WO2006100889A1 - Method for forming organic el layer - Google Patents
Method for forming organic el layer Download PDFInfo
- Publication number
- WO2006100889A1 WO2006100889A1 PCT/JP2006/304063 JP2006304063W WO2006100889A1 WO 2006100889 A1 WO2006100889 A1 WO 2006100889A1 JP 2006304063 W JP2006304063 W JP 2006304063W WO 2006100889 A1 WO2006100889 A1 WO 2006100889A1
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- WO
- WIPO (PCT)
- Prior art keywords
- layer
- organic
- coating
- forming
- unit
- Prior art date
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- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 1
- KCNSDMPZCKLTQP-UHFFFAOYSA-N tetraphenylen-1-ol Chemical compound C12=CC=CC=C2C2=CC=CC=C2C2=CC=CC=C2C2=C1C=CC=C2O KCNSDMPZCKLTQP-UHFFFAOYSA-N 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- IBBLKSWSCDAPIF-UHFFFAOYSA-N thiopyran Chemical compound S1C=CC=C=C1 IBBLKSWSCDAPIF-UHFFFAOYSA-N 0.000 description 1
- RPVGLMKJGQMQSN-UHFFFAOYSA-N tiliquinol Chemical compound C1=CC=C2C(C)=CC=C(O)C2=N1 RPVGLMKJGQMQSN-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 125000006617 triphenylamine group Chemical group 0.000 description 1
- 238000004402 ultra-violet photoelectron spectroscopy Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/50—Forming devices by joining two substrates together, e.g. lamination techniques
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/301—Details of OLEDs
- H10K2102/311—Flexible OLED
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/805—Electrodes
- H10K59/8051—Anodes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/87—Passivation; Containers; Encapsulations
- H10K59/873—Encapsulations
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
Definitions
- the present invention relates to a method for forming an organic EL layer of an organic EL (electral luminance) element used as a surface light source, a display panel, or the like.
- the organic EL element includes a first electrode (anode or cathode) formed on a substrate, an organic EL layer having an organic compound layer including a light emitting layer stacked thereon, and a layer stacked on the light emitting layer. It is a thin film type element having a second electrode (cathode or anode).
- a voltage is applied to such an organic EL element, electrons are injected from the cathode into the organic EL layer and holes are injected from the cathode. 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.
- the organic EL element is a thin film type element
- a surface light source such as a backlight.
- a display device is configured by 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, it is highly visible and has no viewing angle dependency. There are advantages that cannot be obtained with the device.
- JP-A-9-102393 and JP-A-2002-170676 when forming an organic EL layer of an organic EL element, as described in JP-A-9-102393 and JP-A-2002-170676, vapor deposition, sputtering, CVD, Various methods such as PVD and solvent coating can be used. Among these methods, the manufacturing process is simplified, the manufacturing cost is reduced, the workability is improved, and the backlight and illumination light source are flexible. It is known that a wet film forming method such as a coating method is advantageous from the viewpoint of application to a large area device.
- JP 2002-170676 discloses a single wafer glass substrate. A method for forming an organic compound layer on a plate by spin coating is described. Japanese Patent Application Laid-Open No.
- 2003-142260 describes a method of sequentially forming an organic compound layer on a single wafer substrate by an ink jet method.
- Each of these methods uses a single-wafer substrate as a substrate, so there is a limit to increasing production efficiency. From these situations, use a roll-shaped substrate that is highly likely to increase production efficiency, and then form various layers that make up the organic EL element on the substrate. Manufacturing methods (roll-to-roll method) are being studied.
- a method is known in which a roll-like long film is supplied and a light-emitting layer is formed on the film while being conveyed by a wet coating method, and then wound into a rolled core.
- Patent Document 1 As a method of manufacturing an organic EL display using a plastic film as a light-transmitting substrate, a cathode, one or a plurality of light-emitting layers made of an organic material, and an anode layer on the plastic film, an organic material is used.
- a method of producing a pattern of one or a plurality of light-emitting layers and patterning a cathode by a vacuum and a single roll method by vapor deposition under vacuum see, for example, Patent Document 2.
- Patent Document 1 JP-A-10-77467
- Patent Document 2 Pamphlet of International Publication No. 01/5194
- the present invention has been made in view of the above situation, and an object thereof is to provide a method of forming an organic EL layer for a high-quality organic EL element with high productivity.
- An organic EL element having an anode layer including at least a first electrode, an organic EL layer including an organic compound layer including a light emitting layer, and a cathode layer including a second electrode in this order on a strip-shaped flexible support.
- the organic EL layer is formed using a manufacturing apparatus having a supply unit, a pattern coating and drying unit for forming the light emitting layer on the anode layer, and a recovery unit.
- the supply section is supplied with a strip-shaped flexible support A on which an anode layer including at least a first electrode is formed in a roll state, and includes a first accumulator section before the pattern coating and drying section, and a second accumulator section later.
- the accumulator section, and the pattern coating / drying section includes a pattern coating section for forming a coating film for forming a light emitting layer under atmospheric pressure conditions using a wet pattern forming coating apparatus with a coating liquid for forming an organic EL layer.
- Solvent in the organic EL layer under atmospheric pressure conditions 1 unit of the organic EL layer drying unit for forming the organic EL layer, and the pattern coating / drying unit has at least one unit of the pattern coating / drying unit, and the pattern coating / drying unit Then, the organic EL layer is formed on the anode layer to form a strip-like flexible support B, and the recovery unit forms a winding roll on the winding core.
- the wet pattern formation coating apparatus operates in response to the intermittent conveyance of the strip-shaped flexible support A, operates when the strip-shaped flexible support A is stopped, and performs pattern formation coating.
- the method for forming an organic EL layer according to any one of claims 1 to 3, wherein:
- the said pattern application part has the holding means of a strip
- the wet coating / drying unit applies a coating solution for forming an organic compound layer by a wet coating apparatus to form an organic compound layer under atmospheric pressure conditions and a solvent in the organic compound layer by applying the organic compound layer under atmospheric pressure conditions.
- a coating solution for forming an organic compound layer by a wet coating apparatus to form an organic compound layer under atmospheric pressure conditions and a solvent in the organic compound layer by applying the organic compound layer under atmospheric pressure conditions.
- the organic EL layer and the organic compound layer have a dew point temperature of 20 ° C. or less and conformity with JISB 9920, and the measured cleanliness is class 5 or less, and the organic EL layer drying unit, the organic compound layer drying unit, The method for forming an organic EL layer according to any one of claims 1 to 12, wherein the organic EL layer is formed in an atmospheric pressure of 10 to 45 ° C except for a heat treatment portion.
- a method of forming an organic EL layer for a high-quality organic EL element with high productivity can be provided, and a stable organic EL element can be produced.
- FIG. 1 is a schematic cross-sectional view showing an example of a layer structure of an organic EL element.
- FIG. 2 is a schematic view of a manufacturing apparatus having a pattern application / drying unit for forming layers up to an organic EL layer.
- FIG. 3 is an enlarged schematic view of a portion indicated by P in FIG.
- FIG. 4 is a schematic view of a manufacturing apparatus having a wet coating 'drying unit and a pattern coating' drying unit that form up to an organic EL layer.
- FIG. 5 is a schematic diagram of a manufacturing apparatus having a wet coating / drying section before and after a pattern coating / drying section for forming an organic EL layer.
- FIG. 6 is an enlarged schematic plan view of a portion indicated by Q in FIG. Explanation of symbols
- Electron injection layer (electron transport layer)
- Embodiments according to the present invention will be described with reference to FIGS. 1 to 6, but the present invention is not limited thereto.
- FIG. 1 is a schematic cross-sectional view showing an example of the layer structure of an organic EL element.
- FIG. 1 (a) is a schematic cross-sectional view showing the constituent layers of an organic EL element on which a sealing film is formed.
- FIG. 1 (b) is a schematic cross-sectional view showing the constituent layers of an organic EL element formed by adhering a sealing film via an adhesive.
- the layer structure of the organic EL element shown in Fig. 1 (a) will be described.
- la indicates the organic EL element.
- the organic EL element la includes a first electrode (anode) 102, a hole transport layer 103, a light emitting layer 104, an electron injection layer 105, a second electrode (cathode) 106, and a sealing material on a substrate 101. It has a stop layer 107 in this order.
- lb represents an organic EL device.
- the organic EL element lb is formed on a substrate 101 with a first electrode (anode) 102, a hole transport layer (hole injection layer) 103, a light emitting layer 104, an electron injection layer 105, and a second electrode (cathode). ) 106, an adhesive layer 108, and a sealing film 109 are provided in this order.
- a hole injection layer (not shown) may be provided between the first electrode (anode) 102 and the light emitting layer 104 or the hole transport layer 103.
- an electron transport layer may be provided between the second electrode (cathode) 106 and the light emitting layer 104 or the electron injection layer 105.
- a gas barrier film (not shown) between the anode (first electrode) 102 and the substrate 101.
- the present invention relates to a method for forming the light emitting layer 104 shown in the figure.
- the layer structure of the organic EL element shown in this figure is an example, but other typical organic EL elements Examples of the layer structure include the following structures.
- the organic EL layer means a layer structure sandwiched between an anode and a cathode in the layer structure shown in FIG. Each layer constituting the organic EL element will be described later.
- FIG. 2 is a schematic diagram of a manufacturing apparatus having a pattern coating / drying unit for forming layers up to the organic EL layer.
- the following is a method for forming an organic EL layer having a hole transport layer, a light-emitting layer, and an electron transport layer on a strip-shaped flexible support having a first electrode that is patterned and formed as an example. This will be described with reference to the drawings.
- reference numeral 2 denotes a manufacturing apparatus for forming up to the organic EL layer, which is one of the constituent layers of the organic EL element, under atmospheric pressure conditions.
- the manufacturing apparatus 2 includes a supply unit 201, a cleaning surface modification processing unit 202 for a strip-shaped flexible support, a first charge removal processing unit 203, a first accumulator unit 204, a pattern coating / drying unit 205, The heat treatment unit 206, the second static elimination processing unit 207, the second accumulator 208, and the recovery unit B209 are provided.
- the strip-shaped flexible support A201a in which the gas barrier film and the anode layer including the first electrode are already formed in this order is wound around the winding core and supplied in a roll state. It has become.
- 201b shows a strip-like flexible support A201a in a roll state.
- the first electrode (see FIGS. 1 and 6) is formed by patterning (see FIG. 6).
- the cleaning surface modification processing unit 202 includes an anode layer (not shown) including the first electrode of the strip-shaped flexible support A201a sent from the supply unit 201 before being applied by the pattern application / drying unit 205. ) It has cleaning surface modification processing means 202a for cleaning and modifying the surface.
- the cleaning surface modification means 202a include a low-pressure mercury lamp, an excimer lamp, a plasma cleaning apparatus, and the like.
- the conditions for cleaning surface modification with a low-pressure mercury lamp include, for example, wavelength 184.
- the condition for performing the cleaning surface modification treatment by irradiating a 2 nm low-pressure mercury lamp with an irradiation intensity of 5 to 20 mW / cm 2 and a distance of 5 to 15 mm is mentioned.
- atmospheric pressure plasma is preferably used as a condition for the cleaning surface modification treatment by the plasma cleaning apparatus.
- cleaning conditions argon gas containing 1 to 5% by volume of oxygen is used, and cleaning surface modification treatment is performed at a frequency of 100 KHz to 150 MHz, a voltage of 10 V to 10 KV, and an irradiation distance of 5 to 20 mm.
- Examples of the charge removal processing means used in the first charge removal processing unit 203 include a light irradiation method, a corona discharge method, and the like, and these can be appropriately selected and used as necessary.
- Light irradiation type generates weak ions
- corona discharge type generates air ions by corona discharge. The air ions are attracted to the charged object to compensate for the opposite polarity charge and neutralize the static electricity.
- a static eliminator using corona discharge and a static eliminator using soft X-rays can be used. Since the first charge removal processing section removes the charge of the base material, the adhesion of the dust and the dielectric breakdown are prevented, thereby improving the yield of the element.
- the first accumulator unit 204 moves the roll 204a in the vertical direction (in the direction of the arrow in the figure), and the conveyance speed and pattern application of the belt-like flexible support A201a conveyed from the supply unit 201. It is arranged to adjust the difference from the pattern application speed of the drying unit 205, and has a function of accumulating a belt-like flexible support A201a of a certain length, before and after the first accumulator unit 204. It has become possible to change the operation of the strip-shaped flexible support A201a.
- the roll length 204a can be adjusted according to the speed difference.
- the roll 204a is preferably a non-contact roll capable of transporting the layer forming surface in a non-contact manner.
- the pattern coating / drying unit 205 shown in the figure includes a pattern coating unit that forms a light emitting layer under an atmospheric pressure condition by using a wet pattern formation coating apparatus with an organic EL layer forming coating solution, and an atmospheric pressure condition.
- the organic EL layer drying section that removes the solvent in the organic EL layer and forms the organic EL layer is provided as one unit.
- This figure shows the case of having 3 units (first pattern application / drying unit 205a, second pattern application 'drying unit 205b, and third pattern application' drying unit 205c). All have the same configuration.
- the coating liquid for forming an organic EL layer refers to a coating liquid for forming a hole transport layer, a coating liquid for forming a light emitting layer, and a coating liquid for forming an electron transport layer.
- the first pattern application 'drying unit 205a is a first pattern coating unit 205al that forms a hole transport layer under atmospheric pressure conditions by a wet pattern formation coating apparatus using a hole transport layer forming coating solution 205a, and under atmospheric pressure conditions.
- the second pattern coating / drying unit 205b includes a second pattern coating unit 205bl that forms a coating film for forming a light emitting layer under atmospheric pressure conditions by using a wet pattern forming coating apparatus with a coating solution for forming a light emitting layer. And a light emitting layer drying section 205b 2 for removing the solvent in the light emitting layer and forming the light emitting layer.
- the third pattern coating / drying unit 205b includes a second pattern coating unit 205bl that forms an electron transport layer under an atmospheric pressure condition by a wet pattern formation coating apparatus using an electron transport layer forming coating solution, and an electron under an atmospheric pressure condition. It has an electron transport layer drying section 205c2 that removes the solvent in the transport layer and forms an electron transport layer.
- the first pattern application unit 205al includes a wet pattern formation application device 205al l and a holding table 205al 2 which is a means for holding the belt-like flexible support A.
- the second pattern coating unit 205 bl is a holding means for holding a belt-like flexible support formed with a wet pattern formation coating device 205 bl l and a hole transport layer sent from the first pattern coating and drying unit 205 a. It has 20 5bl 2 pedestals.
- the third pattern applicator 205cl is a wet pattern forming applicator 205cl and a second pattern applicator, a holder 205cl that is a means for holding the belt-like flexible support on which the light emitting layer sent from the dryer 205b is formed. And 2.
- the heat treatment unit 206 includes a heat treatment unit 206a provided on the rear side of the hole transport layer drying unit 205a2, a heat treatment unit 206b provided on the rear side of the light emitting layer drying unit 205b2, and a hole transport layer drying unit.
- a heat treatment unit 206c provided on the rear side of the unit 205c2.
- the belt-like flexible support is kept flat.
- a suction table may be used as long as it can be fixed.
- the suction table include a mechanism having a suction hole on the table, a mechanism having a porous surface on which the table is placed, and a table that electrostatically attracts, and can be appropriately selected and used.
- a table having a mechanism in which the mounting surface is porous is used.
- the first pattern application / drying unit 205a fixes the band-shaped flexible support A201a conveyed from the supply unit 201 on the holding base 205al 2 and uses the wet pattern formation coating apparatus 205al 1 to
- the hole transport layer forming coating solution is applied to the region excluding the end of the first electrode formed on the flexible support A201a, and the solvent in the hole transport layer is removed from the hole transport layer drying unit 20
- the hole transport layer 201c is formed by removing with 5a2.
- the formed hole transport layer 201c is subjected to heat treatment by the heat treatment unit 206a.
- the first pattern coating is provided on the belt-like flexible support A on which the first electrode conveyed from the previous step is formed.
- Alignment mark 4 (see FIG. 6) is detected by the detector of the alignment detection means arranged in the first pattern application unit 205al, and the belt-like flexible support A is adsorbed and fixed on the holding table.
- the wet pattern formation coating device 205al l is aligned according to the alignment mark, and the hole layer formation coating is applied to the region of the first electrode except a part of the end portion of the patterned first electrode. The liquid is applied on the electrode.
- the second pattern coating / drying unit 205b fixes the belt-like flexible support on which the hole transport layer 201c conveyed from the first pattern coating / drying unit 205a is formed on the holding table 205bl2. Then, using a wet pattern formation coating apparatus 205bl l, the coating solution for forming the light emitting layer is applied to the pattern of the first electrode, applied onto the formed hole transport layer 201c, and the solvent in the light emitting layer is removed from the light emitting layer drying unit 205b2 To remove the light emitting layer 201d. The formed light emitting layer is subjected to heat treatment by the heat treatment unit 206b.
- the third pattern coating / drying unit 205c fixes the belt-like flexible support on which the light emitting layer 201d conveyed from the second pattern coating / drying unit 205b is formed on the holding table 205cl2, and performs wet processing.
- the electron transport layer 201d is applied onto the light emitting layer 201d on which the electron transport layer forming coating solution has been formed by using a pattern forming coating device 205cl1, and the solvent in the electron transport layer is removed by the electron transport layer drying unit 205c2 to remove the electron transport layer 201e.
- the formed electron transport layer is subjected to a calorie heat treatment in the heat treatment unit 206c.
- the previous process force is provided on the belt-like flexible support A on which the light emitting layer is formed.
- Alignment mark 4 (see Fig. 6) is detected by the detector of the alignment detection means arranged in the third pattern application section 205cl, and the strip-shaped flexible support A with the light emitting layer formed on the holding table
- the wet pattern formation coating apparatus 205cll is aligned according to the alignment mark, and the electron transport layer forming coating solution is applied onto the light emitting layer.
- the first pattern coating / drying unit 205a to the third pattern coating 'drying unit 205c have the hole transport layer 201c, the light emitting layer 201d, and the electron transport layer 201e except for the end of the first electrode.
- a belt-like flexible support B on which an organic EL layer is formed is completed.
- the first pattern application unit 205al to the third pattern application unit 205cl are all applied while being adsorbed and fixed to the holding base, so that the hole transport layer is formed from the first pattern application / drying unit 205a.
- the moving from the drying unit 205 to the collecting unit 209 is performed after the application of each layer is formed in each unit, and thus is intermittent.
- Examples of wet coaters that can be used in the wet pattern forming and coating apparatus 205al l include an inkjet method, a flexographic printing method, an offset printing method, a gravure printing method, a screen printing method, and a mask.
- the use of these wet pattern forming coating machines is the light emitting layer type It is possible to select appropriately according to the material of the composition coating liquid. This figure shows the ink jet method.
- the second static elimination processing unit 207 performs static elimination on the belt-like flexible support having the electron transport layer 201e formed by the third pattern coating / drying unit 205c, and prevents failure due to static electricity in the next process. It has a function to stop and can be arranged as necessary.
- the second static elimination processing unit 207 preferably uses the same static elimination processing means as that used for the first static elimination processing unit 203.
- the second accumulator unit 208 moves the roll 208a in the vertical direction (the direction of the arrow in the figure). It is arranged to adjust the difference in transport speed between the pattern coating / drying unit 205 and the wet coating / drying unit (not shown), and the roll 208a can be added according to the speed difference.
- the second accumulator unit 208 is intermittently conveyed in a state where the belt-like flexible support is stopped in the pattern application / drying unit 205, so that a certain amount is accumulated in the second accumulator unit 208 and collected in the recovery unit 209. It is also possible to use it in a method of scraping off the amount continuously.
- the second accumulator unit 208 preferably has the same function as the first accumulator unit 204 and has the same configuration.
- a strip-shaped flexible support B201f processed by the second static elimination processing unit 207 and having an organic EL layer formed thereon is wound around a winding core as a strip-shaped flexible support B201g in a roll state. It is collected and stored until it is sent to the next process for forming the electron injection layer, the second electrode, the sealing layer and the like.
- FIG. 3 is an enlarged schematic view of a portion indicated by P in FIG.
- the strip-shaped flexible support B on which the organic EL layer is formed is cooled to room temperature with a cooling device (not shown) and then scraped off.
- the light-emitting layer drying unit 205b2 includes a drying air supply header 205b23 having a discharge port 205b21 for discharging a drying air, a drying air supply port 205b22, a non-air opening 205b24, and a transport ronole 205b25. And then sing.
- the heat treatment unit 206b includes a heat treatment apparatus main body 206bl and a back surface of a belt-like flexible support having a light emitting layer 201d formed on the hole transport layer 201d in accordance with the pattern of the first electrode.
- the heat treatment unit 206b has a function of further stabilizing the hole transport layer by heat treatment.
- the hole transport layer drying unit 205a2 and the heat treatment unit 206a and the electron transport layer drying unit 205c2 and the heat treatment unit 206c shown in FIG. 2 have the same structure as the light emitting layer drying unit 205b2 and the heat treatment unit 206b shown in FIG. Have the same function.
- FIG. 4 is a schematic view of a manufacturing apparatus having a wet coating / drying unit and a pattern coating / drying unit for forming layers up to the organic EL layer.
- the following is a method for forming an organic EL layer having a hole transport layer, a light-emitting layer, and an electron transport layer on a strip-like flexible support having a first electrode that is patterned and formed as an example. I will explain it.
- reference numeral 3 denotes a manufacturing apparatus for forming up to the organic EL layer, which is one of the constituent layers of the organic EL element, under atmospheric pressure conditions.
- the production apparatus 3 includes a supply unit 301, a cleaning surface modification processing unit 302 for the strip-shaped flexible support, a static elimination processing unit A303, a wet coating / drying unit 304, a static elimination processing unit B3 05, and a first accumulator.
- the strip-shaped flexible support A301a in which the gas barrier film and the anode layer including the first electrode are already formed in this order is wound around the winding core and supplied in a roll state. It has become.
- 301b shows the roll-shaped flexible support A301a in a roll state.
- the first electrode (see FIGS. 1 and 6) is formed by patterning (see FIGS. 1 and 6).
- the cleaning surface modification processing unit 302 is an anode layer (not shown) including the first electrode of the strip-shaped flexible support A301a that has been fed by the supply unit 301 before being applied by the wet application / drying unit 304. And cleaning surface modification processing means 302a for cleaning and modifying the surface.
- the cleaning surface modification processing means 302a is the same as the cleaning surface modification processing means 202a shown in FIG. 2, has the same function, and can perform the cleaning surface modification processing under the same conditions.
- the static elimination processing unit A303 has a function of removing static electricity from the belt-like flexible support A301a processed by the cleaning surface modification processing unit 302, and preventing a failure due to static electricity in the next process, It can be installed as needed.
- the static elimination processing unit A303 has the same static elimination processing means as the first static elimination processing unit 203 shown in FIG. 2, and has the same function.
- the wet coating / drying unit 304 has a backup roll 304a for holding the strip-shaped flexible support A301a and a belt on the strip-shaped flexible support A301a held by the backup roll 304a. Formed on the first electrode on the strip-shaped flexible support A301a and the wet coating machine 304b that applies the coating solution for forming the hole transport layer to the first electrode formed by turning under atmospheric pressure conditions And a hole transport layer drying section 304c for removing the solvent in the hole transport layer 301c under atmospheric pressure.
- Examples of the wet coater that can be used for the wet coater 304b include a die coating method, a screen printing method, a flexographic printing method, a Mayer bar method, a cap coating method, a spray coating method, a casting method, a roll coating method, It is possible to use a coating machine such as bar coating or gravure coating.
- the use of these wet coaters can be appropriately selected according to the material of the organic compound layer forming coating liquid organic compound layer.
- the heat treatment unit 308 includes a heat treatment unit 308a disposed after the hole transport layer drying unit 304c, a heat treatment unit 308b disposed after the light emitting layer drying unit 307a2, and an electron transport layer drying unit.
- the heat treatment unit 308c is disposed after the drying unit 307b2, and all have the same structure.
- the heat treatment unit 308a heat-treats from the back surface side of the belt-shaped flexible support having the hole transport layer 301d formed by the hole transport layer drying unit 304c by the back surface heat transfer method, and further stabilizes it. It is preferable to dispose as necessary.
- the heat treatment unit 308b heat-treats from the back side of the belt-like flexible support having the light emitting layer 201e formed by the light emitting layer drying unit 307al by the back surface heat transfer method, and further stabilizes the light emitting layer 20 le. It is preferable to dispose as necessary.
- the heat treatment unit 308c is heat-treated by the back surface heat transfer method from the back side of the belt-like flexible support having the electron transport layer 201f formed by the electron transport layer drying unit 307bl, and is further stabilized by the electron transport layer. It has a function of 20 mm and is preferably disposed as necessary.
- the first accumulator unit 306 adjusts the difference in the conveyance speed between the wet coating 'drying unit 304 and the pattern coating' drying unit 307 by moving the roll 306a in the vertical direction (the arrow direction in the figure).
- the roll 306a can be added according to the speed difference.
- the roll 306a is preferably a non-contact roll capable of transporting the hole transport layer surface in a non-contact manner.
- the pattern coating / drying unit 307 includes a pattern coating unit that forms a light emitting layer under a atmospheric pressure condition by using a wet pattern forming coating apparatus with a coating solution for forming a light emitting layer.
- the first pattern coating / drying unit 307a with the drying unit for removing the solvent as one unit, and the pattern coating unit for forming the electron transport layer under the atmospheric pressure condition by the wet pattern formation coating device using the coating liquid for forming the electron transport layer And an electron transport layer drying section that removes the solvent in the electron transport layer under atmospheric pressure conditions, and a second pattern application / drying section 307b.
- the first pattern application 'drying unit 307a and the second pattern application' drying unit 307b have the same configuration.
- the first pattern coating / drying unit 307a is a first pattern coating unit 307al that forms a light emitting layer under an atmospheric pressure condition by using a wet pattern forming coating apparatus with a light emitting layer forming coating solution. And a light emitting layer drying section 307a2 for removing the solvent.
- the second pattern coating / drying unit 307b includes a first pattern coating unit 307bl that forms an electron transport layer under an atmospheric pressure condition by a wet pattern formation coating apparatus using an electron transport layer forming coating solution, and an atmospheric pressure condition. And an electron transport layer drying section 307b2 for removing the solvent in the electron transport layer.
- the static elimination processing section B has a function of performing static elimination on the band-shaped flexible support having the hole transport layer 301d formed by the wet coating / drying section 304 and preventing a failure due to static electricity in the next process. And can be arranged as necessary.
- the first pattern application unit 307al has a wet pattern formation application device 307al and a holding table 307al 2 which is a holding means for the strip-shaped flexible support A on which the hole transport layer is formed.
- the second pattern coating unit 307bl includes a wet pattern formation coating device 307bl and a holding base that is a holding means for the belt-like flexible support A on which the light emitting layer sent from the first pattern coating and drying unit 307a is formed. 307bl 2.
- the first pattern application unit 307al and the second pattern application unit 307bl include alignment detection means (see Fig. 6) and application position correction control means (Fig. 6).
- the holding table 307al 2 (307bl 2) is the same as the holding table shown in FIG.
- the first pattern coating / drying unit 307a fixes the belt-shaped flexible support A on which the hole transport layer transported from the wet coating / drying unit 304 is formed on the holding table 307al 2, and performs wet processing.
- a coating solution for forming a light emitting layer is applied onto the sending layer, and the solvent in the light emitting layer is removed by the light emitting layer drying unit 307a2 to form the light emitting layer 301e.
- the formed light emitting layer 301e is subjected to heat treatment in the heat treatment unit 308b.
- the wet pattern forming coating device 3 07 When coating is performed by the wet pattern forming coating device 3 07all in the first pattern coating 'drying unit 307a, it is provided on the belt-like flexible support A on which the hole transport layer to be transported is formed.
- the alignment mark 4 (see Fig. 6) is detected by the detector of the alignment detection means arranged in the first pattern application section 307al, and the belt-like flexible support A is adsorbed and fixed on the holding table.
- the wet pattern forming and coating device 307al l is aligned according to the alignment mark, and light emission is performed in accordance with the pattern of the first electrode except for a part of the end portion of the first electrode formed by patterning.
- a layer-forming coating solution is applied onto the electrode.
- the second pattern coating / drying unit 307b fixes the belt-shaped flexible support on which the light emitting layer 301e conveyed from the first pattern coating / drying unit 307a is formed on the holding table 307bl 2, and is wet.
- the pattern forming coating apparatus 307bl l applies the electron transport layer forming coating solution onto the light emitting layer 201d, and the solvent in the electron transport layer is removed by the electron transport layer drying unit 307b2 to remove the electron transport layer 301f. Form.
- the formed electron transport layer is subjected to heat treatment in the heat treatment unit 308c.
- the wet pattern forming coating device 3 07bl l in the second pattern coating / drying unit 307b When coating is performed by the wet pattern forming coating device 3 07bl l in the second pattern coating / drying unit 307b, it is provided on the belt-like flexible support A on which the light emitting layer conveyed from the previous step is formed.
- Alignment mark 4 (see Fig. 6) is detected by the detector of the alignment detection means arranged in the third pattern application section 307bl, and the strip-shaped flexible support A on which the light emitting layer is formed is placed on the holding table.
- the wet pattern formation coating device 307bl is aligned according to the alignment mark, and the electron transport layer forming coating solution is applied on the light emitting layer.
- a belt-like flexible support B having a layer formed thereon is completed.
- the wet pattern formation coating apparatus 307al l (307b 11) is the same as the wet pattern formation coating apparatus shown in FIG. This figure shows the case where an ink jet coating device is used.
- the static elimination processing unit C309 performs static elimination on the belt-like flexible support having the electron transport layer 30 If formed by the second pattern coating / drying unit 307b, and prevents a failure due to static electricity in the next process. It has a function and can be arranged as required. In addition, it is preferable to use the same static elimination processing means as the static elimination processing means used for the static elimination processing section A as the static elimination processing means used for the static elimination processing section B305 and the static elimination processing section C309.
- the second accumulator unit 309 is configured such that when a wet application / drying unit (not shown) is disposed after the second accumulator unit 308, the roll 208a moves in the vertical direction (the direction of the arrow in the figure). , Arranged to adjust the difference in transport speed between the pattern coating / drying unit 307 and the wet coating / drying unit (not shown), and the roll 31 la can be added according to the speed difference. .
- the second accumulator unit 311 is intermittently transported while the belt-like flexible support is stopped in the pattern application / drying unit 207, so that a certain amount is accumulated in the second accumulator unit 311 and collected in the collection unit 312. It is also possible to use it in a method of scraping off the amount continuously.
- the second accumulator unit 311 preferably has the same function as the first accumulator unit 306 and has the same configuration.
- the strip-shaped flexible support B301g which is processed by the static elimination processing unit C and formed with the organic EL layer, is wound around the winding core and collected as a rolled strip-shaped flexible support B301h. It is stored until it is sent to the next process for forming the electron injection layer, the second electrode, the sealing layer and the like.
- the belt-shaped flexible support B on which the organic EL layer is formed is cooled to room temperature with a cooling device (not shown) and then wound up.
- FIG. 5 is a schematic diagram of a manufacturing apparatus having a wet coating / drying unit before and after a pattern coating / drying unit for forming up to an organic EL layer.
- the following is a method for forming an organic EL layer having a hole transport layer, a light-emitting layer, and an electron transport layer on a strip-shaped flexible support having a first electrode that is patterned and formed as an example. I will explain it.
- the manufacturing apparatus 4 indicates the shape up to the organic EL layer, which is one of the constituent layers of the organic EL element, under atmospheric pressure conditions.
- the manufacturing apparatus to be formed is shown.
- the manufacturing apparatus 4 includes a supply unit 401, a belt-like flexible substrate cleaning surface modification processing unit 402, a static elimination processing unit a403, a first wet coating / drying unit 404, a heat processing unit 405, and a static elimination treatment.
- a processing unit d414 and a recovery unit 415 are provided.
- the manufacturing apparatus 4 shown in the figure includes a first wet application / drying unit 404 and a heat treatment unit 406 before the first accumulator unit 407, and a second wet application / drying unit 412 after the second accumulator unit 411. And a heat treatment unit 413 are provided.
- the strip-shaped flexible support A401a in which the gas barrier film and the anode layer including the first electrode are already formed in this order is wound around the winding core and supplied in a roll state. It has become.
- 401b shows the roll-shaped flexible support A401a in a roll state.
- the first electrode (see FIGS. 1 and 6) is formed by patterning (see FIGS. 1 and 6).
- the cleaning surface modification processing unit 402 has an anode layer (including a first electrode of the strip-shaped flexible support A401a sent from the supply unit 401 before being applied by the first wet coating / drying unit 404. (Not shown) cleaning surface modification processing means 402a for cleaning and modifying the surface.
- the neutralization processing unit a403 has a function of performing static neutralization of the belt-like flexible support A 401a processed by the cleaning surface modification processing unit 402, and preventing a failure due to static electricity in the next process. It can be arranged as necessary.
- the charge removal processing unit a403 has the same charge removal processing means as the first charge removal processing unit 203 shown in FIG. 2, and has the same function.
- the first wet coating / drying unit 404 is formed with a hole transport layer on the back-up opening 404a holding the strip-shaped flexible support A401a and the strip-shaped flexible support A401a held by the backup roll 404a.
- a transport layer drying section 405c For removing the solvent of the hole transport layer formed on the first electrode on the wet flexible coater 404b and the strip-shaped flexible support A401a under atmospheric pressure conditions.
- the wet coater 404b is the same as the wet coater 304b shown in FIG.
- the heat treatment unit 405 heat-treats from the back side of the belt-shaped flexible support A having the hole transport layer 401c formed by the hole transport layer drying unit 405c by the back surface heat transfer method, and further stabilizes the holes. It has a function of forming the transport layer 401 d and is preferably disposed as necessary.
- the static elimination processing unit b406 performs static elimination on the belt-shaped flexible support A on which the hole transport layer 40 Id formed in the first wet coating / drying unit is formed, and a failure caused by static electricity in the next process. It has a function to prevent this, and can be installed as necessary.
- the static elimination processing unit b406 preferably uses the same static elimination processing unit as that used in the first static elimination processing unit 203 shown in FIG.
- the first accumulator unit 407 adjusts the difference in transport speed between the wet coating / drying unit 404 and the pattern coating / drying unit 408 by moving the roll 407a in the vertical direction (the arrow direction in the figure).
- the roll 407a can be added according to the speed difference.
- the roll 406a is preferably a non-contact roll that can transport the hole transport layer surface in a non-contact manner.
- the first pattern application / drying unit 408 includes a pattern application unit 408a and a light emitting layer drying unit 408b.
- the pattern coating part 408a is a belt-shaped flexible support holding base 408a2 in which the hole transport layer 40 Id is formed, and a large amount of coating solution for forming the light emitting layer is formed on the hole transport layer 401d in accordance with the pattern of the first electrode.
- the light emitting layer drying unit 408b has a function of removing the solvent in the light emitting layer under atmospheric pressure conditions, and has the same configuration as the light emitting layer drying unit 205b2 shown in FIG.
- the holding table 408a2 is not particularly limited as long as the belt-like flexible support can be fixed while maintaining flatness, and it is preferable to use a holding table having the same structure as the holding table shown in FIG.
- the pattern is provided on the belt-like flexible support A on which the hole transport layer to be transported is formed.
- Alignment mark 4 (see Fig. 6) is detected by the detector of the alignment detection means arranged in the pattern application unit 408a, and the belt-like flexible support A on which the hole transport layer is formed is held on the holding base.
- Wet-fixed on top and forms wet pattern according to alignment mark.Applicator 408al is aligned and aligned with the pattern of the first electrode except for a part of the end of the first electrode formed by patterning. Then, the light emitting layer forming coating solution is applied onto the electrode.
- the heat treatment unit 409 heat-treats from the back side of the belt-like flexible support having the light-emitting layer 401e formed by the light-emitting layer drying unit 408b by a back-surface heat transfer method, thereby obtaining a more stable light-emitting layer. It has a function, and it is preferable to arrange as needed.
- the heat treatment unit 409 is shown in FIG. It has the same configuration as the heat treatment part 206b.
- the charge removal processing unit c410 has a function of removing charges from the belt-like flexible support on which the light emitting layer is formed, and preventing a failure caused by static electricity in the next step, and is disposed as necessary. Is becoming possible.
- the static elimination processing unit c410 preferably uses the same static elimination processing unit as the static elimination processing unit used in the first static elimination processing unit 203 shown in FIG.
- the second accumulator unit 411 adjusts the difference in conveyance speed between the pattern coating 'drying unit 408 and the wet coating' drying unit 412 by moving the roll 411a in the vertical direction (the arrow direction in the figure).
- the roll 411a can be added according to the speed difference.
- the second accumulator unit 411 has the same configuration as the first accumulator unit 407.
- the second wet coating / drying unit 412 is formed with a backup roll 412a holding the belt-like flexible support on which the light emitting layer 401e is formed, and a light emitting layer 40le held on the backup roll 412a.
- Wet coater 412b that coats the belt-shaped flexible support with a coating solution for forming an electron transport layer under atmospheric pressure, and an electron transport layer drying unit that removes the solvent of the formed electron transport layer under atmospheric pressure. 412c.
- the electron transport layer drying section 412c has the same configuration as the light emitting layer drying section 205b2 shown in FIG.
- the wet coater 412b is the same as the wet coater 304b shown in FIG.
- the heat treatment unit 413 heat-treats from the back side of the belt-like flexible support having the electron transport layer 401f formed by the electron transport layer drying unit 412c by the back surface heat transfer method, and further stabilizes the electron transport layer 40 If It is preferable to dispose as necessary.
- the heat treatment unit 413 has the same configuration as the heat treatment unit 206b shown in FIG.
- the static elimination processing unit d414 performs static elimination on the band-shaped flexible support having the electron transport layer 401f formed by the second wet coating / drying unit 412 and prevents a failure due to static electricity in the next process. And can be arranged as required.
- the static elimination processing unit d414 preferably uses the same static elimination processing means as that used in the first static elimination processing unit 203 shown in FIG.
- a strip-shaped flexible support B401g which is processed by the static elimination processing unit d414, and on which the organic EL layer is formed, is wound around the winding core as a rolled strip-shaped flexible support B401h. It is collected and stored until it is sent to the next process for forming the electron injection layer, the second electrode, the sealing layer and the like.
- the strip-shaped flexible support B on which the organic EL layer is formed is cooled to room temperature with a cooling device (not shown) and then wound up.
- the coating apparatus 4 shown in this figure is performed in a state where the coating of the light emitting layer forming coating solution in the pattern coating / drying unit 408 is stopped, and when the light emitting layer is completely coated, the next light emitting layer Intermittent conveyance is performed to apply the forming coating solution.
- the first wet application 'drying unit 404 the hole transport layer is continuously applied, and the first wet adjustment' drying unit 404 and the pattern application 'drying unit 408 adjust the speed difference.
- the accumulator section 407 is adjusted so that the required length can be stored.
- the second wet coating / drying unit 412 is continuously coated with an electron transport layer, and the second difference is that the speed difference between the pattern coating / drying unit 408 and the second wet coating / drying unit 412 is adjusted.
- the accumulator unit 411 is adjusted so that the required length can be stored.
- FIG. 6 is an enlarged schematic plan view of a portion indicated by Q in FIG.
- FIG. 6 (a) is an enlarged schematic plan view of the pattern application part indicated by Q in FIG.
- FIG. 6 (b) is an enlarged schematic plan view of the band-shaped flexible support in a state in which a hole transport layer is formed on the first electrode conveyed from the wet coating / drying unit.
- A shows a wet pattern forming coating apparatus for pattern coating of the blue light emitting layer forming coating liquid
- B shows a wet pattern forming coating apparatus for pattern coating of the green light emitting layer forming coating liquid
- C Shows a wet pattern forming coating apparatus for pattern coating the red light emitting layer forming coating liquid.
- a wet pattern forming coating apparatus 205bl is configured.
- Each of the wet pattern forming and coating apparatuses A to C shown in the figure shows a case where an ink jet head is used, and is hereinafter also simply referred to as a head.
- Reference numeral 205bl 3 denotes a stage to which the head 205bl 1 is attached, and the head 205bl ll is disposed on the stage 205bl3 so as to be movable in the width direction (arrow direction in the figure).
- 205 bl4 is a state in which the hole transport layer 201 c is formed on the first electrode 102 in the stage 205 bl 3.
- the stage to be mounted so as to be movable in the transport direction (arrow direction in the figure) of the belt-like flexible support is shown.
- the first electrode 102 is patterned on the strip-shaped flexible support 201m, and is provided in the longitudinal direction of the strip-shaped flexible support 201m continuously at regular intervals.
- each wet pattern forming coating apparatus A to C may be disposed independently, or each wet pattern forming coating apparatus A to C may be combined. It is preferable to select appropriately according to need.
- This figure shows a case where wet pattern forming and coating apparatuses A to C are arranged together.
- Alignment mark 4 is at least two places on the lower right end and upper left end (or upper right end and lower left end) of first electrode 102 with respect to the conveyance direction of strip-shaped flexible support A (the direction of the arrow in the figure). It is preferable from the relation of determining the position of the head 205bl. Of course, the alignment mark 4 may be provided on the lower right end, upper right end, left lower end, and left upper end of the first electrode 102.
- the hole transport layer 201c is formed by applying and drying the entire surface in the first pattern application / drying unit 205b (see FIG. 2), leaving the end 102a of the first electrode 102.
- An example of the detection device 3 is a CCD camera.
- the belt-like flexible support having the hole transport layer 201c, the stage 205bl3, the stage 205bl4, and the head 205bl1 are driven according to the detection information of the alignment mark 4 by the detection device 3 according to the detection information of the coating position correction (non- It can be controlled by (shown).
- FIG. 5 shows a process of applying a light emitting layer forming coating solution on the first electrode 102 arranged in a pattern according to the pattern of the first electrode 102 in the pattern application unit shown in FIG. Shown below when the manufacturing equipment is used.
- the alignment mark 4 provided on the first electrode 102 is detected by the detection device provided in the pattern coating / drying unit 408, whereby the belt-like flexible film having the hole transport layer 401d formed thereon is detected.
- the support is sucked and fixed onto the holding table 408a2.
- the stage 205bl 3 moves based on the information that the belt-like flexible support is sucked and fixed onto the holding table 408a2, and the position of the head is determined.
- the coating solution for forming the blue light emitting layer is applied from head A (see FIG. 6), and the coating solution for forming the green light emitting layer is applied from head B (see FIG. 6). Then, a red light emitting layer forming coating solution is applied onto the first electrode 102 from the head C (see FIG. 6). As the stage 205 bl3 moves in the width direction, each of the first electrodes 102 in which the blue light emitting layer forming coating liquid, the green light emitting layer forming coating liquid, and the red light emitting layer forming coating liquid are patterned is used. Applied to.
- the stage 205bl4 moves in the transport direction by the pitch of the first electrode 102, and is used for forming a blue light emitting layer in the same manner as S4.
- a coating solution, a green light emitting layer forming coating solution, and a red light emitting layer forming coating solution are applied to each of the patterned first electrodes 102.
- S4 and S5 are repeated until all of the patterned first electrodes 102 are coated with the blue light emitting layer forming coating solution, the green light emitting layer forming coating solution, and the red light emitting layer forming coating solution.
- the conveyance of the belt-like flexible support is stopped at the pattern application unit 408a, while the wet coating and drying unit 404 and the heat treatment unit 406 are continuously transporting the holes.
- the first accumulator unit 407 operates to adjust the speed difference between the pattern coating unit 408a, the wet coating / drying unit 404, and the heat treatment unit 405.
- the formed belt-like flexible support is stored.
- each drying section shown in FIGS. 2 to 6 are determined in consideration of drying unevenness of each formed coating film, rough coating of the coating surface, and the like. .:! ⁇ Airflow drying of 5m / s, width direction wind velocity 0.1 ⁇ : 10%.
- the heating conditions in the heat treatment section shown in Figs. 2 to 6 are those that consider the improvement in smoothness of the hole transport layer, light emitting layer, electron transport layer, etc., removal of residual solvent, curing, etc. Decomposes organic compounds that constitute the hole transport layer, light-emitting layer, electron transport layer, etc. at a temperature of -30 to + 30 ° C with respect to the glass transition temperature of the transport layer, light-emitting layer, electron transport layer, etc. It is preferable to perform heat treatment of the back surface heat transfer system at a temperature that does not exceed the temperature.
- the coating liquid for forming the hole transport layer and the coating liquid for forming the electron transport layer are applied by the wet coater shown in FIGS.
- it is preferably 0.2 to 10% with respect to the average conveyance speed.
- the formation of the hole transport layer, the light emitting layer, the electron transport layer, etc. maintains the performance of the hole transport layer, the light emitting layer, the electron transport layer, etc.
- the dew point temperature is -20 ° C or less
- the measured cleanliness is class 5 or less, excluding the drying section and heat treatment section.
- the strip-shaped flexible support B on which an organic EL layer (a hole transport layer, a light emitting layer, an electron transport layer, etc.) is formed is wound around a winding core and recovered as a roll, and the organic EL maintain performance of the layers, taking into account the non-light emission failure or the like, it is good preferable to store under a reduced pressure of 10- 5 10 Pa.
- the storage period is preferably 1 hour to 200 hours in consideration of the removal of oxygen and trace moisture due to the deterioration of the organic EL layer. In some cases, it may be stored in a heated environment.
- a strip-shaped flexible support A having an anode layer including a first electrode is used, and an organic EL layer (hole transport layer) is formed on the first electrode.
- an organic EL layer hole transport layer
- Light emitting layer, electron transport layer to form a strip-shaped flexible support B, and then the organic compound to form the strip-shaped flexible support B on a winding core in the form of a strip-shaped flexible support B
- Pattern application ⁇ By placing the accumulator part before and after the drying part, when applying the coating solution for forming the light emitting layer, it is possible to stop and apply the light, so that accurate and stable light emission is possible. Formation of the layer became possible. [0122] 2) Furthermore, the application position correction control means makes it possible to place the wet pattern forming application device at an accurate position according to the alignment mark, eliminating the misalignment of the light emitting layer, and making it accurate and stable. A light emitting layer can be formed.
- Pattern application ⁇ The accumulator section is placed before and after the drying section, so that wet coating equipment and pattern coating equipment with different coating speeds can be used in combination, enabling continuous production and improving productivity. It became.
- the hole transport layer according to the present invention 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 multiple layers. When a plurality of hole transport layers are provided, it is necessary to increase the wet coating / drying section in accordance with the number of layers, and it is preferable to increase the heat treatment section at the same time.
- each light emitting layer (blue light emitting layer, green light emitting layer, red light emitting layer) is preferably selected in the range of 2 to lOOnm, and more preferably in the range of 2 to 20nm. . There are no particular restrictions on the thickness of the blue, green, and red light emitting layers, but the blue light emitting layer is preferably the thickest among the three color light layers.
- the light-emitting layer according to the present invention is a blue light-emitting layer having a maximum emission wavelength of 430 to 480 nm, a green light-emitting layer having a wavelength of 10 to 550 nm, and a red light-emitting layer having a range of 600 to 640 nm.
- a blue light-emitting layer having a maximum emission wavelength of 430 to 480 nm
- a green light-emitting layer having a wavelength of 10 to 550 nm
- a red light-emitting layer having a range of 600 to 640 nm.
- it includes at least three layers with different emission spectra in the range of these emission maximum wavelengths. If it is 3 layers or more, there is no restriction in particular. When there are more than four layers, there may be a plurality of layers having the same emission spectrum.
- a plurality of light emitting compounds may be mixed in each light emitting layer within the range where the maximum wavelength is maintained.
- 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 material used for the light emitting layer is not particularly limited. For example, Toray Research Center, Inc. The latest trends in flat panel displays The current state of EL displays and the latest technological trends Various materials such as those described on pages 228-332 can be mentioned.
- the light emitting layer formed by applying the coating solution for forming the light emitting layer with a wet pattern forming coating machine and drying it is an electron or hole injected from the electrode, the electron injection layer, or the hole transport layer. Is a layer that emits light by recombination, and the light emitting portion may be in the layer of the light emitting layer or at the interface between the light emitting layer and the adjacent layer.
- Examples of the strip-shaped flexible support used for the strip-shaped flexible support A on which the anode layer including the first electrode according to the present invention has already been formed include a transparent resin film.
- the resin film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cenorelose triacetate, cenorelose acetate butyrate, cenorelose Cellulose esters such as cetate propionate (CAP), cellulose acetate phthalate (TAC), cellulose nitrate or their derivatives, polyvinylidene chloride, polyvinylenoleoleconole, polyethylene butyl alcohol, syndiotactic polystyrene, polycarbonate, Norbornene resin, polymethylpentene, polyetherketone, polyimide, polyethersulfone (PES), polyphenylene sulfide, polysulf
- an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used.
- electrode materials include conductive transparent materials such as metals such as Au, Cul, indium tinoxide (ITO), SnO and ZnO. It is also possible to use an amorphous material such as IDIX ⁇ (InO ⁇ ⁇ ) that can produce a transparent conductive film.
- 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 single photolithography method.
- the electrode material It is also possible to form a pattern through a mask of the desired shape when depositing or sputtering the electrode material. Or when using the substance which can be apply
- the sheet resistance is preferably several hundred ⁇ / mouth or less.
- the film thickness is a force depending on the material, and is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.
- a hole injection layer may exist between the anode and the light emitting layer or the hole transport layer.
- the injection layer is a layer that is provided between the electrode and the organic layer in order to lower the drive voltage and increase the luminance of the light emission.
- anode buffer layer (hole injection layer) The details of the anode buffer layer (hole injection layer) are described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069 and the like.
- One layer of phthalocyanine buffer typified by copper phthalocyanine
- one layer of oxide buffer typified by vanadium oxide
- one layer of amorphous carbon buffer typified by vanadium oxide
- polymer buffer using a conductive polymer such as polyaniline (emeraldine) or polythiophene, etc.
- the thickness of the anode buffer layer (hole injection layer) is preferably in the range of 0.1 ⁇ to 5 ⁇ ⁇ ⁇ , although it depends on the material desired to be a very thin film.
- a gas barrier film may be formed on the surface of the resin film used as the belt-like flexible support, if necessary.
- the gas barrier film include an inorganic film, an organic film, or a hybrid film of both.
- the water vapor permeability is preferably 0.01 g / m 2 'day' atm or less.
- the oxygen permeability 10- 3 g / m 2 / day or less is preferably a high barrier film follows the water vapor transmission rate 10- 5 g / m 2 / day .
- any material may be used as long as it has a function of suppressing intrusion of elements such as moisture and oxygen that cause deterioration of the element.
- silicon oxide, silicon dioxide, silicon nitride, or the like is used. I can do it.
- the order of lamination of the inorganic layer and the organic layer is not particularly limited, but it is preferable to laminate the layers alternately several times.
- the method of forming the nano film for example, vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster-one ion beam, ion plating, plasma polymerization, atmospheric pressure Plasma polymerization method, plasma CV Forces capable of using D method, laser CVD method, thermal CVD method, coating method, etc. Specially, those by atmospheric pressure plasma polymerization method as described in 2004-68143 are particularly preferable.
- the hole transporting material has any of hole injection or transport and electron barrier properties, and may be either organic or inorganic.
- triazole derivatives oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, vinylene diamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone Derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, conductive polymer oligomers, particularly thiophene oligomers, and the like.
- a borfilin compound an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound.
- aromatic tertiary amine compounds and styrylamine compounds include N, N, N ′, N ′ —tetraphenyl-1,4′—diaminophenyl; N, N′—diphenyl-1, N, N ′ —bis.
- a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.
- Inorganic compounds such as P-type-Si and p-type-SiC can also be used as hole injection materials and hole transport materials.
- the thickness of the hole transport layer is not particularly limited, but is usually about 5 nm to 5 zm, preferably 5 to 200 nm.
- the hole transport layer may have a single layer structure composed of one or more of the above materials. It is also possible to use a hole transport layer having a high p property doped with impurities. Examples thereof include those described in JP-A-41-297076, JP-A-2000-196140, JP-A-2001-102175, J. Appl. Phys., 95, 5773 (2004), etc. It is done. It is preferable to use such a high p property hole transport layer because an organic EL device with lower power consumption can be produced.
- Examples of the layer provided adjacent to the light emitting layer include a blocking layer.
- Examples of the blocking layer include a hole blocking layer and an electron blocking layer.
- the blocking layer is provided as necessary in addition to the basic constituent layer of the organic compound thin film.
- the hole blocking layer has a function of an electron transport layer in a broad sense, and is made of a hole blocking material that has a function of transporting electrons but has a very small ability to transport holes.
- the structure of the electron transport layer described later can be used as a hole blocking layer according to the present invention, if necessary, and the hole blocking layer is preferably provided adjacent to the light emitting layer.
- the light emitting layer has a plurality of light emitting layers having different emission colors
- the light emitting layer whose emission maximum wavelength is the shortest is preferably closest to the anode among all the light emitting layers, In such a case, it is preferable to provide an additional hole blocking layer between the shortest wave layer and the light emitting layer next to the anode next to the anode.
- 50% by mass or more of the compound contained in the hole blocking layer provided at the position has an ionization potential of 0.3 eV or more larger than the host compound of the shortest wave emitting layer.
- the ionization potential is defined by the energy required to emit electrons at the H ⁇ M ⁇ (highest occupied molecular orbital) level of a compound to the vacuum level.
- the ionization potential can be obtained by the method shown below. I can do it.
- the ionization potential can be obtained by rounding off the second decimal place of the value (eV unit conversion value) calculated by optimizing the structure using B3LYP / 6_31G *.
- the reason why this calculated value is effective is that there is a high correlation between the calculated value obtained by this method and the experimental value.
- the ionization potential can also be obtained by a direct measurement method using photoelectron spectroscopy.
- a direct measurement method using photoelectron spectroscopy For example, a low-energy electron spectrometer “Model AC-lj” manufactured by Riken Keiki Co., Ltd. or a method known as ultraviolet photoelectron spectroscopy can be preferably used.
- the electron blocking layer has a function of a hole transport layer in a broad sense, and is made of a material having a function of transporting holes and a very small ability to transport electrons, and transports holes.
- the probability of recombination of electrons and holes can be improved.
- the structure of the positive hole transport layer mentioned later can be used as an electron blocking layer as needed.
- the film thickness of the hole blocking layer and the electron transporting layer according to the present invention is preferably 3 nm to:! OOnm, and more preferably 5 nm to 30 nm.
- a known host compound and a known phosphorescent compound are used 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 of which is 20% or more, and the amount of phosphorescent phosphorescence at room temperature (25 ° C).
- a child yield is defined as a compound of less than 0.1.
- the phosphorescence quantum yield is less than 0.01.
- a plurality of host compounds may be used in combination. By using multiple types of host compounds, it is possible to adjust the charge transfer, and the organic EL layer can be made highly efficient.
- these host compounds compounds having a hole transporting ability and an electron transporting ability, preventing the emission of longer wavelengths, and having a high Tg (glass transition temperature) are preferable.
- the following materials are disclosed in Japanese Laid-Open Patent Publication Nos. 2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001. — No. 357977, No. 2002-334786, No. 2002-8860, No. 2002-334787, No. 2002-15871, No. 2002-334788, No. 2002-43056, No.
- the light-emitting layer has a plurality of light-emitting layers, it is easy to obtain uniform film properties over the entire light-emitting layer that 50% by mass or more of the host compound in each layer is the same compound. Furthermore, it is more preferable that the phosphorescence energy of the host compound is 2.9 eV or more because it is advantageous for efficiently suppressing energy transfer from the dopant and obtaining high luminance. preferable.
- Phosphorescence emission energy refers to the peak energy of the 0-0 band of phosphorescence emission measured by measuring the photoluminescence of the deposited film of lOOnm on the substrate with the host compound.
- the host compound is an organic EL element using the organic EL layer of the present invention
- the organic EL element Considering the deterioration of the child over time (decrease in brightness, deterioration of film properties), market needs as a light source, etc.
- the phosphorescence energy is 2.9 eV or more and Tg is 90 ° C or more.
- the phosphorescent 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 is a compound in which light emission from an excited triplet is observed, and is a compound that emits phosphorescence at room temperature (25 ° C). A compound having a rate of 0.01 or more at 25 ° C. When used in combination with the host compound described above, an organic EL device with higher luminous efficiency can be obtained.
- the phosphorescent compound according to the present invention preferably has a phosphorescence quantum yield of 0.1 or more.
- the above phosphorescence quantum yield can be measured by the method described on page 398 (1992 edition, Maruzen) of Spectroscopic II, 4th edition, Experimental Chemistry Course 7.
- the phosphorescence quantum yield in a solution can be measured using various solvents, but the phosphorescent compound used in the present invention can be obtained if the phosphorescence quantum yield is achieved in any solvent. ,.
- the light emission of a phosphorescent compound can be described in two types in principle.
- One is the recombination of the carriers on the host compound to which carriers are transported, resulting in the generation of an excited state of the host compound. When this energy is transferred to the phosphorescent compound, light is emitted from the phosphorescent compound.
- the other is the energy transfer type, and the other is that the phosphorescent compound becomes a carrier trap, which is on the phosphorescent compound.
- the carrier trap type in which carrier recombination occurs and light emission from the phosphorescent compound is obtained, but in either case, the excited state energy of the phosphorescent compound is the excitation of the phosphine H compound. The condition is that it is lower than the energy of the state.
- the phosphorescent compound can be appropriately selected from known compounds used for the light emitting layer of the organic EL layer.
- 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). Of these, rare earth complexes, and most preferred are iridium compounds.
- the phosphorescent maximum wavelength of the phosphorescent compound is not particularly limited, and in principle, a central metal, a ligand, a substituent of the ligand, and the like are selected. so The emission wavelength obtained can be changed.
- the external extraction efficiency at room temperature of light emission of the organic EL element using the organic EL layer according to the present invention is 1. It is preferable that the ratio is 0 or more, more preferably 5% or more.
- the external extraction quantum efficiency (%) the number of photons emitted outside the organic EL element / the number of electrons sent to the organic EL element XI 00.
- 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.
- a color conversion filter When a color conversion filter is used, the maximum light emission of the organic EL element is preferably 480 nm or less.
- an electron transport material also serving as a hole blocking material
- any material that has a function of transmitting electrons injected from the cathode to the light emitting layer is acceptable. It is possible to select and use any of the known compounds of the known compounds, such as nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodis. Examples include methane and anthrone derivatives, oxadiazole derivatives, and the like.
- a thiadiazole derivative in which an oxygen atom of the oxaziazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as an electron transport material.
- a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.
- Metal complexes of 8_quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq), tris (5,7-dichloro-1-8-quinolinol) aluminum, tris (5,7-jib mouthpiece) _8_quinolinol) aluminum, tris (2-methyl _8_quinolinol) aluminum, tris (5-methyl_8_quinolinol) aluminum, bis (8-quinolinol) zinc (Znq) etc., and the central metal of these metal complexes Placed on In, Mg, Cu, Ca, Sn, Ga or Pb
- Alternative metal complexes can also be used as electron transport materials.
- metal-free or metal phthalocyanine or those having an end substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transport material.
- Distyrylpyrazine derivatives can also be used as electron transport materials, and n-type-Si, n-type-SiC and other inorganic semiconductors should be used as electron-transport materials as well as hole injection layers and hole-transport layers. Force S is possible.
- limiting in particular about the film thickness of an electron carrying layer Usually, about 5 nm-5 zm, 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 be used.
- examples thereof include Japanese Patent Application Laid-Open No. 4-297076, Japanese Patent Application Laid-Open No. 10-270172, Japanese Patent Application Laid-Open No. 2000-196140, Japanese Patent Application Laid-Open No. 2001-102175, J. Appl. Phys., 95, 5773 (2004). ) Etc. are mentioned. It is preferable to use such an n-type electron transport layer because a device with lower power consumption can be manufactured.
- a transparent gas barrier layer with a thickness of about 90 nm was formed by atmospheric pressure plasma discharge treatment.
- the water vapor transmission rate by a method based on JlSk-7129B it was 10 ⁇ 3 g / m 2 / day or less.
- the oxygen transmission rate by a method based on JlSk-7126B it was 10 ⁇ 3 g / m 2 / day or less.
- first electrode layer On the formed barrier layer, a 120 nm thick ITO (indium tin oxide) was formed using a plasma ion plating apparatus. Thereafter, a pattern having a width of 110 / im and a spacing of 34 ⁇ m was formed through a photolithography process.
- ITO indium tin oxide
- the host material polyvinyl carbazole (PVK) was prepared by dissolving 5% by mass of the dopant material Ir (ppy) 3 in 1,2-dichloroethane to form a 1% solution as a coating solution for forming an organic compound layer.
- Alq was dissolved in 1,2-dichloroethane to prepare a 0.5% by mass solution as a coating solution for forming an electron transport layer.
- Holes are formed on the first electrode layer of the belt-like flexible support having the gas barrier layer and the first electrode layer in this order on the prepared winding core using the manufacturing apparatus shown in FIG. Change the environmental conditions (dew point temperature, cleanliness) until the transport layer, light-emitting layer, and electron transport layer are formed as shown in Table 1 to form an organic EL layer, heat treatment, charge removal, and room temperature After cooling to the same temperature as in Example 1, sample rolls Nos. 101 to 107 were formed as a wound roll shape on the core. The cleanliness is the value measured according to JISB 9920, and the cleanliness was changed by changing the filter.
- the hole transport layer was formed by applying and drying the following hole transport layer forming coating solution by a wet coating method using an etatrusion coating machine, followed by heat treatment.
- the light-emitting layer is aligned with the wet pattern coating device according to the alignment mark, and is used for forming the light-emitting layer according to the pattern of the first electrode formed as shown in Fig. 6 while being held by the holding means.
- the coating liquid was formed with a wet pattern coating apparatus.
- the following electron transport layer forming coating solution was applied and dried by a wet coating method using an etatrusion coater, followed by heat treatment.
- the cleaning surface modification treatment of the belt-shaped flexible support was performed using a low-pressure mercury lamp with a wavelength of 184.9 nm and an irradiation intensity of 15 mW / cm 2 The distance was 10 mm.
- the charge removal treatment was performed using a static eliminator with weak X-rays.
- the coating solution for forming the hole transport layer was applied so that the thickness after drying was 50 nm.
- the coating solution for forming the light emitting layer was applied so that the thickness after drying was lOOnm.
- the coating solution for forming the electron transport layer was coated so that the thickness after drying was 30 nm.
- the transport speed was 2m / min.
- the coating temperature of the coating solution for forming the hole transport layer, the coating solution for forming the light emitting layer, and the coating solution for forming the electron transport layer is 25 ° C, and the other ambient temperature is 25 ° C except for the drying device and heat treatment device. Performed under atmospheric pressure conditions.
- the light emitting layer drying section and the heat treatment section shown in Fig. 3 are used.
- the height from the slit nozzle type discharge port to the film forming surface is 100 m. m
- a heat treatment was subsequently performed at a temperature of 220 ° C. in the heat treatment section to form a light emitting layer.
- the drying unit and the heat treatment apparatus having the same structure as the light emitting layer drying unit and the heat treatment unit shown in Fig. 3 are used.
- an electron transport layer was formed by subsequently performing a heat treatment at a temperature of 200 ° C. in the heat treatment section.
- the discharge wind speed was measured with a hot air anemometer model 6113 manufactured by Kanomax Co., Ltd., and the wind speed distribution in the width direction was calculated by the following formula.
- Wind speed distribution (maximum wind speed-minimum wind speed) / average wind speed X I 00
- a LiF layer (electron injection layer) with a thickness of 0.5 nm is vapor-deposited under a vacuum of 5 X 10 _4 Pa so that it is perpendicular to the first electrode through the mask.
- a sealing layer is subsequently formed by vapor deposition, cooled to room temperature, A winding roll was formed on the winding core.
- Table 1 shows the results of visually confirming the non-light-emitting failure on sample Nos. 101 to 107 manufactured in this state and evaluating according to the following evaluation rank.
- the prepared sample was stored at a constant temperature of 80 ° C for 1 week, and when it was driven at a constant current of 2.5 mA / cm 2 , it was visually checked for the presence of no light emission. Evaluation rank of non-luminous failure ⁇ : Non-luminous failure is not confirmed,
- sample No. 101 it is presumed that a non-luminous failure has occurred due to the amount of moisture contained in the sample, and in the case of sample No. 104, due to adhering foreign matter. The effectiveness of the present invention was confirmed.
- Samples Nos. 201 to 206 were used under the same conditions except that the conditions under which sample No. 104 produced in Example 1 was stored were changed as shown in Table 2 and processed. The storage period was 5 days.
- the lifetime of the light emitting layer attached to the fabricated sample Nos. 201 to 206 is the time required for the luminance to be half of the initial luminance when driven at a constant current of 2.5 mA / cm 2 (half time)
- Table 2 shows the results of the evaluation using as a life index. Incidentally, the lifetime (relative value) indicates a relative value when storage conditions was 100 life time of 1 X 10- 5 Pa.
Abstract
A method for forming an organic EL layer for forming a high quality organic EL element with high productivity without increasing the cost. The method for forming the organic EL layer of an organic EL element by using a production system having a supply section, a pattern coating/drying section, and a collecting section, characterized in that the supply section is supplied with a rolled strip flexible support A on which an anode layer including a first electrode is formed, a first accumulator section and a second accumulator section are provided respectively in front and rear of the pattern coating/drying section, the pattern coating/drying section has at least one unit of the pattern coating/drying section consisting of a pattern coating section and an organic EL layer drying section, an organic EL layer is formed on the anode layer as a strip flexible support B at the pattern coating/drying section and then rolled at the collecting section.
Description
明 細 書 Specification
有機 EL層の形成方法 Formation method of organic EL layer
技術分野 Technical field
[0001] 本発明は、面光源やディスプレイパネル等として利用される有機 EL (エレクト口 'ル ミネッセンス）素子の有機 EL層の形成方法に関する。 The present invention relates to a method for forming an organic EL layer of an organic EL (electral luminance) element used as a surface light source, a display panel, or the like.
背景技術 Background art
[0002] 近年、有機物質を使用した有機 EL素子は、固体発光型の安価な大面積フルカラ 一表示素子や書き込み光源アレイとしての用途が有望視されており、活発な研究開 発が進められている。有機 EL素子は、基板上に形成された第 1電極（陽極又は陰極 )と、その上に積層された発光層を含む有機化合物層を有する有機 EL層と、この発 光層上に積層された第 2電極（陰極又は陽極）とを有する薄膜型の素子である。この ような有機 EL素子に電圧を印加すると、有機化 EL層に陰極から電子が注入され陽 極から正孔が注入される。この電子と正孔が発光層において再結合し、エネルギー 準位が伝導帯から価電子帯に戻る際にエネルギーを光として放出することにより発光 が得られることが知られてレ、る。 [0002] In recent years, organic EL devices using organic materials have been promising for use as solid-state light-emitting, inexpensive large-area full-color display devices and writing light source arrays, and active research and development have been promoted. Yes. The organic EL element includes a first electrode (anode or cathode) formed on a substrate, an organic EL layer having an organic compound layer including a light emitting layer stacked thereon, and a layer stacked on the light emitting layer. It is a thin film type element having a second electrode (cathode or anode). When a voltage is applied to such an organic EL element, electrons are injected from the cathode into the organic EL layer and holes are injected from the cathode. 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.
[0003] このように、有機 EL素子は薄膜型の素子であるため、 1個又は複数個の有機 EL素 子を基板上に形成した有機 ELパネルをバックライト等の面光源として利用した場合 には、面光源を備えた装置を容易に薄型にすることが出来る。又、画素としての有機 EL素子を基板上に所定個数形成した有機 ELパネルをディスプレイパネルとして用 レ、て表示装置を構成した場合には視認性が高い、視野角依存性がないなど、液晶 表示装置では得られない利点がある。 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. Can easily reduce the thickness of a device provided with a surface light source. In addition, when a display device is configured by 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, it is highly visible and has no viewing angle dependency. There are advantages that cannot be obtained with the device.
[0004] 一方、有機 EL素子の有機 EL層を形成する際には、特開平 9— 102393号公報、 特開 2002— 170676号公報に記載されている様に、蒸着法、スパッタ法、 CVD、 P VD、溶剤を用いた塗布法等の様々な方法が使用出来るが、これらの方法の中で、 製造工程の簡略化、製造コストの低減、加工性の改善、バックライトや照明光源等の フレキシブルな大面積素子への応用等の観点からは塗布法等の湿式製膜法が有利 であることが知られている。例えば、特開 2002— 170676号公報に枚葉のガラス基
板上にスピンコート法により有機化合物層を形成する方法が記載されている。特開 2 003— 142260号公報に枚葉の基板上にインクジェット方式で順次有機化合物層を 形成する方法が記載されてレ、る。これらの方式は何れも基板として枚葉基板を使用 しているため生産効率を上げるのに限度がある。これらの状況から生産効率が挙げら れる可能性が高いロール状の基材を使用し基材上に有機 EL素子を構成する各種 層を形成した後、卷き取りロール状とする有機 EL素子の製造方法（ロールツーロー ル方式）が検討されている。 On the other hand, when forming an organic EL layer of an organic EL element, as described in JP-A-9-102393 and JP-A-2002-170676, vapor deposition, sputtering, CVD, Various methods such as PVD and solvent coating can be used. Among these methods, the manufacturing process is simplified, the manufacturing cost is reduced, the workability is improved, and the backlight and illumination light source are flexible. It is known that a wet film forming method such as a coating method is advantageous from the viewpoint of application to a large area device. For example, JP 2002-170676 discloses a single wafer glass substrate. A method for forming an organic compound layer on a plate by spin coating is described. Japanese Patent Application Laid-Open No. 2003-142260 describes a method of sequentially forming an organic compound layer on a single wafer substrate by an ink jet method. Each of these methods uses a single-wafer substrate as a substrate, so there is a limit to increasing production efficiency. From these situations, use a roll-shaped substrate that is highly likely to increase production efficiency, and then form various layers that make up the organic EL element on the substrate. Manufacturing methods (roll-to-roll method) are being studied.
[0005] 例えば、ロール状の長尺のフィルムを供給し、搬送しながらフィルム上に発光層を、 湿式塗布法により形成した後、卷き芯に卷き取りロール状とする方法が知られている (例えば、特許文献 1を参照。）。透光性基板としてプラスチックフィルムを使用し、こ のプラスチックフィルム上に陰極と、有機物質からなる一つ又は複数の発光層と、陽 極層を設けた有機 ELディスプレイを製造する方法として、有機物質からなる一つ又 は複数の発光層のパターニング及び陰極のパターユングを真空下で蒸着方式で口 一ルツ一ロール方式により作製する方法が知られている（例えば、特許文献 2を参照[0005] For example, a method is known in which a roll-like long film is supplied and a light-emitting layer is formed on the film while being conveyed by a wet coating method, and then wound into a rolled core. (For example, see Patent Document 1). As a method of manufacturing an organic EL display using a plastic film as a light-transmitting substrate, a cathode, one or a plurality of light-emitting layers made of an organic material, and an anode layer on the plastic film, an organic material is used. There is known a method of producing a pattern of one or a plurality of light-emitting layers and patterning a cathode by a vacuum and a single roll method by vapor deposition under vacuum (see, for example, Patent Document 2).
。）。し力しながら、特許文献 1に記載の方法では、フルカラーパネルの生産で必要と なるパターン塗布での生産安定性を得るのは技術的に困難である。又、特許文献 2 に記載の方法では、 1)支持体を搬送しながら発光層等を蒸着方式でパターニング 形成するため、パターユングの位置精度の安定性を制御することが難しぐ発光層の 位置がズレる危険がある。 2)有機物質からなる一つ又は複数の発光層を形成するの に使用する有機化合物の使用効率が低ぐコストが高くなる原因の一つになっている 。 3)有機物質力 なる一つ又は複数の発光層が蒸着方式で形成する方式であるた め、発光層を形成するのに時間が掛力 生産性を上げることが難しい。 . ). However, with the method described in Patent Document 1, it is technically difficult to obtain production stability in pattern coating, which is necessary for production of full-color panels. In addition, in the method described in Patent Document 2, 1) the position of the light emitting layer is difficult to control the stability of the patterning position accuracy because the light emitting layer and the like are patterned by vapor deposition while the support is transported. There is a risk of slipping. 2) This is one of the causes that the use efficiency of the organic compound used to form one or a plurality of light emitting layers made of an organic substance is low and the cost is high. 3) Organic substance power Since one or more light emitting layers are formed by vapor deposition, it takes time to form the light emitting layer, and it is difficult to increase productivity.
[0006] これらの状況より、生産性が高ぐフルカラーパネルに対応した有機 EL素子形成用 の有機化合物層の形成方法の開発が望まれている。 [0006] Under these circumstances, development of a method of forming an organic compound layer for forming an organic EL element corresponding to a full-color panel with high productivity is desired.
特許文献 1 :特開平 10— 77467号公報 Patent Document 1: JP-A-10-77467
特許文献 2 :国際公開第 01/5194号パンフレット Patent Document 2: Pamphlet of International Publication No. 01/5194
発明の開示 Disclosure of the invention
発明が解決しょうとする課題
[0007] 本発明は、上記状況に鑑みなされたものであり、その目的は、生産性が高ぐ高品 質の有機 EL素子用の有機 EL層の形成方法を提供することである。 Problems to be solved by the invention [0007] The present invention has been made in view of the above situation, and an object thereof is to provide a method of forming an organic EL layer for a high-quality organic EL element with high productivity.
課題を解決するための手段 Means for solving the problem
[0008] 本発明の上記目的は、以下の構成により達成された。 [0008] The above object of the present invention has been achieved by the following constitutions.
[0009] (請求の範囲第 1項） [0009] (Claim 1)
帯状可撓性支持体の上に、少なくとも第 1電極を含む陽極層と、発光層を含む有機 化合物層を有する有機 EL層と、第 2電極を含む陰極層とをこの順番で有する有機 E L素子の有機 EL層を、供給部と、前記陽極層上に、前記発光層を形成するパターン 塗布'乾燥部と、回収部とを有する製造装置を用いて形成する有機 EL層の形成方 法において、前記供給部には、少なくとも第 1電極を含む陽極層が形成された帯状 可撓性支持体 Aが、ロール状態で供給され、前記パターン塗布'乾燥部の前に第 1 アキュームレータ部と、後に第 2アキュームレータ部とを有し、前記パターン塗布'乾 燥部は、有機 EL層形成用塗布液を湿式パターン形成塗布装置により大気圧条件で 発光層形成用塗膜を形成するパターン塗布部と、大気圧条件で前記有機 EL層中の 溶媒を除去し、有機 EL層を形成する有機 EL層乾燥部とを 1ユニットとし、前記パタ ーン塗布 ·乾燥部は、少なくとも 1ユニットの前記パターン塗布 ·乾燥部を有し、前記 パターン塗布 ·乾燥部により、前記陽極層上に前記有機 EL層を形成し帯状可撓性 支持体 Bとし、前記回収部で、巻き芯に巻き取りロール状とすることを特徴とする有機 EL層の形成方法。 An organic EL element having an anode layer including at least a first electrode, an organic EL layer including an organic compound layer including a light emitting layer, and a cathode layer including a second electrode in this order on a strip-shaped flexible support. In the method of forming the organic EL layer, the organic EL layer is formed using a manufacturing apparatus having a supply unit, a pattern coating and drying unit for forming the light emitting layer on the anode layer, and a recovery unit. The supply section is supplied with a strip-shaped flexible support A on which an anode layer including at least a first electrode is formed in a roll state, and includes a first accumulator section before the pattern coating and drying section, and a second accumulator section later. The accumulator section, and the pattern coating / drying section includes a pattern coating section for forming a coating film for forming a light emitting layer under atmospheric pressure conditions using a wet pattern forming coating apparatus with a coating liquid for forming an organic EL layer. Solvent in the organic EL layer under atmospheric pressure conditions 1 unit of the organic EL layer drying unit for forming the organic EL layer, and the pattern coating / drying unit has at least one unit of the pattern coating / drying unit, and the pattern coating / drying unit Then, the organic EL layer is formed on the anode layer to form a strip-like flexible support B, and the recovery unit forms a winding roll on the winding core.
[0010] (請求の範囲第 2項） [0010] (Claim 2)
前記帯状可撓性支持体 Aは、ァライメントマークが設けられていることを特徴とする請 求の範囲第 1項に記載の有機 EL層の形成方法。 2. The method for forming an organic EL layer according to claim 1, wherein the belt-like flexible support A is provided with alignment marks.
[0011] (請求の範囲第 3項） [0011] (Claim 3)
前記帯状可撓性支持体 Aは、間欠搬送されることを特徴とする請求の範囲第 1項又 は第 2項に記載の有機 EL層の形成方法。 3. The method for forming an organic EL layer according to claim 1, wherein the belt-like flexible support A is intermittently conveyed.
[0012] (請求の範囲第 4項） [0012] (Claim 4)
前記湿式パターン形成塗布装置は、帯状可撓性支持体 Aの間欠搬送に対応して稼 働し、帯状可撓性支持体 Aが停止しているときに稼働し、パターン形成塗布を行うこ
とを特徴とする請求の範囲第 1項乃至第 3項の何れか 1項に記載の有機 EL層の形 成方法。 The wet pattern formation coating apparatus operates in response to the intermittent conveyance of the strip-shaped flexible support A, operates when the strip-shaped flexible support A is stopped, and performs pattern formation coating. The method for forming an organic EL layer according to any one of claims 1 to 3, wherein:
[0013] (請求の範囲第5項） [0013] (Claim 5 )
前記パターン塗布部は、帯状可撓性支持体の保持手段と、ァライメントマークの検出 手段と、湿式パターン形成塗布装置の塗布位置補正制御手段とを有していることを 特徴とする請求の範囲第 1項乃至第 4項の何れか 1項に記載の有機 EL層の形成方 法。 The said pattern application part has the holding means of a strip | belt-shaped flexible support body, the detection means of an alignment mark, and the application position correction | amendment control means of a wet pattern formation application apparatus, It is characterized by the above-mentioned. 5. The method for forming an organic EL layer according to any one of items 1 to 4.
[0014] (請求の範囲第 6項） [0014] (Claim 6)
前記第 1アキュームレータ部の前もしくは第 2アキュームレータ部の後の何れか一方 に湿式塗布'乾燥部を有することを特徴とする請求の範囲第 1項乃至第 5項の何れ 力、 1項に記載の有機 EL層の形成方法。 6. The force according to any one of claims 1 to 5, further comprising a wet application / drying unit in front of the first accumulator unit or after the second accumulator unit. Formation method of organic EL layer.
[0015] (請求の範囲第 7項） [0015] (Claim 7)
前記第 1アキュームレータ部の前と、第 2アキュームレータ部の後に湿式塗布.乾燥 部を有することを特徴とする請求の範囲第 1項乃至第 5項の何れか 1項に記載の有 機 EL層の形成方法。 The organic EL layer according to any one of claims 1 to 5, further comprising a wet application / drying unit before the first accumulator unit and after the second accumulator unit. Forming method.
[0016] (請求の範囲第 8項） [0016] (Claim 8)
前記湿式塗布 ·乾燥部は有機化合物層形成用塗布液を湿式塗布装置により大気圧 条件で有機化合物層を形成する湿式塗布部と、大気圧条件で塗布し、前記有機化 合物層中の溶媒を除去する有機化合物層乾燥部とを有することを特徴とする請求の 範囲第 6項又は第 7項に記載の有機 EL層の形成方法。 The wet coating / drying unit applies a coating solution for forming an organic compound layer by a wet coating apparatus to form an organic compound layer under atmospheric pressure conditions and a solvent in the organic compound layer by applying the organic compound layer under atmospheric pressure conditions. 8. The method for forming an organic EL layer according to claim 6, further comprising an organic compound layer drying section for removing water.
[0017] (請求の範囲第 9項） [0017] (Claim 9)
前記パターン塗布 ·乾燥部と、湿式塗布 ·乾燥部との後に加熱処理部を有することを 特徴とする請求の範囲第 1項乃至第 8項の何れか 1項に記載の有機 EL層の形成方 法。 The method for forming an organic EL layer according to any one of claims 1 to 8, wherein a heat treatment section is provided after the pattern coating / drying section and the wet coating / drying section. Law.
[0018] (請求の範囲第 10項） [0018] (Claim 10)
前記製造装置は、除電処理部を有していることを特徴とする請求の範囲第 1項乃至 第 9項の何れか 1項に記載の有機 EL層の形成方法。 10. The method for forming an organic EL layer according to claim 1, wherein the manufacturing apparatus includes a charge removal processing unit.
[0019] (請求の範囲第 11項）
前記帯状可撓性支持体 Aは、湿式塗布 ·乾燥部で有機化合物層形成用塗布液を塗 布する前、又はパターン塗布'乾燥部で有機 EL層形成用塗布液を塗布する前に洗 浄表面改質処理手段により洗浄表面改質処理が施されることを特徴とする請求の範 囲第 1項乃至第 10項の何れか 1項に記載の有機 EL層の形成方法。 [0019] (Claim 11) The belt-like flexible support A is washed before applying the organic compound layer forming coating solution in the wet coating / drying unit or before applying the organic EL layer forming coating solution in the pattern coating 'drying unit. The method for forming an organic EL layer according to any one of claims 1 to 10, wherein the cleaning surface modification treatment is performed by a surface modification treatment means.
[0020] (請求の範囲第 12項） [0020] (Claim 12)
前記洗浄表面改質処理手段が酸素プラズマ又は UV照射であることを特徴とする請 求の範囲第 11項に記載の有機 EL層の形成方法。 12. The method of forming an organic EL layer according to claim 11, wherein the cleaning surface modification treatment means is oxygen plasma or UV irradiation.
[0021] (請求の範囲第 13項） [0021] (Claim 13)
前記有機 EL層及び有機化合物層は、露点温度一 20°C以下、且つ JISB 9920に 準拠し、測定した清浄度がクラス 5以下で、且つ、有機 EL層乾燥部と、有機化合物 層乾燥部及び加熱処理部を除き 10〜45°Cの大気圧中で形成されることを特徴とす る請求の範囲第 1項乃至第 12項の何れか 1項に記載の有機 EL層の形成方法。 The organic EL layer and the organic compound layer have a dew point temperature of 20 ° C. or less and conformity with JISB 9920, and the measured cleanliness is class 5 or less, and the organic EL layer drying unit, the organic compound layer drying unit, The method for forming an organic EL layer according to any one of claims 1 to 12, wherein the organic EL layer is formed in an atmospheric pressure of 10 to 45 ° C except for a heat treatment portion.
[0022] (請求の範囲第 14項） [0022] (Claim 14)
前記帯状可撓性支持体 Bを回収部で、巻き芯に巻き取りロール状とした後、 10— 5〜1 OPaの減圧条件下で保管することを特徴とする請求の範囲第 1項乃至第 13項の何 れカ 1項に記載の有機 EL層の形成方法。 In recovery unit the band-shaped flexible support B, wound after the winding roll form a core, to claim 1, wherein, characterized in that the storage under reduced pressure of 10- 5 to 1 OPa first 14. Any method of item 13 The method for forming an organic EL layer according to item 1.
発明の効果 The invention's effect
[0023] 生産性が高ぐ高品質の有機 EL素子用の有機 EL層の形成方法を提供することが 出来、安定した有機 EL素子を製造することが可能となった。 [0023] A method of forming an organic EL layer for a high-quality organic EL element with high productivity can be provided, and a stable organic EL element can be produced.
図面の簡単な説明 Brief Description of Drawings
[0024] [図 1]有機 EL素子の層構成の一例を示す概略断面図である。 FIG. 1 is a schematic cross-sectional view showing an example of a layer structure of an organic EL element.
[図 2]有機 EL層までを形成するパターン塗布 ·乾燥部を有する製造装置の模式図で ある。 FIG. 2 is a schematic view of a manufacturing apparatus having a pattern application / drying unit for forming layers up to an organic EL layer.
[図 3]図 2の Pで示される部分の拡大概略図である。 FIG. 3 is an enlarged schematic view of a portion indicated by P in FIG.
[図 4]有機 EL層までを形成する湿式塗布'乾燥部とパターン塗布'乾燥部とを有する 製造装置の模式図である。 FIG. 4 is a schematic view of a manufacturing apparatus having a wet coating 'drying unit and a pattern coating' drying unit that form up to an organic EL layer.
[図 5]有機 EL層までを形成するパターン塗布 ·乾燥部の前後に湿式塗布 ·乾燥部を 有する製造装置の模式図である。
[図 6]図 2の Qで示される部分の拡大概略平面図である。 符号の説明 FIG. 5 is a schematic diagram of a manufacturing apparatus having a wet coating / drying section before and after a pattern coating / drying section for forming an organic EL layer. FIG. 6 is an enlarged schematic plan view of a portion indicated by Q in FIG. Explanation of symbols
la、 lb 有機 EL素子 la, lb Organic EL device
101 基材 101 substrate
102 第 1電極（陽極） 102 1st electrode (anode)
103 正孔輸送層 103 hole transport layer
104 発光層 104 Light emitting layer
105 電子注入層（電子輸送層) 105 Electron injection layer (electron transport layer)
106 第 2電極（陰極） 106 Second electrode (cathode)
107 封止層 107 Sealing layer
109 封止フィルム 109 Sealing film
2、 3、 4 製造装置 2, 3, 4 Production equipment
201、 301、 401 供給部 201, 301, 401 supply section
201a 帯状可撓性支持体 A 201a Strip flexible support A
202、 302 浄表面改質処理部 202, 302 Surface modification treatment section
203 第 1除電処理部 203 First static elimination processing section
204、 306、 407 第 1アキュームレータ部 204, 306, 407 1st accumulator
205、 307、 408 パターン塗布 ·乾燥部 205, 307, 408 Pattern applicationDry section
205bl l ヘッド 205bl l head
206、 308、 405、 409 カロ熱処理部 206, 308, 405, 409 Calo heat treatment part
207 第 2除電処理部 207 Second static elimination processing section
208、 311、 411 第 2アキュームレータ部 208, 311, 411 Second accumulator
209、 312、 415 回収部 209, 312, 415 Collection unit
301h、 401h 帯状可撓性支持体 B 301h, 401h Strip flexible support B
303 除電処理部 A 303 Static neutralizer A
304 湿式塗布 ·乾燥部 304 Wet applicationDry part
305 除電処理部 B 305 Static elimination processing part B
309 除電処理部 C
404 第 1湿式塗布 ·乾燥部 309 Static elimination processing part C 404 1st wet coating and drying section
403 除電処理部 a 403 Static elimination processing part a
406 除電処理部 b 406 Static neutralizer b
410 除電処理部 c 410 Static elimination processing section c
412 第 2湿式塗布 ·乾燥部 412 Second wet coating and drying section
414 除電処理部 d 414 Static elimination processing part d
発明を実施するための最良の形態 BEST MODE FOR CARRYING OUT THE INVENTION
[0026] 本発明に係る実施の形態を図 1〜図 6を参照しながら説明するが、本発明はこれに 限定されるものではない。 Embodiments according to the present invention will be described with reference to FIGS. 1 to 6, but the present invention is not limited thereto.
[0027] 図 1は有機 EL素子の層構成の一例を示す概略断面図である。図 1の（a)は封止膜 が形成された有機 EL素子の構成層を示す概略断面図である。図 1の（b)は接着剤 を介して封止フィルムを貼着することで形成された有機 EL素子の構成層を示す概略 断面図である。 FIG. 1 is a schematic cross-sectional view showing an example of the layer structure of an organic EL element. FIG. 1 (a) is a schematic cross-sectional view showing the constituent layers of an organic EL element on which a sealing film is formed. FIG. 1 (b) is a schematic cross-sectional view showing the constituent layers of an organic EL element formed by adhering a sealing film via an adhesive.
[0028] 図 1の（a)に示される有機 EL素子の層構成に付き説明する。図中、 laは有機 EL素 子を示す。有機 EL素子 laは、基材 101上に、第 1電極（陽極） 102と、正孔輸送層 1 03と、発光層 104と、電子注入層 105と、第 2電極（陰極） 106と、封止層 107とをこ の順番に有している。 [0028] The layer structure of the organic EL element shown in Fig. 1 (a) will be described. In the figure, la indicates the organic EL element. The organic EL element la includes a first electrode (anode) 102, a hole transport layer 103, a light emitting layer 104, an electron injection layer 105, a second electrode (cathode) 106, and a sealing material on a substrate 101. It has a stop layer 107 in this order.
[0029] 図 1の（b)に示される有機 EL素子の層構成に付き説明する。図中、 lbは有機 EL 素子を示す。有機 EL素子 lbは、基材 101上に、第 1電極（陽極） 102と、正孔輸送 層（正孔注入層） 103と、発光層 104と、電子注入層 105と、第 2電極（陰極） 106と、 接着剤層 108と、封止フィルム 109とをこの順番に有している。本図に示される有機 E L素子において、第 1電極（陽極） 102と発光層 104又は正孔輸送層 103の間に正孔 注入層（不図示）を設けてもよい。又、第 2電極（陰極） 106と発光層 104又は電子注 入層 105との間に電子輸送層（不図示）を設けてもょレ、。本図に示される有機 EL素 子 la及び有機 EL素子 lbでは、陽極（第 1電極） 102と基材 101との間にガスバリア 膜 (不図示）を設けることが好ましレ、。 [0029] The layer structure of the organic EL element shown in Fig. 1 (b) will be described. In the figure, lb represents an organic EL device. The organic EL element lb is formed on a substrate 101 with a first electrode (anode) 102, a hole transport layer (hole injection layer) 103, a light emitting layer 104, an electron injection layer 105, and a second electrode (cathode). ) 106, an adhesive layer 108, and a sealing film 109 are provided in this order. In the organic EL device shown in the figure, a hole injection layer (not shown) may be provided between the first electrode (anode) 102 and the light emitting layer 104 or the hole transport layer 103. In addition, an electron transport layer (not shown) may be provided between the second electrode (cathode) 106 and the light emitting layer 104 or the electron injection layer 105. In the organic EL element la and the organic EL element lb shown in this figure, it is preferable to provide a gas barrier film (not shown) between the anode (first electrode) 102 and the substrate 101.
[0030] 本発明は、本図に示される発光層 104の形成方法に関するものである。本図に示 す有機 EL素子の層構成は一例を示したものであるが、他の代表的な有機 EL素子
の層構成としては次の構成が挙げられる。 The present invention relates to a method for forming the light emitting layer 104 shown in the figure. The layer structure of the organic EL element shown in this figure is an example, but other typical organic EL elements Examples of the layer structure include the following structures.
[0031] (1)基材/陽極/発光層/電子輸送層/陰極/封止層 [0031] (1) Substrate / anode / light emitting layer / electron transport layer / cathode / sealing layer
(2)基材/陽極/正孔輸送層/発光層/正孔阻止層/電子輸送層/陰極/封 止層 (2) Substrate / anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode / sealing layer
(3)基材/陽極/正孔輸送層（正孔注入層）/発光層/正孔阻止層/電子輸送 層/陰極バッファ一層（電子注入層）/陰極/封止層 (3) substrate / anode / hole transport layer (hole injection layer) / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer (electron injection layer) / cathode / sealing layer
(4)基材/陽極/陽極バッファ一層（正孔注入層）/正孔輸送層/発光層/正孔 阻止層/電子輸送層/陰極バッファ一層（電子注入層）/陰極/封止層 (4) Base material / anode / anode buffer layer (hole injection layer) / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer (electron injection layer) / cathode / sealing layer
尚、本発明において有機 EL層とは、図 1に示す層構成において、陽極と陰極とに 挟まれる層構成を言う。有機 EL素子を構成している各層については後に説明する。 In the present invention, the organic EL layer means a layer structure sandwiched between an anode and a cathode in the layer structure shown in FIG. Each layer constituting the organic EL element will be described later.
[0032] 図 2は有機 EL層までを形成するパターン塗布'乾燥部を有する製造装置の模式図 である。以下に、一例としてパターン化されて形成されている第 1電極を有する帯状 可撓性支持体上に正孔輸送層、発光層、電子輸送層とを有する有機 EL層を形成す る方法を本図で説明する。 FIG. 2 is a schematic diagram of a manufacturing apparatus having a pattern coating / drying unit for forming layers up to the organic EL layer. The following is a method for forming an organic EL layer having a hole transport layer, a light-emitting layer, and an electron transport layer on a strip-shaped flexible support having a first electrode that is patterned and formed as an example. This will be described with reference to the drawings.
[0033] 図中、 2は有機 EL素子の構成層の 1つである有機 EL層までを大気圧条件下で形 成する製造装置を示す。製造装置 2は、供給部 201と、帯状可撓性支持体の洗浄表 面改質処理部 202と、第 1除電処理部 203と、第 1アキュームレータ部 204と、パター ン塗布'乾燥部 205と、加熱処理部 206と、第 2除電処理部 207と、第 2アキユームレ 一タ咅 208と回収咅 B209とを有してレ、る。 [0033] In the figure, reference numeral 2 denotes a manufacturing apparatus for forming up to the organic EL layer, which is one of the constituent layers of the organic EL element, under atmospheric pressure conditions. The manufacturing apparatus 2 includes a supply unit 201, a cleaning surface modification processing unit 202 for a strip-shaped flexible support, a first charge removal processing unit 203, a first accumulator unit 204, a pattern coating / drying unit 205, The heat treatment unit 206, the second static elimination processing unit 207, the second accumulator 208, and the recovery unit B209 are provided.
[0034] 供給部 201では、ガスバリア膜と第 1電極を含む陽極層とがこの順番で既に形成さ れた帯状可撓性支持体 A201aが巻き芯に巻き取られロール状態で供給される様に なっている。 201bはロール状態の帯状可撓性支持体 A201aを示す。第 1電極（図 1 、図 6を参照）はパターン化（図 6を参照）されて形成されている。 [0034] In the supply unit 201, the strip-shaped flexible support A201a in which the gas barrier film and the anode layer including the first electrode are already formed in this order is wound around the winding core and supplied in a roll state. It has become. 201b shows a strip-like flexible support A201a in a roll state. The first electrode (see FIGS. 1 and 6) is formed by patterning (see FIG. 6).
[0035] 洗浄表面改質処理部 202は、パターン塗布'乾燥部 205で塗布する前に供給部 2 01から送られてきた帯状可撓性支持体 A201aの第 1電極を含む陽極層（不図示)表 面を洗浄改質する洗浄表面改質処理手段 202aを有してレ、る。洗浄表面改質処理 手段 202aとしては、低圧水銀ランプ、エキシマランプ、プラズマ洗浄装置等が挙げら れる。低圧水銀ランプによる洗浄表面改質処理の条件としては、例えば、波長 184.
2nmの低圧水銀ランプを、照射強度 5〜20mW/cm2で、距離 5〜： 15mmで照射し 洗浄表面改質処理を行う条件が挙げられる。プラズマ洗浄装置による洗浄表面改質 処理の条件としては、例えば、大気圧プラズマが好適に使用される。洗浄条件として はアルゴンガスに酸素 1〜 5体積％含有ガスを用レ、、周波数 100KHz〜150MHz、 電圧 10V〜： 10KV、照射距離 5〜20mmで洗浄表面改質処理を行う条件が挙げら れる。 The cleaning surface modification processing unit 202 includes an anode layer (not shown) including the first electrode of the strip-shaped flexible support A201a sent from the supply unit 201 before being applied by the pattern application / drying unit 205. ) It has cleaning surface modification processing means 202a for cleaning and modifying the surface. Examples of the cleaning surface modification means 202a include a low-pressure mercury lamp, an excimer lamp, a plasma cleaning apparatus, and the like. The conditions for cleaning surface modification with a low-pressure mercury lamp include, for example, wavelength 184. The condition for performing the cleaning surface modification treatment by irradiating a 2 nm low-pressure mercury lamp with an irradiation intensity of 5 to 20 mW / cm 2 and a distance of 5 to 15 mm is mentioned. For example, atmospheric pressure plasma is preferably used as a condition for the cleaning surface modification treatment by the plasma cleaning apparatus. As cleaning conditions, argon gas containing 1 to 5% by volume of oxygen is used, and cleaning surface modification treatment is performed at a frequency of 100 KHz to 150 MHz, a voltage of 10 V to 10 KV, and an irradiation distance of 5 to 20 mm.
[0036] 第 1除電処理部 203に使用する除電処理手段としては、光照射方式とコロナ放電 式等が挙げられ、これらの中から必要に応じて適宜選択使用することが可能である。 光照射式は微弱 X線、コロナ放電式はコロナ放電により空気イオンを生成する。この 空気イオンは、帯電物体に引き寄せられて反対極性の電荷を補い、静電気を中和す る。コロナ放電による除電器、軟 X線による除電器が利用可能である。第 1除電処理 部により、基材の帯電除去が図られるため、ゴミの付着や絶縁破壊が防止されるため 、素子の歩留まりの向上が図られる。 [0036] Examples of the charge removal processing means used in the first charge removal processing unit 203 include a light irradiation method, a corona discharge method, and the like, and these can be appropriately selected and used as necessary. Light irradiation type generates weak ions, and corona discharge type generates air ions by corona discharge. The air ions are attracted to the charged object to compensate for the opposite polarity charge and neutralize the static electricity. A static eliminator using corona discharge and a static eliminator using soft X-rays can be used. Since the first charge removal processing section removes the charge of the base material, the adhesion of the dust and the dielectric breakdown are prevented, thereby improving the yield of the element.
[0037] 第 1アキュームレータ部 204は、ロール 204aが上下方向（図中の矢印方向）に移動 することで、供給部 201から搬送されてくる帯状可撓性支持体 A201aの搬送速度と パターン塗布'乾燥部 205のパターン塗布速度との差を調整するために配設されて おり、一定長さの帯状可撓性支持体 A201aを溜める機能を有しており、第 1アキユー ムレータ部 204の前後で帯状可撓性支持体 A201aの動作を変えることが可能となつ ている。溜める長さの調整は速度差に応じてロール 204aの増設が可能となっている 。ロール 204aは、層形成面を非接触で搬送出来る非接触ロールが好ましい。 [0037] The first accumulator unit 204 moves the roll 204a in the vertical direction (in the direction of the arrow in the figure), and the conveyance speed and pattern application of the belt-like flexible support A201a conveyed from the supply unit 201. It is arranged to adjust the difference from the pattern application speed of the drying unit 205, and has a function of accumulating a belt-like flexible support A201a of a certain length, before and after the first accumulator unit 204. It has become possible to change the operation of the strip-shaped flexible support A201a. The roll length 204a can be adjusted according to the speed difference. The roll 204a is preferably a non-contact roll capable of transporting the layer forming surface in a non-contact manner.
[0038] 本図に示されるパターン塗布 ·乾燥部 205は、有機 EL層形成用塗布液を湿式パタ ーン形成塗布装置により大気圧条件で発光層を形成するパターン塗布部と、大気圧 条件で有機 EL層中の溶媒を除去し、有機 EL層を形成する有機 EL層乾燥部とを 1 ユニットとし設けられている。本図は、 3ユニット（第 1パターン塗布 ·乾燥部 205aと、 第 2パターン塗布'乾燥部 205bと、第 3パターン塗布'乾燥部 205c)を有している場 合を示しており、これらは全て同じ構成となっている。有機 EL層形成用塗布液とは、 正孔輸送層形成用塗布液と、発光層形成用塗布液と、電子輸送層形成用塗布液と を示す。
[0039] 第 1パターン塗布'乾燥部 205aは正孔輸送層形成用塗布液を湿式パターン形成 塗布装置により大気圧条件で正孔輸送層を形成する第 1パターン塗布部 205alと、 大気圧条件で正孔輸送層中の溶媒を除去し、正孔輸送層を形成する正孔輸送層乾 燥部 205a2とを有している。 [0038] The pattern coating / drying unit 205 shown in the figure includes a pattern coating unit that forms a light emitting layer under an atmospheric pressure condition by using a wet pattern formation coating apparatus with an organic EL layer forming coating solution, and an atmospheric pressure condition. The organic EL layer drying section that removes the solvent in the organic EL layer and forms the organic EL layer is provided as one unit. This figure shows the case of having 3 units (first pattern application / drying unit 205a, second pattern application 'drying unit 205b, and third pattern application' drying unit 205c). All have the same configuration. The coating liquid for forming an organic EL layer refers to a coating liquid for forming a hole transport layer, a coating liquid for forming a light emitting layer, and a coating liquid for forming an electron transport layer. [0039] The first pattern application 'drying unit 205a is a first pattern coating unit 205al that forms a hole transport layer under atmospheric pressure conditions by a wet pattern formation coating apparatus using a hole transport layer forming coating solution 205a, and under atmospheric pressure conditions. A hole transport layer drying section 205a2 for removing the solvent in the hole transport layer and forming the hole transport layer.
[0040] 第 2パターン塗布'乾燥部 205bは、発光層形成用塗布液を湿式パターン形成塗布 装置により大気圧条件で発光層形成用塗膜を形成する第 2パターン塗布部 205bl と、大気圧条件で発光層中の溶媒を除去し、発光層を形成する発光層乾燥部 205b 2とを有している。尚、第 2パターン塗布 ·乾燥部 205bの前に第 1除電処理部 203と 同じ除電処理部を設けることが好ましい。 [0040] The second pattern coating / drying unit 205b includes a second pattern coating unit 205bl that forms a coating film for forming a light emitting layer under atmospheric pressure conditions by using a wet pattern forming coating apparatus with a coating solution for forming a light emitting layer. And a light emitting layer drying section 205b 2 for removing the solvent in the light emitting layer and forming the light emitting layer. In addition, it is preferable to provide the same static elimination process part as the 1st static elimination process part 203 before the 2nd pattern application | coating / drying part 205b.
[0041] 第 3パターン塗布'乾燥部 205bは、電子輸送層形成用塗布液を湿式パターン形成 塗布装置により大気圧条件で電子輸送層を形成する第 2パターン塗布部 205blと、 大気圧条件で電子輸送層中の溶媒を除去し、電子輸送層を形成する電子輸送層乾 燥部 205c2とを有している。尚、第 3パターン塗布 ·乾燥部 205cの前に第 1除電処 理部 203と同じ除電処理部を設けることが好ましい。 [0041] The third pattern coating / drying unit 205b includes a second pattern coating unit 205bl that forms an electron transport layer under an atmospheric pressure condition by a wet pattern formation coating apparatus using an electron transport layer forming coating solution, and an electron under an atmospheric pressure condition. It has an electron transport layer drying section 205c2 that removes the solvent in the transport layer and forms an electron transport layer. In addition, it is preferable to provide the same static elimination process part as the 1st static elimination process part 203 before the 3rd pattern application | coating / drying part 205c.
[0042] 第 1パターン塗布部 205alは湿式パターン形成塗布装置 205al lと、帯状可撓性 支持体 Aの保持手段である保持台 205al 2とを有している。第 2パターン塗布部 205 blは湿式パターン形成塗布装置 205bl lと、第 1パターン塗布'乾燥部 205aから送 られてくる正孔輸送層が形成された帯状可撓性支持体の保持手段である保持台 20 5bl 2とを有している。第 3パターン塗布部 205clは湿式パターン形成塗布装置 205 cl lと、第 2パターン塗布.乾燥部 205bから送られてくる発光層が形成された帯状可 橈性支持体の保持手段である保持台 205cl 2とを有している。 [0042] The first pattern application unit 205al includes a wet pattern formation application device 205al l and a holding table 205al 2 which is a means for holding the belt-like flexible support A. The second pattern coating unit 205 bl is a holding means for holding a belt-like flexible support formed with a wet pattern formation coating device 205 bl l and a hole transport layer sent from the first pattern coating and drying unit 205 a. It has 20 5bl 2 pedestals. The third pattern applicator 205cl is a wet pattern forming applicator 205cl and a second pattern applicator, a holder 205cl that is a means for holding the belt-like flexible support on which the light emitting layer sent from the dryer 205b is formed. And 2.
[0043] 第 1パターン塗布部 205al、第 2パターン塗布部 205bl及び第 3パターン塗布部 2 05clには保持手段の他に、ァライメント検出手段（図 6を参照）と、湿式パターン形成 塗布装置の塗布位置補正制御手段（図 6を参照）とを有している [0043] In addition to the holding means, the first pattern application unit 205al, the second pattern application unit 205bl, and the third pattern application unit 205cl, as well as alignment detection means (see FIG. 6) and application of the wet pattern formation application device Position correction control means (see Fig. 6)
加熱処理部 206は正孔輸送層乾燥部 205a2の後側に設けられた加熱処理部 206 aと、発光層乾燥部 205b2の後側に設けられた加熱処理部 206bと、正孔輸送層乾 燥部 205c2の後側に設けられた加熱処理部 206cとを有している。 The heat treatment unit 206 includes a heat treatment unit 206a provided on the rear side of the hole transport layer drying unit 205a2, a heat treatment unit 206b provided on the rear side of the light emitting layer drying unit 205b2, and a hole transport layer drying unit. A heat treatment unit 206c provided on the rear side of the unit 205c2.
[0044] 保持台 205al 2 (205bl 2、 205cl 2)としては帯状可撓性支持体を平面性を保ち
固定出来れば特に限定はなぐ例えば吸引テーブルが挙げられる。吸引テーブルは 、テーブル上に吸着穴を有する機構や、テーブルの載置面が多孔質を有する機構 ゃ静電吸着するもの等が挙げられ、適宜選択し使用することが可能である。好ましく は、載置面が多孔質を有する機構のテーブルが挙げられる。 [0044] As the holding base 205al 2 (205bl 2, 205cl 2), the belt-like flexible support is kept flat. For example, a suction table may be used as long as it can be fixed. Examples of the suction table include a mechanism having a suction hole on the table, a mechanism having a porous surface on which the table is placed, and a table that electrostatically attracts, and can be appropriately selected and used. Preferably, a table having a mechanism in which the mounting surface is porous is used.
[0045] 第 1パターン塗布 ·乾燥部 205aは、供給部 201から搬送されてくる帯状可撓性支 持体 A201aを保持台 205al 2上に固定し、湿式パターン形成塗布装置 205al 1に より、帯状可撓性支持体 A201a上に形成されている第 1電極の端部を除いた領域に 正孔輸送層形成用塗布液を塗布し、正孔輸送層中の溶媒を正孔輸送層乾燥部 20 5a2で除去し正孔輸送層 201 cを形成する。形成された正孔輸送層 201cは加熱処 理部 206aで加熱処理が行われる。第 1パターン塗布'乾燥部 205aで湿式パターン 形成塗布装置 205al lにより塗布が行われるときは、前の工程から搬送されてくる第 1電極が形成された帯状可撓性支持体 Aに設けられたァライメントマーク 4 (図 6を参 照）を第 1パターン塗布部 205alに配設されたァライメント検出手段の検出機により 検出し、帯状可撓性支持体 Aを保持台上に吸着固定し、ァライメントマークに従って 湿式パターン形成塗布装置 205al lの位置合わせが行われ、パターン化されて形 成された第 1電極の端部の一部を除いて第 1電極の領域に、正孔層形成用塗布液 が電極上に塗布される。 [0045] The first pattern application / drying unit 205a fixes the band-shaped flexible support A201a conveyed from the supply unit 201 on the holding base 205al 2 and uses the wet pattern formation coating apparatus 205al 1 to The hole transport layer forming coating solution is applied to the region excluding the end of the first electrode formed on the flexible support A201a, and the solvent in the hole transport layer is removed from the hole transport layer drying unit 20 The hole transport layer 201c is formed by removing with 5a2. The formed hole transport layer 201c is subjected to heat treatment by the heat treatment unit 206a. When coating is performed by the wet pattern forming coating device 205al in the first pattern coating and drying unit 205a, the first pattern coating is provided on the belt-like flexible support A on which the first electrode conveyed from the previous step is formed. Alignment mark 4 (see FIG. 6) is detected by the detector of the alignment detection means arranged in the first pattern application unit 205al, and the belt-like flexible support A is adsorbed and fixed on the holding table. The wet pattern formation coating device 205al l is aligned according to the alignment mark, and the hole layer formation coating is applied to the region of the first electrode except a part of the end portion of the patterned first electrode. The liquid is applied on the electrode.
[0046] 第 2パターン塗布.乾燥部 205bは、第 1パターン塗布'乾燥部 205aから搬送され てくる正孔輸送層 201cが形成された帯状可撓性支持体を保持台 205bl 2上に固定 し、湿式パターン形成塗布装置 205bl lにより、発光層形成用塗布液を第 1電極の パターンに合わせ、形成された正孔輸送層 201cの上に塗布し、発光層中の溶媒を 発光層乾燥部 205b2で除去し発光層 201dを形成する。形成された発光層は加熱 処理部 206bで加熱処理が行われる。第 2パターン塗布 ·乾燥部 205bで湿式パター ン形成塗布装置 205bl lによりパターン塗布が行われるときは、前の工程から搬送さ れてくる正孔輸送層 201cが形成された帯状可撓性支持体に設けられたァライメント マーク 4 (図 6を参照）をパターン塗布部 205bに配設されたァライメント検出手段の検 出機により検出し、帯状可撓性支持体を一旦止め、ァライメントマークに従って湿式 パターン形成塗布装置 205bl lの位置合わせが行われ、パターン化されて形成され
た第 1電極のパターンに従って、発光層形成用塗布液が電極上に塗布される。尚、 湿式パターン形成塗布装置 205bl 1によるパターン形成塗布に関しては図 6で説明 する。 [0046] The second pattern coating / drying unit 205b fixes the belt-like flexible support on which the hole transport layer 201c conveyed from the first pattern coating / drying unit 205a is formed on the holding table 205bl2. Then, using a wet pattern formation coating apparatus 205bl l, the coating solution for forming the light emitting layer is applied to the pattern of the first electrode, applied onto the formed hole transport layer 201c, and the solvent in the light emitting layer is removed from the light emitting layer drying unit 205b2 To remove the light emitting layer 201d. The formed light emitting layer is subjected to heat treatment by the heat treatment unit 206b. When pattern coating is performed by the wet pattern formation coating apparatus 205bl in the second pattern coating / drying unit 205b, a strip-shaped flexible support having the hole transport layer 201c transported from the previous step is formed. Alignment mark 4 (see Fig. 6) provided on the pattern coating unit 205b is detected by a detector of the alignment detection means, and the belt-like flexible support is temporarily stopped, and a wet pattern according to the alignment mark is detected. Forming application device 205bl l is aligned and patterned According to the pattern of the first electrode, the light emitting layer forming coating solution is applied on the electrode. In addition, the pattern formation application by the wet pattern formation application | coating apparatus 205bl1 is demonstrated in FIG.
[0047] 第 3パターン塗布.乾燥部 205cは、第 2パターン塗布'乾燥部 205bから搬送され てくる発光層 201dが形成された帯状可撓性支持体を保持台 205cl 2上に固定し、 湿式パターン形成塗布装置 205cl lにより、電子輸送層形成用塗布液を形成された 発光層 201dの上に塗布し、電子輸送層中の溶媒を電子輸送層乾燥部 205c2で除 去し電子輸送層 201eを形成する。形成された電子輸送層は加熱処理部 206cでカロ 熱処理が行われる。第 3パターン塗布'乾燥部 205cで湿式パターン形成塗布装置 2 05cl lにより塗布が行われるときは、前の工程力 搬送されてくる発光層が形成され た帯状可撓性支持体 Aに設けられたァライメントマーク 4 (図 6を参照）を第 3パターン 塗布部 205clに配設されたァライメント検出手段の検出機により検出し、発光層が形 成された帯状可撓性支持体 Aを保持台上に吸着固定し、ァライメントマークに従って 湿式パターン形成塗布装置 205cl lの位置合わせが行われ、発光層の上に、電子 輸送層形成用塗布液が塗布される。 [0047] The third pattern coating / drying unit 205c fixes the belt-like flexible support on which the light emitting layer 201d conveyed from the second pattern coating / drying unit 205b is formed on the holding table 205cl2, and performs wet processing. The electron transport layer 201d is applied onto the light emitting layer 201d on which the electron transport layer forming coating solution has been formed by using a pattern forming coating device 205cl1, and the solvent in the electron transport layer is removed by the electron transport layer drying unit 205c2 to remove the electron transport layer 201e. Form. The formed electron transport layer is subjected to a calorie heat treatment in the heat treatment unit 206c. When coating is performed by the wet pattern forming coating device 2 05cl in the third pattern coating / drying unit 205c, the previous process force is provided on the belt-like flexible support A on which the light emitting layer is formed. Alignment mark 4 (see Fig. 6) is detected by the detector of the alignment detection means arranged in the third pattern application section 205cl, and the strip-shaped flexible support A with the light emitting layer formed on the holding table The wet pattern formation coating apparatus 205cll is aligned according to the alignment mark, and the electron transport layer forming coating solution is applied onto the light emitting layer.
[0048] 第 1パターン塗布 ·乾燥部 205a〜第 3パターン塗布'乾燥部 205cにより、第 1電極 の端部を除いて正孔輸送層 201cと、発光層 201dと、電子輸送層 201eとを有する 有機 EL層が形成された帯状可撓性支持体 Bが出来上がる。 [0048] The first pattern coating / drying unit 205a to the third pattern coating 'drying unit 205c have the hole transport layer 201c, the light emitting layer 201d, and the electron transport layer 201e except for the end of the first electrode. A belt-like flexible support B on which an organic EL layer is formed is completed.
[0049] 尚、第 1パターン塗布部 205al〜第 3パターン塗布部 205clでの塗布は何れも保 持台に吸着固定した状態で行うため、第 1パターン塗布 ·乾燥部 205aから正孔輸送 層が形成された帯状可撓性支持体 Aの第 2パターン塗布 ·乾燥部 205bへの移動、 第 2パターン塗布 ·乾燥部 205bで発光層が形成された帯状可撓性支持体 Aの第 3 パターン塗布'乾燥部 205への移動、第 3パターン塗布'乾燥部 205から回収部 209 への移動は、各部で各層の塗布が形成された後に行われるため間欠移動となる。 [0049] The first pattern application unit 205al to the third pattern application unit 205cl are all applied while being adsorbed and fixed to the holding base, so that the hole transport layer is formed from the first pattern application / drying unit 205a. Second pattern application of the formed belt-like flexible support A to the drying part 205b, second pattern application.Third pattern application of the belt-like flexible support A with the light emitting layer formed in the drying part 205b 'Moving to the drying unit 205, third pattern application' The moving from the drying unit 205 to the collecting unit 209 is performed after the application of each layer is formed in each unit, and thus is intermittent.
[0050] 湿式パターン形成塗布装置 205al l (205bl l、 205bl l)に使用可能な湿式塗布 機としては、例えば、インクジェット方式、フレキソ印刷方式、オフセット印刷方式、グ ラビア印刷方式、スクリーン印刷方式、マスクを用いたスプレー塗布方式等に使用す る各種塗布装置が挙げられる。これらの湿式パターン形成塗布機の使用は発光層形
成用塗布液の材料に応じて適宜選択することが可能となっている。本図ではインクジ エツト方式の場合を示してレ、る。 [0050] Examples of wet coaters that can be used in the wet pattern forming and coating apparatus 205al l (205bl l, 205bl l) include an inkjet method, a flexographic printing method, an offset printing method, a gravure printing method, a screen printing method, and a mask. Various coating devices used for spray coating methods using the above. The use of these wet pattern forming coating machines is the light emitting layer type It is possible to select appropriately according to the material of the composition coating liquid. This figure shows the ink jet method.
[0051] 第 2除電処理部 207は、第 3パターン塗布 ·乾燥部 205cで形成された電子輸送層 201eを有する帯状可撓性支持体の除電を行い、次工程での静電気に伴う故障を防 止する機能を有し、必要に応じ配設することが可能となっている。第 2除電処理部 20 7は第 1除電処理部 203に使用した除電処理手段と同じ除電処理手段を使用するこ とが好ましい。 [0051] The second static elimination processing unit 207 performs static elimination on the belt-like flexible support having the electron transport layer 201e formed by the third pattern coating / drying unit 205c, and prevents failure due to static electricity in the next process. It has a function to stop and can be arranged as necessary. The second static elimination processing unit 207 preferably uses the same static elimination processing means as that used for the first static elimination processing unit 203.
[0052] 第 2アキュームレータ部 208は、第 2アキュームレータ部 208の後に湿式塗布'乾燥 部（不図示）が配設された場合、ロール 208aが上下方向（図中の矢印方向）に移動 することで、パターン塗布 ·乾燥部 205と湿式塗布 ·乾燥部（不図示）との搬送速度の 差を調整するために配設されており、速度差に応じてロール 208aの増設が可能とな つている。又、第 2アキュームレータ部 208は、パターン塗布'乾燥部 205では帯状可 橈性支持体は停止した状態で間欠搬送されるため、第 2アキュームレータ部 208で 一定量を溜め、回収部 209で溜めた量だけ連続して卷き取る方法に使用することも 可能である。第 2アキュームレータ部 208は、第 1アキュームレータ部 204と同じ機能 を有し、同じ構成となっていることが好ましい。 [0052] When the wet accumulator / drying unit (not shown) is arranged after the second accumulator unit 208, the second accumulator unit 208 moves the roll 208a in the vertical direction (the direction of the arrow in the figure). It is arranged to adjust the difference in transport speed between the pattern coating / drying unit 205 and the wet coating / drying unit (not shown), and the roll 208a can be added according to the speed difference. In addition, the second accumulator unit 208 is intermittently conveyed in a state where the belt-like flexible support is stopped in the pattern application / drying unit 205, so that a certain amount is accumulated in the second accumulator unit 208 and collected in the recovery unit 209. It is also possible to use it in a method of scraping off the amount continuously. The second accumulator unit 208 preferably has the same function as the first accumulator unit 204 and has the same configuration.
[0053] 回収部 209では、第 2除電処理部 207で処理され、有機 EL層が形成された帯状可 橈性支持体 B201fが卷き芯に巻かれロール状態の帯状可撓性支持体 B201gとして 回収され、電子注入層、第 2電極、封止層等を形成する次工程に送る迄保管される。 [0053] In the recovery unit 209, a strip-shaped flexible support B201f processed by the second static elimination processing unit 207 and having an organic EL layer formed thereon is wound around a winding core as a strip-shaped flexible support B201g in a roll state. It is collected and stored until it is sent to the next process for forming the electron injection layer, the second electrode, the sealing layer and the like.
[0054] 図 3は図 2の Pで示される部分の拡大概略図である。尚、回収部 209では、有機 EL 層が形成された帯状可撓性支持体 Bを室温まで冷却装置 (不図示)で冷却した後、 卷き取ることが好ましい。 FIG. 3 is an enlarged schematic view of a portion indicated by P in FIG. In the recovery unit 209, it is preferable that the strip-shaped flexible support B on which the organic EL layer is formed is cooled to room temperature with a cooling device (not shown) and then scraped off.
[0055] 発光層乾燥部 205b2は、乾燥風を吐出する吐出口 205b21と、乾燥風の供給口 2 05b22とを有する乾燥風供給ヘッダー 205b23と、 非気口 205b24と、搬送用ローノレ 205b25とを有してレヽる。 [0055] The light-emitting layer drying unit 205b2 includes a drying air supply header 205b23 having a discharge port 205b21 for discharging a drying air, a drying air supply port 205b22, a non-air opening 205b24, and a transport ronole 205b25. And then sing.
[0056] 加熱処理部 206bは加熱処理装置本体 206blと、第 1電極のパターンに合わせて 正孔輸送層 201 dの上に形成された発光層 201 dを有する帯状可撓性支持体の裏 面側から発光層 201dを裏面伝熱方式で加熱する複数の加熱ローラ 206b2とを有し
ている。加熱処理部 206bで加熱処理することで、更に正孔輸送層を安定化する機 能を有している。図 2示す正孔輸送層乾燥部 205a2と加熱処理部 206a及び電子輸 送層乾燥部 205c2と加熱処理部 206cは本図に示す発光層乾燥部 205b2と加熱処 理部 206bと同じ構造を有し、同じ機能を有している。 [0056] The heat treatment unit 206b includes a heat treatment apparatus main body 206bl and a back surface of a belt-like flexible support having a light emitting layer 201d formed on the hole transport layer 201d in accordance with the pattern of the first electrode. A plurality of heating rollers 206b2 for heating the light emitting layer 201d from the side by a back surface heat transfer method. ing. The heat treatment unit 206b has a function of further stabilizing the hole transport layer by heat treatment. The hole transport layer drying unit 205a2 and the heat treatment unit 206a and the electron transport layer drying unit 205c2 and the heat treatment unit 206c shown in FIG. 2 have the same structure as the light emitting layer drying unit 205b2 and the heat treatment unit 206b shown in FIG. Have the same function.
[0057] 図 4は有機 EL層までを形成する湿式塗布 ·乾燥部とパターン塗布 ·乾燥部とを有す る製造装置の模式図である。以下に、一例としてパターン化されて形成されている第 1電極を有する帯状可撓性支持体上に正孔輸送層、発光層、電子輸送層とを有する 有機 EL層を形成する方法を本図で説明する。 FIG. 4 is a schematic view of a manufacturing apparatus having a wet coating / drying unit and a pattern coating / drying unit for forming layers up to the organic EL layer. The following is a method for forming an organic EL layer having a hole transport layer, a light-emitting layer, and an electron transport layer on a strip-like flexible support having a first electrode that is patterned and formed as an example. I will explain it.
[0058] 図中、 3は有機 EL素子の構成層の 1つである有機 EL層までを大気圧条件下で形 成する製造装置を示す。製造装置 3は、供給部 301と、帯状可撓性支持体の洗浄表 面改質処理部 302と、除電処理部 A303、湿式塗布，乾燥部 304と、除電処理部 B3 05と、第 1アキュームレータ部 306と、パターン塗布'乾燥部 307と、加熱処理部 308 と、除電処理部 C309と、第 2アキュームレータ部 311と回収部 312とを有している。 [0058] In the figure, reference numeral 3 denotes a manufacturing apparatus for forming up to the organic EL layer, which is one of the constituent layers of the organic EL element, under atmospheric pressure conditions. The production apparatus 3 includes a supply unit 301, a cleaning surface modification processing unit 302 for the strip-shaped flexible support, a static elimination processing unit A303, a wet coating / drying unit 304, a static elimination processing unit B3 05, and a first accumulator. A unit 306, a pattern application / drying unit 307, a heat processing unit 308, a charge removal processing unit C 309, a second accumulator unit 311, and a recovery unit 312.
[0059] 供給部 301では、ガスバリア膜と第 1電極を含む陽極層とがこの順番で既に形成さ れた帯状可撓性支持体 A301aが巻き芯に巻き取られロール状態で供給される様に なっている。 301bはロール状態の帯状可撓性支持体 A301aを示す。第 1電極（図 1 、図 6を参照）はパターン化（図 1、図 6を参照）されて形成されている。 [0059] In the supply unit 301, the strip-shaped flexible support A301a in which the gas barrier film and the anode layer including the first electrode are already formed in this order is wound around the winding core and supplied in a roll state. It has become. 301b shows the roll-shaped flexible support A301a in a roll state. The first electrode (see FIGS. 1 and 6) is formed by patterning (see FIGS. 1 and 6).
[0060] 洗浄表面改質処理部 302は、湿式塗布'乾燥部 304で塗布する前に供給部 301 力 送られてきた帯状可撓性支持体 A301aの第 1電極を含む陽極層（不図示)表面 を洗浄改質する洗浄表面改質処理手段 302aとを有してレ、る。洗浄表面改質処理手 段 302aは図 2で示した洗浄表面改質処理手段 202aと同じであり、同じ機能を有し、 同じ条件で洗浄表面改質処理が行うことが可能となっている。 [0060] The cleaning surface modification processing unit 302 is an anode layer (not shown) including the first electrode of the strip-shaped flexible support A301a that has been fed by the supply unit 301 before being applied by the wet application / drying unit 304. And cleaning surface modification processing means 302a for cleaning and modifying the surface. The cleaning surface modification processing means 302a is the same as the cleaning surface modification processing means 202a shown in FIG. 2, has the same function, and can perform the cleaning surface modification processing under the same conditions.
[0061] 除電処理部 A303は、洗浄表面改質処理部 302で処理された帯状可撓性支持体 A301aの除電を行レ、、次工程での静電気に伴う故障を防止する機能を有し、必要 に応じ配設することが可能となっている。除電処理部 A303は図 2に示す第 1除電処 理部 203と同じ除電処理手段を有し、同じ機能を有している。 [0061] The static elimination processing unit A303 has a function of removing static electricity from the belt-like flexible support A301a processed by the cleaning surface modification processing unit 302, and preventing a failure due to static electricity in the next process, It can be installed as needed. The static elimination processing unit A303 has the same static elimination processing means as the first static elimination processing unit 203 shown in FIG. 2, and has the same function.
[0062] 湿式塗布'乾燥部 304は、帯状可撓性支持体 A301aを保持するバックアップロー ノレ 304aと、バックアップロール 304aに保持された帯状可撓性支持体 A301a上にパ
ターン化されて形成されている第 1電極に正孔輸送層形成用塗布液を大気圧条件 下で塗布する湿式塗布機 304bと、帯状可撓性支持体 A301a上の第 1電極上に形 成された正孔輸送層 301c中の溶媒を大気圧条件下で除去する正孔輸送層乾燥部 304cとを有してレ、る。 [0062] The wet coating / drying unit 304 has a backup roll 304a for holding the strip-shaped flexible support A301a and a belt on the strip-shaped flexible support A301a held by the backup roll 304a. Formed on the first electrode on the strip-shaped flexible support A301a and the wet coating machine 304b that applies the coating solution for forming the hole transport layer to the first electrode formed by turning under atmospheric pressure conditions And a hole transport layer drying section 304c for removing the solvent in the hole transport layer 301c under atmospheric pressure.
[0063] 湿式塗布機 304bに使用可能な湿式塗布機としては、例えば、ダイコート方式、スク リーン印刷方式、フレキソ印刷方式、メイヤーバー方式、キャップコート法、スプレー 塗布法、キャスト法、ロールコート法、バーコート法、グラビアコート法等の塗布機の使 用が可能である。これらの湿式塗布機の使用は有機化合物層形成用塗布液有機化 合物層の材料に応じて適宜選択することが可能となっている。 [0063] Examples of the wet coater that can be used for the wet coater 304b include a die coating method, a screen printing method, a flexographic printing method, a Mayer bar method, a cap coating method, a spray coating method, a casting method, a roll coating method, It is possible to use a coating machine such as bar coating or gravure coating. The use of these wet coaters can be appropriately selected according to the material of the organic compound layer forming coating liquid organic compound layer.
[0064] 加熱処理部 308は、正孔輸送層乾燥部 304cの後に配設されている加熱処理部 3 08a、発光層乾燥部 307a2の後に配設されている加熱処理部 308b、電子輸送層乾 燥部 307b2の後に配設されている加熱処理部 308cより構成されており、何れも同じ 構造有している。 [0064] The heat treatment unit 308 includes a heat treatment unit 308a disposed after the hole transport layer drying unit 304c, a heat treatment unit 308b disposed after the light emitting layer drying unit 307a2, and an electron transport layer drying unit. The heat treatment unit 308c is disposed after the drying unit 307b2, and all have the same structure.
[0065] 加熱処理部 308aは、正孔輸送層乾燥部 304cで形成された正孔輸送層 301d、を 有する帯状可撓性支持体の裏面側から裏面伝熱方式で加熱処理し、更に安定化す る機能を有し、必要に応じ配設することが好ましい。 [0065] The heat treatment unit 308a heat-treats from the back surface side of the belt-shaped flexible support having the hole transport layer 301d formed by the hole transport layer drying unit 304c by the back surface heat transfer method, and further stabilizes it. It is preferable to dispose as necessary.
[0066] 加熱処理部 308bは、発光層乾燥部 307alで形成された発光層 201eを有する帯 状可撓性支持体の裏面側から裏面伝熱方式で加熱処理し、更に安定した発光層 20 leとする機能を有し、必要に応じ配設することが好ましい。 [0066] The heat treatment unit 308b heat-treats from the back side of the belt-like flexible support having the light emitting layer 201e formed by the light emitting layer drying unit 307al by the back surface heat transfer method, and further stabilizes the light emitting layer 20 le. It is preferable to dispose as necessary.
[0067] 加熱処理部 308cは、電子輸送層乾燥部 307blで形成された電子輸送層 201fを 有する帯状可撓性支持体の裏面側から裏面伝熱方式で加熱処理し、更に安定した 電子輸送層 20Πとする機能を有し、必要に応じ配設することが好ましい。 [0067] The heat treatment unit 308c is heat-treated by the back surface heat transfer method from the back side of the belt-like flexible support having the electron transport layer 201f formed by the electron transport layer drying unit 307bl, and is further stabilized by the electron transport layer. It has a function of 20 mm and is preferably disposed as necessary.
[0068] 第 1アキュームレータ部 306は、ロール 306aが上下方向（図中の矢印方向）に移動 することで、湿式塗布'乾燥部 304とパターン塗布'乾燥部 307の搬送速度の差を調 整するために配設されており、速度差に応じてロール 306aの増設が可能となってい る。ロール 306aは、正孔輸送層面を非接触で搬送出来る非接触ロールが好ましい。 [0068] The first accumulator unit 306 adjusts the difference in the conveyance speed between the wet coating 'drying unit 304 and the pattern coating' drying unit 307 by moving the roll 306a in the vertical direction (the arrow direction in the figure). The roll 306a can be added according to the speed difference. The roll 306a is preferably a non-contact roll capable of transporting the hole transport layer surface in a non-contact manner.
[0069] パターン塗布 ·乾燥部 307は、発光層形成用塗布液を湿式パターン形成塗布装置 により大気圧条件で発光層を形成するパターン塗布部と、大気圧条件で発光層中の
溶媒を除去する乾燥部とを 1ユニットとした第 1パターン塗布 ·乾燥部 307aと、電子輸 送層形成用塗布液を湿式パターン形成塗布装置により大気圧条件で電子輸送層を 形成するパターン塗布部と、大気圧条件で電子輸送層中の溶媒を除去する電子輸 送層乾燥部とを 1ユニットとした第 2パターン塗布'乾燥部 307bとを有している。第 1 パターン塗布'乾燥部 307aと第 2パターン塗布'乾燥部 307bとは同じ構成となって いる。 [0069] The pattern coating / drying unit 307 includes a pattern coating unit that forms a light emitting layer under a atmospheric pressure condition by using a wet pattern forming coating apparatus with a coating solution for forming a light emitting layer. The first pattern coating / drying unit 307a with the drying unit for removing the solvent as one unit, and the pattern coating unit for forming the electron transport layer under the atmospheric pressure condition by the wet pattern formation coating device using the coating liquid for forming the electron transport layer And an electron transport layer drying section that removes the solvent in the electron transport layer under atmospheric pressure conditions, and a second pattern application / drying section 307b. The first pattern application 'drying unit 307a and the second pattern application' drying unit 307b have the same configuration.
[0070] 第 1パターン塗布'乾燥部 307aは発光層形成用塗布液を湿式パターン形成塗布 装置により大気圧条件で発光層を形成する第 1パターン塗布部 307alと、大気圧条 件で発光層中の溶媒を除去する発光層乾燥部 307a2とを有している。 [0070] The first pattern coating / drying unit 307a is a first pattern coating unit 307al that forms a light emitting layer under an atmospheric pressure condition by using a wet pattern forming coating apparatus with a light emitting layer forming coating solution. And a light emitting layer drying section 307a2 for removing the solvent.
[0071] 第 2パターン塗布 ·乾燥部 307bは、電子輸送層形成用塗布液を湿式パターン形成 塗布装置により大気圧条件下で電子輸送層を形成する第 1パターン塗布部 307bl と、大気圧条件で電子輸送層中の溶媒を除去する電子輸送層乾燥部 307b2とを有 している。 [0071] The second pattern coating / drying unit 307b includes a first pattern coating unit 307bl that forms an electron transport layer under an atmospheric pressure condition by a wet pattern formation coating apparatus using an electron transport layer forming coating solution, and an atmospheric pressure condition. And an electron transport layer drying section 307b2 for removing the solvent in the electron transport layer.
[0072] 除電処理部 Bは、湿式塗布'乾燥部 304で形成された正孔輸送層 301dを有する 帯状可撓性支持体の除電を行い、次工程での静電気に伴う故障を防止する機能を 有し、必要に応じ配設することが可能となっている。 [0072] The static elimination processing section B has a function of performing static elimination on the band-shaped flexible support having the hole transport layer 301d formed by the wet coating / drying section 304 and preventing a failure due to static electricity in the next process. And can be arranged as necessary.
[0073] 第 1パターン塗布部 307alは湿式パターン形成塗布装置 307al lと、正孔輸送層 が形成された帯状可撓性支持体 Aの保持手段である保持台 307al 2とを有している 。第 2パターン塗布部 307blは湿式パターン形成塗布装置 307bl lと、第 1パターン 塗布'乾燥部 307aから送られてくる発光層が形成された帯状可撓性支持体 Aの保 持手段である保持台 307bl 2とを有している。 [0073] The first pattern application unit 307al has a wet pattern formation application device 307al and a holding table 307al 2 which is a holding means for the strip-shaped flexible support A on which the hole transport layer is formed. The second pattern coating unit 307bl includes a wet pattern formation coating device 307bl and a holding base that is a holding means for the belt-like flexible support A on which the light emitting layer sent from the first pattern coating and drying unit 307a is formed. 307bl 2.
[0074] 第 1パターン塗布部 307al、第 2パターン塗布部 307blには保持手段の他に、ァ ライメント検出手段（図 6を参照）と、湿式パターン形成塗布装置の塗布位置補正制 御手段（図 6を参照）とを有している。保持台 307al 2 (307bl 2)としては、図 2に示し た保持台と同じである。 [0074] In addition to the holding means, the first pattern application unit 307al and the second pattern application unit 307bl include alignment detection means (see Fig. 6) and application position correction control means (Fig. 6). The holding table 307al 2 (307bl 2) is the same as the holding table shown in FIG.
[0075] 第 1パターン塗布 ·乾燥部 307aは、湿式塗布'乾燥部 304から搬送されてくる正孔 輸送層が形成された帯状可撓性支持体 Aを保持台 307al 2上に固定し、湿式パタ ーン形成塗布装置 307al lにより、帯状可撓性支持体 A上に形成されている正孔輸
送層上に発光層形成用塗布液を塗布し、発光層中の溶媒を発光層乾燥部 307a2 で除去し発光層 301eを形成する。形成された発光層 301eは加熱処理部 308bで加 熱処理が行われる。第 1パターン塗布'乾燥部 307aで湿式パターン形成塗布装置 3 07al lにより塗布が行われるときは、前の工程力 搬送されてくる正孔輸送層が形成 された帯状可撓性支持体 Aに設けられたァライメントマーク 4 (図 6を参照）を第 1パタ ーン塗布部 307alに配設されたァライメント検出手段の検出機により検出し、帯状可 橈性支持体 Aを保持台上に吸着固定し、ァライメントマークに従って湿式パターン形 成塗布装置 307al lの位置合わせが行われ、パターン化されて形成された第 1電極 の端部の一部を除いて第 1電極のパターンに合わせて、発光層形成用塗布液が電 極上に塗布される。 [0075] The first pattern coating / drying unit 307a fixes the belt-shaped flexible support A on which the hole transport layer transported from the wet coating / drying unit 304 is formed on the holding table 307al 2, and performs wet processing. The hole transport formed on the belt-like flexible support A by the pattern forming coating device 307al l. A coating solution for forming a light emitting layer is applied onto the sending layer, and the solvent in the light emitting layer is removed by the light emitting layer drying unit 307a2 to form the light emitting layer 301e. The formed light emitting layer 301e is subjected to heat treatment in the heat treatment unit 308b. When coating is performed by the wet pattern forming coating device 3 07all in the first pattern coating 'drying unit 307a, it is provided on the belt-like flexible support A on which the hole transport layer to be transported is formed. The alignment mark 4 (see Fig. 6) is detected by the detector of the alignment detection means arranged in the first pattern application section 307al, and the belt-like flexible support A is adsorbed and fixed on the holding table. The wet pattern forming and coating device 307al l is aligned according to the alignment mark, and light emission is performed in accordance with the pattern of the first electrode except for a part of the end portion of the first electrode formed by patterning. A layer-forming coating solution is applied onto the electrode.
[0076] 第 2パターン塗布.乾燥部 307bは、第 1パターン塗布'乾燥部 307aから搬送され てくる発光層 301eが形成された帯状可撓性支持体を保持台 307bl 2上に固定し、 湿式パターン形成塗布装置 307bl lにより、電子輸送層形成用塗布液を形成された 発光層 201dの上に塗布し、電子輸送層中の溶媒を電子輸送層乾燥部 307b2で除 去し電子輸送層 301fを形成する。形成された電子輸送層は加熱処理部 308cで加 熱処理が行われる。第 2パターン塗布'乾燥部 307bで湿式パターン形成塗布装置 3 07bl lにより塗布が行われるときは、前の工程から搬送されてくる発光層が形成され た帯状可撓性支持体 Aに設けられたァライメントマーク 4 (図 6を参照）を第 3パターン 塗布部 307blに配設されたァライメント検出手段の検出機により検出し、発光層が形 成された帯状可撓性支持体 Aを保持台上に吸着固定し、ァライメントマークに従って 湿式パターン形成塗布装置 307bl lの位置合わせが行われ、発光層の上に、電子 輸送層形成用塗布液が塗布される。 [0076] The second pattern coating / drying unit 307b fixes the belt-shaped flexible support on which the light emitting layer 301e conveyed from the first pattern coating / drying unit 307a is formed on the holding table 307bl 2, and is wet. The pattern forming coating apparatus 307bl l applies the electron transport layer forming coating solution onto the light emitting layer 201d, and the solvent in the electron transport layer is removed by the electron transport layer drying unit 307b2 to remove the electron transport layer 301f. Form. The formed electron transport layer is subjected to heat treatment in the heat treatment unit 308c. When coating is performed by the wet pattern forming coating device 3 07bl l in the second pattern coating / drying unit 307b, it is provided on the belt-like flexible support A on which the light emitting layer conveyed from the previous step is formed. Alignment mark 4 (see Fig. 6) is detected by the detector of the alignment detection means arranged in the third pattern application section 307bl, and the strip-shaped flexible support A on which the light emitting layer is formed is placed on the holding table. The wet pattern formation coating device 307bl is aligned according to the alignment mark, and the electron transport layer forming coating solution is applied on the light emitting layer.
[0077] 湿式塗布'乾燥部 304〜第 2パターン塗布'乾燥部 307bにより、第 1電極の端部を 除いて正孔輸送層 301dと、発光層 301eと、電子輸送層 301fとを有する有機 EL層 が形成された帯状可撓性支持体 Bが出来上がる。 [0077] An organic EL having a hole transport layer 301d, a light-emitting layer 301e, and an electron transport layer 301f by wet coating 'drying unit 304 to second pattern coating' drying unit 307b except for the end of the first electrode A belt-like flexible support B having a layer formed thereon is completed.
[0078] 尚、第 1パターン塗布部 307alと第 2パターン塗布部 307blでの塗布は何れも保 持台に吸着固定した状態で行うため、第 1パターン塗布 ·乾燥部 307aから発光層が 形成された帯状可撓性支持体 Aの第 2パターン塗布.乾燥部 307bへの移動、第 2パ
ターン塗布 ·乾燥部 307bから回収部 312への移動は、各部で各層の塗布が形成さ れた後に行われるため間欠移動となる。湿式パターン形成塗布装置 307al l (307b 11)は、図 2で示した湿式パターン形成塗布装置と同じである。本図ではインクジエツ ト塗布装置を使用した場合を示している。 It should be noted that since the application at the first pattern application unit 307al and the second pattern application unit 307bl is performed while being adsorbed and fixed to the holding base, a light emitting layer is formed from the first pattern application / drying unit 307a. Apply the second pattern of the strip-shaped flexible support A. Move to the drying unit 307b, the second pattern The movement from the turn coating / drying unit 307b to the collection unit 312 is performed after the coating of each layer is formed in each unit, and thus is intermittent. The wet pattern formation coating apparatus 307al l (307b 11) is the same as the wet pattern formation coating apparatus shown in FIG. This figure shows the case where an ink jet coating device is used.
[0079] 除電処理部 C309は、第 2パターン塗布'乾燥部 307bで形成された電子輸送層 30 Ifを有する帯状可撓性支持体の除電を行い、次工程での静電気に伴う故障を防止 する機能を有し、必要に応じ配設することが可能となっている。尚、除電処理部 B30 5と除電処理部 C309に使用す除電処理手段は、除電処理部 Aに使用した除電処 理手段と同じ除電処理手段を使用することが好ましい。 [0079] The static elimination processing unit C309 performs static elimination on the belt-like flexible support having the electron transport layer 30 If formed by the second pattern coating / drying unit 307b, and prevents a failure due to static electricity in the next process. It has a function and can be arranged as required. In addition, it is preferable to use the same static elimination processing means as the static elimination processing means used for the static elimination processing section A as the static elimination processing means used for the static elimination processing section B305 and the static elimination processing section C309.
[0080] 第 2アキュームレータ部 309は、第 2アキュームレータ部 308の後に湿式塗布'乾燥 部（不図示）が配設された場合、ロール 208aが上下方向（図中の矢印方向）に移動 することで、パターン塗布 ·乾燥部 307と湿式塗布 ·乾燥部（不図示）との搬送速度の 差を調整するために配設されており、速度差に応じてロール 31 laの増設が可能とな つている。又、第 2アキュームレータ部 311は、パターン塗布'乾燥部 207では帯状可 橈性支持体は停止した状態で間欠搬送されるため、第 2アキュームレータ部 311で 一定量を溜め、回収部 312で溜めた量だけ連続して卷き取る方法に使用することも 可能である。第 2アキュームレータ部 311は、第 1アキュームレータ部 306と同じ機能 を有し、同じ構成となっていることが好ましい。 [0080] The second accumulator unit 309 is configured such that when a wet application / drying unit (not shown) is disposed after the second accumulator unit 308, the roll 208a moves in the vertical direction (the direction of the arrow in the figure). , Arranged to adjust the difference in transport speed between the pattern coating / drying unit 307 and the wet coating / drying unit (not shown), and the roll 31 la can be added according to the speed difference. . In addition, the second accumulator unit 311 is intermittently transported while the belt-like flexible support is stopped in the pattern application / drying unit 207, so that a certain amount is accumulated in the second accumulator unit 311 and collected in the collection unit 312. It is also possible to use it in a method of scraping off the amount continuously. The second accumulator unit 311 preferably has the same function as the first accumulator unit 306 and has the same configuration.
[0081] 回収部 312では、除電処理部 Cで処理され、有機 EL層が形成された帯状可撓性 支持体 B301gが卷き芯に巻かれロール状態の帯状可撓性支持体 B301hとして回 収され、電子注入層、第 2電極、封止層等を形成する次工程に送る迄保管される。尚 、回収部 312では、有機 EL層が形成された帯状可撓性支持体 Bを室温まで冷却装 置 (不図示）で冷却した後、巻き取ることが好ましい。 [0081] In the collection unit 312, the strip-shaped flexible support B301g, which is processed by the static elimination processing unit C and formed with the organic EL layer, is wound around the winding core and collected as a rolled strip-shaped flexible support B301h. It is stored until it is sent to the next process for forming the electron injection layer, the second electrode, the sealing layer and the like. In the collection unit 312, it is preferable that the belt-shaped flexible support B on which the organic EL layer is formed is cooled to room temperature with a cooling device (not shown) and then wound up.
[0082] 図 5は有機 EL層までを形成するパターン塗布 ·乾燥部の前後に湿式塗布 ·乾燥部 を有する製造装置の模式図である。以下に、一例としてパターン化されて形成されて いる第 1電極を有する帯状可撓性支持体上に正孔輸送層、発光層、電子輸送層とを 有する有機 EL層を形成する方法を本図で説明する。 FIG. 5 is a schematic diagram of a manufacturing apparatus having a wet coating / drying unit before and after a pattern coating / drying unit for forming up to an organic EL layer. The following is a method for forming an organic EL layer having a hole transport layer, a light-emitting layer, and an electron transport layer on a strip-shaped flexible support having a first electrode that is patterned and formed as an example. I will explain it.
[0083] 図中、 4は有機 EL素子の構成層の 1つである有機 EL層までを大気圧条件下で形
成する製造装置を示す。製造装置 4は、供給部 401と、帯状可撓性支持体の洗浄表 面改質処理部 402と、除電処理部 a403、第 1湿式塗布 ·乾燥部 404と、加熱処理部 405と、除電処理部 b406と、第 1アキュームレータ部 407と、パターン塗布'乾燥部 4 08と、加熱処理部 409と、除電処理部 c410と、第 2アキュームレータ部 411と、第 2 湿式塗布 ·乾燥部 412と、除電処理部 d414と、回収部 415とを有している。 [0083] In the figure, 4 indicates the shape up to the organic EL layer, which is one of the constituent layers of the organic EL element, under atmospheric pressure conditions. The manufacturing apparatus to be formed is shown. The manufacturing apparatus 4 includes a supply unit 401, a belt-like flexible substrate cleaning surface modification processing unit 402, a static elimination processing unit a403, a first wet coating / drying unit 404, a heat processing unit 405, and a static elimination treatment. Part b406, first accumulator part 407, pattern application / drying part 408, heat treatment part 409, static elimination process part c410, second accumulator part 411, second wet application / drying part 412, static elimination A processing unit d414 and a recovery unit 415 are provided.
[0084] 本図に示す製造装置 4は、第 1アキュームレータ部 407の前に第 1湿式塗布.乾燥 部 404と加熱処理部 406と、第 2アキュームレータ部 411の後に第 2湿式塗布'乾燥 部 412と加熱処理部 413とを配設した構成となっている。 The manufacturing apparatus 4 shown in the figure includes a first wet application / drying unit 404 and a heat treatment unit 406 before the first accumulator unit 407, and a second wet application / drying unit 412 after the second accumulator unit 411. And a heat treatment unit 413 are provided.
[0085] 供給部 401では、ガスバリア膜と第 1電極を含む陽極層とがこの順番で既に形成さ れた帯状可撓性支持体 A401aが巻き芯に巻き取られロール状態で供給される様に なっている。 401bはロール状態の帯状可撓性支持体 A401aを示す。第 1電極（図 1 、図 6を参照）はパターン化（図 1、図 6を参照）されて形成されている。 [0085] In the supply unit 401, the strip-shaped flexible support A401a in which the gas barrier film and the anode layer including the first electrode are already formed in this order is wound around the winding core and supplied in a roll state. It has become. 401b shows the roll-shaped flexible support A401a in a roll state. The first electrode (see FIGS. 1 and 6) is formed by patterning (see FIGS. 1 and 6).
[0086] 洗浄表面改質処理部 402は、第 1湿式塗布 ·乾燥部 404で塗布する前に供給部 4 01から送られてきた帯状可撓性支持体 A401aの第 1電極を含む陽極層（不図示)表 面を洗浄改質する洗浄表面改質処理手段 402aとを有している。 The cleaning surface modification processing unit 402 has an anode layer (including a first electrode of the strip-shaped flexible support A401a sent from the supply unit 401 before being applied by the first wet coating / drying unit 404. (Not shown) cleaning surface modification processing means 402a for cleaning and modifying the surface.
[0087] 除電処理部 a403は、洗浄表面改質処理部 402で処理された帯状可撓性支持体 A 401aの除電を行レ、、次工程での静電気に伴う故障を防止する機能を有し、必要に 応じ配設することが可能となっている。除電処理部 a403は図 2に示す第 1除電処理 部 203と同じ除電処理手段を有し、同じ機能を有している。 [0087] The neutralization processing unit a403 has a function of performing static neutralization of the belt-like flexible support A 401a processed by the cleaning surface modification processing unit 402, and preventing a failure due to static electricity in the next process. It can be arranged as necessary. The charge removal processing unit a403 has the same charge removal processing means as the first charge removal processing unit 203 shown in FIG. 2, and has the same function.
[0088] 第 1湿式塗布 ·乾燥部 404は、帯状可撓性支持体 A401aを保持するバックアップ口 一ノレ 404aと、バックアップロール 404aに保持された帯状可撓性支持体 A401aに正 孔輸送層形成用塗布液を大気圧条件下で塗布する湿式塗布機 404bと、帯状可撓 性支持体 A401a上の第 1電極上に形成された正孔輸送層の溶媒を大気圧条件下 で除去する正孔輸送層乾燥部 405cとを有している。 [0088] The first wet coating / drying unit 404 is formed with a hole transport layer on the back-up opening 404a holding the strip-shaped flexible support A401a and the strip-shaped flexible support A401a held by the backup roll 404a. For removing the solvent of the hole transport layer formed on the first electrode on the wet flexible coater 404b and the strip-shaped flexible support A401a under atmospheric pressure conditions. A transport layer drying section 405c.
[0089] 湿式塗布機 404bは、図 4に示した湿式塗布機 304bと同じである。加熱処理部 40 5は、正孔輸送層乾燥部 405cで形成された正孔輸送層 401cを有する帯状可撓性 支持体 Aの裏面側から裏面伝熱方式で加熱処理し、更に安定した正孔輸送層 401 d とする機能を有し、必要に応じ配設することが好ましい。
[0090] 除電処理部 b406は、第 1湿式塗布 ·乾燥部で形成された正孔輸送層 40 Idが形成 された帯状可撓性支持体 Aの除電を行い、次工程での静電気に伴う故障を防止す る機能を有し、必要に応じ配設することが可能となっている。除電処理部 b406は図 2 に示す第 1除電処理部 203に使用した除電処理手段と同じ除電処理手段を使用す ることが好ましい。 The wet coater 404b is the same as the wet coater 304b shown in FIG. The heat treatment unit 405 heat-treats from the back side of the belt-shaped flexible support A having the hole transport layer 401c formed by the hole transport layer drying unit 405c by the back surface heat transfer method, and further stabilizes the holes. It has a function of forming the transport layer 401 d and is preferably disposed as necessary. [0090] The static elimination processing unit b406 performs static elimination on the belt-shaped flexible support A on which the hole transport layer 40 Id formed in the first wet coating / drying unit is formed, and a failure caused by static electricity in the next process. It has a function to prevent this, and can be installed as necessary. The static elimination processing unit b406 preferably uses the same static elimination processing unit as that used in the first static elimination processing unit 203 shown in FIG.
[0091] 第 1アキュームレータ部 407は、ロール 407aが上下方向（図中の矢印方向）に移動 することで、湿式塗布 ·乾燥部 404とパターン塗布 ·乾燥部 408の搬送速度の差を調 整するために配設されており、速度差に応じてロール 407aの増設が可能となってい る。ロール 406aは、正孔輸送層面を非接触で搬送出来る非接触ロールが好ましい。 [0091] The first accumulator unit 407 adjusts the difference in transport speed between the wet coating / drying unit 404 and the pattern coating / drying unit 408 by moving the roll 407a in the vertical direction (the arrow direction in the figure). The roll 407a can be added according to the speed difference. The roll 406a is preferably a non-contact roll that can transport the hole transport layer surface in a non-contact manner.
[0092] 第 1パターン塗布 ·乾燥部 408は、パターン塗布部 408aと、発光層乾燥部 408bを 有している。パターン塗布部 408aは正孔輸送層 40 Idが形成された帯状可撓性支 持体の保持台 408a2と、正孔輸送層 401d上に第 1電極のパターンに合わせ発光層 形成用塗布液を大気圧条件下でパターン塗布する湿式パターン形成塗布装置 408 a2とを有している。発光層乾燥部 408bは発光層中の溶媒を大気圧条件下で除去す る機能を有しており、図 3に示す発光層乾燥部 205b2と同じ構成を有している。保持 台 408a2としては帯状可撓性支持体を平面性を保ち固定出来れば特に限定はなく 、図 2に示す保持台と同じ構造の保持台の使用が好ましい。 The first pattern application / drying unit 408 includes a pattern application unit 408a and a light emitting layer drying unit 408b. The pattern coating part 408a is a belt-shaped flexible support holding base 408a2 in which the hole transport layer 40 Id is formed, and a large amount of coating solution for forming the light emitting layer is formed on the hole transport layer 401d in accordance with the pattern of the first electrode. A wet pattern formation coating apparatus 408 a2 for pattern coating under atmospheric pressure conditions. The light emitting layer drying unit 408b has a function of removing the solvent in the light emitting layer under atmospheric pressure conditions, and has the same configuration as the light emitting layer drying unit 205b2 shown in FIG. The holding table 408a2 is not particularly limited as long as the belt-like flexible support can be fixed while maintaining flatness, and it is preferable to use a holding table having the same structure as the holding table shown in FIG.
[0093] パターン塗布'乾燥部 408で湿式パターン形成塗布装置 408alにより塗布が行わ れるときは、前の工程力 搬送されてくる正孔輸送層が形成された帯状可撓性支持 体 Aに設けられたァライメントマーク 4 (図 6を参照）をパターン塗布部 408aに配設さ れたァライメント検出手段の検出機により検出し、正孔輸送層が形成された帯状可撓 性支持体 Aを保持台上に吸着固定し、ァライメントマークに従って湿式パターン形成 塗布装置 408alの位置合わせが行われ、パターン化されて形成された第 1電極の端 部の一部を除いて第 1電極のパターンに合わせて、発光層形成用塗布液が電極上 に塗布される。 [0093] When coating is performed by the wet pattern formation coating apparatus 408al in the pattern coating / drying unit 408, the pattern is provided on the belt-like flexible support A on which the hole transport layer to be transported is formed. Alignment mark 4 (see Fig. 6) is detected by the detector of the alignment detection means arranged in the pattern application unit 408a, and the belt-like flexible support A on which the hole transport layer is formed is held on the holding base. Wet-fixed on top and forms wet pattern according to alignment mark.Applicator 408al is aligned and aligned with the pattern of the first electrode except for a part of the end of the first electrode formed by patterning. Then, the light emitting layer forming coating solution is applied onto the electrode.
[0094] 加熱処理部 409は、発光層乾燥部 408bで形成された発光層 401eを有する帯状 可撓性支持体の裏面側から裏面伝熱方式で加熱処理し、更に安定した発光層とす る機能を有し、必要に応じ配設することが好ましい。加熱処理部 409は図 3に示す加
熱処理部 206bと同じ構成を有している。 [0094] The heat treatment unit 409 heat-treats from the back side of the belt-like flexible support having the light-emitting layer 401e formed by the light-emitting layer drying unit 408b by a back-surface heat transfer method, thereby obtaining a more stable light-emitting layer. It has a function, and it is preferable to arrange as needed. The heat treatment unit 409 is shown in FIG. It has the same configuration as the heat treatment part 206b.
[0095] 除電処理部 c410は、発光層が形成された帯状可撓性支持体の除電を行い、次ェ 程での静電気に伴う故障を防止する機能を有し、必要に応じ配設することが可能とな つている。除電処理部 c410は図 2に示す第 1除電処理部 203に使用した除電処理 手段と同じ除電処理手段を使用することが好ましい。 [0095] The charge removal processing unit c410 has a function of removing charges from the belt-like flexible support on which the light emitting layer is formed, and preventing a failure caused by static electricity in the next step, and is disposed as necessary. Is becoming possible. The static elimination processing unit c410 preferably uses the same static elimination processing unit as the static elimination processing unit used in the first static elimination processing unit 203 shown in FIG.
[0096] 第 2アキュームレータ部 411は、ロール 411aが上下方向（図中の矢印方向）に移動 することで、パターン塗布'乾燥部 408と湿式塗布'乾燥部 412との搬送速度の差を 調整するために配設されており、速度差に応じてロール 411aの増設が可能となって いる。第 2アキュームレータ部 411は、第 1アキュームレータ部 407と同じ構成をして いる。 [0096] The second accumulator unit 411 adjusts the difference in conveyance speed between the pattern coating 'drying unit 408 and the wet coating' drying unit 412 by moving the roll 411a in the vertical direction (the arrow direction in the figure). The roll 411a can be added according to the speed difference. The second accumulator unit 411 has the same configuration as the first accumulator unit 407.
[0097] 第 2湿式塗布 ·乾燥部 412は、発光層 401eが形成された帯状可撓性支持体を保 持するバックアップロール 412aと、バックアップロール 412aに保持された発光層 40 leが形成された帯状可撓性支持体に電子輸送層形成用塗布液を大気圧条件下で 塗布する湿式塗布機 412bと、形成された電子輸送層の溶媒を大気圧条件下で除 去する電子輸送層乾燥部 412cとを有している。電子輸送層乾燥部 412cは図 3に示 す発光層乾燥部 205b2と同じ構成を有している。湿式塗布機 412bは、図 4に示した 湿式塗布機 304bと同じである。加熱処理部 413は、電子輸送層乾燥部 412cで形 成された電子輸送層 401fを有する帯状可撓性支持体の裏面側から裏面伝熱方式 で加熱処理し、更に安定した電子輸送層 40 Ifとする機能を有し、必要に応じ配設す ることが好ましい。加熱処理部 413は、図 3に示す加熱処理部 206bと同じ構成を有 している。 [0097] The second wet coating / drying unit 412 is formed with a backup roll 412a holding the belt-like flexible support on which the light emitting layer 401e is formed, and a light emitting layer 40le held on the backup roll 412a. Wet coater 412b that coats the belt-shaped flexible support with a coating solution for forming an electron transport layer under atmospheric pressure, and an electron transport layer drying unit that removes the solvent of the formed electron transport layer under atmospheric pressure. 412c. The electron transport layer drying section 412c has the same configuration as the light emitting layer drying section 205b2 shown in FIG. The wet coater 412b is the same as the wet coater 304b shown in FIG. The heat treatment unit 413 heat-treats from the back side of the belt-like flexible support having the electron transport layer 401f formed by the electron transport layer drying unit 412c by the back surface heat transfer method, and further stabilizes the electron transport layer 40 If It is preferable to dispose as necessary. The heat treatment unit 413 has the same configuration as the heat treatment unit 206b shown in FIG.
[0098] 除電処理部 d414は、第 2湿式塗布 ·乾燥部 412で形成された電子輸送層 401fを 有する帯状可撓性支持体の除電を行い、次工程での静電気に伴う故障を防止する 機能を有し、必要に応じ配設することが可能となっている。除電処理部 d414は図 2 に示す第 1除電処理部 203に使用した除電処理手段と同じ除電処理手段を使用す ることが好ましい。 [0098] The static elimination processing unit d414 performs static elimination on the band-shaped flexible support having the electron transport layer 401f formed by the second wet coating / drying unit 412 and prevents a failure due to static electricity in the next process. And can be arranged as required. The static elimination processing unit d414 preferably uses the same static elimination processing means as that used in the first static elimination processing unit 203 shown in FIG.
[0099] 回収部 415では、除電処理部 d414で処理され、有機 EL層が形成された帯状可撓 性支持体 B401gが卷き芯に巻かれロール状態の帯状可撓性支持体 B401hとして
回収され、電子注入層、第 2電極、封止層等を形成する次工程に送る迄保管される。 尚、回収部 415では、有機 EL層が形成された帯状可撓性支持体 Bを室温まで冷却 装置 (不図示）で冷却した後、巻き取ることが好ましレ、。 [0099] In the collection unit 415, a strip-shaped flexible support B401g, which is processed by the static elimination processing unit d414, and on which the organic EL layer is formed, is wound around the winding core as a rolled strip-shaped flexible support B401h. It is collected and stored until it is sent to the next process for forming the electron injection layer, the second electrode, the sealing layer and the like. In the recovery unit 415, it is preferable that the strip-shaped flexible support B on which the organic EL layer is formed is cooled to room temperature with a cooling device (not shown) and then wound up.
[0100] 本図で示す塗布装置 4は、パターン塗布'乾燥部 408での発光層形成用塗布液の 塗布が停止した状態で行われ、発光層の塗布が終了した時点で、次の発光層形成 用塗布液の塗布を行う間欠搬送となっている。一方、第 1湿式塗布'乾燥部 404では 連続的に正孔輸送層が塗布されており、第 1湿式塗布'乾燥部 404とパターン塗布' 乾燥部 408との速度差を調整するのが第 1アキュームレータ部 407となっており、必 要とする長さが溜められる様に調整されている。又、第 2湿式塗布'乾燥部 412では、 連続的に電子輸送層が塗布されており、パターン塗布'乾燥部 408と第 2湿式塗布' 乾燥部 412との速度差を調整するのが第 2アキュームレータ部 411となっており、必 要とする長さが溜められる様に調整されている。 [0100] The coating apparatus 4 shown in this figure is performed in a state where the coating of the light emitting layer forming coating solution in the pattern coating / drying unit 408 is stopped, and when the light emitting layer is completely coated, the next light emitting layer Intermittent conveyance is performed to apply the forming coating solution. On the other hand, in the first wet application 'drying unit 404, the hole transport layer is continuously applied, and the first wet adjustment' drying unit 404 and the pattern application 'drying unit 408 adjust the speed difference. The accumulator section 407 is adjusted so that the required length can be stored. The second wet coating / drying unit 412 is continuously coated with an electron transport layer, and the second difference is that the speed difference between the pattern coating / drying unit 408 and the second wet coating / drying unit 412 is adjusted. The accumulator unit 411 is adjusted so that the required length can be stored.
[0101] 図 2〜図 5に示される製造装置を使用して、有機 EL層を形成した帯状可撓性支持 体を卷き芯に卷き取る際、通気性のある合紙や有機 EL層面に空間を持たせるスぺ ーサテープを介し卷き取ることが好ましレ、。 [0101] When using the manufacturing apparatus shown in Fig. 2 to Fig. 5 and stripping the strip-shaped flexible support with the organic EL layer formed on the core, air-permeable interleaf or organic EL layer surface It is preferable to use a spacer tape to create space.
[0102] 図 6は図 2の Qで示される部分の拡大概略平面図である。図 6の（a)は図 2の Qで示 されるパターン塗布部の拡大概略平面図である。図 6の（b)は湿式塗布'乾燥部から 搬送されてくる第 1電極の上に正孔輸送層が形成された状態の帯状可撓性支持体 の拡大概略平面図である。 [0102] FIG. 6 is an enlarged schematic plan view of a portion indicated by Q in FIG. FIG. 6 (a) is an enlarged schematic plan view of the pattern application part indicated by Q in FIG. FIG. 6 (b) is an enlarged schematic plan view of the band-shaped flexible support in a state in which a hole transport layer is formed on the first electrode conveyed from the wet coating / drying unit.
[0103] 図中、 Aは青色発光層形成用塗布液をパターン塗布する湿式パターン形成塗布 装置を示し、 Bは緑色発光層形成用塗布液をパターン塗布する湿式パターン形成塗 布装置を示し、 Cは赤色発光層形成用塗布液をパターン塗布する湿式パターン形成 塗布装置を示し、本図の場合は湿式パターン形成塗布装置 205blを構成している。 本図に示す各湿式パターン形成塗布装置 A〜Cはインクジェットヘッドを使用してい る場合を示しており、以下、単にヘッドとも言う。 [0103] In the figure, A shows a wet pattern forming coating apparatus for pattern coating of the blue light emitting layer forming coating liquid, B shows a wet pattern forming coating apparatus for pattern coating of the green light emitting layer forming coating liquid, and C Shows a wet pattern forming coating apparatus for pattern coating the red light emitting layer forming coating liquid. In the case of this figure, a wet pattern forming coating apparatus 205bl is configured. Each of the wet pattern forming and coating apparatuses A to C shown in the figure shows a case where an ink jet head is used, and is hereinafter also simply referred to as a head.
[0104] 205bl 3はヘッド 205bl lを取り付けるステージを示し、ヘッド 205bl l lは幅方向（ 図中の矢印方向）に移動可能となる様に、ステージ 205bl3に配設されている。 205 bl4はステージ 205bl 3を第 1電極 102の上に正孔輸送層 201cが形成された状態
の帯状可撓性支持体の搬送方向（図中の矢印方向）に移動可能となる様に取り付け るステージを示す。第 1電極 102は帯状可撓性支持体 201m上にパターンィ匕して、 一定間隔で連続して帯状可撓性支持体 201mの長さ方向に設けられている。 3は第 1電極 102を含む陽極層が帯状可撓性支持体 201m上に形成された帯状可撓性支 持体 Aに設けられたァライメントマーク 4の検出装置を示す。検出装置 3はァライメント マーク 4の位置に合わせ湿式パターン形成塗布装置 205blのフレーム（不図示）に 配設されている。ヘッドのステージ 205bl 3への配設方法は特に限定はなぐ例えば 各湿式パターン形成塗布装置 A〜Cを単独に配設してもよぐ各湿式パターン形成 塗布装置 A〜Cを纏めてもよぐ必要に合わせて適宜選択することが好ましい。本図 は各湿式パターン形成塗布装置 A〜Cを纏めて配設した場合を示している。 Reference numeral 205bl 3 denotes a stage to which the head 205bl 1 is attached, and the head 205bl ll is disposed on the stage 205bl3 so as to be movable in the width direction (arrow direction in the figure). 205 bl4 is a state in which the hole transport layer 201 c is formed on the first electrode 102 in the stage 205 bl 3. The stage to be mounted so as to be movable in the transport direction (arrow direction in the figure) of the belt-like flexible support is shown. The first electrode 102 is patterned on the strip-shaped flexible support 201m, and is provided in the longitudinal direction of the strip-shaped flexible support 201m continuously at regular intervals. 3 shows a detection device for the alignment mark 4 provided on the strip-shaped flexible support A in which the anode layer including the first electrode 102 is formed on the strip-shaped flexible support 201m. The detection device 3 is arranged on the frame (not shown) of the wet pattern formation coating device 205bl in accordance with the position of the alignment mark 4. There is no particular limitation on the method of disposing the head on the stage 205bl 3. For example, each wet pattern forming coating apparatus A to C may be disposed independently, or each wet pattern forming coating apparatus A to C may be combined. It is preferable to select appropriately according to need. This figure shows a case where wet pattern forming and coating apparatuses A to C are arranged together.
[0105] ァライメントマーク 4は帯状可撓性支持体 Aの搬送方向（図中の矢印方向）に対して 第 1電極 102の右下端と左上端 (或いは右上端と左下端)の少なくとも 2箇所に設け ること力 ヘッド 205bl lの位置を決める関係から好ましい。勿論、ァライメントマーク 4を第 1電極 102の右下端、右上端、左下端、左上端に設けてもかまわない。正孔輸 送層 201cは第 1電極 102の端部 102aを残して第 1パターン塗布.乾燥部 205b (図 2を参照）で全面に塗布'乾燥し形成されている。検出装置 3としては、 CCDカメラ等 が挙げられる。正孔輸送層 201cを有する帯状可撓性支持体と、ステージ 205bl 3と 、ステージ 205bl4と、ヘッド 205bl lの駆動は、検出装置 3によりァライメントマーク 4 の検出情報に従って塗布位置補正制御手段（不図示）により制御可能となっている。 [0105] Alignment mark 4 is at least two places on the lower right end and upper left end (or upper right end and lower left end) of first electrode 102 with respect to the conveyance direction of strip-shaped flexible support A (the direction of the arrow in the figure). It is preferable from the relation of determining the position of the head 205bl. Of course, the alignment mark 4 may be provided on the lower right end, upper right end, left lower end, and left upper end of the first electrode 102. The hole transport layer 201c is formed by applying and drying the entire surface in the first pattern application / drying unit 205b (see FIG. 2), leaving the end 102a of the first electrode 102. An example of the detection device 3 is a CCD camera. The belt-like flexible support having the hole transport layer 201c, the stage 205bl3, the stage 205bl4, and the head 205bl1 are driven according to the detection information of the alignment mark 4 by the detection device 3 according to the detection information of the coating position correction (non- It can be controlled by (shown).
[0106] 本図に示すパターン塗布部で、パターン化されて配設された第 1電極 102上に、第 1電極 102のパターンに合わせて発光層形成用塗布液を塗布する過程を図 5に示す 製造装置を使用し場合に付き、以下に示す。 FIG. 5 shows a process of applying a light emitting layer forming coating solution on the first electrode 102 arranged in a pattern according to the pattern of the first electrode 102 in the pattern application unit shown in FIG. Shown below when the manufacturing equipment is used.
[0107] S1では、前工程の第 1湿式塗布.乾燥部 404と加熱処理部 405でパターン化され て配設された第 1電極 102上に正孔輸送層 401dが形成された帯状可撓性支持体が 、パターン塗布'乾燥部 408のパターン塗布部 408aに送られてくる。 [0107] In S1, the first wet coating in the previous step, a strip-shaped flexible film in which a hole transport layer 401d is formed on the first electrode 102 that is patterned and disposed in the drying unit 404 and the heat treatment unit 405. The support is sent to the pattern coating unit 408a of the pattern coating / drying unit 408.
[0108] S2では、第 1電極 102に設けられたァライメントマーク 4をパターン塗布'乾燥部 40 8に配設された検出装置により検知することで正孔輸送層 401dが形成された帯状可 橈性支持体が保持台 408a2上に吸引固定される。
[0109] S3では、帯状可撓性支持体が保持台 408a2上に吸引固定された情報に基づき、 ステージ 205bl 3 (図 6を参照）が移動し、ヘッドの位置が決められる。 [0108] In S2, the alignment mark 4 provided on the first electrode 102 is detected by the detection device provided in the pattern coating / drying unit 408, whereby the belt-like flexible film having the hole transport layer 401d formed thereon is detected. The support is sucked and fixed onto the holding table 408a2. In S3, the stage 205bl 3 (see FIG. 6) moves based on the information that the belt-like flexible support is sucked and fixed onto the holding table 408a2, and the position of the head is determined.
[0110] S4では、第 1電極 102のパターに合わせ、青色発光層形成用塗布液をヘッド A (図 6を参照）から、緑色発光層形成用塗布液をヘッド B (図 6を参照）から、赤色発光層 形成用塗布液をヘッド C (図 6を参照）から第 1電極 102上に塗布する。ステージ 205 bl3が幅方向に移動することで、青色発光層形成用塗布液、緑色発光層形成用塗 布液、赤色発光層形成用塗布液がパターン化された第 1電極 102の各 1本毎に塗布 される。 [0110] In S4, in accordance with the pattern of the first electrode 102, the coating solution for forming the blue light emitting layer is applied from head A (see FIG. 6), and the coating solution for forming the green light emitting layer is applied from head B (see FIG. 6). Then, a red light emitting layer forming coating solution is applied onto the first electrode 102 from the head C (see FIG. 6). As the stage 205 bl3 moves in the width direction, each of the first electrodes 102 in which the blue light emitting layer forming coating liquid, the green light emitting layer forming coating liquid, and the red light emitting layer forming coating liquid are patterned is used. Applied to.
[0111] S5では、 S4で幅方向の塗布が終了すると、ステージ 205bl4 (図 6を参照）が第 1 電極 102のピッチ分だけ搬送方向に移動し、 S4と同じ様にして青色発光層形成用 塗布液、緑色発光層形成用塗布液、赤色発光層形成用塗布液がパターン化された 第 1電極 102の各 1本毎に塗布される。以下、パターン化された第 1電極 102の全て に青色発光層形成用塗布液、緑色発光層形成用塗布液、赤色発光層形成用塗布 液が塗布される迄、 S4と S5を繰り返す。 [0111] In S5, when application in the width direction is completed in S4, the stage 205bl4 (see Fig. 6) moves in the transport direction by the pitch of the first electrode 102, and is used for forming a blue light emitting layer in the same manner as S4. A coating solution, a green light emitting layer forming coating solution, and a red light emitting layer forming coating solution are applied to each of the patterned first electrodes 102. Thereafter, S4 and S5 are repeated until all of the patterned first electrodes 102 are coated with the blue light emitting layer forming coating solution, the green light emitting layer forming coating solution, and the red light emitting layer forming coating solution.
[0112] S6では、パターン化された第 1電極 102の全てに青色発光層形成用塗布液、緑色 発光層形成用塗布液、赤色発光層形成用塗布液が塗布終了すると、吸引固定が解 除され塗布された部分が発光層乾燥部 408bに送られる。 [0112] In S6, when the coating solution for forming the blue light emitting layer, the coating solution for forming the green light emitting layer, and the coating solution for forming the red light emitting layer is completely applied to all the patterned first electrodes 102, the suction fixation is released. The applied portion is sent to the light emitting layer drying unit 408b.
[0113] S7では、新たな第 1電極 102部がパターン塗布部 408aに送られてくる。以下、 S6 迄のステップが繰り返され、順次、帯状可撓性支持体の搬送方向に設けられた第 1 電極 102上に青色発光層形成用塗布液、緑色発光層形成用塗布液、赤色発光層 形成用塗布液が塗布される。 [0113] In S7, 102 parts of the new first electrode are sent to the pattern application part 408a. Thereafter, the steps up to S6 are repeated, and the blue light emitting layer forming coating solution, the green light emitting layer forming coating solution, and the red light emitting layer are sequentially formed on the first electrode 102 provided in the transport direction of the belt-like flexible support. A forming coating solution is applied.
[0114] S1〜S7では、パターン塗布部 408aで帯状可撓性支持体の搬送は停止しており、 一方湿式塗布'乾燥部 404と加熱処理部 406では連続して搬送しながらされ正孔輸 送層が形成されており、パターン塗布部 408aと湿式塗布 ·乾燥部 404と加熱処理部 405との速度差を調整するのに第 1アキュームレータ部 407が作動し、速度差分だけ 正孔輸送層が形成された帯状可撓性支持体が溜められる様になつている。 [0114] In S1 to S7, the conveyance of the belt-like flexible support is stopped at the pattern application unit 408a, while the wet coating and drying unit 404 and the heat treatment unit 406 are continuously transporting the holes. The first accumulator unit 407 operates to adjust the speed difference between the pattern coating unit 408a, the wet coating / drying unit 404, and the heat treatment unit 405. The formed belt-like flexible support is stored.
[0115] 図 2〜図 6に示される各乾燥部における乾燥条件としては、形成された各塗布膜の 乾燥ムラ、塗膜表面の吹き荒れ等を考慮し、吐出口からの乾燥風の吐出風速 0.：!〜
5m/s、幅手方向の風速分布が 0. 1〜： 10%の気流乾燥が挙げられる。 [0115] The drying conditions in each drying section shown in FIGS. 2 to 6 are determined in consideration of drying unevenness of each formed coating film, rough coating of the coating surface, and the like. .:! ~ Airflow drying of 5m / s, width direction wind velocity 0.1 ~: 10%.
[0116] 図 2〜図 6に示される加熱処理部における加熱条件は、正孔輸送層、発光層、電 子輸送層等の平滑性向上、残留溶媒の除去、硬化等を考慮し、正孔輸送層、発光 層、電子輸送層等のガラス転移温度に対して— 30〜 + 30°C、且つ、正孔輸送層、 発光層、電子輸送層等を構成してレ、る有機化合物の分解温度を超えなレ、温度で裏 面伝熱方式の熱処理を行うことが好ましい。 [0116] The heating conditions in the heat treatment section shown in Figs. 2 to 6 are those that consider the improvement in smoothness of the hole transport layer, light emitting layer, electron transport layer, etc., removal of residual solvent, curing, etc. Decomposes organic compounds that constitute the hole transport layer, light-emitting layer, electron transport layer, etc. at a temperature of -30 to + 30 ° C with respect to the glass transition temperature of the transport layer, light-emitting layer, electron transport layer, etc. It is preferable to perform heat treatment of the back surface heat transfer system at a temperature that does not exceed the temperature.
[0117] 図 4、図 5に示される湿式塗布機で正孔輸送層形成用塗布液及び電子輸送層形 成用塗布液等を塗布するときの帯状可撓性支持体の搬送速度のバラツキは、長手 方向の塗膜厚みムラ等を考慮し、平均搬送速度に対して 0. 2〜： 10%であることが好 ましい。 [0117] When the coating liquid for forming the hole transport layer and the coating liquid for forming the electron transport layer are applied by the wet coater shown in FIGS. In consideration of unevenness in the thickness of the coating film in the longitudinal direction, it is preferably 0.2 to 10% with respect to the average conveyance speed.
[0118] 図 2、図 4、図 5で示される製造装置は、正孔輸送層、発光層、電子輸送層等の形 成は、正孔輸送層、発光層、電子輸送層等の性能維持、異物付着に伴う故障欠陥 の防止等を考慮し、露点温度— 20°C以下、且つ JISB 9920に準拠し、測定した清 浄度がクラス 5以下で、且つ、乾燥部、加熱処理部を除き 10〜45°Cの大気圧条件下 で形成されることが好ましレ、。 [0118] In the manufacturing apparatus shown in FIGS. 2, 4, and 5, the formation of the hole transport layer, the light emitting layer, the electron transport layer, etc. maintains the performance of the hole transport layer, the light emitting layer, the electron transport layer, etc. Considering the prevention of failure defects due to foreign matter adhesion, etc., the dew point temperature is -20 ° C or less, conforms to JISB 9920, and the measured cleanliness is class 5 or less, excluding the drying section and heat treatment section. Preferably formed under atmospheric pressure conditions, 10-45 ° C.
[0119] 本発明においては、有機 EL層（正孔輸送層、発光層、電子輸送層等）が形成され た帯状可撓性支持体 Bが巻き芯に巻かれロール状態として回収され、有機 EL層の 性能維持、未発光故障等を考慮し、 10— 5〜10Paの減圧条件下で保管することが好 ましい。収納期間は、有機 EL層の劣化に起因する酸素や微量水分の除去を考慮し 、 1時間〜 200時間が好ましい。場合によっては加熱環境下で保存してもよい。 In the present invention, the strip-shaped flexible support B on which an organic EL layer (a hole transport layer, a light emitting layer, an electron transport layer, etc.) is formed is wound around a winding core and recovered as a roll, and the organic EL maintain performance of the layers, taking into account the non-light emission failure or the like, it is good preferable to store under a reduced pressure of 10- 5 10 Pa. The storage period is preferably 1 hour to 200 hours in consideration of the removal of oxygen and trace moisture due to the deterioration of the organic EL layer. In some cases, it may be stored in a heated environment.
[0120] 図 2〜図 6に示す製造装置で、第 1電極を含む陽極層が形成された帯状可撓性支 持体 Aを使用し、第 1電極上に有機 EL層（正孔輸送層、発光層、電子輸送層）を形 成し帯状可撓性支持体 Bとした後、帯状可撓性支持体 Bを巻き芯に巻き取りロール 状の帯状可撓性支持体 Bにする有機化合物層の形成方法により蒸着方式に比べ、 次の効果が得られる。 [0120] In the manufacturing apparatus shown in Figs. 2 to 6, a strip-shaped flexible support A having an anode layer including a first electrode is used, and an organic EL layer (hole transport layer) is formed on the first electrode. , Light emitting layer, electron transport layer) to form a strip-shaped flexible support B, and then the organic compound to form the strip-shaped flexible support B on a winding core in the form of a strip-shaped flexible support B The following effects can be obtained by the layer formation method compared to the vapor deposition method.
[0121] 1)パターン塗布 ·乾燥部の前後にアキュームレータ部を配置したことで、発光層形 成用塗布液を塗布するとき、一旦止めて塗布することが可能になり、正確で安定な発 光層の形成が可能となった。
[0122] 2)更に、塗布位置補正制御手段により、ァライメントマークに従って正確な位置に 湿式パターン形成塗布装置を配置することが可能になり、発光層の位置ズレがなくな り、正確で安定な発光層の形成が可能となった。 [0121] 1) Pattern application · By placing the accumulator part before and after the drying part, when applying the coating solution for forming the light emitting layer, it is possible to stop and apply the light, so that accurate and stable light emission is possible. Formation of the layer became possible. [0122] 2) Furthermore, the application position correction control means makes it possible to place the wet pattern forming application device at an accurate position according to the alignment mark, eliminating the misalignment of the light emitting layer, and making it accurate and stable. A light emitting layer can be formed.
[0123] 3)パターン塗布 ·乾燥部の前後にアキュームレータ部を配置したことで、塗布速度 が異なる湿式塗布装置とパターン塗布装置の組合せ使用が可能となり、連続生産が 可能となり、生産性向上が可能となった。 [0123] 3) Pattern application · The accumulator section is placed before and after the drying section, so that wet coating equipment and pattern coating equipment with different coating speeds can be used in combination, enabling continuous production and improving productivity. It became.
[0124] 4)有機物質からなる 1つ又は複数の発光層を形成するのに使用する有機化合物 の使用効率が高くコストを抑えることが可能となる。 [0124] 4) The use efficiency of the organic compound used to form the light-emitting layer or layers made of an organic substance is high, and the cost can be reduced.
[0125] 本発明に係わる正孔輸送層とは、正孔を輸送する機能を有する正孔輸送材料から なり、広い意味で正孔注入層、電子阻止層も正孔輸送層に含まれる。正孔輸送層は 単層又は複数層設けることが出来る。正孔輸送層を複数層設ける場合、湿式塗布- 乾燥部は層の数に合わせ増設する必要があり、同時に加熱処理部も増設することが 好ましい。 [0125] The hole transport layer according to the present invention 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 multiple layers. When a plurality of hole transport layers are provided, it is necessary to increase the wet coating / drying section in accordance with the number of layers, and it is preferable to increase the heat treatment section at the same time.
[0126] 発光層（青色発光層、緑色発光層、赤色発光層）の個々の膜厚は、好ましくは 2〜 lOOnmの範囲で選ばれ、 2〜20nmの範囲にあるのが更に好ましレ、。青、緑、赤の 各発光層の膜厚の関係については、特に制限はないが、 3色の光層中、青発光層が 最も厚いことが好ましい。 [0126] The thickness of each light emitting layer (blue light emitting layer, green light emitting layer, red light emitting layer) is preferably selected in the range of 2 to lOOnm, and more preferably in the range of 2 to 20nm. . There are no particular restrictions on the thickness of the blue, green, and red light emitting layers, but the blue light emitting layer is preferably the thickest among the three color light layers.
[0127] 本発明に係わる発光層は、発光極大波長が 430〜480nmにある層を青発光層、 5 10〜550nmにある層を緑発光層、 600〜640nmの範囲にある層を赤発光層と言う 。これらの発光極大波長の範囲にある発光スペクトルの異なる少なくとも 3層以上の 層を含む。 3層以上であれば、特に制限はない。 4層より多い場合には、同一の発光 スペクトルを有する層が複数層あってもよい。又、前記の極大波長を維持する範囲に おいて、各発光層には複数の発光性化合物を混合してもよい。例えば、青発光層に 、極大波長 430〜480nmの青発光性化合物と、同 510〜550nmの緑発光性化合 物を混合して用いてもよい。発光層に使用する材料は特に限定はなぐ例えば、株式 会社 東レリサーチセンター フラットパネルディスプレイの最新動向 ELディスプレ ィの現状と最新技術動向 228〜332頁に記載されている如き各種材料が挙げられ る。
[0128] 湿式パターン形成塗布機で発光層形成用塗布液を塗布し、乾燥することで形成さ れた発光層は、電極又は電子注入層、正孔輸送層から注入されてくる電子及び正孔 が再結合して発光する層であり、発光する部分は発光層の層内であっても発光層と 隣接層との界面であってもよい。 [0127] The light-emitting layer according to the present invention is a blue light-emitting layer having a maximum emission wavelength of 430 to 480 nm, a green light-emitting layer having a wavelength of 10 to 550 nm, and a red light-emitting layer having a range of 600 to 640 nm. Say. It includes at least three layers with different emission spectra in the range of these emission maximum wavelengths. If it is 3 layers or more, there is no restriction in particular. When there are more than four layers, there may be a plurality of layers having the same emission spectrum. In addition, a plurality of light emitting compounds may be mixed in each light emitting layer within the range where the maximum wavelength is maintained. 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 material used for the light emitting layer is not particularly limited. For example, Toray Research Center, Inc. The latest trends in flat panel displays The current state of EL displays and the latest technological trends Various materials such as those described on pages 228-332 can be mentioned. [0128] The light emitting layer formed by applying the coating solution for forming the light emitting layer with a wet pattern forming coating machine and drying it is an electron or hole injected from the electrode, the electron injection layer, or the hole transport layer. Is a layer that emits light by recombination, and the light emitting portion may be in the layer of the light emitting layer or at the interface between the light emitting layer and the adjacent layer.
[0129] 本発明に係わる第 1電極を含む陽極層が既に形成された帯状可撓性支持体 Aに 使用する帯状可撓性支持体としては、透明樹脂フィルムが挙げられる。樹脂フィルム としては、例えば、ポリエチレンテレフタレート（PET)、ポリエチレンナフタレート（PE N)等のポリエステル、ポリエチレン、ポリプロピレン、セロファン、セルロースジァセテ ート、セノレローストリアセテート、セノレロースアセテートブチレート、セノレロースァセテ ートプロピオネート（CAP)、セルロースアセテートフタレート（TAC)、セルロースナイ トレート等のセルロースエステル類又はそれらの誘導体、ポリ塩化ビニリデン、ポリビ ニノレアノレコーノレ、ポリエチレンビュルアルコール、シンジォタクティックポリスチレン、 ポリカーボネート、ノルボルネン榭脂、ポリメチルペンテン、ポリエーテルケトン、ポリイ ミド、ポリエーテルスルホン（PES)、ポリフエ二レンスルフイド、ポリスルホン類、ポリエ 一テルイミド、ポリエーテルケトンイミド、ポリアミド、フッ素樹脂、ナイロン、ポリメチルメ タクリレート、アクリル或いはポリアリレート類、アートン（商品名 JSR社製）或いはァぺ ル (商品名三井化学社製）とレ、つたシクロォレフイン系樹脂等を挙げられる。 [0129] Examples of the strip-shaped flexible support used for the strip-shaped flexible support A on which the anode layer including the first electrode according to the present invention has already been formed include a transparent resin film. Examples of the resin film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cenorelose triacetate, cenorelose acetate butyrate, cenorelose Cellulose esters such as cetate propionate (CAP), cellulose acetate phthalate (TAC), cellulose nitrate or their derivatives, polyvinylidene chloride, polyvinylenoleoleconole, polyethylene butyl alcohol, syndiotactic polystyrene, polycarbonate, Norbornene resin, polymethylpentene, polyetherketone, polyimide, polyethersulfone (PES), polyphenylene sulfide, polysulfones, polyester Luimide, polyether ketone imide, polyamide, fluororesin, nylon, polymethylmethacrylate, acrylic or polyarylate, Arton (trade name, manufactured by JSR) or pellets (trade name, manufactured by Mitsui Chemicals) and Tetsu, cycloolefin resin Etc.
[0130] 陽極としては、仕事関数の大きい (4eV以上)金属、合金、電気伝導性化合物及び これらの混合物を電極物質とするものが好ましく用いられる。このような電極物質の具 体例としては Au等の金属、 Cul、インジウムチンォキシド（ITO)、 Sn〇、 Zn〇等の導 電性透明材料が挙げられる。又、 IDIX〇（In O · ΖηΟ)等非晶質で透明導電膜を作 製可能な材料を用いてもょレ、。陽極はこれらの電極物質を蒸着やスパッタリング等の 方法により、薄膜を形成させ、フォトリソグラフィ一法で所望の形状のパターンを形成 してもよく、或いはパターン精度をあまり必要としなレ、場合は（100 μ m以上程度）、 上記電極物質の蒸着やスパッタリング時に所望の形状のマスクを介してパターンを 形成してもよレ、。或いは、有機導電性化合物のように塗布可能な物質を用いる場合 には、印刷方式、コーティング方式など湿式製膜法を用いることも出来る。この陽極よ り発光を取り出す場合には、透過率を 10%より大きくすることが望ましぐ又陽極とし
てのシート抵抗は数百 Ω /口以下が好ましい。更に膜厚は材料にもよる力 通常 10 〜1000nm、好ましくは 10〜200nmの範囲で選ばれる。 [0130] As the anode, 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 electrode materials include conductive transparent materials such as metals such as Au, Cul, indium tinoxide (ITO), SnO and ZnO. It is also possible to use an amorphous material such as IDIX ○ (InO · ΖηΟ) that can produce a transparent conductive film. 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 single photolithography method. It is also possible to form a pattern through a mask of the desired shape when depositing or sputtering the electrode material. Or when using the substance which can be apply | coated like an organic electroconductivity compound, wet film forming methods, such as a printing system and a coating system, can also be used. When light emission is extracted from this anode, it is desirable that the transmittance be greater than 10%. The sheet resistance is preferably several hundred Ω / mouth or less. Further, the film thickness is a force depending on the material, and is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.
[0131] 陽極と発光層又は正孔輸送層の間、正孔注入層（陽極バッファ一層）を存在させて もよレ、。注入層とは、駆動電圧低下や発光輝度向上のために電極と有機層間に設け られる層のことで、「有機 EL素子とその工業化最前線（1998年 11月 30日ェヌ'ティ 一-エス社発行）」の第 2編第 2章「電極材料」（123〜166頁）に詳細に記載されてい る。 [0131] A hole injection layer (anode buffer layer) may exist between the anode and the light emitting layer or the hole transport layer. The injection layer is a layer that is provided between the electrode and the organic layer in order to lower the drive voltage and increase the luminance of the light emission. “The organic EL element and its forefront of industrialization (November 30, 1998 The details are described in Volume 2, Chapter 2, “Electrode Materials” (pages 123-166).
[0132] 陽極バッファ一層（正孔注入層）は、特開平 9— 45479号公報、同 9一 260062号 公報、同 8— 288069号公報等にもその詳細が記載されており、具体例として、銅フ タロシアニンに代表されるフタロシアニンバッファ一層、酸化バナジウムに代表される 酸化物バッファ一層、アモルファスカーボンバッファ一層、ポリア二リン（ェメラルディ ン)やポリチォフェン等の導電性高分子を用いた高分子バッファ一層等が挙げられる 。陽極バッファ一層（正孔注入層）はごく薄い膜であることが望ましぐ素材にもよるが その膜厚は 0. 1ηιη〜5 μ ΐηの範囲が好ましい。 [0132] The details of the anode buffer layer (hole injection layer) are described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069 and the like. One layer of phthalocyanine buffer typified by copper phthalocyanine, one layer of oxide buffer typified by vanadium oxide, one layer of amorphous carbon buffer, one layer of polymer buffer using a conductive polymer such as polyaniline (emeraldine) or polythiophene, etc. Can be mentioned. The thickness of the anode buffer layer (hole injection layer) is preferably in the range of 0.1ηιη to 5μ が η, although it depends on the material desired to be a very thin film.
[0133] 帯状可撓性支持体として使用する樹脂フィルムの表面にはガスバリア膜が必要に 応じて形成されていてもよい。ガスバリア膜としては無機物、有機物の被膜又はその 両者のハイブリッド被膜が挙げられる。ガスバリア膜の特性としては、水蒸気透過度 が 0. 01g/m2' day' atm以下であることが好ましい。更には、酸素透過度 10— 3g/m 2/day以下、水蒸気透過度 10— 5g/m2/day以下の高バリア性フィルムであることが 好ましい。 [0133] A gas barrier film may be formed on the surface of the resin film used as the belt-like flexible support, if 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, the oxygen permeability 10- 3 g / m 2 / day or less, is preferably a high barrier film follows the water vapor transmission rate 10- 5 g / m 2 / day .
[0134] バリア膜を形成する材料としては、水分や酸素など素子の劣化をもたらすものの浸 入を抑制する機能を有する材料であればよぐ例えば、酸化珪素、二酸化珪素、窒 化珪素などを用いることが出来る。更に該膜の脆弱性を改良するためにこれら無機 層と有機材料からなる層の積層構造を持たせることがより好ましい。無機層と有機層 の積層順については特に制限はないが、両者を交互に複数回積層させることが好ま しい。ノ^ァ膜の形成方法については、特に限定はなぐ例えば真空蒸着法、スパッ タリング法、反応性スパッタリング法、分子線エピタキシー法、クラスタ一イオンビーム 法、イオンプレーティング法、プラズマ重合法、大気圧プラズマ重合法、プラズマ CV
D法、レーザー CVD法、熱 CVD法、コーティング法などを用いることが出来る力 特 開 2004— 68143号に記載されているような大気圧プラズマ重合法によるものが特に 好ましい。 [0134] As a material for forming the barrier film, any material may be used as long as it has a function of suppressing intrusion of elements such as moisture and oxygen that cause deterioration of the element. For example, silicon oxide, silicon dioxide, silicon nitride, or the like is used. I can do it. 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. The order of lamination of the inorganic layer and the organic layer is not particularly limited, but it is preferable to laminate the layers alternately several times. There are no particular restrictions on the method of forming the nano film, for example, vacuum deposition, sputtering, reactive sputtering, molecular beam epitaxy, cluster-one ion beam, ion plating, plasma polymerization, atmospheric pressure Plasma polymerization method, plasma CV Forces capable of using D method, laser CVD method, thermal CVD method, coating method, etc. Specially, those by atmospheric pressure plasma polymerization method as described in 2004-68143 are particularly preferable.
[0135] 正孔輸送材料としては、正孔の注入又は輸送、電子の障壁性の何れ力、を有するも のであり、有機物、無機物の何れであってもよレ、。例えば、トリァゾール誘導体、ォキ サジァゾール誘導体、イミダゾール誘導体、ポリアリールアルカン誘導体、ピラゾリン 誘導体及びピラゾロン誘導体、フヱニレンジァミン誘導体、ァリールァミン誘導体、アミ ノ置換カルコン誘導体、ォキサゾール誘導体、スチリルアントラセン誘導体、フルォレ ノン誘導体、ヒドラゾン誘導体、スチルベン誘導体、シラザン誘導体、ァニリン系共重 合体、又導電性高分子オリゴマー、特にチォフェンオリゴマー等が挙げられる。 [0135] The hole transporting material has any 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, vinylene diamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone Derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, conductive polymer oligomers, particularly thiophene oligomers, and the like.
[0136] 本発明に係わる正孔輸送に使用する材料としては、ボルフイリンィ匕合物、芳香族第 3級ァミン化合物及びスチリルァミン化合物、特に芳香族第 3級ァミン化合物を用いる ことが好ましレ、。芳香族第 3級ァミン化合物及びスチリルアミン化合物の代表例として は、 N, N, N' , N' —テトラフエニル一 4, 4' —ジァミノフエニル； N, N' —ジフエ ニル一 N, N' —ビス（3—メチルフエ二ル）一〔1 , 1' —ビフエ二ル〕一 4, 4' —ジァ ミン (TPD) ; 2, 2—ビス（4—ジ一 p—トリルァミノフエニル）プロパン； 1 , 1—ビス（4— ジ一 p—トリルァミノフエニル）シクロへキサン； N, N, N' , N' —テトラ一 p—トリノレ一 4, 4' —ジアミノビフエニル； 1 , 1—ビス（4—ジ一 p—トリルァミノフエ二ル）一 4—フエ ニルシクロへキサン；ビス（4 -ジメチルァミノ一 2—メチルフエニル）フエニルメタン；ビ ス（4—ジ一 p—トリルァミノフエニル）フエニルメタン； N, N' —ジフエ二ノレ一 N, N' —ジ（4—メトキシフエ二ル）一 4, 一ジアミノビフエニル； N, N, N' , N' —テトラ フエ二ノレ一 4, 一ジアミノジフエニルエーテル； 4, 一ビス（ジフエニルァミノ）ク オードリフエニル； N， N， N—トリ（p—トリル）ァミン； 4_ (ジ— p—トリルァミノ）—4' - [4- (ジ一 p—トリルァミノ）スチリル〕スチルベン；4 _N， N_ジフヱニルァミノ一（2 —ジフエ二ルビニル）ベンゼン； 3—メトキシ一 _N, N—ジフエニルアミノスチルべ ンゼン； N _フヱニルカルバゾール、更には米国特許第 5， 061 , 569号明細書に記 載されている 2個の縮合芳香族環を分子内に有するもの、例えば、 4, Α' 一ビス〔Ν - (1—ナフチル） _Ν_フエニルァミノ〕ビフヱニル（NPD)、特開平 4— 308688号
公報に記載されているトリフエニルァミンユニットが 3つスターバースト型に連結された 4, 4' , A" —トリス〔N— (3—メチルフエ二ル）一 N—フエニルァミノ〕トリフエニルアミ ン（MTDATA)等が挙げられる。 [0136] As a material used for hole transport according to the present invention, it is preferable to use a borfilin 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-1,4′—diaminophenyl; N, N′—diphenyl-1, N, N ′ —bis. (3-methylphenyl) 1 [1, 1'-biphenyl] 1, 4, 4'-diamine (TPD); 2, 2-bis (4-di-1-p-tolylaminophenyl) propane; 1, 1-bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ′, N ′ —tetra-p-trinore 4, 4′—diaminobiphenyl; 1, 1— Bis (4-di-1-p-tolylaminophenyl) 1-4-phenylcyclohexane; Bis (4-dimethylamino-1-methylphenyl) phenylmethane; Bis (4-di-1-p-tolylaminophenyl) phenylmethane; N, N'—Diphenylol N, N ′ —Di (4-methoxyphenyl) -1,4 diaminobiphenyl; N, N, N ′, N ′ Tetraphenylol 4, monodiaminodiphenyl ether; 4, monobis (diphenylamino) quaternary phenyl; 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-1-N, N-diphenylaminostilbenzene; N _F ヱNylcarbazole and, further, those having two condensed aromatic rings described in US Pat. No. 5,061,569 in the molecule, for example, 4, Α 'bis [Ν-(1- Naphthyl) _phenylamine] biphenyl (NPD), Japanese Patent Laid-Open No. 4-308688 4, 4 ', A "—Tris [N— (3-methylphenyl) -1-N-phenylamino] triphenylamine (MTDATA), in which three triphenylamine units described in the publication are linked in a starburst type Etc.
[0137] 更にこれらの材料を高分子鎖に導入した、又はこれらの材料を高分子の主鎖とした 高分子材料を用いることも出来る。又、 P型— Si、 p型— SiC等の無機化合物も正孔 注入材料、正孔輸送材料として使用することが出来る。 [0137] Further, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used. Inorganic compounds such as P-type-Si and p-type-SiC can also be used as hole injection materials and hole transport materials.
[0138] 又、特開平 1 1— 251067号公報、 J. Huang et. al.著文献 (Applied Physics [0138] Also, Japanese Patent Laid-Open No. 11-251067, J. Huang et. Al. (Applied Physics
Letters 80 (2002) , p. 139)に記載されているような所謂 p型正孔輸送材料を用 レ、ることも出来る。本発明においては、より高効率の発光素子が得られることから、こ れらの材料を用いることが好ましい。 It is also possible to use a so-called p-type hole transport material as described in Letters 80 (2002), p. 139). In the present invention, it is preferable to use these materials because a light emitting element with higher efficiency can be obtained.
[0139] 正孔輸送層の膜厚については特に制限はないが、通常は 5nm〜5 z m程度、好ま しくは 5〜200nmである。この正孔輸送層は上記材料の 1種又は 2種以上からなる一 層構造であってもよい。又、不純物をドープした p性の高い正孔輸送層を用いることも 出来る。その例としては、特開平 4一 297076号、特開 2000— 196140号、特開 20 01— 102175号、 J. Appl. Phys. , 95, 5773 (2004)などに記載されたもの力 S挙 げられる。このような p性の高い正孔輸送層を用いることが、より低消費電力の有機 E L素子を作製することが出来るため好ましい。 [0139] The thickness of the hole transport layer is not particularly limited, but is usually about 5 nm to 5 zm, preferably 5 to 200 nm. The hole transport layer may have a single layer structure composed of one or more of the above materials. It is also possible to use a hole transport layer having a high p property doped with impurities. Examples thereof include those described in JP-A-41-297076, JP-A-2000-196140, JP-A-2001-102175, J. Appl. Phys., 95, 5773 (2004), etc. It is done. It is preferable to use such a high p property hole transport layer because an organic EL device with lower power consumption can be produced.
[0140] 次に、本発明に係る有機 EL層の構成に使用される他の構成部材に付き説明する 。発光層に隣接して設けられる層として阻止層が挙げられる。阻止層としては正孔阻 止層、電子阻止層が挙げられる。阻止層は、有機化合物薄膜の基本構成層の他に 必要に応じて設けられるものである。例えば、特開平 1 1— 204258号公報、同 1 1— 204359号公報、及び「有機 EL素子とその工業化最前線（1998年 1 1月 30日ェヌ · ティー.エス社発行）」の 237頁等に記載されている正孔阻止（ホールブロック)層があ る。正孔阻止層とは広い意味では電子輸送層の機能を有し、電子を輸送する機能を 有しつつ正孔を輸送する能力が著しく小さい正孔阻止材料からなり、電子を輸送し つつ正孔を阻止することで電子と正孔の再結合確率を向上させることが出来る。又、 後述する電子輸送層の構成を必要に応じて、本発明に係わる正孔阻止層として用い ることが出来、正孔阻止層は、発光層に隣接して設けられていることが好ましい。
[0141] 発光層が、複数の発光色の異なる発光層を有する場合には、その発光極大波長が 最も短波にある発光層が、全発光層中、最も陽極に近レ、ことが好ましいが、このような 場合、該最短波層と、該層の次に陽極に近い発光層との間に正孔阻止層を追加し て設けることが好ましい。更には、該位置に設けられる正孔阻止層に含有される化合 物の 50質量％以上が、前記最短波発光層のホスト化合物に対し、そのイオン化ポテ ンシャルが 0. 3eV以上大きいことが好ましい。 [0140] Next, other components used for the configuration of the organic EL layer according to the present invention will be described. Examples of the layer provided adjacent to the light emitting layer include a blocking layer. Examples of the blocking layer include a hole blocking layer and an electron blocking layer. The blocking layer is provided as necessary in addition to the basic constituent layer of the organic compound thin film. For example, JP-A-11-204258, 11-204359, and “Organic EL device and its industrialization front line (published on January 30, 1998 by NTS)” on page 237. There is a hole blocking layer described in the above. The hole blocking layer has a function of an electron transport layer in a broad sense, and is made of a hole blocking material that has a function of transporting electrons but has a very small ability to transport holes. By blocking this, the recombination probability of electrons and holes can be improved. Further, the structure of the electron transport layer described later can be used as a hole blocking layer according to the present invention, if necessary, and the hole blocking layer is preferably provided adjacent to the light emitting layer. [0141] When the light emitting layer has a plurality of light emitting layers having different emission colors, the light emitting layer whose emission maximum wavelength is the shortest is preferably closest to the anode among all the light emitting layers, In such a case, it is preferable to provide an additional hole blocking layer between the shortest wave layer and the light emitting layer next to the anode next to the anode. Further, it is preferable that 50% by mass or more of the compound contained in the hole blocking layer provided at the position has an ionization potential of 0.3 eV or more larger than the host compound of the shortest wave emitting layer.
[0142] イオン化ポテンシャルは化合物の H〇M〇（最高被占分子軌道）レベルにある電子 を真空準位に放出するのに必要なエネルギーで定義され、例えば下記に示すような 方法により求めることが出来る。 （1)米国 Gaussian社製の分子軌道計算用ソフトゥェ ァである Gaussian98 (Gaussian98、 Revision A. 11. 4， M. J. Frisch, et al, Gaussian, Inc. , Pittsburgh PA, 2002. )を用レ、、キーワードとして B3LYP/6 _ 31G *を用いて構造最適化を行うことにより算出した値 (eV単位換算値)の小数 点第 2位を四捨五入した値としてイオン化ポテンシャルを求めることが出来る。この計 算値が有効な背景には、この手法で求めた計算値と実験値の相関が高いためであ る。 （2)イオン化ポテンシャルは光電子分光法で直接測定する方法により求めること も出来る。例えば、理研計器社製の低エネルギー電子分光装置「Model AC- lj を用いて、或いは紫外光電子分光として知られてレ、る方法を好適に用いることが出 来る。 [0142] The ionization potential is defined by the energy required to emit electrons at the H ○ M ○ (highest occupied molecular orbital) level of a compound to the vacuum level. For example, the ionization potential can be obtained by the method shown below. I can do it. (1) US Gaussian molecular orbital calculation software Gaussian98 (Gaussian98, Revision A. 11.4, MJ Frisch, et al, Gaussian, Inc., Pittsburgh PA, 2002.) As a result, the ionization potential can be obtained by rounding off the second decimal place of the value (eV unit conversion value) calculated by optimizing the structure using B3LYP / 6_31G *. The reason why this calculated value is effective is that there is a high correlation between the calculated value obtained by this method and the experimental value. (2) The ionization potential can also be obtained by a direct measurement method using photoelectron spectroscopy. For example, a low-energy electron spectrometer “Model AC-lj” manufactured by Riken Keiki Co., Ltd. or a method known as ultraviolet photoelectron spectroscopy can be preferably used.
[0143] 一方、電子阻止層とは広い意味では正孔輸送層の機能を有し、正孔を輸送する機 能を有しつつ電子を輸送する能力が著しく小さい材料からなり、正孔を輸送しつつ電 子を阻止することで電子と正孔の再結合確率を向上させることが出来る。又、後述す る正孔輸送層の構成を必要に応じて電子阻止層として用いることが出来る。本発明 に係わる正孔阻止層、電子輸送層の膜厚としては好ましくは 3nm〜： !OOnmであり、 更に好ましくは 5nm〜30nmである。 [0143] On the other hand, the electron blocking layer has a function of a hole transport layer in a broad sense, and is made of a material having a function of transporting holes and a very small ability to transport electrons, and transports holes. However, by blocking electrons, the probability of recombination of electrons and holes can be improved. Moreover, the structure of the positive hole transport layer mentioned later can be used as an electron blocking layer as needed. The film thickness of the hole blocking layer and the electron transporting layer according to the present invention is preferably 3 nm to:! OOnm, and more preferably 5 nm to 30 nm.
[0144] 本発明の有機 EL層を構成している発光層には、発光層の発光効率を高くするた めに公知のホストィヒ合物と公知のリン光性化合物（リン光発光性化合物とも言う）を含 有することが好ましい。ホストイ匕合物とは、発光層に含有される化合物の内で、その層 中での質量比が 20%以上であり、且つ室温（25°C)においてリン光発光のリン光量
子収率が、 0. 1未満の化合物と定義される。好ましくはリン光量子収率が 0. 01未満 である。ホストイ匕合物を複数種併用して用いてもよい。ホスト化合物を複数種用いるこ とで、電荷の移動を調整することが可能であり、有機 EL層を高効率化することが出来 る。又、リン光性化合物を複数種用いることで、異なる発光を混ぜることが可能となり、 これにより任意の発光色を得ることが出来る。リン光性化合物の種類、ドープ量を調 整することで白色発光が可能であり、照明、ノ ックライトへの応用も出来る。 [0144] In the light emitting layer constituting the organic EL layer of the present invention, a known host compound and a known phosphorescent compound (also called a phosphorescent compound) are used in order to increase the light emission efficiency of the light emitting layer. ) Is preferable. The host compound is a compound contained in the light-emitting layer, the mass ratio of which is 20% or more, and the amount of phosphorescent phosphorescence at room temperature (25 ° C). A child yield is defined as a compound of less than 0.1. Preferably, the phosphorescence quantum yield is less than 0.01. A plurality of host compounds may be used in combination. By using multiple types of host compounds, it is possible to adjust the charge transfer, and the organic EL layer can be made highly efficient. In addition, by using a plurality of phosphorescent compounds, it is possible to mix different light emission, thereby obtaining an arbitrary emission color. White light emission is possible by adjusting the type of phosphorescent compound and the amount of doping, and it can also be applied to lighting and knocklights.
[0145] これらのホストイ匕合物としては、正孔輸送能、電子輸送能を有しつつ、且つ発光の 長波長化を防ぎ、尚且つ高 Tg (ガラス転移温度）である化合物が好ましい。公知のホ ス卜ィ匕合物としては、 ί列えは、、特開 2001— 257076号公幸艮、同 2002— 308855号 公報、同 2001— 313179号公報、同 2002— 319491号公報、同 2001— 357977 号公報、同 2002— 334786号公報、同 2002— 8860号公報、同 2002— 334787 号公報、同 2002— 15871号公報、同 2002— 334788号公報、同 2002— 43056 号公報、同 2002— 334789号公報、同 2002— 75645号公報、同 2002— 33857 9号公報、同 2002— 105445号公報、同 2002— 343568号公報、同 2002— 141 173号公報、同 2002— 352957号公報、同 2002— 203683号公報、同 2002— 3 63227号公報、同 2002— 231453号公報、同 2003— 3165号公報、同 2002— 2 34888号公報、同 2003— 27048号公報、同 2002— 255934号公報、同 2002— 260861号公報、同 2002— 280183号公報、同 2002— 299060号公報、同 2002 — 302516号公報、同 2002— 305083号公報、同 2002— 305084号公報、同 20 02— 308837号公報等に記載の化合物が挙げられる。 [0145] As these host compounds, compounds having a hole transporting ability and an electron transporting ability, preventing the emission of longer wavelengths, and having a high Tg (glass transition temperature) are preferable. As a known host compound, the following materials are disclosed in Japanese Laid-Open Patent Publication Nos. 2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001. — No. 357977, No. 2002-334786, No. 2002-8860, No. 2002-334787, No. 2002-15871, No. 2002-334788, No. 2002-43056, No. 2002- 334789, 2002-75645, 2002-33857 9, 2002-105445, 2002-343568, 2002-141 173, 2002-352957, 2002 -203683, 2002- 3 63227, 2002-231453, 2003-3165, 2002-2 34888, 2003-27048, 2002-255934, 2002-260861, 2002-280183, 2002-299060, 2002-302516, 2002-305083, 2002-305084 A compound according to the 20 02 308 837 JP-like.
[0146] 発光層が複数の発光層を有する場合、これら各層のホストィヒ合物の 50質量％以上 が同一の化合物であることが、発光層全体に渡って均質な膜性状を得やすレ、ことか ら好ましく、更にはホストイ匕合物のリン光発光エネルギーが 2. 9eV以上であることが、 ドーパントからのエネルギー移動を効率的に抑制し、高輝度を得る上で有利となるこ とからより好ましい。リン光発光エネルギーとは、ホストイ匕合物を基板上に lOOnmの 蒸着膜のフォトルミネッセンスを測定し、そのリン光発光の 0— 0バンドのピークェネル ギーを言う。 [0146] When the light-emitting layer has a plurality of light-emitting layers, it is easy to obtain uniform film properties over the entire light-emitting layer that 50% by mass or more of the host compound in each layer is the same compound. Furthermore, it is more preferable that the phosphorescence energy of the host compound is 2.9 eV or more because it is advantageous for efficiently suppressing energy transfer from the dopant and obtaining high luminance. preferable. Phosphorescence emission energy refers to the peak energy of the 0-0 band of phosphorescence emission measured by measuring the photoluminescence of the deposited film of lOOnm on the substrate with the host compound.
[0147] ホストイ匕合物は、本発明の有機 EL層を使用して有機 EL素子としたとき、有機 EL素
子の経時での劣化 (輝度低下、膜性状の劣化）、光源としての市場ニーズ等を考慮し[0147] When the host compound is an organic EL element using the organic EL layer of the present invention, the organic EL element Considering the deterioration of the child over time (decrease in brightness, deterioration of film properties), market needs as a light source, etc.
、リン光発光エネルギーが 2. 9eV以上且つ Tgが 90°C以上のものであることが好まし レ、。即ち、輝度と耐久性の両方を満足するためには、リン光発光エネルギーが 2. 9e V以上且つ Tgが 90°C以上のものであることが好ましレ、。 Tgは、更に好ましくは 100 °C以上である。 It is preferable that the phosphorescence energy is 2.9 eV or more and Tg is 90 ° C or more. In other words, in order to satisfy both luminance and durability, it is preferable that the phosphorescent energy is 2.9 eV or more and Tg is 90 ° C or more. Tg is more preferably 100 ° C or higher.
[0148] リン光性化合物（リン光発光性化合物）とは、励起三重項からの発光が観測される 化合物であり、室温（25°C)にてリン光発光する化合物であり、リン光量子収率が、 25 °Cにおいて 0. 01以上の化合物である。先に説明したホストイ匕合物と合わせ使用する ことで、より発光効率の高い有機 EL素子とすることが出来る。 [0148] A phosphorescent compound (phosphorescent compound) is a compound in which light emission from an excited triplet is observed, and is a compound that emits phosphorescence at room temperature (25 ° C). A compound having a rate of 0.01 or more at 25 ° C. When used in combination with the host compound described above, an organic EL device with higher luminous efficiency can be obtained.
[0149] 本発明に係るリン光性化合物は、リン光量子収率は好ましくは 0. 1以上である。上 記リン光量子収率は、第 4版実験化学講座 7の分光 IIの 398頁（1992年版、丸善）に 記載の方法により測定出来る。溶液中でのリン光量子収率は種々の溶媒を用いて測 定出来るが、本発明に用いられるリン光性化合物は、任意の溶媒の何れかにおいて 上記リン光量子収率が達成されればょレ、。 [0149] The phosphorescent compound according to the present invention preferably has a phosphorescence quantum yield of 0.1 or more. The above phosphorescence quantum yield can be measured by the method described on page 398 (1992 edition, Maruzen) of Spectroscopic II, 4th edition, Experimental Chemistry Course 7. The phosphorescence quantum yield in a solution can be measured using various solvents, but the phosphorescent compound used in the present invention can be obtained if the phosphorescence quantum yield is achieved in any solvent. ,.
[0150] リン光性化合物の発光は原理としては 2種挙げられ、 1つはキャリアが輸送されるホ ストィ匕合物上出来ャリアの再結合が起こってホストイ匕合物の励起状態が生成し、この エネルギーをリン光性化合物に移動させることでリン光性化合物からの発光を得ると レ、うエネルギー移動型、もう 1つはリン光性化合物がキャリアトラップとなり、リン光性化 合物上でキャリアの再結合が起こりリン光性化合物からの発光が得られるというキヤリ アトラップ型であるが、何れの場合においても、リン光性化合物の励起状態のェネル ギ一はホス H匕合物の励起状態のエネルギーよりも低いことが条件である。 [0150] The light emission of a phosphorescent compound can be described in two types in principle. One is the recombination of the carriers on the host compound to which carriers are transported, resulting in the generation of an excited state of the host compound. When this energy is transferred to the phosphorescent compound, light is emitted from the phosphorescent compound. The other is the energy transfer type, and the other is that the phosphorescent compound becomes a carrier trap, which is on the phosphorescent compound. The carrier trap type, in which carrier recombination occurs and light emission from the phosphorescent compound is obtained, but in either case, the excited state energy of the phosphorescent compound is the excitation of the phosphine H compound. The condition is that it is lower than the energy of the state.
[0151] リン光性化合物は、有機 EL層の発光層に使用される公知のものの中から適宜選択 して用いることが出来る。リン光性化合物としては、好ましくは元素の周期表で 8族〜 10族の金属を含有する錯体系化合物であり、更に好ましくはイリジウム化合物、ォス ミゥム化合物、又は白金化合物（白金錯体系化合物）、希土類錯体であり、中でも最 も好ましいのはイリジウム化合物である。 [0151] The phosphorescent compound can be appropriately selected from known compounds used for the light emitting layer of the organic EL layer. 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). Of these, rare earth complexes, and most preferred are iridium compounds.
[0152] 本発明においては、リン光性化合物のリン光発光極大波長としては特に制限される ものではなく、原理的には中心金属、配位子、配位子の置換基等を選択することで
得られる発光波長を変化させることが出来る。 [0152] In the present invention, the phosphorescent maximum wavelength of the phosphorescent compound is not particularly limited, and in principle, a central metal, a ligand, a substituent of the ligand, and the like are selected. so The emission wavelength obtained can be changed.
[0153] 本発明の有機 EL層や本発明に係る化合物の発光する色は、「新編色彩科学ハン ドブック」（日本色彩学会編、東京大学出版会、 1985)の 108頁の図 4、図 16におい て、分光放射輝度計 CS _ 1000 (コニ力ミノルタセンシング社製）で測定した結果を C[0153] The light emission color of the organic EL layer of the present invention and the compound according to the present invention is shown in Fig. 4 and Fig. 16 on page 108 of "New Color Science Handbook" (Edited by the Japan Color Society, University of Tokyo Press, 1985). The result of measurement with a spectral radiance meter CS_1000 (manufactured by Koni Force Minolta Sensing Co., Ltd.)
IE色度座標に当てはめたときの色で決定される。 It is determined by the color when applied to IE chromaticity coordinates.
[0154] 本発明に係わる有機 EL層を使用した有機 EL素子の発光の室温における外部取り 出し効率は 1。/0以上であることが好ましぐより好ましくは 5%以上である。ここに、外部 取り出し量子効率（％) =有機 EL素子外部に発光した光子数/有機 EL素子に流し た電子数 X I 00である。 [0154] The external extraction efficiency at room temperature of light emission of the organic EL element using the organic EL layer according to the present invention is 1. It is preferable that the ratio is 0 or more, more preferably 5% or more. Here, the external extraction quantum efficiency (%) = the number of photons emitted outside the organic EL element / the number of electrons sent to the organic EL element XI 00.
[0155] 又、カラーフィルタ一等の色相改良フィルタ一等を併用しても、有機 EL素子からの 発光色を蛍光体を用いて多色へ変換する色変換フィルターを併用してもよい。色変 換フィルターを用いる場合においては、有機 EL素子の発光の maxは 480nm以下 が好ましい。 [0155] 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. When a color conversion filter is used, the maximum light emission of the organic EL element is preferably 480 nm or less.
[0156] 電子輸送層に用いられる電子輸送材料 (正孔阻止材料を兼ねる）としては、陰極よ り注入された電子を発光層に伝達する機能を有していればよぐその材料としては従 来公知の化合物の中力 任意のものを選択して用いることが出来、例えば、ニトロ置 換フルオレン誘導体、ジフヱ二ルキノン誘導体、チォピランジオキシド誘導体、カルボ ジイミド、フレオレニリデンメタン誘導体、アントラキノジメタン及びアントロン誘導体、 ォキサジァゾール誘導体等が挙げられる。更に、上記ォキサジァゾール誘導体にお いて、ォキサジァゾール環の酸素原子を硫黄原子に置換したチアジアゾール誘導体 、電子吸引基として知られているキノキサリン環を有するキノキサリン誘導体も、電子 輸送材料として用いることが出来る。更にこれらの材料を高分子鎖に導入した、又は これらの材料を高分子の主鎖とした高分子材料を用いることも出来る。 [0156] As an electron transport material (also serving as a hole blocking material) used for the electron transport layer, any material that has a function of transmitting electrons injected from the cathode to the light emitting layer is acceptable. It is possible to select and use any of the known compounds of the known compounds, such as nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodis. Examples include methane and anthrone derivatives, oxadiazole derivatives, and the like. Furthermore, in the above oxadiazole derivative, a thiadiazole derivative in which an oxygen atom of the oxaziazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as an 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.
[0157] 又、 8 _キノリノール誘導体の金属錯体、例えば、トリス（8—キノリノール）アルミユウ ム（Alq)、トリス（5， 7—ジクロロ一 8—キノリノール）アルミニウム、トリス（5, 7—ジブ口 モ _ 8_キノリノール）アルミニウム、トリス（2—メチル _8 _キノリノール）アルミニウム 、トリス（5—メチル _ 8 _キノリノール）アルミニウム、ビス（8—キノリノール）亜鉛（Znq )等、及びこれらの金属錯体の中心金属が In、 Mg、 Cu、 Ca、 Sn、 Ga又は Pbに置き
替わった金属錯体も、電子輸送材料として用いることが出来る。その他、メタルフリー もしくはメタルフタロシアニン、又はそれらの末端がアルキル基ゃスルホン酸基等で 置換されているものも、電子輸送材料として好ましく用いることが出来る。又、ジスチリ ルピラジン誘導体も、電子輸送材料として用いることが出来るし、正孔注入層、正孔 輸送層と同様に、 n型— Si、 n型— SiC等の無機半導体も電子輸送材料として用いる こと力 S出来る。電子輸送層の膜厚については特に制限はないが、通常は 5nm〜5 z m程度、好ましくは 5〜200nmである。電子輸送層は上記材料の 1種又は 2種以上 力、らなる一層構造であってもよい。 [0157] Metal complexes of 8_quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq), tris (5,7-dichloro-1-8-quinolinol) aluminum, tris (5,7-jib mouthpiece) _8_quinolinol) aluminum, tris (2-methyl _8_quinolinol) aluminum, tris (5-methyl_8_quinolinol) aluminum, bis (8-quinolinol) zinc (Znq) etc., and the central metal of these metal complexes Placed on In, Mg, Cu, Ca, Sn, Ga or Pb Alternative metal complexes can also be used as electron transport materials. In addition, metal-free or metal phthalocyanine, or those having an end substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron transport material. Distyrylpyrazine derivatives can also be used as electron transport materials, and n-type-Si, n-type-SiC and other inorganic semiconductors should be used as electron-transport materials as well as hole injection layers and hole-transport layers. Force S is possible. Although there is no restriction | limiting in particular about the film thickness of an electron carrying layer, Usually, about 5 nm-5 zm, 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.
[0158] 又、不純物をドープした n性の高い電子輸送層を用いることも出来る。その例として は、特開平 4一 297076号公報、特開平 10— 270172号公報、特開 2000— 19614 0号公報、特開 2001— 102175号公報、 J. Appl. Phys.， 95, 5773 (2004)など に記載されたものが挙げられる。このような n性の高い電子輸送層を用いることがより 低消費電力の素子を作製することが出来るため好ましい。 [0158] Further, an electron transport layer having a high n property doped with impurities can be used. Examples thereof include Japanese Patent Application Laid-Open No. 4-297076, Japanese Patent Application Laid-Open No. 10-270172, Japanese Patent Application Laid-Open No. 2000-196140, Japanese Patent Application Laid-Open No. 2001-102175, J. Appl. Phys., 95, 5773 (2004). ) Etc. are mentioned. It is preferable to use such an n-type electron transport layer because a device with lower power consumption can be manufactured.
[0159] 以下、実施例を挙げて本発明の具体的な効果を示すが、本発明の態様はこれに 限定されるものではない。 [0159] Hereinafter, specific effects of the present invention will be described with reference to examples, but the embodiments of the present invention are not limited thereto.
実施例 Example
[0160] 実施例 1 [0160] Example 1
〈ガスバリア層と第 1電極層とをこの順番で有する帯状可撓性支持体の準備〉厚さ 2 00 z mのポリエーテルスルホン（住友ベークライト社製フィルム、以下、 PESと略記す る）を用レ、、以下に示す方法でガスバリア層と第 1電極層とを形成し、卷き芯に卷き取 り口ール状としたガスバリア層と第 1電極層とをこの順番で有する帯状可撓性支持体 を準備した。 <Preparation of a strip-shaped flexible support having a gas barrier layer and a first electrode layer in this order> A polyethersulfone (film manufactured by Sumitomo Bakelite Co., Ltd., hereinafter abbreviated as PES) having a thickness of 200 zm was used. The belt-like flexibility having the gas barrier layer and the first electrode layer formed in the order shown in the following by forming the gas barrier layer and the first electrode layer in the manner described above. A support was prepared.
[0161] (透明性ガスバリア層の形成） [0161] (Formation of transparent gas barrier layer)
準備した PES上に、大気圧プラズマ放電処理法で、厚さ約 90nmの透明ガスバリア 層を形成した。 JlSk— 7129Bに準拠した方法により水蒸気透過率を測定した結果、 10— 3g/m2/day以下であった。 JlSk— 7126Bに準拠した方法により酸素透過率を 測定した結果、 10— 3g/m2/day以下であった。 On the prepared PES, a transparent gas barrier layer with a thickness of about 90 nm was formed by atmospheric pressure plasma discharge treatment. As a result of measuring the water vapor transmission rate by a method based on JlSk-7129B, it was 10 −3 g / m 2 / day or less. As a result of measuring the oxygen transmission rate by a method based on JlSk-7126B, it was 10 −3 g / m 2 / day or less.
[0162] (第 1電極層の形成）
形成したバリア層の上に厚さ 120nmの IT〇（インジウムチンォキシド）をプラズマィ オンプレーティング装置にて形成した。その後、フォトリソ工程を経て幅 110 /i mで間 隔 34 μ mのパターンを形成した。 [0162] (Formation of first electrode layer) On the formed barrier layer, a 120 nm thick ITO (indium tin oxide) was formed using a plasma ion plating apparatus. Thereafter, a pattern having a width of 110 / im and a spacing of 34 μm was formed through a photolithography process.
[0163] (正孔輸送層形成用塗布液の準備） [0163] (Preparation of coating liquid for hole transport layer formation)
ポリエチレンジォキシチォフェン ·ポリスチレンスルホネート（PED〇T/PSS、 Baye r社製 Bytron P AI 4083)を純水で 65%、メタノール 5%で希釈した溶液を正 孔輸送層形成用塗布液として準備した。 Polyethylenedioxythiophene · Polystyrene sulfonate (PED * T / PSS, Baytron P AI 4083 manufactured by Bayer) diluted with 65% pure water and 5% methanol prepared as a coating solution for pore transport layer formation did.
[0164] (発光層形成用塗布液の準備） [0164] (Preparation of light emitting layer forming coating solution)
青色発光層形成用塗布液の準備ホスト材のポリビュル力ルバゾール (PVK)にドー パント材 Fir (pic) 3を 5質量％を 1， 2—ジクロロェタン中に溶解し 1%溶液とし有機化 合物層形成用塗布液として準備した。 Preparation of coating solution for forming blue light-emitting layer Organic compound layer by dissolving 5% by mass of dopant Fir (pic) 3 in 1,2-dichloroethane in polybur rubazole (PVK) as a host material A coating solution for forming was prepared.
[0165] 緑色発光層形成用塗布液の準備 [0165] Preparation of coating solution for green light emitting layer formation
ホスト材のポリビニルカルバゾール（PVK)にドーパント材 Ir (ppy) 3を 5質量％を 1, 2—ジクロロェタン中に溶解し 1 %溶液とし有機化合物層形成用塗布液として準備し た。 The host material polyvinyl carbazole (PVK) was prepared by dissolving 5% by mass of the dopant material Ir (ppy) 3 in 1,2-dichloroethane to form a 1% solution as a coating solution for forming an organic compound layer.
[0166] 赤色発光層形成用塗布液の準備 [0166] Preparation of coating solution for forming red light emitting layer
ホスト材のポリビニルカルバゾール（PVK)にドーパント材 Btc Ir (acac) 3を 5質量 5 masses of dopant material Btc Ir (acac) 3 on polyvinylcarbazole (PVK) host material
%を 1， 2—ジクロロェタン中に溶解し 1 %溶液とし有機化合物層形成用塗布液として 準備した。 % Was dissolved in 1,2-dichloroethane to prepare a 1% solution, which was prepared as a coating solution for forming an organic compound layer.
[0167] 電子輸送層形成用塗布液の準備 [0167] Preparation of coating liquid for electron transport layer formation
電子輸送層は Alqを 1, 2—ジクロロェタン中に溶解し 0. 5質量％溶液とし電子輸 送層形成用塗布液とした。 For the electron transport layer, Alq was dissolved in 1,2-dichloroethane to prepare a 0.5% by mass solution as a coating solution for forming an electron transport layer.
[0168] 〈発光層の形成〉 <Formation of light emitting layer>
図 3に示す製造装置を使用し、準備した巻き芯に巻き取りロール状としたガスバリア 層と第 1電極層とをこの順番で有する帯状可撓性支持体の第 1電極層の上に正孔輸 送層、発光層、電子輸送層を形成するまでの環境条件 (露点温度、清浄度）を表 1に 示す様に変えて有機 EL層を形成し、加熱処理した後、除電処理し、室温と同じ温度 になるまで冷却した後、卷き芯に卷き取りロール状とし試料 No. 101〜107とした。
尚、清浄度は JISB 9920に準拠し測定した値を示し、清浄度の変化はフィルターを 変えることで行った。 Holes are formed on the first electrode layer of the belt-like flexible support having the gas barrier layer and the first electrode layer in this order on the prepared winding core using the manufacturing apparatus shown in FIG. Change the environmental conditions (dew point temperature, cleanliness) until the transport layer, light-emitting layer, and electron transport layer are formed as shown in Table 1 to form an organic EL layer, heat treatment, charge removal, and room temperature After cooling to the same temperature as in Example 1, sample rolls Nos. 101 to 107 were formed as a wound roll shape on the core. The cleanliness is the value measured according to JISB 9920, and the cleanliness was changed by changing the filter.
[0169] 尚、正孔輸送層は以下に示す正孔輸送層形成用塗布液をエタストルージョン塗布 機を使用した湿式塗布方式により塗布 ·乾燥した後加熱処理を行レ、形成した。発光 層は、ァライメントマークに従って湿式パターン塗布装置の位置合わせを行い、保持 手段で保持した状態で図 6に示す様にパターン化して形成されている第 1電極のパ ターンに合わせ発光層形成用塗布液を湿式パターン塗布装置により形成した。電子 輸送層は以下に示す電子輸送層形成用塗布液をエタストルージョン塗布機を使用し た湿式塗布方式により塗布 ·乾燥した後加熱処理を行レヽ形成した。 [0169] The hole transport layer was formed by applying and drying the following hole transport layer forming coating solution by a wet coating method using an etatrusion coating machine, followed by heat treatment. The light-emitting layer is aligned with the wet pattern coating device according to the alignment mark, and is used for forming the light-emitting layer according to the pattern of the first electrode formed as shown in Fig. 6 while being held by the holding means. The coating liquid was formed with a wet pattern coating apparatus. For the electron transport layer, the following electron transport layer forming coating solution was applied and dried by a wet coating method using an etatrusion coater, followed by heat treatment.
[0170] 正孔輸送層形成用塗布液を塗布する前に、帯状可撓性支持体の洗浄表面改質処 理を、波長 184. 9nmの低圧水銀ランプを使用し、照射強度 15mW/cm2、距離 10 mmで実施した。帯電除去処理は、微弱 X線による除電器を使用し行った。 [0170] Before applying the coating liquid for forming the hole transport layer, the cleaning surface modification treatment of the belt-shaped flexible support was performed using a low-pressure mercury lamp with a wavelength of 184.9 nm and an irradiation intensity of 15 mW / cm 2 The distance was 10 mm. The charge removal treatment was performed using a static eliminator with weak X-rays.
[0171] 正孔輸送層形成用塗布液は乾燥後の厚みが 50nmになるように塗布した。発光層 形成用塗布液は乾燥後の厚みが lOOnmになるように塗布した。 [0171] The coating solution for forming the hole transport layer was applied so that the thickness after drying was 50 nm. The coating solution for forming the light emitting layer was applied so that the thickness after drying was lOOnm.
[0172] 電子輸送層形成用塗布液は乾燥後の厚みが 30nmになるように塗布した。尚、搬 送速度は 2m/minで実施した。 [0172] The coating solution for forming the electron transport layer was coated so that the thickness after drying was 30 nm. The transport speed was 2m / min.
[0173] (塗布条件） [0173] (Application conditions)
正孔輸送層形成用塗布液、発光層形成用塗布液及び電子輸送層形成用塗布液 の塗布温度を 25°Cとし、乾燥装置及び加熱処理装置は除き他の環境温度は 25°C で大気圧条件で行った。 The coating temperature of the coating solution for forming the hole transport layer, the coating solution for forming the light emitting layer, and the coating solution for forming the electron transport layer is 25 ° C, and the other ambient temperature is 25 ° C except for the drying device and heat treatment device. Performed under atmospheric pressure conditions.
[0174] (乾燥及び加熱処理条件） [0174] (Drying and heat treatment conditions)
正孔輸送層形成用塗布液を塗布した後、図 3に示す発光層乾燥部及び加熱処理 部と同じ構造の乾燥部及び加熱処理装置を使用し、乾燥部ではスリットノズノレ形式の 吐出ロカ 製膜面に向け高さ 100mm、吐出風速 lm/s、幅手の風速分布 5%、温 度 100°Cで溶媒を除去した後、引き続き、加熱処理装置で温度 200°Cで裏面伝熱 方式の熱処理を行い正孔輸送層を形成した。 After coating the hole transport layer forming coating solution, use the drying unit and heat treatment device with the same structure as the light emitting layer drying unit and heat treatment unit shown in FIG. After removing the solvent at a height of 100 mm, discharge air velocity of lm / s, wide air velocity distribution of 5%, and temperature of 100 ° C, heat treatment using the backside heat transfer method was subsequently performed at a temperature of 200 ° C using a heat treatment device. And a hole transport layer was formed.
[0175] 発光層形成用塗布液を塗布した後、図 3に示す発光層乾燥部及び加熱処理部を 使用し、発光層乾燥部ではスリットノズノレ形式の吐出口から製膜面に向け高さ 100m
m、温度 60°Cで溶媒を除去した後、引き続き、加熱処理部で温度 220°Cで加熱処理 を行い発光層を形成した。 [0175] After the light emitting layer forming coating solution is applied, the light emitting layer drying section and the heat treatment section shown in Fig. 3 are used. In the light emitting layer drying section, the height from the slit nozzle type discharge port to the film forming surface is 100 m. m After removing the solvent at a temperature of 60 ° C., a heat treatment was subsequently performed at a temperature of 220 ° C. in the heat treatment section to form a light emitting layer.
[0176] 電子輸送層形成用塗布液を塗布した後、図 3に示す発光層乾燥部及び加熱処理 部と同じ構造の乾燥部及び加熱処理装置を使用し、乾燥部ではスリットノズル形式の 吐出ロカ 製膜面に向け高さ 100mm、温度 60°Cで溶媒を除去した後、引き続き、 加熱処理部で温度 200°Cで加熱処理を行い電子輸送層を形成した。尚、吐出風速 はカノマックス（株)製 熱風風速計 モデル 6113で測定し、幅手方向の風速分布は 次式により計算で求めた。 [0176] After the coating liquid for forming the electron transport layer is applied, the drying unit and the heat treatment apparatus having the same structure as the light emitting layer drying unit and the heat treatment unit shown in Fig. 3 are used. After removing the solvent at a height of 100 mm and a temperature of 60 ° C. toward the film forming surface, an electron transport layer was formed by subsequently performing a heat treatment at a temperature of 200 ° C. in the heat treatment section. The discharge wind speed was measured with a hot air anemometer model 6113 manufactured by Kanomax Co., Ltd., and the wind speed distribution in the width direction was calculated by the following formula.
[0177] 風速分布 = (最大風速一最小風速) /平均風速 X I 00 [0177] Wind speed distribution = (maximum wind speed-minimum wind speed) / average wind speed X I 00
評価 Evaluation
作製した試料 No. 101〜107に付き、 5 X 10_4Pa真空下にて厚さ 0. 5nmの LiF 層（電子注入層）を全面蒸着し、マスクを介して第 1電極とは直交するように幅 350 μ m、間隔 80 μ mのパターン形成された厚さ lOOnmのアルミ層（第 2電極）を蒸着方式 で形成した後、引き続き封止層の形成を蒸着で行い、室温まで冷却し、巻き芯に卷 き取りロール状とした。この状態で作製した試料 No. 101〜107に付き未発光故障 を目視で確認し、次の評価ランクに従って評価した結果を表 1に示す。 For the prepared sample Nos. 101 to 107, a LiF layer (electron injection layer) with a thickness of 0.5 nm is vapor-deposited under a vacuum of 5 X 10 _4 Pa so that it is perpendicular to the first electrode through the mask. After forming an aluminum layer (second electrode) with a thickness of 350 μm and an interval of 80 μm with a thickness of lOOnm by vapor deposition, a sealing layer is subsequently formed by vapor deposition, cooled to room temperature, A winding roll was formed on the winding core. Table 1 shows the results of visually confirming the non-light-emitting failure on sample Nos. 101 to 107 manufactured in this state and evaluating according to the following evaluation rank.
[0178] 未発光故障の確認方法 [0178] How to check for non-luminous failure
作製した試料を 1週間 80°Cの恒温条件で保管した後、 2. 5mA/cm2の一定電流 で駆動したとき、発光しない箇所の有無を目視で確認した。未発光故障の評価ランク 〇：未発光故障が確認されなレ、 The prepared sample was stored at a constant temperature of 80 ° C for 1 week, and when it was driven at a constant current of 2.5 mA / cm 2 , it was visually checked for the presence of no light emission. Evaluation rank of non-luminous failure 〇: Non-luminous failure is not confirmed,
△：実技上問題とならなレ、僅力な未発光故障が認められる △: If it is not a practical problem, a slight non-luminous failure is recognized
X：実技上問題となる未発光故障が散見される X: There are some non-luminous failures that are practical problems
[0179] [表 1]
[0179] [Table 1]
[0180] 試料 No. 101の場合は、試料中に含まれる水分量により、又、試料 No. 104の場 合は、付着した異物により未発光故障が発生したものと推測される。本発明の有効性 が確認された。 [0180] In the case of sample No. 101, it is presumed that a non-luminous failure has occurred due to the amount of moisture contained in the sample, and in the case of sample No. 104, due to adhering foreign matter. The effectiveness of the present invention was confirmed.
[0181] 実施例 2 [0181] Example 2
実施例 1で作製した試料 No. 104を保管する条件を表 2に示す様に変えて処理し た他は全て同じ条件とし試料 No. 201〜206とした。尚、保管期間 5日間とした。 Samples Nos. 201 to 206 were used under the same conditions except that the conditions under which sample No. 104 produced in Example 1 was stored were changed as shown in Table 2 and processed. The storage period was 5 days.
[0182] 評価 [0182] Evaluation
作製した試料 No. 201〜206に付き、発光層の寿命は、 2. 5mA/ cm2の一定電 流で駆動したときの輝度が初期の輝度の半分になるのに要した時間（半減時間）を 寿命の指標とし、評価を行った結果を表 2に示す。尚、寿命 (相対値）は保管条件が 1 X 10— 5Paのときの寿命を 100としたときの相対値を示す。 The lifetime of the light emitting layer attached to the fabricated sample Nos. 201 to 206 is the time required for the luminance to be half of the initial luminance when driven at a constant current of 2.5 mA / cm 2 (half time) Table 2 shows the results of the evaluation using as a life index. Incidentally, the lifetime (relative value) indicates a relative value when storage conditions was 100 life time of 1 X 10- 5 Pa.
[0183] [表 2] [0183] [Table 2]
[0184] 本発明の有効性が確認された。
[0184] The effectiveness of the present invention was confirmed.
Claims
[1] 帯状可撓性支持体の上に、少なくとも第 1電極を含む陽極層と、発光層を含む有機 化合物層を有する有機 EL層と、第 2電極を含む陰極層とをこの順番で有する有機 E L素子の有機 EL層を、供給部と、前記陽極層上に、前記発光層を形成するパターン 塗布'乾燥部と、回収部とを有する製造装置を用いて形成する有機 EL層の形成方 法において、前記供給部には、少なくとも第 1電極を含む陽極層が形成された帯状 可撓性支持体 Aが、ロール状態で供給され、前記パターン塗布'乾燥部の前に第 1 アキュームレータ部と、後に第 2アキュームレータ部とを有し、前記パターン塗布'乾 燥部は、有機 EL層形成用塗布液を湿式パターン形成塗布装置により大気圧条件で 発光層形成用塗膜を形成するパターン塗布部と、大気圧条件で前記有機 EL層中の 溶媒を除去し、有機 EL層を形成する有機 EL層乾燥部とを 1ユニットとし、前記パタ ーン塗布 ·乾燥部は、少なくとも 1ユニットの前記パターン塗布 ·乾燥部を有し、前記 パターン塗布 ·乾燥部により、前記陽極層上に前記有機 EL層を形成し帯状可撓性 支持体 Bとし、前記回収部で、巻き芯に巻き取りロール状とすることを特徴とする有機 EL層の形成方法。 [1] On a belt-like flexible support, at least an anode layer including a first electrode, an organic EL layer including an organic compound layer including a light emitting layer, and a cathode layer including a second electrode are provided in this order. Forming an organic EL layer of an organic EL element using a manufacturing apparatus having a supply unit, a pattern coating / drying unit for forming the light emitting layer on the anode layer, and a recovery unit In the method, a strip-shaped flexible support A on which an anode layer including at least a first electrode is formed is supplied to the supply unit in a roll state, and a first accumulator unit and a first accumulator unit are provided before the pattern coating and drying unit. And a second accumulator section, and the pattern coating / drying section is a pattern coating section for forming a light emitting layer forming coating film under an atmospheric pressure condition using an organic EL layer forming coating solution by a wet pattern forming coating apparatus. And the solvent in the organic EL layer under atmospheric pressure conditions The pattern coating / drying unit has at least one unit of the pattern coating / drying unit, and the pattern coating / drying unit. The organic EL layer is formed on the anode layer by a portion to form a strip-like flexible support B, and the winding portion is formed into a winding roll shape in the recovery portion.
[2] 前記帯状可撓性支持体 Aは、ァライメントマークが設けられていることを特徴とする請 求の範囲第 1項に記載の有機 EL層の形成方法。 [2] The method for forming an organic EL layer according to item 1 of the claim, wherein the belt-like flexible support A is provided with alignment marks.
[3] 前記帯状可撓性支持体 Aは、間欠搬送されることを特徴とする請求の範囲第 1項又 は第 2項に記載の有機 EL層の形成方法。 [3] The method for forming an organic EL layer according to [1] or [2], wherein the belt-like flexible support A is intermittently conveyed.
[4] 前記湿式パターン形成塗布装置は、帯状可撓性支持体 Aの間欠搬送に対応して稼 働し、帯状可撓性支持体 Aが停止しているときに稼働し、パターン形成塗布を行うこ とを特徴とする請求の範囲第 1項乃至第 3項の何れか 1項に記載の有機 EL層の形 成方法。 [4] The wet pattern formation coating apparatus operates in response to the intermittent conveyance of the strip-shaped flexible support A, operates when the strip-shaped flexible support A is stopped, and performs pattern formation coating. The method for forming an organic EL layer according to any one of claims 1 to 3, wherein the organic EL layer is formed.
[5] 前記パターン塗布部は、帯状可撓性支持体の保持手段と、ァライメントマークの検出 手段と、湿式パターン形成塗布装置の塗布位置補正制御手段とを有してレ、ることを 特徴とする請求の範囲第 1項乃至第 4項の何れか 1項に記載の有機 EL層の形成方 法。 [5] The pattern application unit has a belt-like flexible support holding means, alignment mark detection means, and application position correction control means of a wet pattern formation application apparatus. The method for forming an organic EL layer according to any one of claims 1 to 4, wherein:
[6] 前記第 1アキュームレータ部の前もしくは第 2アキュームレータ部の後の何れか一方
に湿式塗布'乾燥部を有することを特徴とする請求の範囲第 1項乃至第 5項の何れ 力 1項に記載の有機 EL層の形成方法。 [6] Either before the first accumulator part or after the second accumulator part 6. The method for forming an organic EL layer according to any one of claims 1 to 5, further comprising a wet coating and drying unit.
[7] 前記第 1アキュームレータ部の前と、第 2アキュームレータ部の後に湿式塗布.乾燥 部を有することを特徴とする請求の範囲第 1項乃至第 5項の何れか 1項に記載の有 機 EL層の形成方法。 [7] The organic device according to any one of claims 1 to 5, further comprising a wet application / drying unit before the first accumulator unit and after the second accumulator unit. EL layer formation method.
[8] 前記湿式塗布 ·乾燥部は有機化合物層形成用塗布液を湿式塗布装置により大気圧 条件で有機化合物層を形成する湿式塗布部と、大気圧条件で塗布し、前記有機化 合物層中の溶媒を除去する有機化合物層乾燥部とを有することを特徴とする請求の 範囲第 6項又は第 7項に記載の有機 EL層の形成方法。 [8] The wet coating / drying unit coats the organic compound layer forming coating solution with a wet coating apparatus under an atmospheric pressure condition with a wet coating apparatus, and the organic compound layer. 8. The method for forming an organic EL layer according to claim 6, further comprising an organic compound layer drying unit for removing the solvent therein.
[9] 前記パターン塗布'乾燥部と、湿式塗布'乾燥部との後に加熱処理部を有することを 特徴とする請求の範囲第 1項乃至第 8項の何れか 1項に記載の有機 EL層の形成方 法。 [9] The organic EL layer according to any one of [1] to [8], wherein a heat treatment unit is provided after the pattern coating 'drying unit and the wet coating' drying unit. How to form
[10] 前記製造装置は、除電処理部を有していることを特徴とする請求の範囲第 1項乃至 第 9項の何れか 1項に記載の有機 EL層の形成方法。 [10] The method for forming an organic EL layer according to any one of [1] to [9], wherein the manufacturing apparatus includes a charge removal processing unit.
[11] 前記帯状可撓性支持体 Aは、湿式塗布 ·乾燥部で有機化合物層形成用塗布液を塗 布する前、又はパターン塗布'乾燥部で有機 EL層形成用塗布液を塗布する前に洗 浄表面改質処理手段により洗浄表面改質処理が施されることを特徴とする請求の範 囲第 1項乃至第 10項の何れか 1項に記載の有機 EL層の形成方法。 [11] The belt-like flexible support A is applied before applying the organic compound layer forming coating solution in the wet coating / drying unit, or before applying the organic EL layer forming coating solution in the pattern coating / drying unit. 11. The method for forming an organic EL layer according to any one of claims 1 to 10, wherein the cleaning surface modification treatment is performed by a cleaning surface modification treatment means.
[12] 前記洗浄表面改質処理手段が酸素プラズマ又は UV照射であることを特徴とする請 求の範囲第 11項に記載の有機 EL層の形成方法。 [12] The method for forming an organic EL layer according to item 11, wherein the cleaning surface modification means is oxygen plasma or UV irradiation.
[13] 前記有機 EL層及び有機化合物層は、露点温度 20°C以下、且つ JISB 9920に 準拠し、測定した清浄度がクラス 5以下で、且つ、有機 EL層乾燥部と、有機化合物 層乾燥部及び加熱処理部を除き 10〜45°Cの大気圧中で形成されることを特徴とす る請求の範囲第 1項乃至第 12項の何れか 1項に記載の有機 EL層の形成方法。 [13] The organic EL layer and the organic compound layer have a dew point temperature of 20 ° C or less, conformity to JISB 9920, and a measured cleanliness of class 5 or less, and an organic EL layer drying section and an organic compound layer drying The method for forming an organic EL layer according to any one of claims 1 to 12, wherein the organic EL layer is formed in an atmospheric pressure of 10 to 45 ° C, excluding the heat treatment part and the heat treatment part. .
[14] 前記帯状可撓性支持体 Bを回収部で、巻き芯に巻き取りロール状とした後、 10— 5〜1 OPaの減圧条件下で保管することを特徴とする請求の範囲第 1項乃至第 13項の何 れカ、 1項に記載の有機 EL層の形成方法。
[14] The band-shaped flexible support B in the recovery section, wound after the winding roll form a core, 10- 5-1 range first claim, characterized in that the storage under reduced pressure of OPa 14. The method for forming an organic EL layer according to any one of items 13 to 13.
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|---|---|---|---|
| JP2007509175A JP5125503B2 (en) | 2005-03-23 | 2006-03-03 | Manufacturing method of organic EL element |
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| JP2005083324 | 2005-03-23 | ||
| JP2005-083324 | 2005-03-23 |
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| Publication Number | Publication Date |
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| WO2006100889A1 true WO2006100889A1 (en) | 2006-09-28 |
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| WO (1) | WO2006100889A1 (en) |
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| US8841653B2 (en) | 2009-05-29 | 2014-09-23 | Semiconductor Energy Laboratory Co., Ltd. | Light-emitting element, light-emitting device, lighting device, and electronic appliance |
| JP2011049084A (en) * | 2009-08-28 | 2011-03-10 | Konica Minolta Holdings Inc | Method of manufacturing organic electroluminescence panel |
| US8486543B2 (en) | 2009-12-01 | 2013-07-16 | Semiconductor Energy Laboratory Co., Ltd. | Light-emitting element, light-emitting device, electronic device, and lighting device |
| US9698354B2 (en) | 2009-12-01 | 2017-07-04 | Semiconductor Energy Laboratory Co., Ltd. | Light-emitting element, light-emitting device, electronic device, and lighting device |
| US10756287B2 (en) | 2009-12-01 | 2020-08-25 | Semiconductor Energy Laboratory Co., Ltd. | Light-emitting element, light-emitting device, electronic device, and lighting device |
| US8809091B2 (en) | 2009-12-11 | 2014-08-19 | Konica Minolta Holdings, Inc. | Method of manufacturing organic electroluminescence element |
| JP5821853B2 (en) * | 2010-08-26 | 2015-11-24 | コニカミノルタ株式会社 | Method for manufacturing organic electroluminescence element |
| JPWO2012026363A1 (en) * | 2010-08-26 | 2013-10-28 | コニカミノルタ株式会社 | Method for manufacturing organic electroluminescence element |
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| Publication number | Publication date |
|---|---|
| JP5125503B2 (en) | 2013-01-23 |
| JPWO2006100889A1 (en) | 2008-08-28 |
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