposition (vapor phase) is formed on the first electrode except for one end of the first electrode formed on the glass substrate. Deposited).

(Formation of light emitting layer)
Using each glass substrate on which the hole transport layer is formed, aligning with the pattern of the first electrode on the hole transport layer, using Alq ₃ as the light emitting layer forming material, and a vacuum of 5 × 10 ⁻⁴ Pa Below, it vapor-deposited with the light emitting layer formation vapor deposition apparatus.

(Formation of electron transport layer)
Using a glass substrate on which a light emitting layer is formed, using LiF as a material for forming an electron transport layer in a region where a hole transport layer is formed including the light emitting layer, under a vacuum of 5 × 10 ⁻⁴ Pa LiF was deposited using an electron transport layer forming vapor deposition apparatus.

(Formation of second electrode)
Using a glass substrate on which an electron transport layer is formed, using Al as the second electrode forming material in a direction perpendicular to the first electrode on the electron transport layer, and under a vacuum of 5 × 10 ⁻⁴ Pa Then, Al was vapor-deposited by a second electrode forming vapor deposition apparatus. The formed second electrode had a width of 2 mm, a length of 35 mm, an interval of 2 mm, a thickness of 150 nm, and a 10-row pattern.

(Coating with liquid sealant)
Using the manufacturing apparatus shown in FIG. 4, an ultraviolet curable liquid sealant (manufactured by ThreeBond 3124C, manufactured by Three Bond Co., Ltd.) is used as the sealant, and the first electrode, the hole transport layer, and the light emission on the belt-like flexible support. As shown in FIG. 6 (b), a sealing agent is applied to the light emitting region on the organic EL element formed by laminating the layer, the electron transport layer, and the second electrode, as shown in FIG. 6 (b). Then, an organic EL element C was formed, and a sealant was applied around the light emitting region as shown in FIG. The viscosity of the sealing agent was 270 Pa · s. The sealing agent was applied so that the light emitting region had a thickness of 60 μm, and the periphery of the light emitting region had a thickness of 300 μm and a width of 500 μm.
(Preparation of flexible sealing member)
As shown in Table 3, flexible sealing members having different water absorption rates at the time of sealing were prepared. 2-1 to 2-7. The prepared flexible sealing member has a two-layer configuration using PEN as a resin base material and aluminum foil as a barrier layer. The change in water absorption was adjusted by drying the flexible sealing member and changing the heating temperature and heating time in an oven. The water content was measured according to ASTM D570. The thickness of the resin substrate was 100 μm, and the thickness of the barrier layer was 7 μm.
The water vapor permeability measured by the MOCON method by a method based on the JIS K-7129B method (1992) was 0.01 g / m ² · day.
The oxygen permeability measured mainly by the MOCON method by a method based on JIS K7126B method (1987) was 0.01 ml / m ² · day · atm.

(Production of organic EL panel)
Using the organic EL element C and the organic EL element D formed up to the second electrode coated with the sealing agent, as shown in Table 1, each flexible sealing member No. After bonding 2-1 to 2-7 with the bonding part shown in FIG. 9, while detecting the alignment mark attached on the strip | belt-shaped flexible support body to the unnecessary location of a flexible sealing member, FIG. An organic EL panel is manufactured by punching and removing with a punching and cutting apparatus shown in FIG. 201-214.

(Evaluation)
Each prepared sample No. 201 to 214 were stored for 300 hours under conditions of a temperature of 60 ° C. and a humidity of 90% RH, and then the presence or absence of dark spots (light emission unevenness) was tested by the same test method as in Example 1, and the same evaluation as in Example 1 was performed. The results of evaluation according to the rank are shown in Table 4.

  The effectiveness of the present invention was confirmed.

Example 3
(Production of organic EL element)
An organic EL element using the same material as in Example 1 and having a first electrode, a hole transport layer, a light emitting layer, an electron transport layer, and a second electrode laminated in this order on a belt-like flexible support. Produced.

(Coating with sealant)
Using the manufacturing apparatus shown in FIG. 3, an ultraviolet curable liquid sealant (manufactured by ThreeBond 3124C, manufactured by ThreeBond Co., Ltd.) is used as the sealant, and the prepared organic EL element is subjected to the sealant coating apparatus shown in FIG. 7. As shown in FIG. 6C, a sealant was applied around the light emitting region. The viscosity of the sealing agent was 270 Pa · s. The sealing agent was coated around the light emitting region so as to have a thickness of 300 μm and a width of 500 μm.

(Preparation of flexible sealing member)
As shown in Table 5, flexible sealing members having different equilibrium water absorption at atmospheric pressure (20 ° C., 65% RH) were prepared. 3-1 to 3-8. In addition, the prepared flexible sealing member was made into the 2 layer structure which used the resin base material and the silica as a barrier layer. Changes in the equilibrium water absorption rate are adjusted by changing the conditions of the resin substrate material, resin material density, molecular weight distribution, multilayering by coextrusion with different types of resin materials, and multilayering by changing the stretching angle. did. The equilibrium water absorption was measured according to ASTM D570 after leaving the prepared flexible sealing member in the atmosphere (20 ° C., 65% RH) for 100 hours. The thickness of the resin substrate was 100 μm, and the thickness of the barrier layer was 300 nm. After the prepared flexible sealing member was dried in an oven at a heating temperature of 105 ° C. and a heating time of 20 hours, the water absorption measured according to ASTM D570 was 0.2% to 0.8%.

The water vapor permeability measured by the MOCON method by a method based on the JIS K-7129B method (1992) was 0.01 g / m ² · day.

The oxygen permeability measured mainly by the MOCON method by a method based on the JIS K-7126B method (1987) was 0.01 ml / m ² · day · atm.

(Production of organic EL panel)
Each flexible sealing member No. 1 using a strip-like flexible support on which a second electrode coated with a sealant was formed and having a different equilibrium water absorption rate as shown in Table 5 was used. After bonding 3-1 to 3-8 at the bonding part shown in FIG. 7, while detecting the alignment mark attached on the strip-shaped flexible supporter to the unnecessary part of the flexible sealing member, FIG. An organic EL element (a state in which a plurality of organic EL elements are formed on a belt-like flexible support (see FIG. 8)) is manufactured by punching and removing with a punching and cutting apparatus shown in FIG. 301 to 308.
(Evaluation)
Each prepared sample No. 301 to 308 (a state in which a plurality of organic EL elements are formed on a strip-like flexible support (see FIG. 8)) is cut to produce a single organic EL element having a temperature of 60 ° C. and a humidity of 90% RH. After storage for 300 hours under the conditions, the presence or absence of dark spots (light emission unevenness) was tested by the same test method as in Example 1, and the results evaluated according to the same evaluation rank as in Example 1 are shown in Table 6.

  The effectiveness of the present invention was confirmed.

Example 4
(Production of organic EL element)
<Preparation of flexible multilayer resin member having first electrode layer>
As the substrate, as shown in Table 7, flexible multilayer resin members having different water absorption rates when sealed with a flexible sealing member were prepared. 4-1 to 4-7. The prepared flexible multilayer resin member has a two-layer structure using PEN as a resin base material and silica as a barrier layer. The change in water absorption was adjusted by drying the flexible multilayer resin member and changing the heating temperature and heating time in an oven. The prepared flexible multilayer resin member No. For each of 4-1 to 4-7, two members were prepared, one side was made into a panel, the other side was taken out just before sealing, and the water absorption rate at the time of sealing was measured. The water absorption was measured according to ASTM D570. The thickness of the resin substrate was 100 μm, and the thickness of the barrier layer was 300 nm. The water vapor permeability measured by the MOCON method by a method based on the JIS K-7129B method (1992) was 0.01 g / m ² · day. The oxygen permeability measured mainly by the MOCON method by a method based on the JIS K-7126B method (1987) was 0.01 ml / m ² · day · atm.

(Production of organic EL panel)
Each of the prepared flexible multilayer resin members No. The same material as that of Example 1 was used on the barrier layers 4-1 to 4-7, and the first electrode layer, the hole transport layer, the light emitting layer, the electron transport layer, and the second electrode were sequentially laminated in the same manner. Thereafter, the sealing agent is applied to the light emitting region as shown in FIG. 6 (b) by the sealing agent coating apparatus shown in FIG. 7 to obtain an organic EL element E, which is shown in FIG. 6 (c). As shown, a sealant was applied around the light emitting region to obtain an organic EL element F. The viscosity of the sealing agent was 270 Pa · s. The sealant was applied to the light emitting region so as to have a thickness of 60 μm and around the light emitting region so as to have a thickness of 300 μm and a width of 500 μm. Then, after using the organic EL element E and the organic EL element F in which even the 2nd electrode coated with the sealing agent was formed and pasting the flexible sealing member shown below, the same as in Example 1 An unnecessary portion of the flexible sealing member is punched and removed by a method to prepare an organic EL panel (a state in which a plurality of organic EL panels are formed on a strip-shaped flexible support (see FIG. 8)). 401 to 414.

Flexible sealing member The prepared flexible sealing member was made into 2 layer structure which used PEN as a resin base material and a silica as a barrier layer. The water absorption was 0.4%. The water absorption was adjusted by drying the flexible sealing member and changing the heating temperature and heating time in an oven. The water absorption was measured according to ASTM D570. The thickness of the resin substrate was 100 μm, and the thickness of the barrier layer was 300 nm. The water vapor permeability measured by the MOCON method by a method based on the JIS K-7129B method (1992) was 0.01 g / m ² · day. The oxygen permeability measured mainly by the MOCON method by a method based on the JIS K-7126B method (1987) was 0.01 ml / m ² · day · atm.

Evaluation Each sample No. 401 to 414 (a state in which a plurality of organic EL panels are formed on a strip-shaped flexible support (see FIG. 8)) is cut to produce a single organic EL panel, and dark spots (light emission unevenness) are generated. Presence or absence was tested by the same method as in Example 1, and the results of evaluation according to the same evaluation rank as in Example 1 are shown in Table 8.

  The effectiveness of the present invention was confirmed.

Example 5
(Production of organic EL element)
<Preparation of flexible multilayer resin member having first electrode layer>
As a substrate, as shown in Table 9, flexible multilayer resin members having different equilibrium water absorption at atmospheric pressure (20 ° C., 65% RH) were prepared. 5-1 to 5-8. The prepared flexible multilayer resin member has a two-layer structure using a resin base material and silica as a barrier layer. Change in equilibrium water absorption is adjusted by changing the conditions of resin base material, density of resin material, molecular weight distribution, multi-layer by co-extrusion with different resin materials, and multi-layer by bonding with different stretching angles. did. The equilibrium water absorption was measured according to ASTM D570 after the prepared flexible multilayer resin member was left in the atmosphere (20 ° C., 65% RH) for 100 hours. The thickness of the resin substrate was 100 μm, and the thickness of the barrier layer was 300 nm. After the prepared flexible multilayer resin member is dried in an oven at a heating temperature of 105 ° C. and a heating time of 20 hours, the flexible multilayer resin member is sealed with a flexible sealing member measured according to ASTM D570. The water absorption rate of the member was 0.8%. The water vapor permeability measured by the MOCON method by a method based on the JIS K-7129B method (1992) was 0.01 g / m ² · day. The oxygen permeability measured mainly by the MOCON method by a method based on the JIS K-7126B method (1987) was 0.01 ml / m ² · day · atm.

(Production of organic EL panel)
Each of the prepared flexible multilayer resin members No. The same material as that of Example 1 was used on the barrier layers 5-1 to 5-8, and the first electrode layer, the hole transport layer, the light emitting layer, the electron transport layer, and the second electrode were sequentially laminated in the same manner. Thereafter, the sealing agent was applied to the light emitting region as shown in FIG. 6B by a sealing agent coating apparatus shown in FIG. 7 to obtain an organic EL element. The viscosity of the sealing agent was 270 Pa · s. The sealant was applied to the light emitting region so as to have a thickness of 60 μm and around the light emitting region so as to have a thickness of 300 μm and a width of 500 μm. Then, after using the organic EL element in which even the 2nd electrode which apply | coated the sealing agent was formed, the flexible sealing member same as Example 4 was bonded, and it is flexible by the same method as Example 1. An unnecessary portion of the conductive sealing member is punched and removed to prepare an organic EL panel (a state in which a plurality of organic EL panels are formed on a strip-like flexible support (see FIG. 8)). 501-508.

Evaluation Each sample No. 501 to 508 (a state in which a plurality of organic EL panels are formed on a strip-like flexible support (see FIG. 8)) is cut to produce a single organic EL panel, and dark spots (light emission unevenness) are generated. Presence or absence was tested by the same method as in Example 1, and the results of evaluation according to the same evaluation rank as in Example 1 are shown in Table 10.

  The effectiveness of the present invention was confirmed.

It is a schematic sectional drawing which shows an example of the laminated constitution of an organic electroluminescent panel. It is an expansion schematic sectional drawing of the part shown by T of FIG. It is a schematic diagram which shows an example of the process of producing the organic electroluminescent panel at the time of using a strip | belt-shaped flexible support body for a base material. It is a schematic diagram of the manufacturing method of the organic electroluminescent panel which uses a sheet | seat sheet-like board | substrate. It is a schematic diagram which shows the state of the organic EL element formed on the board | substrate. It is the schematic which shows the state which coated the sealing agent in order to bond the flexible sealing member which does not have a sealant layer (sealing agent) on an organic EL element. FIG. 4 is an enlarged schematic view of a portion indicated by Q in FIG. 3. FIG. 7A is an enlarged schematic perspective view of a portion indicated by Q in FIG. It is an expansion schematic perspective view of the part shown by R of FIG. FIG. 5 is an enlarged schematic view of a portion indicated by S in FIG. 4.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Organic electroluminescent panel 101 Base material 102 Anode layer 103 Hole transport layer (hole injection layer)
104 Organic compound layer (light emitting layer)
DESCRIPTION OF SYMBOLS 105 Electron injection layer 106 Cathode layer 107 Sealant layer 108 Sealing layer 108a Resin base material 108b Barrier layer 108 'Flexible sealing member 2, 8 Manufacturing apparatus 3 Organic compound layer formation process 4 Cathode layer formation process 5 Flexibility Sealing member bonding step 6, 8i Punching and cutting step 7, 8j Recovery step 8a Supply step 8b First electrode formation step 8c Hole transport layer formation step 8d Light emitting layer formation step 8e Electron injection layer formation step 8f Second electrode formation step 8g Sealant coating process 8h Flexible sealing member bonding process 10b, 11b, 301i1 Organic EL element

Claims (10)

In an organic electroluminescence panel having an anode layer including at least a first electrode, an organic compound layer including a light emitting layer, a cathode layer including a second electrode, and a sealing layer on a substrate,
The sealing layer is composed of a flexible sealing member having at least one resin base material and at least one barrier layer,
An organic electroluminescence panel characterized by having a water absorption of 1.0% or less measured according to ASTM D570 when the flexible sealing member is sealed. 2. The organic electroluminescence panel according to claim 1, wherein the flexible sealing member has an equilibrium water absorption of 2.0% or less in the atmosphere (20 ° C., 65% RH). The substrate is a flexible multilayer resin member having at least one resin base material and at least one barrier layer, and the water absorption rate of the flexible multilayer resin member during sealing of the flexible sealing member The organic electroluminescence panel according to claim 1 or 2, wherein the value measured in accordance with ASTM D570 is 1.0% or less. 4. The organic electroluminescence panel according to claim 3, wherein the flexible multilayer resin member has an equilibrium water absorption of 2.0% or less in the atmosphere (20 ° C., 65% RH). 5. The organic electroluminescence panel according to any one of claims 1 to 4, wherein the barrier layer includes at least one metal or non-metal oxide layer. A step of sequentially forming an anode layer including at least a first electrode, an organic electroluminescence layer including an organic compound layer including a light emitting layer, a cathode layer including a second electrode, and a sealing layer on a substrate; In the method for producing an organic electroluminescence panel, the formation of the sealing layer is to produce an organic electroluminescence panel by laminating and arranging a flexible sealing member around a light emitting region and a sealant.
The flexible sealing member is a multi-layered resin base material having a barrier layer,
A method for producing an organic electroluminescence panel, wherein the water absorption measured in accordance with ASTM D570 when the flexible sealing member is sealed is 1.0% or less. The method for producing an organic electroluminescence panel according to claim 6, wherein the flexible sealing member has an equilibrium water absorption rate of 2.0% or less in the atmosphere (20 ° C., 65% RH). The substrate is a flexible multilayer resin member having at least one resin base material and at least one barrier layer, and the water absorption rate of the flexible multilayer resin member during sealing of the flexible sealing member The value measured according to ASTM D570 is 1.0% or less, The manufacturing method of the organic electroluminescent panel of Claim 6 or 7 characterized by the above-mentioned. The method for producing an organic electroluminescence panel according to claim 8, wherein the flexible multilayer resin member has an equilibrium water absorption rate of 2.0% or less in the atmosphere (20 ° C., 65% RH). The method for manufacturing an organic electroluminescence panel according to any one of claims 6 to 9, wherein the barrier layer includes at least one metal or non-metal oxide layer.

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