JP2007200591A - Organic electro-luminescence panel and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing an organic EL (electro-luminescence) panel in which process steps are not increased and performance of an organic EL element is not deteriorated, when a sealing member is adhered with adhesives for manufacturing the organic EL panel to be sealed by adhesion-sealing, and to provide the organic EL panel. <P>SOLUTION: An organic EL element has a first electrode, at least one organic compound layer containing a light emitting layer, and a second electrode on a substrate. The EL element is adhered with the sealing member through the adhesives. The method of manufacturing the organic EL panel includes at least one cleaning process step for cleaning one of the sealing member, the organic EL element, and adhering surfaces of the adhesive; and making the number of foreign substances 100 pieces/cm<SP>2</SP>or less with particle sizes of 1 μm or more which mix in one of the sealing member, the organic EL element, and the adhering surfaces of the adhesive. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

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

  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.

  By the way, organic substances such as organic light-emitting materials used in organic EL elements are weak against moisture and oxygen, and their performance deteriorates. Also, the characteristics of electrodes deteriorate rapidly in the atmosphere due to oxidation, so that these deteriorations can be prevented. In general, a sealing layer is provided as the uppermost layer.

  Many studies have been made on the organic EL element sealing method so far, and it is roughly classified into two methods, a casing type sealing method and a close contact type sealing method.

  The casing type sealing method is to seal an organic EL element by placing it in a case and blocking the outside, and filling the case with a predetermined gas or fluid for sealing together with the organic EL element. Is the method. The close-contact type sealing method is a method of sealing by sealing a sealing member such as a glass plate to the back surface of the organic EL element formed on the substrate (the surface of the organic EL element as viewed from the substrate side) with an adhesive. It is a way to stop.

  In the case of a casing type sealing method, there are problems such as being unsuitable for mass production, which requires a process for filling the case with a sealing gas or fluid, which cannot be made thin, Since it can be made thin, relatively easy to mass-produce, and can easily obtain a high sealing effect, a close-contact type sealing method has become the mainstream and is being studied.

  As a close-contact type sealing method, for example, sealing with a sealing film including a barrier layer and a sealant layer made of a thermoplastic adhesive resin having a melt flow rate of 5 g / 10 min or more and 20 g / 10 min or less according to JIS K 7210 Such an organic EL element is known (for example, see Patent Document 1). As an adhesive layer on the organic EL element, the adhesive shrinkage of the adhesive on the organic EL element side is set to two layers by using an adhesive smaller than the shrinkage ratio of the adhesive on the sealing member side to cure the adhesive. A method of fixing a sealing member with an adhesive so that the light emitting element is not affected by stress due to shrinkage is known (see, for example, Patent Document 2).

  By the close-contact type sealing method described in Patent Document 1 and Patent Document 2, mass production is relatively easy, damage to the light-emitting element due to shrinkage during curing of the adhesive, and a thin organic material having a high sealing effect Although it is possible to deal with EL elements, damage to light-emitting elements due to adhesion sealing (surface adhesion on organic electroluminescence elements) is still seen, which is one of the factors that does not increase production efficiency. Therefore, the response to the influence on the light emitting element due to the shrinkage at the time of curing of the adhesive is insufficient.

From such a situation, in order to manufacture an organic EL panel in which an organic electroluminescence element (hereinafter also referred to as an organic EL element) is sealed by an adhesion type sealing method in which a sealing material is fixed via an adhesive, Development of an organic EL panel manufacturing method and an organic EL panel that do not cause deterioration in performance of the organic EL element when the sealing member is fixed with an adhesive is desired. In the present invention, a state where the first electrode, the organic layer, and the second electrode are formed on the substrate is referred to as an organic EL element, and a state in which the first electrode, the organic layer, and the second electrode are tightly sealed with a sealing member is referred to as an organic EL panel.
JP 2001-307871 A JP 2003-109750 A

  The present invention has been made in view of the above-mentioned situation, and its purpose is to manufacture an organic EL panel sealed with a close-contact type sealing method, when fixing a sealing member with an adhesive. An object of the present invention is to provide an organic EL panel manufacturing method and an organic EL panel which do not increase the performance of the organic EL element without causing deterioration.

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

1. An adhesion sealing structure in which an organic electroluminescence element having a first electrode, at least one organic compound layer including a light-emitting layer, and a second electrode is bonded on a substrate with an adhesive interposed therebetween. In the manufacturing method of the organic electroluminescence panel that forms the first and second supply steps for supplying the sealing member, the second supply step for supplying the organic electroluminescence element, the placement step of the adhesive, and the sealing It has the manufacturing apparatus which has the bonding process which bonds a member and the said organic electroluminescent element through the said adhesive agent, and a collection | recovery process, The said manufacturing apparatus is a said 1st supply process or a said 2nd supply process. At least one cleaning step between the bonding step, and in the cleaning step, the adhesive placement surface of the sealing member, the sealing member or the organic elect The organic electroluminescence element and the sealing member are bonded in the bonding step by washing either the bonding surface of the adhesive disposed on the luminescence element or the bonding surface of the adhesive of the organic electroluminescence element. After the bonding is completed, the particles mixed into the bonding surface of the sealing member and the adhesive, the bonding layer of the adhesive and the organic electroluminescence element in the layer of the adhesive, A method for producing an organic electroluminescence panel, wherein the number of foreign matters having a diameter of 1 μm or more is set to 100 pieces / cm ² or less.

  2. The cleaning step is arranged between the first supply step and the arrangement step, and the adhesive arrangement surface of the sealing member or the surface of the adhesive arranged on the organic electroluminescence element is washed. The manufacturing method of the organic electroluminescent panel of said 1 said.

  3. The cleaning step is disposed between the placement step and the second supply step, and cleans the adhesive bonding surface of the sealing member or the adhesive placement surface of the organic electroluminescence element. 3. The method for producing an organic electroluminescence panel as described in 1 or 2 above.

  4). Any one of said 1-3 characterized by the said washing | cleaning process being arrange | positioned between a 2nd supply process and the bonding process, and wash | cleaning the surface of the adhesive agent arrange | positioned at an organic electroluminescent element. The manufacturing method of the organic electroluminescent panel of description.

  5. The cleaning process is disposed between the first supply process and the bonding process, and the surface of the adhesive disposed on the sealing member is cleaned. The manufacturing method of the organic electroluminescent panel of description.

  6). 6. The method for manufacturing an organic electroluminescence panel according to any one of 1 to 5, wherein the bonding step is an environment having a cleanness class of 1000 (US Federal Standard 209D) or less.

  7). 7. The organic electroluminescence according to any one of 1 to 6, wherein the substrate and / or the sealing member is a flexible sealing member having a resin base material and a gas barrier layer. Panel manufacturing method.

  8). The method for producing an organic electroluminescence panel according to any one of 1 to 6, wherein the substrate and / or the sealing member is a glass plate.

  9. 7. The method for manufacturing an organic electroluminescence panel according to any one of 1 to 6, wherein the substrate and / or the sealing member is a metal sheet.

10. Organic electroluminescence in which an organic electroluminescence element having a first electrode, at least one organic compound layer including a light-emitting layer, and a second electrode on a substrate is tightly sealed with a sealing member via an adhesive layer In the panel, the number of foreign matters having a particle diameter of 1 μm or more mixed into any of the bonding surface of the sealing member, the adhesive layer, or the bonding surface of the organic electroluminescence element is 100 / cm ^2. An organic electroluminescence panel characterized by the following.

  11. 11. The organic electroluminescence panel element as described in 10 above, wherein the substrate and / or the sealing member is a flexible member having a resin base material and a gas barrier layer.

  12 11. The organic electroluminescence panel as described in 10 above, wherein the substrate and / or the sealing member is glass.

  13. 11. The organic electroluminescence panel as described in 10 above, wherein the substrate and / or the sealing member is a metal sheet.

  Manufacturing an organic EL panel that does not cause deterioration in performance of the organic EL element without increasing the number of steps when the sealing member is fixed with an adhesive to manufacture an organic EL panel sealed with a close-contact type sealing method A method and an organic EL panel can be provided, and a high-quality thin and lightweight organic EL panel can be produced without increasing the number of steps and without reducing the production efficiency.

  Embodiments of the present invention will be described with reference to FIGS. 1 to 9, 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 adhesive layer 107, and the sealing member 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. 102a indicates an external extraction electrode for the first electrode, and 102b indicates an external extraction electrode for the second electrode.

  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 other typical organic EL elements.

(1) Substrate / anode (first electrode) / light emitting layer / electron transport layer / cathode (second electrode) / sealing member (2) substrate / anode (first electrode) / hole transport layer / light emitting layer / positive Hole blocking layer / electron transport layer / cathode (second electrode) / sealing member (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 member (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 member In the case of an organic EL panel, the anode (first electrode) 102 side is usually the observation side The anode (first electrode) 102 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.

  The present invention uses the flexible sealing member shown in FIG. 1, and seals at least one organic EL element formed on a glass substrate by using a sealing member and closely sealing it with an adhesive. Method of organic EL panel that defines the size and the number of foreign matters mixed in any of the bonding surface of the adhesive and the adhesive, the adhesive layer, the bonding surface of the adhesive and the organic EL element, and the organic EL panel It is about. In addition, the foreign material in an adhesive bond layer refers to the state pushed in in the adhesive bond layer in the bonding surface of a sealing member and an adhesive agent, and the bonding surface of an adhesive agent and an organic EL element.

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

  The sealing member 108 is composed of a flexible sealing member having a resin base material 108a and a gas barrier layer 108b. Note that a protective layer (not shown) may be provided on the gas barrier layer 108b (in the drawing, between the gas barrier layer 108b and the adhesive layer). The resin base material 108a may be a single body or a laminate, and can be appropriately selected as necessary. The gas barrier layer 108b may be a single body or a laminate, and can be appropriately selected as necessary. The sealing member 108 is bonded to the second electrode and the peripheral surface of the second electrode via an adhesive.

  This figure shows a case where a flexible sealing member having a resin base material 108a and a gas barrier layer 108b is used as the sealing member 108, but other sealing members 108 include a glass plate, a metal, and the like. Sheets can be used.

As a characteristic of the gas barrier layer 108b, the water vapor transmission rate is 0.01 g / m ^{2 in} consideration of crystallization of the organic layer, generation of dark spots due to peeling of the second electrode, and extension of the lifetime of the organic EL element. -It is preferable that it is below day. 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 0.01 ml / m ² · day · atm or less in consideration of generation of dark spots due to crystallization of the organic layer, peeling of the second electrode, etc., and extension of the lifetime of the organic EL element. It is preferable. The oxygen permeability is a value measured mainly by the MOCON method by a method based on JIS K7126B method (1987).

  The thickness of the flexible sealing member to be used is preferably 10 to 500 μm in consideration of handleability during production, tensile strength, stress cracking resistance of the gas barrier layer, and the like. Thickness shows the average value which measured 10 each in the vertical direction and the width direction using the micrometer.

  The amount of moisture measured according to ASTM D570 when sealing the flexible sealing member is the generation of dark spots due to crystallization of the organic layer due to moisture brought in by the flexible sealing member, peeling of the second electrode, etc. In consideration of extending the life of the organic EL element and the like, 1.0% or less is preferable.

  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), polyethylene naphthalate (PEN), polycarbonate (PC), polyimide, polyether styrene (PES), etc. The thermoplastic resin film material currently used for the film 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 moisture-proof layer include inorganic vapor-deposited films and metal foils. 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 , SiN Single crystal Si, amorphous Si, W, or the like is 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.

  The thickness of the glass plate to be used is preferably 0.1 to 2.0 mm in consideration of handling at the time of production, thinning of the panel, and the like. Thickness shows the average value which measured 10 each in the vertical direction and the width direction using the micrometer. The glass is not particularly limited, and examples thereof include silicate glass, alkali silicate glass, lead alkali glass, soda lime glass, potassium lime glass, barium glass, borosilicate glass, and phosphate glass.

  The thickness of the metal sheet to be used is preferably 20 μm to 2 mm in consideration of handling at the time of manufacture and thinning of the panel. Thickness shows the average value which measured 10 each in the vertical direction and the width direction using the micrometer. There is no limitation in particular as a metal, For example, metal materials, such as aluminum, copper, and nickel, alloy materials, such as stainless steel and an aluminum alloy, etc. are mentioned.

  FIG. 3 is a schematic view of a manufacturing process of an organic EL panel that is tightly sealed with a sealing member. The manufacturing process shown in the figure shows a case where an adhesive is disposed on the sealing member.

  In the figure, 2 indicates a manufacturing process. In the manufacturing process 2, the first supply process 201 of the sealing member 201a, the second supply process 202 of the organic EL element 202a, the adhesive arrangement process 203, the sealing member 201a and the organic EL element 202a are bonded to each other. It has the bonding process 204 which bonds through, the collection | recovery process 205, and the washing | cleaning processes 206a-206c.

  The first supply step 201 is a supply robot 201c including a storage box 201b of a single-sealed sealing member 201a cut to the size of the organic EL element 202a, and a suction plate 201c1 for taking out the sealing member 201a from the storage box 201b. have. The supply robot 201c can move in the vertical direction (arrow A direction in the figure), move in the horizontal direction (arrow B direction in the figure), and rotate (arrow C direction in the figure).

  The sealing member 201a taken out from the storage box 201b by the supply robot 201c is placed on the placing table 207. The mounting table 207 preferably has suction means (not shown) for mounting and fixing the sealing member 201a. In addition, it is possible to move in the X-axis and Y-axis directions and change the angle for positioning when the adhesive is placed on the sealing member 201a in the adhesive placement step 203. After the sealing member 201a is placed and fixed on the mounting table 207, it is sent to the cleaning step 206a by the moving means. The mounting table 207 can be sequentially moved from the first supply process 201 to the bonding process 204 along the guide rail 208 by a moving means (not shown). When the mounting table 207 moves to each process along the guide rail 208 by the moving means, each process is provided with a detection device (not illustrated) that detects an alignment mark (not illustrated) attached to the mounting table 207. In accordance with information from a detection device (not shown), control is performed so as to stop at a specified position in the main body. The type of the detection device (not shown) is not particularly limited, and examples thereof include image recognition means using a CCD camera.

  The cleaning process 206a is arranged between the first supply process 201 and the adhesive placement process 203, and the surface of the sealing member 201a on which the adhesive is placed is cleaned before the adhesive is placed. Is called. It is preferable to dispose a charge removing means (not shown) before or in the cleaning process 206a, and in particular, a non-contact type charge removing means (not shown) is more preferable to avoid generation of dust due to contact, Examples thereof include a corona discharge ionizer, a soft X-ray ionizer, and an ultraviolet irradiation ionizer.

  The cleaning process 206a includes a cleaning device 206a1, and the cleaning device 206a1 is preferably a dry cleaning method. For example, a gas spraying method, an ultrasonic gas spraying method, a combined gas spraying method and a suction method, or an ultrasonic gas spraying method and an aspiration method. A combined use system, an adhesive roll system, etc. are mentioned. The type of gas is not particularly limited, and an inert gas is preferable in consideration of chemical damage to the organic EL element, and examples thereof include nitrogen gas, helium gas, and argon gas. In the case of this figure, the case of the combined system of gas spraying and suction is shown. The cleaning means 206a1 will be described with reference to FIG.

  After cleaning in the cleaning step 206a, the adhesive is moved to the adhesive placement step 203 by a moving means (not shown) while being mounted on the mounting table.

  The placement step 203 includes an adhesive placement device 203a. As the placement device 203a, the adhesive to be used may be a molten type or a sheet-like type, so that it is possible to cope with the type of adhesive. For example, when the adhesive is a melt type, an acrylic acid oligomer, a photocuring and thermosetting adhesive having a reactive vinyl group of a methacrylic acid oligomer, an adhesive such as a moisture curing type such as 2-cyanoacrylate, Examples include epoxy and other heat and chemical curable (two-component mixed) adhesives, cationic curable ultraviolet curable epoxy resin adhesives, and the like. Among these, it is preferable that a cationic curing type ultraviolet curing epoxy resin adhesive is applied by screen printing in consideration of production efficiency and film thickness stability.

  In the case of a sheet-like type, a sheet-like adhesive and a thermoplastic resin are exemplified. The sheet-like adhesive refers to an adhesive 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. As an adhesive to be used, for example, a photocurable resin mainly composed of a compound having an ethylenic double bond at the terminal or side chain of a molecule and a photopolymerization initiator can be mentioned. 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. The thermoplastic resin 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. Density polyethylene 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 A combination (EVOH), ethylene-propylene copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, vinylidene chloride (PVDC), or 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. As the arrangement method, various generally known methods such as a wet lamination method, a dry lamination method, a hot melt lamination method, an extrusion lamination method, and a thermal lamination method can be used.

  The thickness of the adhesive to be arranged is preferably 5 to 100 μm in consideration of the curing reaction time, the influence on the organic layer, the moisture penetration from the edge, etc. for both the melt type and the sheet type. After the adhesive is arranged on the sealing member, the adhesive is moved along the guide rail 208 by the moving means (not shown) in the cleaning process 206c while being placed on the mounting table.

  The cleaning step 206c is disposed between the adhesive placement step 203 and the bonding step 204, and the surface of the adhesive placed on the sealing member 201a is washed. It is preferable to dispose a charge removing means (not shown) in the cleaning step 206c. In particular, a non-contact type charge removing means (not shown) is more preferable to avoid generation of dust due to contact. For example, a corona discharge ionizer, Examples include soft X-ray ionizers and ultraviolet irradiation ionizers.

  The cleaning process 206c includes a cleaning device 206c1. The cleaning device 206c1 is preferably a dry cleaning method, and examples thereof include gas spraying, ultrasonic gas spraying, a combined gas spraying and suction method, and a combined ultrasonic gas spraying and suction method.

  The second supply process 202 includes a supply robot 202c having a shelf storage box 202b for the organic EL elements 202a and two extraction arms 202c1 for extracting the organic EL elements 202a from the shelf storage box 202b. The take-out arm 202c1c is moved to and held in the horizontal direction (in the direction of arrow D in the drawing) in order to hold both ends of the organic EL element 202a stored and stored in the shelf-type storage box 202b. It is possible to move in the vertical direction (in the direction of arrow E in the figure) in order to place 202a and to take out the organic EL element 202a housed in the lower stage from the upper stage of the shelf type storage box 202b. The organic EL element 202a taken out from the shelf-type storage box 202b by the supply robot 202c is placed on the placement table 209 and sent to the cleaning step 206b by the moving means. The surface of the organic EL element 202a stored in the shelf-type storage box 202b (the surface on which the sealing member is bonded) is in a downward state. The mounting table 209 holds the four end sides of the organic EL element 202a, and the central part is a cavity for cleaning the surface of the organic EL element 202a from below in the cleaning step 206b.

  The cleaning process 206b is disposed between the second supply process 202 and the bonding process 204, and before the sealing member 201a is bonded to the surface sealed by the sealing member 201a of the organic EL element 202a. Cleaning is performed. It is preferable to dispose a charge removing means (not shown) before or in the cleaning process 206b, and in particular to avoid damage to the second electrode surface of the organic EL element 202a due to contact, a non-contact type charge removing means. (Not shown) is more preferable, and examples thereof include a corona discharge ionizer, a soft X-ray ionizer, and an ultraviolet irradiation ionizer.

  The cleaning process 206b includes a cleaning device 206b1. The cleaning device 206b1 is preferably a dry cleaning method, and examples thereof include gas spraying, ultrasonic gas spraying, a combined gas spraying and suction method, and a combined ultrasonic gas spraying and suction method. The cleaning device 206b1 will be described with reference to FIG. After cleaning in the cleaning step 206b, the moving unit (not shown) moves to the bonding step 204 in a state of being mounted on the mounting table 209.

The bonding step 204 includes a supply robot 204a, a bonding device 204b, and a curing processing device 204c. The supply robot 204a has the same mechanism and function as the supply robot 201c, and moves in the vertical direction (arrow G direction in the figure), moves in the horizontal direction (arrow H direction in the figure), and rotates (in the figure). Movement in the direction of arrow I) is possible. In the bonding step 204, the cleaned organic EL element 202a in a state of being mounted on the mounting table 208 by the supply robot 204a is applied to the surface of the adhesive 201a1 of the sealing member 201a mounted on the mounting table 207. The second electrode side is overlapped, and thereafter, pressure bonding is performed by the bonding apparatus 204b and processing is performed by the curing processing apparatus 204c, whereby the adhesion sealing of the organic EL element 202a by the sealing member 201a is completed and an organic EL panel is completed. After the close sealing has been completed, it is recovered in the recovery step 205. Incidentally, the surface pressure at the time of bonding by the bonding apparatus 204b is bonded to the sealing member polymerizable, considering the damage or the like of the organic EL device, preferably ^{0.5 × 10 4 Pa~9.8 × 10 4} Pa . Bonding by the bonding apparatus 204b is preferably performed in a reduced pressure environment of 1 Pa to 30 kPa in consideration of air bubbles.

  The curing processing device 204c can be changed according to the type of adhesive used. For example, when the adhesive is a thermosetting type, it becomes a curing processing apparatus having a heating device, and when it is an ultraviolet curing type, it becomes a curing processing apparatus having an ultraviolet irradiation device. Depending on the curing time and tact of the adhesive to be selected, the curing processing device 204c can be used as a temporary curing device and a main curing device. In addition, although the case where the bonding apparatus 204b and the hardening processing apparatus 204c are isolate | separated is shown in this figure, it is also possible to give the function of the hardening processing apparatus 204c to the bonding apparatus 204b. From the viewpoint of reducing the lifetime due to the deterioration of the organic EL element, it is important that the moisture concentration and the oxygen concentration are low until the curing treatment by the above curing treatment apparatus 204c. It is preferable to carry out below.

  The cleaning devices 206a1 to 206c1 of the cleaning steps 206a to 206c shown in this figure may be different and only need to have at least one cleaning step between the first supply step 201 and the bonding step. In this figure, it is arranged between the first supply process 201 and the adhesive arrangement process 203, between the second supply process 202 and the bonding process 204, and between the adhesive arrangement process 203 and the bonding process 204. The case where it is provided is shown. The cleaning devices 206a1 to 206c1 also show the same method.

  FIG. 4 is a schematic view of another manufacturing process of an organic EL panel that is tightly sealed with a sealing member. The manufacturing process shown in this figure shows a case where an adhesive is disposed on the organic EL element.

  In the figure, 3 indicates a manufacturing process. In the manufacturing process 3, the second supply process 301 of the organic EL element 301a, the first supply process 302 of the sealing member 302a, the adhesive disposing process 303, the organic electroluminescence element 301a and the sealing member 302a are bonded. It has the bonding process 304 which bonds through an agent, the collection | recovery process 305, and the washing | cleaning processes 306a-306c.

  The second supply process 301 includes a supply robot 301c including a shelf-type storage box 301b for the organic EL elements 301a and two extraction arms 301c1 for extracting the organic EL elements 301a from the shelf-type storage box 301b. The take-out arm 301c1c moves in the horizontal direction (arrow J direction in the figure) and holds the organic EL element on the mounting table 307 in order to hold both ends of the organic EL element 301a stored and stored in the shelf-type storage box 301b. It is possible to move in the vertical direction (in the direction of arrow K in the figure) in order to place 301a and to take out the organic EL element 301a stored in the lower stage from the upper stage of the shelf-type storage box 301b. The organic EL element 301a taken out from the shelf-type storage box 301b by the supply robot 301c is mounted on the mounting table 307 and fixed, and then moved along the guide rail 308 for movement by the moving means (not shown). Sent to 306a. The surface of the organic EL element 301a stored in the shelf-type storage box 301b (the surface on which the sealing member is bonded) is in an upward state. The organic EL element 301a is mounted on the mounting table 307 and fixed, and then sent to the cleaning step 306a along the moving guide rail 308 by a moving means (not shown). The mounting table 307 has the same mechanism and function as the mounting table 207 shown in FIG.

  The cleaning step 306a is arranged between the second supply step 301 and the adhesive placement step 303, and the surface on which the adhesive of the organic EL element 301a is placed is cleaned before the adhesive is placed. Is called. It is preferable to dispose a charge removing means (not shown) before or in the cleaning process 306a. In order to avoid damage to the second electrode due to contact, in particular, a non-contact type charge removing means (not shown) Are more preferable, and examples thereof include a corona discharge ionizer, a soft X-ray ionizer, and an ultraviolet irradiation ionizer.

  The cleaning process 306a includes a cleaning device 306b1. The cleaning device 306b1 is preferably a dry cleaning method, and examples thereof include air blowing, ultrasonic air blowing, a combined air blowing and suction method, and a combined ultrasonic air blowing and suction method. The cleaning device 306a1 has the same structure as the cleaning device 206a1 shown in FIG. After cleaning in the cleaning process 306b, the sheet is moved along the guide rail 308 by a moving means (not shown) to the bonding process 304 in a state of being mounted on the mounting table 307.

  The arrangement process 303 includes an adhesive arrangement device 303a. As the arrangement device 303a, the adhesive to be used may be a melt type or a sheet type, so that it can correspond to the type of adhesive, and is the same as the adhesive arrangement device 203a shown in FIG. Has function and structure. Further, the same adhesive as the adhesive placement device 203a shown in FIG. 3 can be used. The thickness of the adhesive to be arranged is preferably 5 to 100 μm in consideration of the curing reaction time, the influence on the organic layer, the moisture penetration from the edge, etc. for both the melt type and the sheet type.

  After the adhesive is disposed on the organic EL element 301a, it moves along the guide rail 308 by the moving means (not shown) to the cleaning step 306c in a state of being placed on the mounting table.

  The cleaning step 306c is disposed between the adhesive placement step 303 and the bonding step 304, and the surface of the adhesive placed on the organic EL element 301a is cleaned. It is preferable to dispose a charge removing means (not shown) in the cleaning step 306c, and in particular, a non-contact type charge removing means (not shown) is more preferable in order to avoid generation of dust due to contact, for example, a corona discharge ionizer, Examples include soft X-ray ionizers and ultraviolet irradiation ionizers. The cleaning step 306c has a cleaning device 306c1. The cleaning device 306c1 has the same structure as the cleaning device 306a1.

  In the first supply step 302, a supply robot 302c including a storage box 302b of a single-sealed sealing member 302a cut to the size of the organic EL element 301a and a suction plate 302c1 for taking out the sealing member 302a from the storage box 302b. have. The supply robot 302c has the same mechanism and function as the supply robot 201c shown in FIG. The sealing member 302a taken out from the storage box 302b by the supply robot 302c is placed on the placing table 309 and sent to the cleaning step 306b by the moving means. The sealing member 302a stored in the shelf-type storage box 302b has a surface (surface on which the organic EL element 301a is bonded) facing downward. The mounting table 309 holds four end sides of the sealing member 302a, and the central portion is a cavity for cleaning the surface of the sealing member 302a from below in the cleaning step 306b. The mounting table 309 preferably has the same structure as the mounting table 209 shown in FIG.

  The cleaning process 306b is disposed between the first supply process 302 and the bonding process 304, and before the bonding of the surface to be bonded to the adhesive on the organic EL element 301a of the sealing member 302a is bonded. Done. It is preferable to dispose a charge removing means (not shown) before or in the cleaning process 306a, and in particular, a non-contact type charge removing means (not shown) is more preferable in order to avoid generation of dust due to contact, Examples thereof include a corona discharge ionizer, a soft X-ray ionizer, and an ultraviolet irradiation ionizer.

  The cleaning device 306b1 in the cleaning step 306b has the same structure as the cleaning device 206b1 shown in FIG. 3, and the sealing member cleaning method is also the same. After washing in the washing process 306a, the sheet is moved along the guide rail 308 for movement by the moving means (not shown) to the bonding process 304 in a state of being placed on the placing table.

The bonding step 304 includes a supply robot 304a, a bonding device 304b, and a curing processing device 304c. The supply robot 304a has the same mechanism and function as the supply robot 204a shown in FIG. In the bonding step 304, the cleaned sealing member 302a in a state of being mounted on the mounting table 309 by the supply robot 304a onto the adhesive surface 301a1 of the organic EL element 301a mounted on the mounting table 307. After that, by adhering with the bonding device 304b and processing with the curing device 304c, the organic EL element 301a is completely sealed by the sealing member 302a and the organic EL panel is completed. After the close sealing has been completed, it is recovered in the recovery step 305. Incidentally, the surface pressure at the time of bonding by the bonding apparatus 304b is bonded to the sealing member polymerizable, considering the damage or the like of the organic EL device, preferably ^{0.5 × 10 4 Pa~9.8 × 10 4} Pa . It is preferable to perform bonding by the bonding apparatus 304b in a reduced pressure environment of 1 Pa to 30 kPa in consideration of air bubbles.

  The curing processing device 304c can be changed according to the type of adhesive used. For example, when the adhesive is a thermosetting type, it becomes a curing processing apparatus having a heating device, and when it is an ultraviolet curing type, it becomes a curing processing apparatus having an ultraviolet irradiation device. Depending on the curing time and tact of the selected adhesive, the curing processing device 304c can be used as a temporary curing device and a main curing device. In addition, although the case where the bonding apparatus 304b and the hardening processing apparatus 304c are isolate | separated is shown in this figure, it is also possible to give the function of the hardening processing apparatus 304c to the bonding apparatus 304b. From the viewpoint of life reduction due to deterioration of the organic EL element, it is important that the water concentration and the oxygen concentration are low until the above-described curing processing by the curing processing device 304c. It is preferable to carry out below.

  The cleaning apparatuses 306a1 to 306c1 of the cleaning steps 306a to 306c shown in this drawing may be different and only need to have at least one cleaning step between the second supply step 301 and the bonding step 303. . In this figure, it is arranged between the second supply step 301 and the adhesive placement step 303, between the first supply step 302 and the pasting step 304, and between the adhesive placement step 303 and the pasting step 304. The case where it is provided is shown. Further, the cleaning apparatuses 306a1 to 306c1 have the same method and the same case as the cleaning apparatuses 306a1 to 306c1 shown in FIG.

  FIG. 5 is an enlarged schematic view of the cleaning apparatus in the first supply step shown in FIG.

  The cleaning device 206a1 has a box structure having a side wall 206a5, a side wall 206a6, a bottom surface 206a7, a top surface 206a8, an inlet 206a2, and an outlet 206a9. The entrance 206a2 has a shutter 206a10, and the exit 206a9 also has a shutter 206a11. The entrance 206a2 is closed during cleaning to increase the cleaning effect, and is opened after cleaning. Reference numeral 206a12 denotes a gas supply pipe connected to an air supply pump (not shown), and 206a13 denotes an exhaust pipe connected to a suction pump (not shown), which is attached to the top surface 206a8. Reference numeral 206a14 denotes a header attached in the cleaning device 206a1, and has a plurality of air blowing nozzles 206a15. The nozzle 206a15 is 30-90 ° with respect to the gas blowing surface (in this case, the surface of the sealing member 201a on the mounting table 207) in consideration of foreign matter removal performance, prevention of foreign matter reattachment due to turbulent flow, etc. It is attached to the header 206a14 at an angle of. The gas sent from the gas supply pipe 206a12 to the header 206a14 is blown from the nozzle 206a15 to the surface of the sealing member 201a, exhausted from the exhaust pipe 206a13, and the surface of the sealing member 201a is cleaned. The arrows in the figure indicate the air flow.

The cleaning conditions when the sealing member by the combined gas spraying and suction method is a sealing member composed of a resin base material and a gas barrier layer are, for example, a gas blowing air volume of 5.5 m ³ / min, a gas blowing The wind speed is 100 m / sec and the time is 3 min.

Examples of the cleaning conditions when the sealing member is a glass plate include a gas blowing rate of 7 m ³ / min, a gas blowing rate of 140 m / sec, and a time of 3 min.

The cleaning conditions when the sealing member is a metal sheet include, for example, a gas blowing rate of 8 m ³ / min, a gas blowing rate of 150 m / sec, and a time of 3 min.

  The gas blowing air volume is a value obtained by measuring the air volume in the gas supply pipe with a flow meter and the cross-sectional area of the gas supply pipe. The gas blowing wind speed indicates an average wind speed value of the gas blowing portion calculated from the air volume and the nozzle cross-sectional area.

The cleaning device 206c1 also has the same structure as the cleaning device 206a1 shown in the figure, and as a cleaning condition of the surface of the adhesive disposed on the sealing member, for example, a gas blowing air volume of 7 m ³ / min, gas blowing wind speed 140 m / sec, 3 min.

  The above conditions are the same when the sealing member is a flexible member, a glass plate, or a metal sheet.

The cleaning device 306a1 shown in FIG. 4 also has the same structure as the cleaning device 206a1 shown in this figure. As a cleaning condition in the case of an organic EL element using glass as a base material by a combination method of air blowing and suction methods. For example, the gas blowing air volume is 5.5 m ³ / min, the gas blowing air speed is 100 m / sec, and the time is 3 min.

Examples of cleaning conditions when a flexible base material is used as the base material include a gas blowing rate of 7 m ³ / min, a gas blowing rate of 140 m / sec, and a time of 3 min.

The cleaning conditions when a metal sheet is used as the substrate include, for example, a gas blowing rate of 8 m ³ / min, a gas blowing rate of 150 m / sec, and a time of 3 min.

The cleaning device 306c1 shown in FIG. 4 also has the same structure as the cleaning device 206a1 shown in this figure. The cleaning condition for the surface of the adhesive disposed on the organic EL element is, for example, a gas blowing air volume Examples include 7 m ³ / min, gas blowing speed, wind speed 140 m / sec, and time 3 min. The above conditions are the same when the substrate is a flexible member, a glass plate, or a metal sheet.

  FIG. 6 is an enlarged schematic view of the cleaning apparatus in the second supply step shown in FIG. FIG. 6A is an enlarged schematic perspective view of the cleaning device in the second supply step shown in FIG. FIG. 6B is an enlarged schematic cross-sectional view along the line BB ′ in FIG.

  The cleaning device 206b1 has a box structure having a side wall 206b5, a side wall 206b6, a bottom surface 206b7, a top surface 206b8, an inlet 206a2, and an outlet 206b9. The entrance 206b2 has a shutter 206b10, and the exit 206b9 also has a shutter 206b11. The entrance 206b2 is closed during cleaning and opened after cleaning to enhance the cleaning effect. Reference numeral 206b12 denotes a gas supply pipe connected to a gas supply pump (not shown), which is attached to the side wall 206b5. Reference numeral 206b13 denotes an exhaust pipe connected to a suction pump (not shown), which is attached to the side wall 206b6. Reference numeral 206b14 denotes a header mounted in the cleaning device 206b1, and has a plurality of nozzles 206b15 for blowing air. The nozzle 206b15 is 30 ° to 90 ° with respect to the air blowing surface (in this case, the surface of the sealing member 201a on the mounting table 207) in consideration of foreign matter removal performance, prevention of foreign matter reattachment due to turbulent flow, etc. It is attached to the header 206b14 at an angle of. Reference numeral 206b16 denotes a pressing plate that is pressed from the back side and fixed to the mounting table 208 so that the organic EL element 202a mounted on the mounting table 209 does not move during cleaning. Reference numeral 206b17 denotes a movement axis for moving the pressing plate 206b16 in the vertical direction (the direction of arrow L in the figure), and is connected to the drive source 206b18.

  The gas sent from the gas supply pipe 206b12 to the header 206b14 is supplied from the nozzle 206b15 to the cavity 209a of the mounting table 209, and sprayed onto the surface of the organic EL element 202a from below to perform cleaning. The gas used for cleaning is exhausted from the side surface of the mounting table through the exhaust pipe 206b13. An arrow M in the figure indicates a gas flow.

The conditions for cleaning the surface of the organic EL element 202a by the cleaning device 206b1 shown in this figure are shown below. Examples of cleaning conditions when the substrate of the organic EL element 202a is a flexible member include a gas blowing air volume of 5.5 m ³ / min, a gas blowing air speed of 100 m / sec, and a time of 3 min.

Examples of the cleaning conditions when the substrate of the organic EL element 202a is a glass plate include a gas blowing air volume of 5.5 m ³ / min, a gas blowing air speed of 100 m / sec, and a time of 3 min.

Examples of cleaning conditions when the substrate of the organic EL element 202a is a metal sheet include a gas blowing air volume of 5.5 m ³ / min, a gas blowing air speed of 100 m / sec, and a time of 3 min. The gas blowing air volume is a value obtained by measuring the air volume in the gas supply pipe with a flow meter and the cross-sectional area of the gas supply pipe. The gas blowing speed indicates an average wind speed value of the gas blowing portion calculated from the air volume and the nozzle cross-sectional area.

Note that the cleaning device 306b1 of the cleaning step 302b of the first supply step 302 shown in FIG. 4 has the same structure as the cleaning device 206b1 shown in this figure, and is a sealing member placed on the mounting table 304. Examples of conditions for cleaning the bonding surface with the organic EL element include a gas blowing air amount of 7 m ³ / min and a gas blowing air velocity of 140 m / sec for 3 minutes. The above conditions are the same when the sealing member is a flexible member, a glass plate, or a metal sheet.

Using the cleaning apparatus shown in FIGS. 5 and 6, the organic electroluminescence element and the sealing member are bonded in the bonding step by cleaning under the conditions shown above, and then the sealing member, the adhesive layer, and The number of foreign matters having a particle size of 1 μm or more mixed in any of the bonding surfaces of the adhesive layer and the bonding surface of the adhesive layer and the organic electroluminescence element is 100 / cm ² or less, preferably 75. In the following, it is particularly possible to make the number 50 or less.

When the number of foreign matters having a particle size of 1 μm or more exceeds 100 / cm ² , the stress concentration occurrence points at the time of bonding and crimping due to the inclusion of foreign matters increase, and the probability of occurrence of damage to the organic electroluminescence element increases. .

In addition, the measurement of the foreign material was performed by dark field observation using a metal microscope (Olympus BX61). About each member (sealing member, organic EL element, adhesive) bonding surface before bonding, sample 1 cm ² was randomly sampled at five locations, and the average value of counting foreign matters having a particle size of 1 μm or more was shown. The total of the average values in was used as the number of foreign matters mixed in the bonding surface after the bonding.
Moreover, when a sealing member is light-transmitting, after finishing bonding an organic EL element and a sealing member, a foreign material is counted by the same measuring method from the sealing member side surface, and the foreign material mixed in the bonding surface It is also possible to use the number. The particle size of the foreign matter was measured with a metal microscope (Olympus BX61), and the maximum length in the projected shape of the foreign matter was taken as the particle size.

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

  Examples of the substrate according to the present invention include a single wafer substrate and a strip-shaped flexible substrate. Examples of the single-wafer substrate include a transparent glass plate, a metal sheet, and a sheet-like transparent resin film. The same glass as the sealing member can be used as the transparent glass plate. As the metal sheet, the same metal sheet as the sealing member can be used. 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, Cycloolefin resins such as polyether imide, polyether ketone imide, polyamide, fluororesin, nylon, polymethyl methacrylate, acrylic or polyarylate, Arton (trade name, manufactured by JSR) or Appel (trade name, manufactured by Mitsui Chemicals) Is mentioned. A transparent resin film is mentioned as a strip | belt-shaped flexible board | substrate, The same resin film as a single wafer 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 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 gas barrier film is not particularly limited. For example, the vacuum deposition method, the sputtering method, the reactive sputtering method, the molecular beam epitaxy method, the cluster ion beam method, the ion plating method, the plasma polymerization method, the atmospheric pressure plasma weighting. A combination method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, and 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.

  According to 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 light emitting layer according to 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 less than 0.1 at room temperature (25 ° C.) Is defined as Preferably the phosphorescence quantum yield is 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 emissions, 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 emission energy is 2.9 eV or more because it is advantageous for efficiently suppressing energy transfer from the dopant and obtaining high luminance. Phosphorescence emission energy refers to the peak energy of 0-0 band of phosphorescence emission measured by measuring photoluminescence of a deposited film of 100 nm 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 element over time (decrease in luminance and film properties), market needs as a light source, and the like. It is preferable. 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 0 at 25 ° C. .01 or more compounds. 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 phosphorescent quantum yield of 0.1 or more. The phosphorescent quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, 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 is only required to achieve the above phosphorescence quantum yield in any solvent.

  There are two types of light emission of phosphorescent compounds in principle. One is the recombination of carriers on the host compound to which carriers are transported to generate an excited state of the host compound, and this energy is transferred to the phosphorescent compound. Energy transfer type to obtain light emission from the phosphorescent compound, and the other is that the phosphorescent compound becomes a carrier trap, and recombination of the carriers on the phosphorescent compound occurs and light emission from the phosphorescent compound is obtained. Although it is a trap type, 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), a rare earth complex. Of these, iridium compounds are most preferred.

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

  The light emission color of the organic EL device according to 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 a luminance meter 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 according to 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 according to the present invention is preferably used in combination with the following method 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).

  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 according to the present invention can be processed to provide, for example, a structure on a microlens array on the light extraction side of the substrate in order to efficiently extract the light generated in the light emitting layer, or so-called collection. By combining with the light sheet, the luminance in the specific direction can be increased by condensing light in a specific direction, for example, 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.

EXAMPLES Hereinafter, although an Example is given and the specific effect of this invention is shown, the aspect of this invention is not limited to this Example 1
<Production of organic EL element>
A first electrode, a hole transport layer, a light emitting layer, an electron transport layer, and a second electrode are formed on the substrate in this order. One dot has a size of 2 mm × 2 mm, and 7 dots × 10 An organic EL element composed of a total of 70 dots (light emitting region) was prepared by the method described below.

(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. Then, using a vapor deposition apparatus, using indium tin oxide (ITO) under a vacuum of 5 × 10 ⁻⁴ Pa, the width of the deposited film formation region (first electrode formation region) of the prepared glass substrate The patterned 1st electrode of 2 mm, length 58mm, space | interval 2mm, thickness 150nm, and 7 rows was formed.

(Formation of hole transport layer)
A glass substrate on which the first electrode is formed is used, and N is used as a hole transport layer forming material on the first electrode except for an end portion for forming an external extraction electrode of the first electrode formed on the glass substrate. , N′-diphenyl-N, N′-m-tolyl 4,4′-diamino-1,1′-biphenyl (hereinafter referred to as TPD) and vapor phase deposition under a vacuum of 5 × 10 ⁻⁴ Pa Vapor deposition (vapor deposition) was performed using an apparatus. The thickness of the hole transport layer was 50 nm.

(Formation of light emitting layer)
Using a glass substrate on which a hole transport layer is formed, Alq ₃ is used as a light emitting layer forming material on the hole transport layer, and vapor deposition is performed in a vapor deposition apparatus under a vacuum of 5 × 10 ⁻⁴ Pa. did. The thickness of the light emitting layer was 50 nm.

(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 vapor-deposited with a vapor deposition apparatus. The thickness of the electron transport layer was 0.5 nm.

(Formation of second electrode)
A glass substrate on which an electron transport layer is formed is used, and as shown in FIG. 3, Al is used as the second electrode forming material on the electron transport layer, and the second electrode is formed under a vacuum of 5 × 10 ⁻⁴ Pa. Al was vapor-deposited by an electrode forming vapor deposition apparatus. In addition, the formed 2nd electrode was made into the pattern of width 2mm, length 38mm, space | interval 2mm, thickness 150nm, and 10 rows so that it may orthogonally cross with the 1st electrode.

(Cleaning of sealing member)
A flexible sealing member having a configuration of PET 120 μm / SiO 30 nm μm / SiN 100 nm was prepared, and the cleaning apparatus shown in FIG. 5 in the first supply step of the manufacturing apparatus shown in FIG. The surface of the flexible sealing member is washed and no. 1-1 to 1-3. In addition, a flexible sealing member that is not cleaned is prepared. 1-4. The water vapor permeability of the used flexible sealing member measured by the MOCON method mainly in accordance with JIS K7129B 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.

  The number of foreign matters having a particle size of 1 μm or more on the surface of the flexible sealing member was measured by the following method.

Number of foreign substances Five 1 cm ² surfaces of the flexible sealing member were randomly selected, and foreign substances having a particle diameter of 1 μm or more were counted by dark field observation using a metal microscope (Olympus BX61). The average value of five locations was taken as the number of foreign matters.

  In addition, an angle shows the spray angle of the gas with respect to the surface of the sealing member on the mounting base of the nozzle of a washing | cleaning apparatus.

(Arrangement of adhesive on flexible sealing member)
Using the adhesive placement apparatus of the manufacturing process shown in FIG. 3, an ultraviolet curable liquid adhesive (manufactured by ThreeBond 3124C, manufactured by Three Bond Co., Ltd.) was used, and the prepared flexible sealing member No. 1-1 to 1-4 was placed at a thickness of 50 μm by screen printing, and then the surface of the adhesive was washed under a washing condition as shown in Table 2 with a washing device. 1-a to 1-e. Also, a flexible sealing member that does not clean the surface of the adhesive is prepared. 1-f to 1-h.

  The number of foreign matters having a particle size of 1 μm or more on the surface of the adhesive was measured by the same method as that for the flexible sealing member.

  In addition, an angle shows the spray angle of the gas with respect to the surface of the adhesive agent on the mounting base of the nozzle of a washing | cleaning apparatus.

<Cleaning of organic EL elements>
The surface to which the flexible sealing member of the prepared organic EL element is bonded is subjected to the cleaning conditions as shown in Table 3 in the cleaning apparatus shown in FIG. 6 in the second supply step of the manufacturing apparatus shown in FIG. The surface (side on which the sealing member is pasted) was washed and No. 1-A to 1-C. Moreover, the organic EL element which does not wash | clean the surface (side which bonds a sealing member) of an organic EL element is prepared, and No. 1-D.

  The number of foreign matters having a particle size of 1 μm or more on the surface of the organic EL element was measured by the same method as that for the flexible sealing member. In addition, an angle shows the spray angle of the gas with respect to the surface of the organic EL element on the mounting base of the nozzle of a washing | cleaning apparatus.

<Adhesive sealing of organic EL element by flexible sealing member>
In the bonding process of the manufacturing apparatus shown in FIG. 1-A to 1-D and the prepared flexible sealing member No. 1-a to 1-h were combined and bonded as shown in Table 4 to produce a sealed organic EL panel. 101-132. Bonding is performed by pressing with a pressing force of 0.1 MPa under a reduced pressure environment of 1 × 10 ⁻² Pa, and irradiation with ultraviolet light having a dominant wavelength of 365 nm from the flexible sealing member side (90 sec at 100 mW / cm ² ). Curing treatment was performed. In addition, the bonding process was performed in an environment of cleanliness class 1000 (US Federal Standard 209D) or lower.
(Evaluation)
Each prepared sample No. Table 4 shows the results of tests 101 to 132 and the dark spot (spot-like non-light emitting portion) generation rate tested by the test method shown below and evaluated according to the evaluation rank shown below.
Test Method of Dark Spot Generation Ratio Using a constant voltage power source, DC 5V was applied to one dot of the organic EL element, and the presence or absence of the dark spot was visually observed using a loupe (magnification 8 times). Measurement was performed for all 70 dots (light emitting area), and the dark spot generation ratio was calculated from the number of dots where dark spots were generated.
Evaluation rank of dark spot generation rate A: Occurrence rate 0% (no dark spots are generated)
○: Occurrence rate 1% or more and less than 5% △: Occurrence rate 5% or more and less than 20% ×: Occurrence rate 20% or more and less than 50% XX: Occurrence rate 50% or more

  The effectiveness of the present invention was confirmed.

Example 2
<Preparation of organic EL elements>
The same material as in Example 1 was used, and an organic EL element having the same configuration was prepared.

<Cleaning of organic EL elements>
The surface to which the flexible sealing member of the prepared organic EL element is bonded is organic EL element under the cleaning conditions as shown in Table 5 in the cleaning apparatus shown in FIG. 5 of the first supply step of the manufacturing apparatus shown in FIG. The surface (side on which the sealing member is pasted) was washed and No. 2-A to 2-C. Moreover, the organic EL element which does not wash | clean the surface (side which bonds a sealing member) of an organic EL element is prepared, and No. 2-D.
The number of foreign matters having a particle diameter of 1 μm or more on the surface of the organic EL element was measured by the following method.

Number of foreign objects Five 1 cm ² surfaces of the organic EL element were randomly selected, and foreign objects having a particle diameter of 1 μm or more were counted by dark field observation using a metal microscope (Olympus BX61). The average value of five locations was taken as the number of foreign matters.

  In addition, an angle shows the spray angle of the gas with respect to the surface of the organic EL element on the mounting base of the nozzle of a washing | cleaning apparatus.

(Adhesive placement on the surface of the organic EL element and cleaning of the adhesive surface)
In the adhesive placement apparatus in the manufacturing process shown in FIG. 4, an ultraviolet curable liquid adhesive (ThreeBond 3124C, manufactured by Three Bond Co., Ltd.) was used, and the prepared organic EL element No. After the surface of 1-A to 1-D is arranged to a thickness of 50 μm by the screen printing method, the surface of the adhesive is cleaned under the cleaning conditions shown in Table 6 with a cleaning device provided after the adhesive placement device. No. 2-a to 2-e. Also, a flexible sealing member that does not clean the surface of the adhesive is prepared. 2-f to 2-h. The number of foreign matters having a particle size of 1 μm or more adhering to the surface of the adhesive was measured by the same method as that for the surface of the organic EL element. In addition, an angle shows the spray angle of the gas with respect to the surface of the adhesive agent on the mounting base of the nozzle of a washing | cleaning apparatus.

(Cleaning of sealing member)
As shown in Table 7, a flexible sealing member having a configuration of PET 120 μm / adhesive 5 μm / Al foil 20 μm is prepared and the cleaning device shown in FIG. 6 in the second supply step of the manufacturing apparatus shown in FIG. 4 is used. Clean the surface of the flexible sealing member under various cleaning conditions. 2-1 to 2-3. In addition, a flexible sealing member that is not cleaned is prepared. 2-4. The water vapor permeability of the used flexible sealing member measured by the MOCON method mainly in accordance with JIS K7129B 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.

  The number of foreign matters having a particle diameter of 1 μm or more on the surface of the flexible sealing member was measured by the same method as the organic EL element.

  In addition, an angle shows the spray angle of the gas with respect to the surface of the sealing member on the mounting base of the nozzle of a washing | cleaning apparatus.

<Adhesive sealing of organic EL element by flexible sealing member>
In the bonding process of the manufacturing apparatus shown in FIG. 4, the prepared adhesive-adjusted organic EL elements 2-a to 2-h and the prepared flexible sealing members No. 2-1 to 2-4 were combined and bonded as shown in Table 8 to produce a sealed organic EL panel. 201-232. Bonding is performed by pressing with a pressing force of 0.1 MPa under a reduced pressure environment of 1 × 10 ⁻² Pa, and irradiation with ultraviolet light having a dominant wavelength of 365 nm from the flexible sealing member side (90 sec at 100 mW / cm ² ). Curing treatment was performed. In addition, the bonding process was performed in an environment of cleanliness class 1000 (US Federal Standard 209D) or less.
(Evaluation)
Each prepared sample No. Table 8 shows the results of evaluating the occurrence ratio of dark spots (spot-like non-light emitting portions) in 201 to 232 by the same test method as in Example 1 and evaluating according to the same evaluation rank as in Example 1.
Dark spot generation rate test method

  The effectiveness of the present invention was confirmed.

Example 3
Sample No. 2 of Example 2 The process which changed the cleanliness of the bonding process as shown in Table 9 in the bonding process of the manufacturing apparatus shown in FIG. 4 with the prepared organic EL element and the prepared flexible sealing member when producing 208. An organic EL element bonded and sealed in an environment was prepared. 301 to 303. Bonding is performed by pressing with a pressing force of 0.1 MPa under a reduced pressure environment of 1 × 10 ⁻² Pa, and irradiation with ultraviolet light having a dominant wavelength of 365 nm from the flexible sealing member side (90 sec at 100 mW / cm ² ). Curing treatment was performed.
(Evaluation)
Each prepared sample No. Table 5 shows the results of the evaluation of the dark spot generation ratios 301 to 303 by the same test method as in Example 1 and the evaluation according to the same evaluation rank as in Example 1.

  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 EL element. It is an expansion schematic sectional drawing of the part shown by T of FIG. It is a schematic diagram of the manufacturing process of the organic EL element tightly sealed by the sealing member. It is a schematic diagram of the other manufacturing process of the organic EL element tightly sealed by the sealing member. FIG. 4 is an enlarged schematic view of the cleaning device in the first supply process shown in FIG. 3. FIG. 4 is an enlarged schematic view of the cleaning device in the second supply step shown in FIG. 3.

Explanation of symbols

1 Organic EL Panel 101 Substrate 102 Anode Layer 103 Hole Transport Layer (Hole Injection Layer)
104 Organic compound layer (light emitting layer)
105 Electron injection layer 106 Cathode layer 107 Adhesive layer 108, 201a, 302a Sealing member 108a Resin substrate 108b Gas barrier layer 2, 3 Manufacturing process 201, 302 First supply process 202, 301 Second supply process 202a, 301a Organic EL Element 203, 303 Adhesive arrangement process 204, 304 Bonding process 205, 305 Recovery process 206a-206c, 306a-306c Cleaning process 206a1, 206b1 Cleaning device 206a14, 206b14 Header 206a15, 206b15 Nozzle

Claims (13)

An adhesion sealing structure in which an organic electroluminescence element having a first electrode, at least one organic compound layer including a light-emitting layer, and a second electrode is bonded on a substrate with an adhesive interposed therebetween. In the manufacturing method of the organic electroluminescence panel forming
A first supply step for supplying the sealing member; a second supply step for supplying the organic electroluminescence element; an arrangement step for the adhesive; and the sealing member and the organic electroluminescence element. Having a manufacturing process having a bonding step and a recovery step for bonding via
The manufacturing apparatus includes at least one cleaning step between the first supply step or the second supply step and the bonding step,
In the cleaning step, the adhesive placement surface of the sealing member, the adhesive bonding surface placed on the sealing member or the organic electroluminescence element, and the adhesive placement of the organic electroluminescence element. By cleaning one of the surfaces,
After the bonding of the organic electroluminescent element and the sealing member in the bonding step, the bonding surface of the sealing member and the adhesive, the layer of the adhesive, the adhesive and the organic electro The manufacturing method of the organic electroluminescent panel characterized by making the number of the foreign materials with a particle size of 1 micrometer or more mixed into any of the bonding surfaces with a luminescence element into 100 pieces / cm < ² > or less. The cleaning step is arranged between the first supply step and the arrangement step, and the adhesive arrangement surface of the sealing member or the surface of the adhesive arranged on the organic electroluminescence element is washed. The manufacturing method of the organic electroluminescent panel of Claim 1. The cleaning step is disposed between the placement step and the second supply step, and cleans the adhesive bonding surface of the sealing member or the adhesive placement surface of the organic electroluminescence element. The manufacturing method of the organic electroluminescent panel of Claim 1 or 2 characterized by the above-mentioned. The said washing | cleaning process is arrange | positioned between the 2nd supply process and the bonding process, and wash | cleans the surface of the adhesive agent arrange | positioned at an organic electroluminescent element. The manufacturing method of the organic electroluminescent panel of description. The said washing | cleaning process is arrange | positioned between the 1st supply process and the bonding process, and wash | cleans the surface of the adhesive agent arrange | positioned at the sealing member. The manufacturing method of the organic electroluminescent panel of description. The method for producing an organic electroluminescence panel according to any one of claims 1 to 5, wherein the bonding step is an environment having a cleanness class of 1000 (US Federal Standard 209D) or less. 7. The organic electro of claim 1, wherein the substrate and / or the sealing member is a flexible sealing member having a resin base material and a gas barrier layer. Manufacturing method of luminescence panel. The method for producing an organic electroluminescence panel according to any one of claims 1 to 6, wherein the substrate and / or the sealing member is a glass plate. The method for producing an organic electroluminescence panel according to any one of claims 1 to 6, wherein the substrate and / or the sealing member is a metal sheet. Organic electroluminescence in which an organic electroluminescence element having a first electrode, at least one organic compound layer including a light-emitting layer, and a second electrode on a substrate is tightly sealed with a sealing member via an adhesive layer In the panel,
The number of foreign matters having a particle diameter of 1 μm or more mixed in any of the bonding surface of the sealing member, the adhesive layer, or the bonding surface of the organic electroluminescence element is 100 / cm ² or less. An organic electroluminescence panel characterized by that. The organic electroluminescence panel according to claim 10, wherein the substrate and / or the sealing member is a flexible member having a resin base material and a gas barrier layer. The organic electroluminescence panel according to claim 10, wherein the substrate and / or the sealing member is made of glass. The organic electroluminescence panel according to claim 10, wherein the substrate and / or the sealing member is a metal sheet.

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