WO2013151170A1 - 塗布システムおよび発光装置の製造方法 - Google Patents
塗布システムおよび発光装置の製造方法 Download PDFInfo
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Images
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- C—CHEMISTRY; METALLURGY
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- G05D11/132—Controlling ratio of two or more flows of fluid or fluent material characterised by the use of electric means by measuring the values related to the quantity of the individual components by controlling the flow of the individual components
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- 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
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/312—Non-condensed aromatic systems, e.g. benzene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
- C08G2261/3142—Condensed aromatic systems, e.g. perylene, anthracene or pyrene fluorene-based, e.g. fluorene, indenofluorene, or spirobifluorene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
- C08G2261/342—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing only carbon atoms
- C08G2261/3422—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing only carbon atoms conjugated, e.g. PPV-type
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/90—Applications
- C08G2261/95—Use in organic luminescent diodes
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- 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
Definitions
- the present invention relates to a coating system and a method for manufacturing a light emitting device using the coating system.
- a light-emitting device (organic electroluminescence element) includes, as main components, an anode, a cathode, and a light-emitting layer disposed between the anode and the cathode.
- the light-emitting layer includes a light-emitting material that is an organic compound, and emits light when a voltage is applied between the anode and the cathode.
- organic electroluminescent elements are required to have various emission colors, and light emitting materials having various emission colors have been developed.
- the luminescent color is adjusted by mixing three kinds of powders each containing luminescent materials having three luminescent colors. Therefore, for example, when a light emitting layer having a plurality of types of luminescent colors is separately formed in a single organic electroluminescent element, or when it is required to continuously manufacture a wide variety of organic electroluminescent elements, a plurality of types of Each of the inks corresponding to the luminescent colors had to be prepared in advance, and complicated processes such as replacing the tank storing each ink at a necessary timing were necessary.
- the present invention has been made in view of the above, and can be turned on without performing complicated steps such as preparing a plurality of types of ink in advance or replacing a tank storing each ink at a necessary timing. It is an object of the present invention to provide an application system that can prepare and apply ink of a desired luminescent color on demand, and an application method using the application system.
- a raw material ink supply unit that supplies a raw material ink that is a coating liquid containing a light emitting material that is an organic compound used in the coating method;
- a first pipe connected to the raw material ink supply unit;
- An agitation tank provided with an ink agitation mechanism and connected to the raw material ink supply unit by the first pipe;
- a supply adjusting unit that is provided in the first pipe and adjusts the supply amount of the plurality of types of raw material inks to the stirring tank;
- a controller that is connected to the supply controller by an electric communication line, determines a mixing ratio of a plurality of types of raw material inks, and controls the operation of the supply controller based on the mixing ratio;
- a coating system comprising: an ink transport unit connected to the agitation tank by a second pipe; and a coating device having an ink discharge unit connected to the ink transport unit by a third pipe.
- the supply adjusting unit is provided in the first pipe, and is provided in the first pipe and a flow rate measuring unit connected to the control unit by the telecommunication line, and the telecommunication line.
- the supply adjusting unit is provided in the first pipe, and is provided in the first pipe and a front valve connected to the control unit by the electric communication line, and the electric communication line.
- the coating system according to [1] comprising: a diaphragm metering pump connected to the control unit by: and a rear valve connected to the control unit by the electric communication line.
- the cleaning unit further includes a cleaning liquid supply unit connected to the stirring tank by a cleaning liquid supply pipe and an inert gas supply unit connected to the stirring tank by an inert gas supply pipe.
- the coating system according to any one of [3].
- the step of determining the mixing ratio of the plurality of types of raw material inks The control unit comparing a standard ink data group including three or more standard ink data with the required ink data; The control unit obtains distance data by calculating a distance between coordinates in chromaticity coordinates of each of the standard ink data and coordinates in chromaticity coordinates of the required ink data; The control unit rearranges the distance data having a shorter distance and the corresponding standard ink data based on the obtained distance data so as to be higher in rank.
- the control unit obtains a relational expression of a first straight line passing through the first coordinate of the first rank and the second coordinate of the second rank;
- the control unit determines the a-th coordinate corresponding to the a-th position, which is the highest level excluding the first coordinate and the second coordinate in the standard ink data group, as the first coordinate, the second coordinate, and the a-th Determining that the coordinates of the required ink data are included in an area formed by connecting the coordinates with a straight line; and
- the control unit obtaining a relational expression of a second straight line passing through the determined a-th coordinate and the required ink data;
- the control unit acquires the coordinates of the intersection of the first straight line and the second straight line, and does the control unit satisfy at least one of the following conditions (1) and (2)?
- the control unit obtains a first distance value from the first coordinate to the coordinate of the intersection and a second distance value from the second coordinate to the coordinate of the intersection; The control unit, based on the first distance value and the second distance value, determining a mixing ratio of the raw material ink at the intersection; The control unit acquires a third distance value from the a-coordinate to the coordinate of the requested ink data and a fourth distance value from the coordinate of the requested ink data to the coordinate of the intersection; And a step of determining a mixing ratio of raw material inks for the required ink data based on the third distance value and the fourth distance value.
- a coating system capable of preparing and coating ink of a desired luminescent color on demand, and a method for manufacturing a light emitting device using the coating system.
- FIG. 1 is a functional block diagram of the coating system.
- FIG. 2 is a diagram illustrating a configuration example of the coating system.
- FIG. 3A is a functional block diagram of a supply adjusting unit used in the coating system.
- FIG. 3-2 is a functional block diagram of a control unit used in the coating system.
- FIG. 4 is a flowchart for explaining a method of manufacturing a light emitting device using the coating system.
- FIG. 5 is a diagram (1) illustrating an example of chromaticity coordinates for determining the mixing ratio of the raw material inks.
- FIG. 6 is a diagram (2) illustrating an example of chromaticity coordinates for determining the mixing ratio of the raw material inks.
- FIG. 7 is a diagram (3) illustrating an example of chromaticity coordinates for determining the mixing ratio of the raw material inks.
- FIG. 8 is a schematic graph for explaining the step of determining the mixing ratio of the raw material inks.
- FIG. 1 is a functional block diagram of the coating system.
- the coating system 10 includes a raw ink supply unit 20, a first pipe 90 a connected to the raw ink supply part 20, and an ink stirring mechanism 52, and the raw ink is supplied by the first pipe 90 a.
- An agitation tank 50 connected to the supply unit 20, a supply adjustment unit 30 that is provided in the first pipe 90 a and adjusts the supply amount of each of a plurality of types of raw material ink to the agitation tank 50, and the supply adjustment unit 30.
- a control tank 70 for determining a mixing ratio of a plurality of types of raw material inks and controlling the operation of the supply adjusting unit 30 based on the mixing ratio, and a second tank 90b. 50 and an application device 100 having an ink ejection unit 130 connected to the ink transport unit 120 by a third pipe 90c.
- Raw material ink is a coating liquid containing a luminescent material that is an organic compound used in the coating method, and the luminescent color of the organic electroluminescent element when a light emitting layer is formed using such a coating liquid, It means the ink specified in the CIE (International Commission on Illumination) 1931 chromaticity coordinates (hereinafter simply referred to as “chromaticity coordinates”).
- CIE International Commission on Illumination
- the coating process can be performed using two or more kinds of raw material inks.
- the coating system 10 is preferable because it can reproduce a wide range of emission colors by using three types of raw material inks having different emission colors (for example, red emission color, green emission color, and blue emission color). If you want to further expand the emission color reproduction area, use four or more types of raw material inks with different emission colors (for example, four types of red emission color, green emission color, blue emission color, and yellow emission color). It is also possible to use it.
- FIG. 2 is a diagram illustrating a configuration example of the coating system.
- the coating system 10 of this configuration example includes a raw material ink supply unit 20 that can supply three types of raw material inks.
- the ink supply unit 20 includes a first raw ink tank 22a for storing the first raw ink, a second raw ink tank 22b for storing the second raw ink, and a third raw ink tank 22c for storing the third raw ink. ing.
- the coating system 10 includes a first pipe 90 a that is connected to the raw material ink supply unit 20 at one end side.
- the first pipe 90a has a first pipe part 90aa connected at one end to the first raw ink tank 22a, a second pipe part 90ab connected at one end to the second raw ink tank 22b, and a third raw ink tank 22c.
- the third piping part 90ac is connected to one end side.
- a stirring tank 50 is connected to the other end of the first pipe 90a.
- a supply adjustment unit 30 including a flow rate measurement unit 32 and an adjustment unit 34 is provided in the first pipe 90a.
- the flow rate measurement unit 32 is provided closer to the raw material ink supply unit 20 than the adjustment unit 34 (hereinafter, focusing on the direction in which the raw material ink flows, “near the raw material ink supply unit 20”). May be referred to as “upstream side”, and “near the stirring tank 50” may be referred to as “downstream side”).
- the flow rate measurement unit 32 includes a first sensor 32a provided in the first piping unit 90aa, a second sensor 32b provided in the second piping unit 90ab, and a third piping. And a third sensor 32c provided in the portion 90ac.
- the adjusting unit 34 includes a first adjusting valve 34a provided in the first piping unit 90aa, a second adjusting valve 34b provided in the second piping unit 90ab, and a first adjusting valve provided in the third piping unit 90ac. 3 adjustment valve 34c.
- the stirring tank 50 has an ink stirring mechanism 52 therein.
- One end side of the second pipe 90 b is connected to the stirring tank 50.
- the coating device 100 is connected to the other end side of the second pipe 90b.
- the coating apparatus 100 includes an ink transport unit 120, a third pipe 90c having one end connected to the ink transport unit 120, and an ink discharge unit 130 connected to the other end of the third pipe 90c. Yes.
- the raw material ink supply unit 20 (first raw ink tank 22a, second raw ink tank 22b, and third raw ink tank 22c) has a function of supplying a plurality of types of raw ink to the stirring tank 50.
- Each of the first raw ink tank 22a, the second raw ink tank 22b, and the third raw ink tank 22c is preferably configured as an airtight container.
- the material constituting each of the first raw ink tank 22a, the second raw ink tank 22b, and the third raw ink tank 22c is arbitrarily suitable on the condition that it does not deteriorate due to the raw ink and that there is no elution component into the raw ink. The material can be selected.
- Each of the first raw ink tank 22a, the second raw ink tank 22b, and the third raw ink tank 22c is preferably configured to be removable and replaceable with a raw ink tank storing other different raw inks.
- the first raw ink tank 22a, the second raw ink tank 22b, and the third raw ink tank 22c store raw inks having different emission colors.
- each of the first raw material ink tank 22a, the second raw material ink tank 22b, and the third raw material ink tank 22c has a raw material ink sending mechanism for sending the raw material ink outside the tank.
- a raw material ink delivery mechanism an inert gas such as air or nitrogen gas is supplied into each of the first raw ink tank 22a, the second raw ink tank 22b, and the third raw ink tank 22c, and The mechanism which can send raw material ink to the 1st piping 90a by pressing down the surface (liquid level) and pushing down the surface of raw material ink is mentioned.
- the first pipe 90a (the first pipe section 90aa, the second pipe section 90ab, the third pipe section 90ac), the second pipe 90b, and the third pipe 90c (sometimes collectively referred to as the pipe 90) are the raw ink supply section 20. It functions as a route for transporting the raw ink stored in the tank.
- the first pipe 90 a functions as a path for supplying the raw ink sent from the raw ink supply unit 20 to the stirring tank 50.
- the second pipe 90 b functions as a path for supplying the mixed ink sent from the stirring tank 50 to the coating apparatus 100.
- the third pipe 90 c functions as a path for supplying the mixed ink from the ink transport unit 120 to the ink discharge unit 130.
- the piping 90 should not be deteriorated by the ink used in the coating process in which the raw material ink or a plurality of types of raw material inks are mixed (sometimes referred to as mixed ink), and that there is no elution component to the raw material ink or mixed ink.
- a cylindrical body (pipe) formed of a suitable material that can be used in a conventionally known coating apparatus such as polytetrafluoroethylene and stainless steel can be used.
- the agitation tank 50 is connected to the raw material ink supply unit 20 by a first pipe 90a.
- a predetermined amount of the third raw material ink to be supplied can be mixed to prepare a mixed ink having a desired luminescent color, and the prepared mixed ink can be stored.
- the material constituting the agitation tank 50 is arbitrarily suitable formed of a suitable material such as stainless steel, for example, provided that it does not deteriorate due to the raw material ink and the mixed ink and that there is no elution component to the raw material ink or the mixed ink.
- a vessel having a simple shape can be used.
- the material, shape, and capacity of the agitation tank 50 can be set to any suitable aspect corresponding to a desired embodiment.
- the stirring tank 50 includes an ink stirring mechanism 52.
- the ink stirring mechanism 52 has a function of mixing ink by stirring and mixing a plurality of types of raw material ink supplied into the stirring tank 50.
- Examples of the ink stirring mechanism 52 include (1) a mechanism that includes a propeller (wing-like body) disposed inside the stirring tank 50 and rotates the propeller in the liquid layer of the raw material ink supplied to the stirring tank 50 (for example, a propeller type stirring device), (2) a mechanism (for example, an ultrasonic generator) capable of applying fine vibrations such as ultrasonic waves to the liquid layer of the raw material ink supplied to the stirring tank 50, and (3) a stirring tank
- the mechanism for example, a circulation pump and piping which can generate a flow in stirring tank 50 by circulating raw material ink supplied to 50 in stirring tank 50 is mentioned.
- the stirring tank 50 is formed in a cylindrical shape so that the raw material ink flows inside, and the cylindrical inner portion (flow path) is provided with irregularities to generate a vortex in the flow of the raw material ink.
- the stirring tank 50 itself may be configured so that it can be used. In this case, the stirring tank 50 itself has the function of the ink stirring mechanism 52.
- the coating system 10 includes a cleaning unit 60.
- the cleaning unit 60 has a function of cleaning and drying the inside of the agitation tank 50 when changing the mixing ratio of the raw material inks or when changing the type of the raw material inks.
- the cleaning section 60 has a cleaning liquid supply section 62 connected to the stirring tank 50 by a cleaning liquid supply pipe 66 and an inert gas supply section 64 connected to the stirring tank 50 by an inert gas supply pipe 68.
- the cleaning liquid supply unit 62 has a function of supplying the cleaning liquid to the stirring tank 50.
- the cleaning liquid supply unit 62 can be configured by, for example, a tank that can store the cleaning liquid and a commercially available pump that can supply the cleaning liquid from the tank into the stirring tank 50.
- the cleaning liquid it is preferable to use a solvent that can dissolve or disperse the solute contained in the raw material ink and the mixed ink supplied to the stirring tank 50.
- the solvent that can be used as the cleaning liquid is preferably capable of being mixed with the solvent of the raw material ink in which the solid content in the raw ink and the mixed ink is dissolved or dispersed.
- the cleaning liquid may be a solvent used in the raw material ink and the mixed ink.
- the cleaning liquid can be appropriately selected in consideration of the above. Examples of the cleaning liquid include organic solvents such as tetrahydrofuran, xylene, and toluene, and mixed solvents containing these organic solvents.
- the inert gas supply unit 64 has a function of supplying an inert gas for drying the interior of the stirring tank 50 after being cleaned.
- the inert gas can be appropriately selected in consideration of the components of the raw material ink and the mixed ink used.
- Examples of the inert gas supplied by the inert gas supply unit 64 include argon gas and nitrogen gas. Moreover, you may use air as an inert gas.
- a cylindrical body made of any suitable material such as stainless steel can be used on the condition that it is not deteriorated by the supplied solvent and inert gas.
- the supply adjusting unit 30 is provided in the first pipe 90a.
- the supply adjusting unit 30 is disposed in the flow path of the raw material ink from the raw material ink tank 20 to the stirring tank 50.
- the supply adjusting unit 30 has a function of adjusting the supply amount of the raw material ink to the stirring tank 50.
- the supply adjusting unit 30 can individually adjust the supply amount of each raw material ink supplied to the stirring tank 50 through the first piping unit 90aa, the second piping unit 90ab, and the third piping unit 90ac.
- the supply adjusting unit 30 includes, for example, a flow rate measuring unit 32 and an adjusting unit 34.
- the flow rate measuring unit 32 has a function of measuring the flow rates of each of a plurality of types of raw material inks that pass through the first pipe 90a (the first pipe part 90aa, the second pipe part 90ab, and the third pipe part 90ac). Yes.
- various flow rate sensors available on the market can be used. Examples of such flow sensors include Coriolis flow sensors, thermal diffusion detection flow sensors, and the like.
- the adjustment unit 34 has a function of variably controlling the flow rate of the raw material ink as required. Thereby, the amount of each of the plurality of types of raw material inks passing through the first pipe 90a can be adjusted.
- various types of flow valves such as an electromagnetic valve and an air operation valve available on the market can be used on condition that the flow rate can be variably controlled according to demand.
- a mass flow controller in which the flow rate measuring unit 32 and the adjusting unit 34 are integrally configured can be used.
- the mass flow controller for example, a flow rate sensor corresponding to the flow rate measurement unit 32 and a flow rate control valve corresponding to the adjustment unit 34 are integrally configured, and the measured value acquired by the flow rate sensor is compared with the set flow rate value.
- a mass flow controller having a function of controlling the flow rate by automatically controlling the opening / closing amount of the flow rate control valve so that these values coincide is preferable.
- various mass flow controllers available on the market can be used.
- FIG. 3A is a functional block diagram of a supply adjusting unit used in the coating system.
- the supply adjusting unit 30 includes a front valve 35 provided on the most upstream side, a diaphragm metering pump 36 disposed on the downstream side of the front valve 35, and a diaphragm type A rear valve 37 disposed downstream of the metering pump 36 is provided.
- the front valve 35, the diaphragm metering pump 36, and the rear valve 37 together correspond to the supply adjusting unit 30.
- the front valve 35, the diaphragm metering pump 36, and the rear valve 37 are all provided in the first pipe 90a.
- the front valve 35, the diaphragm metering pump 36, and the rear valve 37 are respectively provided in the first piping unit 90 aa, the second piping unit 90 ab, and the third piping unit 90 ac. Will be provided.
- the front valve 35 and the rear valve 37 have a configuration in which the opening degree can be adjusted or the flow path can be closed, whereby the flow of the raw ink can be adjusted or the flow of the raw ink can be stopped. have.
- Such valves are available in the market with various configurations.
- the diaphragm type metering pump 36 has a function of measuring a predetermined amount of the raw material ink out of the raw material ink passing through the first pipe 90 a and supplying it to the stirring tank 50.
- An example of such a diaphragm type metering pump is a rolling diaphragm pump described in Japanese Patent Application Laid-Open No. 2007-23935.
- FIG. 3-2 is a functional block diagram of a control unit used in the coating system.
- the control unit 70 includes a flow rate measurement unit 32 (first sensor 32a, second sensor 32b, and third sensor 32c) provided in the first pipe 90a, and an adjustment unit 34 (first unit provided in the first pipe 90a.
- the first and second adjustment valves 34a, 34b and 34c) are connected to each of the supply control units 30 by an electric communication line 80.
- control unit 70 is connected to the input unit 72 connected to the flow rate measurement unit 32, the calculation unit 74 connected to the input unit 72, and the calculation unit 74. And an output unit 76 connected to the adjusting unit 34.
- the control unit 70 includes a flow rate measurement unit 32 (first sensor 32a, second sensor 32b, and third sensor 32c), an adjustment unit 34 (first adjustment valve 34a, second adjustment valve 34b, and third adjustment valve 34c), front
- the operation of the valve 35, the diaphragm metering pump 36, and the rear valve 37 can be controlled independently via the electric communication line 80.
- the control unit 70 is configured to be able to control the function of the supply adjusting unit 30 connected by the telecommunication line 80.
- the control unit 70 can be realized by computer hardware including, for example, a microprocessor corresponding to the calculation unit 74, and, for example, serial connection and parallel connection interfaces corresponding to the input unit 72 and the output unit 76.
- the telecommunication line 80 is a wired or wireless information line using a medium such as electricity or light, and has a function and a configuration capable of exchanging control signals between the control unit 70 and the supply adjusting unit 30. Yes.
- the coating system 10 includes a coating device 100.
- the coating apparatus 100 is connected to the stirring tank 50 by the second pipe 90b.
- the coating system 100 has a function of receiving supply of mixed ink from the agitation tank 50 and coating the ink on an object to be coated such as a substrate.
- the coating apparatus 100 includes an ink transport unit 120 and an ink discharge unit 130.
- the ink transport unit 120 is connected to the second pipe 90b and has a function of transporting the mixed ink stored in the stirring tank 50.
- As the ink transport unit 120 pumps having various configurations available on the market can be used.
- the ink discharge unit 130 is connected to the ink transport unit 120 through the third pipe 90c, and has a function of discharging the mixed ink supplied from the ink transport unit 120 and applying the mixed ink to the application target. ing.
- the ink ejection unit 130 is a functional unit corresponding to a nozzle that ejects ink, and has various configurations corresponding to the selected application method.
- a coating apparatus capable of performing a coating process by any suitable coating method can be used.
- the coating method performed by the coating apparatus 100 include a spin coating method, a slit die method, a spray method, and a capillary coating method.
- FIG. 4 is a flowchart for explaining a method of manufacturing the light emitting device.
- FIG. 5 is a diagram (1) illustrating an example of chromaticity coordinates for determining the mixing ratio of the raw material inks.
- FIG. 6 is a diagram (2) illustrating an example of chromaticity coordinates for determining the mixing ratio of the raw material inks.
- FIG. 7 is a diagram (3) illustrating an example of chromaticity coordinates for determining the mixing ratio of the raw material inks.
- FIG. 8 is a schematic graph showing the main part of FIG. 7 extracted and enlarged to explain the step of determining the mixing ratio of the raw material inks.
- control unit 70 acquires the required ink data, and the control unit 70 acquires the standard ink data group.
- the control unit 70 determines the operation of the supply adjustment unit 30 to supply the determined amount of raw material ink, and causes the output unit 76 to output a setting signal for executing the operation;
- the supply adjusting unit 30 supplies the stirring tank 50 with a determined amount of each of a plurality of types of raw ink based on the input setting signal, and an ink stirrer provided in the stirring tank 50
- the 52 including a step of applying the steps of: preparing a mixed ink coating by stirring the supplied plurality of types of raw materials ink, the mixed ink prepared in object of application.
- the coating system 10 is used in a light emitting layer forming process performed by applying mixed ink. Therefore, a light emitting layer forming process using the coating system 10, that is, a coating process including preparation of mixed ink using the coating system 10 will be described with a specific example. In addition, the example used for the following description is a specific illustration, and this invention is not limited to this.
- ⁇ Process for collecting standard ink data> In carrying out the process of forming the light emitting layer, for a known mixed ink, the mixing ratio (denoted as P (m, n)) of a predetermined raw material ink expressed by weight ratio (weight% concentration) and the color of the luminescent color Standard ink data correlating the degree C, that is, the coordinates C in the chromaticity coordinates (denoted as (Cx (n), Cy (n))) is collected.
- a plurality of collected standard ink data is collectively referred to as a standard ink data group.
- n is an integer greater than or equal to 1, and is a continuous unique number assigned to each standard ink data.
- the maximum value of n corresponds to the total number of standard ink data. Therefore, in the following description, the total number of standard ink data is expressed as n max .
- m is a continuous unique number assigned to each raw ink.
- the total number of standard ink data constituting the standard ink data group is 21, and as raw material ink, raw material ink 1 whose emission color is blue, raw material ink 2 whose emission color is green, and raw material whose emission color is red
- raw material ink 1 whose emission color is blue
- raw material ink 2 whose emission color is green
- n max that is the maximum value of n is 21 and the maximum value of m is 3
- the total number n max of standard ink data constituting the standard ink data group is preferably larger because the emission color of the mixed ink can be adjusted with higher accuracy.
- the standard ink data constituting the standard ink data group can be calculated more reliably in the mixing ratio of the raw material inks, so the chromaticity coordinates can be selected so that the coordinates are distributed over a wider range. preferable.
- the standard ink data group is stored in an external storage device such as a hard disk drive connected to the control unit 70 so that the control unit 70 can read and write the standard ink data group. It is preferable to configure so that it can be read.
- the calculation unit 74 of the control unit 70 acquires the required ink data G (Gx, Gy).
- the required ink data G is mixed ink to be applied to an object to be applied, and means data representing the luminescent color of the mixed ink prepared by the coating system 10 as coordinates of chromaticity coordinates. Examples of required ink data G are shown in Table 2 below and FIG.
- the calculation unit 74 may acquire the required ink data G input from the input unit 72, or may acquire the required ink data G once stored in the external storage device.
- the control unit acquires a standard ink data group and determines a mixing ratio of plural types of raw material inks based on the standard ink data group and the required ink data>
- the calculation unit 74 of the control unit 70 acquires a standard ink data group, and determines a mixing ratio of a plurality of types of raw material inks based on the standard ink data group and the required ink data G.
- the steps included in this process are as follows. 1.
- the calculation unit 74 of the control unit 70 compares n max (21 in this example) standard ink data included in the standard ink data group with the required ink data G (S1). 2.
- the calculation unit 74 of the control unit 70 calculates the distance between the coordinates in the chromaticity coordinates of each standard ink data and the coordinates in the chromaticity coordinates of the requested ink data G, and acquires the distance data L (S2). The results are shown in Table 3 below.
- the calculation unit 74 of the control unit 70 rearranges the distance data L having a shorter distance and the corresponding standard ink data so that the rank W is higher (S3) (n is changed to W).
- S3 the rank W is higher
- W (1) 11.
- the calculation unit 74 of the control unit 70 performs the first coordinate (Cx (W (1)), Cy (W (1))) and the second coordinate which are coordinates in the chromaticity coordinate of the standard ink data having the first rank W.
- the coordinates (Cx (W (a)), Cy (W (a))) where the rank W is the a-th are referred to as a-th coordinates.
- a is an integer of 1 or more and n max or less.
- the calculation unit 74 of the control unit 70 includes the coordinates (required ink data G) in an area formed by connecting the first coordinate, the second coordinate, and the a-th coordinate (a ⁇ 3) with a straight line in the standard ink data group. Gx, Gy) is included.
- This step further includes the following steps.
- the computing unit 74 acquires a relational expression of the second straight line T that passes through the a-th coordinate and the coordinates (Gx, Gy) of the required ink data G (S5).
- the computing unit 74 acquires the coordinates (Kx, Ky) of the intersection K between the first straight line S and the second straight line T (S6). As shown in Table 5 below, in this example, the coordinates (Kx, Ky) of the intersection K were (0.3139, 0.3060). [4] The computing unit 74 determines whether or not at least one of the following conditions (1) and (2) is satisfied (S7).
- the coordinates of the required ink data G are the first coordinates (Cx (W (1)), Cy (W (1))).
- the second coordinate (Cx (W (2)), Cy (W (2))) and the a-th coordinate (Cx (W (a)), Cy (W (a))) are connected to each other by a straight line. It is included in the area of
- the calculation unit 74 determines the intersection K from the first coordinate.
- a first distance value Q1 to the coordinates and a second distance value Q2 from the second coordinates to the coordinates of the intersection K are acquired (S9).
- Q1 in this example was 0.0234 and Q2 was 0.0542.
- the a-th coordinate is determined by the above steps.
- the calculation unit 74 of the control unit 70 performs the raw material ink (raw material ink 1, raw material ink 2 and raw material ink 3) at the intersection K based on the first distance value Q1 and the second distance value Q2. Is determined (S10).
- the mixing ratio of the raw material ink 1, the raw material ink 2 and the raw material ink 3 is obtained by the following equation by linearly approximating the first straight line S and the second straight line T.
- the mixing ratio (Pk (m)) of the raw material ink at the intersection K is represented by the following formula.
- Pk (m) P (m, W (1)) + (P (m, W (2)) ⁇ P (m, W (1))) ⁇ Q1 / (Q1 + Q2)
- the mixing ratio Pk of the raw material ink at the intersection K is 96.50 (% by weight) for the mixing ratio Pk (1) of the raw ink 1, and at the intersection K.
- the Pk (2) that is the mixing ratio of the raw material ink 2 is 0.62 (% by weight)
- the Pk (3) that is the mixing ratio of the raw material ink 3 at the intersection K is 2.88 (% by weight). .
- the calculation unit 74 of the control unit 70 causes the third distance value R1 from the a-th coordinate to the coordinates (Gx, Gy) of the requested ink data G and the coordinates (Gx, Gy) of the requested ink data G. ) To the coordinates of the intersection K are acquired (S11). As shown in Table 5 below, R1 in this example was 0.0718 and R2 was 0.0151.
- the calculation unit 74 determines the mixing ratio of the raw material inks (raw material ink 1, raw material ink 2 and raw material ink 3) corresponding to the required ink data G (S12). ).
- the mixing ratio Pg (m) of the raw material ink at the coordinates (Gx, Gy) of the required ink data G can be obtained by the following equation by linearly approximating the first straight line S and the second straight line T.
- Pg (m) P (m, W (a)) + (Pk (m) ⁇ P (m, W (a))) ⁇ R1 / (R1 + R2)
- the mixing ratio Pg (1) of the raw ink 1 is 96.87 ( Pg (2), which is the mixing ratio of the raw material ink 2 according to the coordinates (Gx, Gy) of the required ink data G, is 0.51 (% by weight), and the coordinates (Gx , Gy) Pg (3), which is the mixing ratio of the raw material ink 3 in this case, is 2.62 (wt%).
- the calculation unit 74 determines whether a is smaller than n max , in other words, all chromaticity data of the standard ink data. Is determined (S13).
- the required ink data G is included in an area formed by connecting the first coordinate, the second coordinate, and the a coordinate with a straight line. Since there is no standard ink data that can include coordinates (Gx, Gy), the calculation unit 74 selects another standard ink data group to which ⁇ ( ⁇ is an integer of 1 or more) standard ink data is added, for example. Then, the standard ink data is compared with the required ink data G (S15). Next, the process returns to S2, and the steps after S2 are repeated.
- the mixing ratio of the raw inks (raw ink 1, raw ink 2, and raw ink 3) corresponding to the required ink data G is determined by the calculation unit 74.
- the present invention is not limited to this example, and can be applied to an embodiment using four or more kinds of raw material inks.
- four types of raw material ink are used, four standard ink data are selected, these are compared with the required ink data, and the following steps are performed in the same manner as when using the above three types of raw material inks.
- the mixing ratio of the four types of raw material inks corresponding to the required ink data can be determined.
- the calculation unit 74 of the control unit 70 has a plurality of types (three types in this example) of raw material inks (raw material ink 1, raw material ink 2 and raw material ink 3) based on the determined mixing ratio and the required amount of mixed ink. Each necessary amount, that is, the amount to be supplied to the stirring vessel 50 is determined.
- the raw material ink supply unit 20 starts sending the raw ink (raw ink 1, raw ink 2, and raw ink 3),
- the flow rate measurement unit 32 (the first sensor 32a, the second sensor 32b, and the third sensor 32c) of the supply adjustment unit 30 starts measuring the flow rate of the raw material ink to be delivered.
- the flow rate measurement unit 32 (the first sensor 32a, the second sensor 32b, and the third sensor 32c) transmits data about the measured flow rate of the raw material ink (flow rate measurement data) to the control unit 70 via the electric communication line 80. To do.
- the input unit 72 of the control unit 70 causes the calculation unit 74 to acquire flow rate measurement data input via the telecommunication line 80.
- the calculation unit 74 of the control unit 70 that has acquired the flow rate measurement data determines the operation of the adjustment unit 34 (the first adjustment valve 34a, the second adjustment valve 34b, and the third adjustment valve 34c).
- an operation of changing the opening degree of the control valve which is the adjusting unit 34 based on the flow rate measurement data can be cited.
- the calculation unit 74 generates a setting signal for causing the adjustment unit 34 to execute such an operation, and causes the adjustment unit 34 to output the setting signal via the telecommunication line 80.
- the supply adjusting unit 30 appropriately adjusts the opening degree of each of the first adjusting valve 34a, the second adjusting valve 34b, and the third adjusting valve 34c, which are the adjusting unit 34, based on the input setting signal.
- the supply amount of (raw material ink 1, raw material ink 2 and raw material ink 3) is adjusted, and each of the raw material inks is supplied to the agitation tank 50 by the determined required amount.
- the calculation unit 74 of the control unit 70 outputs a setting signal via the electric communication line 80, and the rear valve 37 of the supply adjusting unit 30 is closed and the front valve 35 is opened according to the input setting signal. As a result, the raw material ink is supplied to the diaphragm type metering pump 36. 2.
- the calculation unit 74 of the control unit 70 outputs a setting signal via the electric communication line 80, and the raw material ink is supplied into the cylinder of the diaphragm metering pump 36 of the supply adjusting unit 30 according to the input setting signal. , Stored.
- the amount of the raw ink stored in the cylinder is adjusted by the operation amount of the diaphragm.
- the amount of the raw material ink is the amount determined by the steps described above. 3.
- the calculation unit 74 of the control unit 70 outputs a setting signal via the telecommunication line 80, and the front valve 35 of the supply adjusting unit 30 is closed and the rear valve 37 is opened according to the input setting signal.
- the control unit 70 (calculation unit 74) outputs a setting signal via the telecommunication line 80, operates the diaphragm of the diaphragm type metering pump 36 in accordance with the setting signal, and pushes out the raw material ink in the cylinder to determine. Only the necessary amount of raw material ink is supplied to the stirring tank 50.
- the mixed ink stored in the stirring tank 50 is supplied to the various types of coating apparatuses 100 described above.
- the mixed ink is transported to the ink ejecting unit 130 by the ink transporting unit 120, and the mixed ink ejected from the ink ejecting unit 130 is applied to an application target such as a substrate on which electrodes are formed.
- mixed inks corresponding to a plurality of different types of luminescent colors can be prepared and applied on demand on different substrates. . Therefore, it is not necessary to carry out complicated steps such as preparing each ink corresponding to the luminescent color in advance or replacing the tank storing each ink at a necessary timing. Therefore, a plurality of types of light-emitting devices having a plurality of types of emission colors can be continuously manufactured by applying a plurality of types of mixed inks. As described above, various kinds of light emitting devices having different light emitting colors of the light emitting layers can be manufactured more quickly by a simple process.
- the operation (cleaning step) of the cleaning unit 60 will be described.
- the raw material ink and the mixed ink stored in the stirring tank 50 are all discharged from, for example, a discharge pipe (not shown), a discharge liquid tank connected thereto, an ink discharge section 130, and the like using the ink transport section 120 of the coating apparatus 100.
- the inert gas supply unit 62 is operated to supply the cleaning liquid to the stirring tank 50.
- the inside of the stirring tank 50 is cleaned by operating the ink stirring mechanism 52 to stir the cleaning liquid.
- the cleaning liquid (discharge liquid) in the stirring tank 50 is discharged out of the coating system 10 from the discharge pipe, the discharge liquid tank, and the ink discharge section 130 by the ink transport section 120.
- the light-emitting device of the present invention mainly includes an anode, a cathode, and a light-emitting layer sandwiched between the pair of electrodes.
- Examples of the layer provided between the cathode and the light emitting layer include an electron injection layer, an electron transport layer, and a hole blocking layer.
- the layer in contact with the cathode is referred to as an electron injection layer, and the layer excluding this electron injection layer is referred to as an electron transport layer.
- the electron injection layer has a function of improving electron injection efficiency from the cathode.
- the electron transport layer has a function of improving electron injection from the cathode, the electron injection layer, or the electron transport layer closer to the cathode.
- the hole blocking layer is a layer having a function of blocking hole transport. In the case where the electron injection layer and / or the electron transport layer have a function of blocking hole transport, these layers may also serve as the hole blocking layer.
- the hole blocking layer has a function of blocking hole transport makes it possible to produce a light emitting device that allows only hole current to flow, for example, and confirm the blocking effect by reducing the current value.
- Examples of the layer provided between the anode and the light emitting layer include a hole injection layer, a hole transport layer, and an electron block layer.
- the layer in contact with the anode is called a hole injection layer, and the layers other than the hole injection layer are positive. It is called a hole transport layer.
- the hole injection layer has a function of improving hole injection efficiency from the anode.
- the hole transport layer has a function of improving hole injection from the anode, the hole injection layer, or the hole transport layer closer to the anode.
- the electron blocking layer has a function of blocking electron transport. In the case where the hole injection layer and / or the hole transport layer has a function of blocking electron transport, these layers may also serve as an electron blocking layer.
- the electron blocking layer has a function of blocking electron transport can be confirmed, for example, by producing a light-emitting device that allows only electron current to flow, and confirming the effect of blocking electron transport by decreasing the measured current value.
- Examples of layer structures that can be taken by the light-emitting device are shown below.
- the light emitting device of the present invention may have a single light emitting layer or two or more light emitting layers.
- the configuration of the light emitting device having two light emitting layers is as follows: The layer configuration shown in j) below can be given.
- the two (structural unit A) layer structures may be the same or different.
- the charge generation layer is a layer that generates holes and electrons by applying an electric field.
- Examples of the charge generation layer include a thin film made of vanadium oxide, indium tin oxide (abbreviated as ITO), molybdenum oxide, or the like.
- (structural unit A) / charge generation layer is “structural unit B”
- examples of the configuration of a light emitting device having three or more light emitting layers include the layer configuration shown in k) below.
- k) Anode / (Structural unit B) x / (Structural unit A) / Cathode Note that the symbol “x” represents an integer of 2 or more, and “(Structural unit B) x” is the structural unit B stacked in x stages. Represents a laminated body.
- a plurality of (structural units B) may have the same or different layer structure.
- a light-emitting device in which a plurality of light-emitting layers are directly stacked may be configured without providing a charge generation layer.
- a light emitting device having the above structure is usually provided on a substrate.
- the order of the layers to be formed, the number of layers, and the thickness of each layer can be appropriately set in consideration of luminous efficiency and lifetime.
- the light emitting device is usually provided on the substrate with the anode disposed on the substrate side, but may be disposed on the substrate with the cathode disposed on the substrate side.
- each layer is stacked on the substrate in order from the anode side (left side of each configuration a to k).
- the light emitting device may be a bottom emission type that emits light from the substrate side or a top emission type that emits light from the side opposite to the substrate.
- a substrate that does not change chemically in the process of manufacturing the light emitting device is suitably used.
- glass, plastic, a polymer film, a silicon plate, and a substrate in which these are laminated are used.
- a driving circuit for driving the light emitting device may be formed in advance on the substrate.
- an electrode having optical transparency is used for the anode.
- the electrode exhibiting light transmittance a thin film of metal oxide, metal sulfide, metal or the like having high electrical conductivity can be used, and a thin film having high light transmittance is preferably used.
- a thin film made of indium oxide, zinc oxide, tin oxide, ITO, indium zinc oxide (abbreviated as IZO), gold, platinum, silver, copper, or the like is used.
- ITO, IZO, or oxidation is used.
- a thin film made of tin is preferably used.
- Examples of the method for forming the anode include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method.
- an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof may be used as the anode.
- a material that reflects light may be used, and the material is preferably a metal, metal oxide, or metal sulfide having a work function of 3.0 eV or more.
- the thickness of the anode can be appropriately determined in consideration of light transmittance, electrical conductivity, and the like.
- the thickness of the anode is, for example, 10 nm to 10 ⁇ m, preferably 20 nm to 1 ⁇ m, and more preferably 50 nm to 500 nm.
- the hole injection material constituting the hole injection layer examples include oxides such as vanadium oxide, molybdenum oxide, ruthenium oxide, and aluminum oxide, phenylamine compounds, starburst amine compounds, phthalocyanine compounds, amorphous carbon, polyaniline, And polythiophene derivatives.
- Examples of the method for forming the hole injection layer include film formation from ink containing a hole injection material.
- the hole injection layer can be formed by the coating method described above or a predetermined known method different from this method.
- the thickness of the hole injection layer varies depending on the material used, and is appropriately determined in consideration of the required characteristics and the ease of film formation.
- the thickness of the hole injection layer is, for example, 1 nm to 1 ⁇ m, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.
- the hole transport layer included in the light emitting device of the present invention contains a hole transport material.
- the hole transport material is not particularly limited as long as it is an organic compound having a hole transport function.
- Specific examples of the organic compound having a hole transport function include polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine residue in a side chain or a main chain, a pyrazoline derivative, an arylamine derivative, a stilbene Derivative, triphenyldiamine derivative, polyaniline or derivative thereof, polythiophene or derivative thereof, polypyrrole or derivative thereof, polyarylamine or derivative thereof, poly (p-phenylene vinylene) or derivative thereof, polyfluorene derivative, aromatic amine residue And a polymer compound having poly (2,5-thienylene vinylene) or a derivative thereof.
- the organic compound having a hole transport function is preferably a polymer compound, for example, a polymer. This is because when the organic compound is a polymer compound, the film forming property is improved and the light emitting property of the light emitting device is made uniform.
- the organic compound has a polystyrene-equivalent number average molecular weight of 10,000 or more, preferably 3.0 ⁇ 10 4 to 5.0 ⁇ 10 5 , more preferably 6.0 ⁇ 10 4 to 1.2. ⁇ 10 5
- the organic compound has a polystyrene-equivalent weight average molecular weight of 1.0 ⁇ 10 4 or more, preferably 5.0 ⁇ 10 4 to 1.0 ⁇ 10 6 , more preferably 1.0 ⁇ 10 6. It is a polymer that is 5 to 6.0 ⁇ 10 5 .
- examples of the hole transport material include JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, Examples thereof include compounds described in Japanese Laid-Open Patent Publication Nos. 2-209998, 3-37992, and 3-152184.
- organic compounds having a hole transport function include polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine residue in a side chain or a main chain, polyaniline or a derivative thereof, polythiophene Or a derivative thereof, a polyfluorene derivative, a polymer compound having an aromatic amine residue, poly (p-phenylenevinylene) or a derivative thereof, and a polymer hole such as poly (2,5-thienylenevinylene) or a derivative thereof Transport materials are preferred, more preferably polyvinyl carbazole or derivatives thereof, polysilane or derivatives thereof, polysiloxane derivatives having aromatic amine residues in the side chain or main chain, polyfluorene derivatives, and polymer compounds having aromatic amine residues. It is.
- the organic compound having a hole transport function is a low molecule, it is preferably used by being dispersed in a polymer binder.
- Polyvinylcarbazole or a derivative thereof can be obtained, for example, from a vinyl monomer by cation polymerization or radical polymerization.
- polysilane or derivatives thereof examples include compounds described in Chem. Rev. 89, 1359 (1989), and British Patent No. 2300196 published specification.
- synthesis method methods described in these documents can be used.
- Kipping method is particularly preferably used.
- a compound having a structure of a low molecular hole transport material in the side chain or main chain is preferably used.
- compounds having a hole-transporting aromatic amine residue in the side chain or main chain can be mentioned.
- the “polymer (compound)” means a polymer having a molecular weight distribution and a polystyrene-equivalent number average molecular weight of 1 ⁇ 10 3 to 1 ⁇ 10 8 .
- Low molecule (compound) means a compound having no molecular weight distribution and a molecular weight of 1 ⁇ 10 4 or less.
- the organic compound having a hole transport function is preferably a polymer having a fluorenediyl group represented by the following formula (1). This is because when the hole transport layer of the organic light emitting device is brought into contact with an organic compound having a condensed ring or a plurality of aromatic rings, the hole injection efficiency is improved and the current density during driving is increased.
- R 1 and R 2 may be the same or different and each independently represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or a monovalent heterocyclic group.
- the alkyl group include groups having 1 to 10 carbon atoms.
- the alkoxy group include groups having 1 to 10 carbon atoms.
- the aryl group include a phenyl group and a naphthyl group.
- the monovalent heterocyclic group include a pyridyl group. The aryl group and the monovalent heterocyclic group may have a substituent.
- substituents examples include an alkyl group having 1 to 10 carbon atoms because the solubility of the polymer can be improved, Examples thereof include an alkoxy group having 1 to 10 carbon atoms.
- the substituent that the aryl group and the monovalent heterocyclic group may have may have a crosslinking group.
- crosslinking group examples include vinyl group, ethynyl group, butenyl group, group having acrylic structure, group having acrylate structure, group having acrylamide structure, group having methacrylic structure, group having methacrylate structure, and methacrylamide structure.
- a particularly preferred hole transporting organic compound is a polymer containing the fluorenediyl group and the structure of an aromatic tertiary amine compound as structural units, for example, a polyarylamine polymer.
- Ar 1 , Ar 2 , Ar 3 and Ar 4 each independently represent an arylene group or a divalent heterocyclic group.
- Ar 5 , Ar 6 and Ar 7 each independently represents an aryl group or a monovalent heterocyclic group.
- Ar 6 and Ar 7 may together form a ring together with the nitrogen atom to which Ar 6 and Ar 7 are bonded, instead of representing the above group.
- m and n each independently represents 0 or 1.
- Examples of the arylene group include a phenylene group, and examples of the divalent heterocyclic group include a pyridinediyl group. These groups may have a substituent.
- Examples of the aryl group include a phenyl group and a naphthyl group, and examples of the monovalent heterocyclic group include a pyridyl group, and these groups may have a substituent.
- Examples of monovalent heterocyclic groups include thienyl group, furyl group, pyridyl group and the like.
- Examples of the substituent that the arylene group, aryl group, divalent heterocyclic group, and monovalent heterocyclic group may have include an alkyl group, since the solubility of the polymer compound can be improved.
- An alkoxy group and an aryl group are preferable, and an alkyl group is more preferable.
- Examples of the alkyl group include groups having 1 to 10 carbon atoms.
- Examples of the alkoxy group include groups having 1 to 10 carbon atoms.
- Examples of the aryl group include a phenyl group and a naphthyl group.
- These substituents may have a crosslinking group.
- the crosslinking group include vinyl group, ethynyl group, butenyl group, group having acrylic structure, group having acrylate structure, group having acrylamide structure, group having methacrylic structure, group having methacrylate structure, and methacrylamide structure.
- Ar 1 , Ar 2 , Ar 3 , and Ar 4 are preferably arylene groups, and more preferably phenylene groups.
- Ar 5 , Ar 6 and Ar 7 are preferably aryl groups, and more preferably phenyl groups.
- the carbon atom in Ar 2 and the carbon atom in Ar 3 are directly bonded, or the carbon atom in Ar 2 and the carbon atom in Ar 3 are divalent such as —O— and —S—. It may be bonded via the group.
- m and n are preferably 0.
- the solvent that can be used in the film forming method using a solution is not particularly limited as long as it is a solvent that can dissolve the hole transport material.
- the solvent include chloride solvents such as chloroform, methylene chloride, dichloroethane, ether solvents such as tetrahydrofuran, aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as acetone and methyl ethyl ketone, ethyl acetate, butyl acetate, Examples include ester solvents such as ethyl cellosolve acetate.
- Examples of film formation methods using solutions include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, and screen printing.
- Examples thereof include coating methods such as a printing method, a flexographic printing method, an offset printing method, and an inkjet printing method.
- the polymer binder that can be mixed in the solution, a binder that does not extremely inhibit charge transport is preferable, and a binder that weakly absorbs visible light is preferably used.
- the polymer binder include polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane and the like.
- the thickness of the hole transport layer differs depending on the material used and may be selected so that the drive voltage and light emission efficiency are appropriate. However, at least a thickness that does not cause pinholes is required. If it is too thick, the driving voltage of the element may be increased.
- the thickness of the hole transport layer is, for example, 1 nm to 1 ⁇ m, preferably 2 nm to 500 nm, more preferably 5 nm to 200 nm.
- the light emitting layer usually contains an organic substance that mainly emits fluorescence and / or phosphorescence, or an organic substance and a dopant that assists the organic substance.
- the dopant is added, for example, to improve the luminous efficiency or change the emission wavelength.
- the organic substance is preferably a polymer compound from the viewpoint of solubility.
- the light emitting layer preferably contains a polymer compound having a polystyrene-equivalent number average molecular weight of 10 3 to 10 8 .
- Examples of the light emitting material constituting the light emitting layer include the following dye materials, metal complex materials, polymer materials, and dopant materials.
- coloring materials include cyclopentamine derivatives, tetraphenylbutadiene derivative compounds, triphenylamine derivatives, oxadiazole derivatives, pyrazoloquinoline derivatives, distyrylbenzene derivatives, distyrylarylene derivatives, pyrrole derivatives, thiophene ring compounds, pyridines.
- examples include ring compounds, perinone derivatives, perylene derivatives, oligothiophene derivatives, oxadiazole dimers, pyrazoline dimers, quinacridone derivatives, coumarin derivatives, and the like.
- Metal complex materials examples include rare earth metals such as Tb, Eu, and Dy, or Al, Zn, Be, Pt, Ir, and the like as a central metal, and an oxadiazole, thiadiazole, phenylpyridine, phenylbenzimidazole, and quinoline structure.
- a metal complex having light emission from a triplet excited state such as an iridium complex or a platinum complex, an aluminum quinolinol complex, a benzoquinolinol beryllium complex, or a benzoxazolyl zinc complex.
- Benzothiazole zinc complex azomethyl zinc complex, porphyrin zinc complex, phenanthroline europium complex, and the like.
- polymer material examples include a polyparaphenylene vinylene derivative, a polythiophene derivative, a polyparaphenylene derivative, a polysilane derivative, a polyacetylene derivative, a polyfluorene derivative, a polyvinylcarbazole derivative, and a material obtained by polymerizing the above dye material and metal complex material. Can be mentioned.
- Dopant material examples include perylene derivatives, coumarin derivatives, rubrene derivatives, quinacridone derivatives, squalium derivatives, porphyrin derivatives, styryl dyes, tetracene derivatives, pyrazolone derivatives, decacyclene, phenoxazone, and the like.
- the thickness of the light emitting layer is usually about 2 nm to 200 nm.
- the light emitting layer is applied with a method of applying an ink (mixed ink) containing a light emitting material to an application target using the coating system 10 of the present invention.
- the steps already described using the coating system 10 may be performed twice or more.
- a known material can be used as the electron transport material constituting the electron transport layer.
- the electron transport material constituting the electron transport layer include oxadiazole derivatives, anthraquinodimethane or derivatives thereof, benzoquinone or derivatives thereof, naphthoquinone or derivatives thereof, anthraquinones or derivatives thereof, tetracyanoanthraquinodimethane or derivatives thereof.
- Fluorenone derivatives diphenyldicyanoethylene or derivatives thereof, diphenoquinone derivatives, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline or derivatives thereof, polyfluorene or derivatives thereof, and the like.
- electron transport materials include oxadiazole derivatives, benzoquinone or derivatives thereof, anthraquinones or derivatives thereof, metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline or derivatives thereof, polyfluorenes Or a derivative thereof, preferably 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole, benzoquinone, anthraquinone, tris (8-quinolinol) aluminum, and polyquinoline. preferable.
- the method for forming the electron transport layer there is no particular limitation on the method for forming the electron transport layer.
- examples of the method for forming the electron transport layer include vacuum deposition from powder, film formation from a solution or a molten state, and a polymer electron transport material is used.
- film formation from a solution or a molten state can be mentioned.
- a polymer binder may be used in combination.
- the electron transport layer can be formed by a predetermined known method.
- the thickness of the electron transport layer varies depending on the material used, and is appropriately determined in consideration of the required characteristics and the ease of film formation.
- the thickness of the electron transport layer is, for example, 1 nm to 1 ⁇ m, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.
- ⁇ Electron injection layer> As the material constituting the electron injection layer, an optimum material is appropriately selected according to the type of the light emitting layer.
- Examples of the material constituting the electron injection layer include alkali metals, alkaline earth metals, alloys containing at least one of alkali metals and alkaline earth metals, oxides of alkali metals or alkaline earth metals, halides , Carbonate, or a mixture of these substances.
- alkali metals, alkali metal oxides, halides, and carbonates include lithium, sodium, potassium, rubidium, cesium, lithium oxide, lithium fluoride, sodium oxide, sodium fluoride, potassium oxide, potassium fluoride , Rubidium oxide, rubidium fluoride, cesium oxide, cesium fluoride, lithium carbonate and the like.
- alkaline earth metals, alkaline earth metal oxides, halides and carbonates include magnesium, calcium, barium, strontium, magnesium oxide, magnesium fluoride, calcium oxide, calcium fluoride, barium oxide, Examples include barium fluoride, strontium oxide, strontium fluoride, and magnesium carbonate.
- An electron injection layer may be comprised by the laminated body which laminated
- the electron injection layer can be formed by a predetermined known method such as an evaporation method, a sputtering method, or a printing method.
- the thickness of the electron injection layer is preferably about 1 nm to 1 ⁇ m.
- a material for the cathode is preferably a material having a low work function, easy electron injection into the light emitting layer, and high electrical conductivity.
- the cathode material has a visible light reflectance. High materials are preferred.
- the material of the cathode for example, alkali metal, alkaline earth metal, transition metal, Group 13 metal of the periodic table, and the like can be used.
- cathode material examples include lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and the like.
- An alloy, graphite, or a graphite intercalation compound is used.
- the alloy examples include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, calcium-aluminum alloy, and the like.
- a transparent conductive electrode made of a conductive metal oxide, a conductive organic material, or the like can be used as the cathode.
- the conductive metal oxide examples include indium oxide, zinc oxide, tin oxide, ITO, and IZO.
- the conductive organic substance examples include polyaniline or a derivative thereof, polythiophene or a derivative thereof.
- the cathode may be composed of a laminate in which two or more layers are laminated. In some cases, the electron injection layer is used as a cathode.
- the thickness of the cathode is appropriately set in consideration of electric conductivity and durability.
- the thickness of the cathode is, for example, 10 nm to 10 ⁇ m, preferably 20 nm to 1 ⁇ m, and more preferably 50 nm to 500 nm.
- Examples of the method for forming the cathode include a vacuum deposition method, a sputtering method, and a laminating method in which a metal thin film is thermocompression bonded.
- the light emitting device described above can be suitably used for a curved or flat illumination device, for example, a planar light source used as a light source of a scanner, and a display device.
- Examples of the display device provided with the light emitting device include a segment display device and a dot matrix display device.
- the dot matrix display device includes an active matrix display device and a passive matrix display device.
- the light emitting device is used as a light emitting element constituting each pixel in an active matrix display device and a passive matrix display device.
- the light-emitting device is used as a light-emitting element or a backlight constituting each segment in the segment display device, and is used as a backlight in the liquid crystal display device.
- the number average molecular weight and the weight average molecular weight were determined as a number average molecular weight and a weight average molecular weight in terms of polystyrene by size exclusion chromatography (SEC).
- SEC size exclusion chromatography
- GPC gel permeation chromatography
- the measurement sample was dissolved in tetrahydrofuran at a concentration of about 0.05% by weight, and 10 ⁇ L was injected into GPC (manufactured by Shimadzu Corporation, trade name: LC-10Avp). Tetrahydrofuran was flowed as a mobile phase of GPC at a flow rate of 2.0 mL / min.
- GPC GPC
- PLgel MIXED-B manufactured by Polymer Laboratories
- the detector a UV-VIS detector (manufactured by Shimadzu Corporation, trade name: SPD-10Avp) was used.
- the emission spectrum was measured to form a thickness of about 60 nm on a quartz substrate using a solution in which a polymer material was dissolved in xylene by adjusting conditions such as solution concentration and rotation speed by spin coating. Performed on thin film.
- a fluorescence spectrophotometer manufactured by JASCO Corporation, MODEL: FP-6500 was used as an emission spectrum measuring apparatus.
- the blue light emitting polymer material A was polymerized by the Suzuki polymerization method.
- the molar ratio was calculated based on the charging ratio.
- the weight average molecular weight in terms of polystyrene was 229000.
- the blue light-emitting polymer material A was dissolved in a mixed solvent of anisole and cyclohexylbenzene (weight ratio 1: 1) to obtain a raw material ink 1 having a solid content of 1.2% by weight.
- a raw material ink 1 having a solid content of 1.2% by weight.
- a thin film having a thickness of 60 nm was formed.
- the peak wavelength of the emission spectrum of this thin film was 461 nm.
- the green light emitting polymer material B was polymerized by the Suzuki polymerization method.
- this green light-emitting polymer material B was dissolved in a mixed solvent of anisole and cyclohexylbenzene (weight ratio 1: 1) to obtain a raw material ink 2 having a solid content of 1.2% by weight.
- a raw material ink 2 having a solid content of 1.2% by weight.
- a thin film having a thickness of 60 nm was formed.
- the emission peak wavelength of the emission spectrum of this thin film was 527 nm.
- a raw material ink containing the blue light emitting polymer material C was formed as a thin film having a thickness of 60 nm by spin coating.
- the emission peak wavelength of the emission spectrum of this thin film was 452 nm.
- a blue luminescent polymer material C and an iridium (Ir) complex D represented by the following formula D are mixed in a weight ratio of 92.5: 7.5 in a mixed solvent of anisole and cyclohexylbenzene (weight ratio 1: 1).
- the raw material ink 3 having a solid content of 1.2% by weight was obtained.
- a thin film having a thickness of 60 nm was formed using the raw material ink 3.
- the emission peak wavelength of the emission spectrum of this thin film was 600 nm.
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Abstract
Description
[1] 塗布法に用いられる有機化合物である発光材料を含む塗工液である原料インキを供給する原料インキ供給部と、
前記原料インキ供給部に接続されている第1配管と、
インキ攪拌機構を備え、前記第1配管により前記原料インキ供給部と接続されている攪拌槽と、
前記第1配管に設けられており、複数種類の原料インキそれぞれの前記撹拌槽への供給量を調節する供給調節部と、
前記供給調節部と電気通信回線により接続されており、複数種類の原料インキの混合比を決定し、該混合比に基づいて前記供給調節部の動作を制御する制御部と、
第2配管により前記攪拌槽に接続されているインキ輸送部、および第3配管により前記インキ輸送部に接続されているインキ吐出部を有する塗布装置と
を備える塗布システム。
[2] 前記供給調節部が、前記第1配管に設けられており、前記電気通信回線により前記制御部に接続されている流量測定部と、第1配管に設けられており、前記電気通信回線により前記制御部に接続されている調節部とを有する、[1]に記載の塗布システム。
[3] 前記供給調節部が、前記第1配管に設けられており、前記電気通信回線により前記制御部に接続されている前バルブと、前記第1配管に設けられており、前記電気通信回線により前記制御部に接続されているダイヤフラム式定量ポンプと、前記電気通信回線により前記制御部に接続されている後バルブとを有する、[1]に記載の塗布システム。
[4] 前記攪拌槽に洗浄液供給管により接続されている洗浄液供給部と、前記攪拌槽に不活性ガス供給管により接続されている不活性ガス供給部とを有する洗浄部をさらに備える、[1]~[3]のいずれか1つに記載の塗布システム。
[5] 前記塗布装置により実施される塗布法が、スピンコート法、スリットダイ法、スプレー法またはキャピラリーコート法である、[1]~[4]のいずれか1つに記載の塗布システム。
[6] [1]~[5]のいずれか1つに記載の塗布システムを用いる発光装置の製造方法において、
制御部が、要求インキデータを取得する工程と、
前記制御部が、標準インキデータ群を取得して、該標準インキデータ群および前記要求インキデータに基づいて、複数種類の原料インキの混合比を決定する工程と、
前記制御部が、決定された混合比に基づいて、攪拌槽に供給される複数種類の原料インキの量を決定する工程と、
前記制御部が、決定された量の原料インキをそれぞれ供給するために、供給調節部の動作を決定し、出力部に、該動作を実行するための設定信号を出力させる工程と、
前記供給調節部が、前記攪拌槽に、入力された設定信号に基づいて複数種類の原料インキそれぞれを決定された量ずつ供給する工程と、
前記攪拌槽内に設けられているインキ攪拌機構により、供給された複数種類の原料インキを攪拌して塗布用の混合インキを調製する工程と、
調製された前記混合インキを被塗布対象に塗布する工程と
を含む、発光装置の製造方法。
[7] [6]に記載の発光装置の製造方法において、
複数種類の前記原料インキの混合比を決定する工程が、
前記制御部が、3個以上の標準インキデータを含む標準インキデータ群と、前記要求インキデータとを対照するステップと、
前記制御部が、前記標準インキデータそれぞれの色度座標における座標と前記要求インキデータの色度座標における座標との間の距離を演算して距離データを取得するステップと、
前記制御部が、得られた前記距離データに基づいて、距離が短い前記距離データおよび対応する標準インキデータほど上位の順位となるように並べ替えるステップと、
前記制御部が、前記順位が第1位の第1座標および第2位の第2座標を通る第1直線の関係式を取得するステップと、
前記制御部が、前記標準インキデータ群のうちの第1座標および第2座標を除き最上位である第a位に対応する第a座標を、前記第1座標、前記第2座標および前記第a座標を互いに直線で結んでなる領域内に、前記要求インキデータの座標が含まれるように決定するステップと、
前記制御部が、決定された前記第a座標と前記要求インキデータの座標とを通る第2直線の関係式を取得するステップと、
前記制御部が、前記第1直線と、前記第2直線との交点の座標を取得するステップと、 前記制御部が、下記(1)および(2)の条件のうちの少なくとも一方を充足するか否かを判定するステップと、
(1)第a座標のx座標の値≧要求インキデータのx座標の値≧交点のx座標の値
(2)第a座標のx座標の値≦要求インキデータのx座標の値≦交点のx座標の値
前記制御部が、前記第1座標から前記交点の座標までの第1距離値および前記第2座標から前記交点の座標までの第2距離値を取得するステップと、
前記制御部が、前記第1距離値および第2距離値に基づいて、前記交点における前記原料インキの混合比を決定するステップと、
前記制御部が、前記第a座標から前記要求インキデータの座標までの第3距離値および前記要求インキデータの座標から前記交点の座標までの第4距離値を取得するステップと、
前記制御部が、前記第3距離値および前記第4距離値に基づいて、前記要求インキデータについての原料インキの混合比を決定するステップと
を含む、発光装置の製造方法。
[8] 前記混合インキを被塗布対象に塗布する工程が、スピンコート法、スリットダイ法、スプレー法またはキャピラリーコート法により行われる、[6]または[7]に記載の発光装置の製造方法。
[9] 複数種類の混合インキを塗布して、複数種類の発光色を有する複数種類の発光装置を連続的に製造する、[6]~[8]のいずれか1つに記載の発光装置の製造方法。
図1を参照して、本発明の実施形態にかかる塗布システムの構成例につき説明する。図1は、塗布システムの機能ブロック図である。
原料インキ供給部20(第1原料インキ槽22a、第2原料インキ槽22b、第3原料インキ槽22c)は、複数種類の原料インキを撹拌槽50に供給する機能を有している。
第1原料インキ槽22a、第2原料インキ槽22bおよび第3原料インキ槽22cそれぞれは、脱着自在かつ他の異なる原料インキを貯留している原料インキ槽と交換できるように構成することが好ましい。
第1配管90a(第1配管部90aa、第2配管部90ab、第3配管部90ac)、第2配管90b、第3配管90c(配管90と総称する場合がある)は、原料インキ供給部20に貯留されている原料インキを、輸送する経路として機能する。第1配管90aは、原料インキ供給部20から送出される原料インキを撹拌槽50に供給する経路として機能する。第2配管90bは、撹拌槽50から送出される混合インキを塗布装置100に供給する経路として機能する。第3配管90cは、混合インキをインキ輸送部120からインキ吐出部130に供給する経路として機能する。
攪拌槽50は、第1配管90aにより原料インキ供給部20と接続されている。攪拌槽50では、第1原料インキ槽22aから供給される所定量の第1原料インキと、第2原料インキ槽22bから供給される所定量の第2原料インキと、第3原料インキ槽22cから供給される所定量の第3原料インキとを混合し、所望の発光色を有する混合インキを調製することができ、調製された混合インキを貯留しておくことができる機能を有している。
攪拌槽50を構成する材料は、原料インキおよび混合インキにより劣化しないこと、および原料インキ又は混合インキへの溶出成分が無いことを条件として、例えばステンレス鋼などの好適な材料により形成された任意好適な形状の器を用いることができる。攪拌槽50の例えば材質、形状、容量は、所望の実施態様に対応した任意好適な態様とすることができる。
塗布システム10は、洗浄部60を備えている。洗浄部60は、原料インキの混合比を変更する場合、原料インキの種類を変更する場合などに、攪拌槽50内を洗浄し、乾燥させる機能を有する。
供給調節部30は、第1配管90aに設けられている。換言すると供給調節部30は、原料インキ槽20から攪拌槽50へと至る原料インキの流路に配置されている。供給調節部30は、原料インキの攪拌槽50への供給量を調節できる機能を有している。供給調節部30は、第1配管部90aa、第2配管部90ab、第3配管部90acそれぞれを経て攪拌槽50に供給される各原料インキの供給量を個別に調節することができる。供給調節部30は、例えば流量測定部32と調節部34とを備えている。
調節部34は、原料インキの流量を要求に応じて可変に制御することができる機能を有している。これにより複数種類の原料インキそれぞれが第1配管90aを通る量を調節することができる。調節部34としては、要求に応じて可変に流量を制御することができることを条件として、例えば市場にて入手可能な電磁弁、エアオペレーションバルブなどの種々の方式の流量弁を用いることができる。
図3-2を参照して制御部70の構成例について説明する。図3-2は、塗布システムに用いられる制御部の機能ブロック図である。
制御部70は、第1配管90aに設けられている流量測定部32(第1センサ32a、第2センサ32b、第3センサ32c)と、第1配管90aに設けられている調節部34(第1調整弁34a、第2調整弁34b、第3調整弁34c)とを含む供給調節部30それぞれと電気通信回線80により接続されている。
塗布システム10は、塗布装置100を含んでいる。塗布装置100は、攪拌槽50に第2配管90bにより接続されている。塗布システム100は、攪拌槽50から混合インキの供給を受け、基板などの被塗布対象に対しインキを塗布成膜する機能を有している。
図4、図5、図6、図7および図8を参照して、上記塗布システム10を用いる発光装置の製造方法について説明する。
なお下記の説明に用いられる例は、具体的な例示であり、本発明はこれに限定されない。
発光層の形成工程を実施するにあたり、既知の混合インキについて、重量比(重量%濃度)で表される所定の原料インキの混合比(P(m、n)と表記する)と発光色の色度C、すなわち色度座標における座標C((Cx(n),Cy(n))と表記する)とを相関させた標準インキデータを収集しておく。収集された複数の標準インキデータを総称して標準インキデータ群という。
標準インキデータ群を構成する標準インキデータの総数nmaxは、混合インキの発光色をより精度よく調整できるので、より多いことが好ましい。また標準インキデータ群を構成する標準インキデータは、原料インキの混合比の計算をより確実に実施することができるので、色度座標においてその座標がより広い範囲に分散するように選択することが好ましい。
次に制御部70の演算部74が、要求インキデータG(Gx,Gy)を取得する。要求インキデータGとは、被塗布対象に塗布されるべき混合インキであって、塗布システム10によって調製される混合インキの発光色を色度座標の座標として表したデータを意味する。
要求インキデータGの例を下記表2および図6に示す。
次に制御部70の演算部74が、標準インキデータ群を取得して標準インキデータ群および要求インキデータGに基づいて、複数種類の原料インキの混合比を決定する。
本工程に含まれるステップは下記の通りである。
1.制御部70の演算部74が、標準インキデータ群に含まれるnmax個(本例では21個)の標準インキデータと、要求インキデータGとを対照する(S1)。
2.制御部70の演算部74が、標準インキデータそれぞれの色度座標における座標と要求インキデータGの色度座標における座標との間の距離を演算して距離データLを取得する(S2)。結果を下記表3に示す。
[1]演算部74が、第a座標を選択する。なお、初回に演算を行う場合、第a座標は標準インキデータ群のうちの第1座標および第2座標を除き最上位である第3座標を選択する。すなわちa=3となる。また、後述の(S8)および(S13)の判定の結果、再度演算が繰り返された場合は、aは3より大きな整数となる。
[2]演算部74が、第a座標と要求インキデータGの座標(Gx,Gy)とを通る第2直線Tの関係式を取得する(S5)。
[3]演算部74が、第1直線Sと第2直線Tとの交点Kの座標(Kx,Ky)を取得する(S6)。下記表5に示されるように、本例においては交点Kの座標(Kx,Ky)は、(0.3139,0.3060)であった。
[4]演算部74が、下記(1)および(2)の条件のうちの少なくとも一方を充足するか否かを判定する(S7)。
(1)第a座標のx座標の値(Cx(W(a)))≧要求インキデータのx座標の値(Gx)≧交点Kのx座標の値(Kx)
(2)第a座標のx座標の値(Cx(W(a)))≦要求インキデータのx座標の値(Gx)≦交点Kのx座標の値(Kx)
以上のステップにより、第a座標が決定される。
式:Pk(m)=P(m,W(1))+(P(m,W(2))-P(m,W(1)))×Q1/(Q1+Q2)
要求インキデータGの座標(Gx,Gy)における原料インキの混合比Pg(m)は、第1直線Sおよび第2直線Tに直線近似させて下記式により求めることができる。
式:Pg(m)=P(m,W(a))+(Pk(m)-P(m,W(a)))×R1/(R1+R2)
次いで上記S2に戻ってS2以後のステップを繰り返す。
制御部70の演算部74は、決定された混合比と必要な混合インキの量に基づいて、複数種類(本例では3種類)の原料インキ(原料インキ1、原料インキ2および原料インキ3)それぞれの必要量、すなわち攪拌槽50に供給すべき量を決定する。
原料インキ供給部20(第1原料インキ槽22a、第2原料インキ槽22bおよび第3原料インキ槽22c)は、原料インキ(原料インキ1、原料インキ2および原料インキ3)の送出を開始し、かつ供給調節部30の流量測定部32(第1センサ32a、第2センサ32bおよび第3センサ32c)は送出される原料インキの流量の測定を開始する。
流量測定部32(第1センサ32a、第2センサ32bおよび第3センサ32c)は、測定された原料インキの流量についてのデータ(流量測定データ)を電気通信回線80を介して制御部70に送信する。
流量測定データを取得した制御部70の演算部74は、調節部34(第1調整弁34a、第2調整弁34bおよび第3調整弁34c)の動作を決定する。この動作の態様としては、流量測定データに基づいて、調節部34である調節弁の開度を変更する動作などが挙げられる。
供給調節部30は、入力された設定信号に基づいて、調節部34である例えば第1調整弁34a、第2調整弁34bおよび第3調整弁34cそれぞれの開度を適宜調節することにより原料インキ(原料インキ1、原料インキ2および原料インキ3)の供給量を調節して、原料インキそれぞれを決定された必要量だけ攪拌槽50に供給する。
2.制御部70の演算部74は、電気通信回線80を介して設定信号を出力し、入力された設定信号に応じて供給調節部30のダイヤフラム式定量ポンプ36のシリンダ内には原料インキが供給され、貯留される。ここでシリンダ内に貯留される原料インキの量は、ダイヤフラムの作動量により調節される。原料インキの量は、既に説明したステップにより決定された量とされる。
3.制御部70の演算部74は、電気通信回線80を介して設定信号を出力し、入力された設定信号に応じて供給調節部30の前バルブ35は閉じられ、後バルブ37は開かれる。制御部70(演算部74)は、電気通信回線80を介して設定信号を出力し、この設定信号に応じてダイヤフラム式定量ポンプ36のダイヤフラムを作動させてシリンダ内の原料インキを押し出して、決定された必要量の原料インキのみを攪拌槽50に供給する。
必要量の原料インキ(原料インキ1、原料インキ2および原料インキ3)の供給を受けた攪拌槽50では、攪拌槽50内に設けられているインキ攪拌機構52により、供給された原料インキが攪拌され、均一に調製された混合インキとされる。
攪拌槽50に貯留された混合インキは、既に説明した種々の方式の塗布装置100に供給される。混合インキはインキ輸送部120によりインキ吐出部130に輸送され、インキ吐出部130から吐出された混合インキが例えば電極が形成されている基板などの被塗布対象に塗布されることとなる。
ここで洗浄部60の動作(洗浄ステップ)について説明する。
まず攪拌槽50に貯留されている原料インキ、混合インキを塗布装置100のインキ輸送部120を用いて例えば図示しない排出管およびこれに接続されている排出液槽、インキ吐出部130などからすべて排出する。
次いで不活性ガス供給部62を動作させて洗浄液を攪拌槽50に供給する。さらに例えばインク攪拌機構52を動作させて洗浄液を攪拌するなどして、攪拌槽50内を洗浄する。
次に攪拌槽50内の洗浄液(排出液)をインキ輸送部120により上記排出管、排出液槽、インキ吐出部130から塗布システム10外に排出する。
正孔ブロック層は、正孔の輸送を堰き止める機能を有する層である。なお電子注入層、及び/又は電子輸送層が正孔の輸送を堰き止める機能を有する場合には、これらの層が正孔ブロック層を兼ねることがある。
電子ブロック層は、電子の輸送を堰き止める機能を有する。なお正孔注入層、及び/又は正孔輸送層が電子の輸送を堰き止める機能を有する場合には、これらの層が電子ブロック層を兼ねることがある。
a)陽極/発光層/陰極
b)陽極/正孔注入層/発光層/陰極
c)陽極/正孔注入層/発光層/電子注入層/陰極
d)陽極/正孔注入層/発光層/電子輸送層/電子注入層/陰極
e)陽極/正孔注入層/正孔輸送層/発光層/陰極
f)陽極/正孔注入層/正孔輸送層/発光層/電子注入層/陰極
g)陽極/正孔注入層/正孔輸送層/発光層/電子輸送層/電子注入層/陰極
h)陽極/発光層/電子注入層/陰極
i)陽極/発光層/電子輸送層/電子注入層/陰極
(ここで、記号「/」は、記号「/」を挟む各層が隣接して積層されていることを示す。以下同じ。)
j)陽極/(構造単位A)/電荷発生層/(構造単位A)/陰極
k)陽極/(構造単位B)x/(構造単位A)/陰極
なお記号「x」は、2以上の整数を表し、「(構造単位B)x」は、構造単位Bがx段積層された積層体を表す。また複数ある(構造単位B)の層構成は同じでも、異なっていてもよい。
発光装置は通常、陽極を基板側に配置して基板上に設けられるが、陰極を基板側に配置して基板上に設けてもよい。例えば構成a)~k)の各発光装置を基板上に作製する場合、陽極を基板側に配置する形態では陽極側(各構成a~kの左側)から順に各層を基板上に積層し、陰極を基板側に配置する形態では陰極(各構成a~kの右側)から順に各層を基板上に積層する。発光装置は、基板側から光を出射するボトムエミッション型であっても、基板とは反対側から光を出射するトップエミッション型であってもよい。
基板は、発光装置を製造する工程において化学的に変化しないものが好適に用いられ、例えばガラス、プラスチック、高分子フィルム、およびシリコン板、並びにこれらを積層した基板などが用いられる。なお基板には発光装置を駆動する駆動回路があらかじめ形成されていてもよい。
発光層から放射される光が陽極を通して出射する構成の発光装置の場合、陽極には光透過性を示す電極が用いられる。光透過性を示す電極としては、電気伝導度の高い金属酸化物、金属硫化物および金属などの薄膜を用いることができ、光透過率の高い薄膜が好適に用いられる。例えば酸化インジウム、酸化亜鉛、酸化スズ、ITO、インジウム亜鉛酸化物(Indium Zinc Oxide:略称IZO)、金、白金、銀、および銅などからなる薄膜が用いられ、これらの中でもITO、IZO、または酸化スズからなる薄膜が好適に用いられる。陽極の形成方法としては、例えば真空蒸着法、スパッタリング法、イオンプレーティング法、メッキ法などが挙げられる。また、該陽極として、ポリアニリンもしくはその誘導体、ポリチオフェンもしくはその誘導体などの有機物の透明導電膜を用いてもよい。
正孔注入層を構成する正孔注入材料としては、例えば酸化バナジウム、酸化モリブデン、酸化ルテニウム、および酸化アルミニウムなどの酸化物、フェニルアミン化合物、スターバースト型アミン化合物、フタロシアニン化合物、アモルファスカーボン、ポリアニリン、およびポリチオフェン誘導体などが挙げられる。
本発明の発光装置が有する正孔輸送層は正孔輸送材料を含む。正孔輸送材料は正孔輸送機能を奏する有機化合物であれば特に限定されない。正孔輸送機能を奏する有機化合物の具体例としては、ポリビニルカルバゾール若しくはその誘導体、ポリシラン若しくはその誘導体、側鎖若しくは主鎖に芳香族アミン残基を有するポリシロキサン誘導体、ピラゾリン誘導体、アリールアミン誘導体、スチルベン誘導体、トリフェニルジアミン誘導体、ポリアニリン若しくはその誘導体、ポリチオフェン若しくはその誘導体、ポリピロール若しくはその誘導体、ポリアリールアミン若しくはその誘導体、ポリ(p-フェニレンビニレン)若しくはその誘導体、ポリフルオレン誘導体、芳香族アミン残基を有する高分子化合物、及びポリ(2,5-チエニレンビニレン)若しくはその誘導体が挙げられる。
発光層は、通常、主として蛍光及び/又はりん光を発光する有機物、または該有機物とこれを補助するドーパントとを含む。ドーパントは、例えば発光効率を向上させたり、発光波長を変化させたりするために加えられる。なお有機物としては、溶解性の観点からは高分子化合物が好ましい。発光層は、ポリスチレン換算の数平均分子量が、103~108である高分子化合物を含むことが好ましい。発光層を構成する発光材料としては、例えば以下の色素材料、金属錯体材料、高分子材料、ドーパント材料が挙げられる。
色素材料としては、例えばシクロペンダミン誘導体、テトラフェニルブタジエン誘導体化合物、トリフェニルアミン誘導体、オキサジアゾール誘導体、ピラゾロキノリン誘導体、ジスチリルベンゼン誘導体、ジスチリルアリーレン誘導体、ピロール誘導体、チオフェン環化合物、ピリジン環化合物、ペリノン誘導体、ペリレン誘導体、オリゴチオフェン誘導体、オキサジアゾールダイマー、ピラゾリンダイマー、キナクリドン誘導体、クマリン誘導体などが挙げられる。
金属錯体材料としては、例えばTb、Eu、Dyなどの希土類金属、またはAl、Zn、Be、Pt、Irなどを中心金属に有し、オキサジアゾール、チアジアゾール、フェニルピリジン、フェニルベンゾイミダゾール、キノリン構造などを配位子に有する金属錯体を挙げることができ、例えばイリジウム錯体、白金錯体などの三重項励起状態からの発光を有する金属錯体、アルミニウムキノリノール錯体、ベンゾキノリノールベリリウム錯体、ベンゾオキサゾリル亜鉛錯体、ベンゾチアゾール亜鉛錯体、アゾメチル亜鉛錯体、ポルフィリン亜鉛錯体、フェナントロリンユーロピウム錯体などが挙げられる。
高分子材料としては、例えばポリパラフェニレンビニレン誘導体、ポリチオフェン誘導体、ポリパラフェニレン誘導体、ポリシラン誘導体、ポリアセチレン誘導体、ポリフルオレン誘導体、ポリビニルカルバゾール誘導体、上記色素材料や金属錯体材料を高分子化した材料などが挙げられる。
ドーパント材料としては、例えばペリレン誘導体、クマリン誘導体、ルブレン誘導体、キナクリドン誘導体、スクアリウム誘導体、ポルフィリン誘導体、スチリル色素、テトラセン誘導体、ピラゾロン誘導体、デカシクレン、フェノキサゾンなどが挙げられる。
発光層は既に説明したとおり、本発明の塗布システム10を用いて発光材料を含むインキ(混合インキ)を被塗布対象に塗布する方法が用いられる。2層以上の発光層を形成する場合には、塗布システム10を用いて既に説明した工程を2回以上実施すればよい。
電子輸送層を構成する電子輸送材料としては、公知の材料を使用できる。電子輸送層を構成する電子輸送材料としては、例えばオキサジアゾール誘導体、アントラキノジメタン若しくはその誘導体、ベンゾキノン若しくはその誘導体、ナフトキノン若しくはその誘導体、アントラキノン若しくはその誘導体、テトラシアノアントラキノジメタン若しくはその誘導体、フルオレノン誘導体、ジフェニルジシアノエチレン若しくはその誘導体、ジフェノキノン誘導体、又は8-ヒドロキシキノリン若しくはその誘導体の金属錯体、ポリキノリン若しくはその誘導体、ポリキノキサリン若しくはその誘導体、ポリフルオレン若しくはその誘導体などが挙げられる。
電子注入層を構成する材料は、発光層の種類に応じて最適な材料が適宜選択される。電子注入層を構成する材料の例としては、アルカリ金属、アルカリ土類金属、アルカリ金属およびアルカリ土類金属のうちの1種類以上を含む合金、アルカリ金属若しくはアルカリ土類金属の酸化物、ハロゲン化物、炭酸塩、またはこれらの物質の混合物などが挙げられる。アルカリ金属、アルカリ金属の酸化物、ハロゲン化物、および炭酸塩の例としては、リチウム、ナトリウム、カリウム、ルビジウム、セシウム、酸化リチウム、フッ化リチウム、酸化ナトリウム、フッ化ナトリウム、酸化カリウム、フッ化カリウム、酸化ルビジウム、フッ化ルビジウム、酸化セシウム、フッ化セシウム、炭酸リチウムなどが挙げられる。また、アルカリ土類金属、アルカリ土類金属の酸化物、ハロゲン化物、炭酸塩の例としては、マグネシウム、カルシウム、バリウム、ストロンチウム、酸化マグネシウム、フッ化マグネシウム、酸化カルシウム、フッ化カルシウム、酸化バリウム、フッ化バリウム、酸化ストロンチウム、フッ化ストロンチウム、炭酸マグネシウムなどが挙げられる。電子注入層は、2層以上を積層した積層体で構成されてもよく、例えばLiF/Caなどが挙げられる。電子注入層は、蒸着法、スパッタリング法、印刷法などの所定の公知の方法によって形成することができる。電子注入層の厚さは、1nm~1μm程度が好ましい。
陰極の材料としては、仕事関数が小さく、発光層への電子注入が容易で、電気伝導度の高い材料が好ましい。また陽極側から光を取出す発光装置では、発光層から放射される光を陰極で陽極側に反射することが発光効率を向上するためには好ましく、そのため、陰極の材料としては可視光反射率の高い材料が好ましい。陰極の材料としては、例えばアルカリ金属、アルカリ土類金属、遷移金属および周期表第13族金属などを用いることができる。陰極の材料としては、例えばリチウム、ナトリウム、カリウム、ルビジウム、セシウム、ベリリウム、マグネシウム、カルシウム、ストロンチウム、バリウム、アルミニウム、スカンジウム、バナジウム、亜鉛、イットリウム、インジウム、セリウム、サマリウム、ユーロピウム、テルビウム、イッテルビウムなどの金属、前記金属のうちの2種以上の合金、前記金属のうちの1種以上と、金、銀、白金、銅、マンガン、チタン、コバルト、ニッケル、タングステン、錫のうちの1種以上との合金、またはグラファイト若しくはグラファイト層間化合物などが用いられる。合金の例としては、マグネシウム-銀合金、マグネシウム-インジウム合金、マグネシウム-アルミニウム合金、インジウム-銀合金、リチウム-アルミニウム合金、リチウム-マグネシウム合金、リチウム-インジウム合金、カルシウム-アルミニウム合金などが挙げられる。また陰極としては導電性金属酸化物および導電性有機物などからなる透明導電性電極を用いることができる。具体的には、導電性金属酸化物として、例えば酸化インジウム、酸化亜鉛、酸化スズ、ITO、およびIZOを挙げることができ、導電性有機物としてポリアニリンもしくはその誘導体、ポリチオフェンもしくはその誘導体などが挙げられる。なお、陰極は、2層以上を積層した積層体で構成されていてもよい。なお、電子注入層が陰極として用いられる場合もある。
以下に、既に説明した原料インキ1~3の調製例を説明する。なお、調製例1~3に記載される化学構造式におけるアルキル基は、通常、直鎖状のアルキル基である。
まず、青色発光高分子材料Aを鈴木重合法により重合した。得られた青色発光高分子材料Aは下記式で示される構成単位a、構成単位b、構成単位c、構成単位d及び構成単位eが、構成単位a:構成単位b:構成単位c:構成単位d:構成単位e=50:32:10:3:5のモル比からなる重合体である。モル比は仕込み比に基づいて算出した。ポリスチレン換算の重量平均分子量は229000であった。
まず、緑色発光高分子材料Bを鈴木重合法により重合した。得られた緑色発光高分子材料Bは下記式で表される構成単位f、前記構成単位c、前記構成単位d、構成単位g及び構成単位hが、構成単位f:構成単位c:構成単位d:構成単位g:構成単位h=80:10:5:3:2のモル比からなる重合体である。モル比は仕込み比に基づいて算出した。ポリスチレン換算の重量平均分子量は202000であった。
まず青色発光高分子材料Cを鈴木重合法を用いて重合した。得られた青色発光高分子材料Cは前記構成単位f、下記式で示される構成単位i、前記構成単位c、前記構成単位dが、構成単位f:構成単位i:構成単位c:構成単位d=50:32:15:5のモル比からなる重合体である。モル比は仕込み比に基づいて算出した。ポリスチレン換算の重量平均分子量は257000であった。
20 原料インキ供給部
22a 第1原料インキ槽
22b 第2原料インキ槽
22c 第3原料インキ槽
30 供給調節部
32 流量測定部
32a 第1センサ
32b 第2センサ
32c 第3センサ
34 調節部
34a 第1調節弁
34b 第2調節弁
34c 第3調節弁
35 前バルブ
36 ダイヤフラム式定量ポンプ
37 後バルブ
50 攪拌槽
52 インキ攪拌機構
60 洗浄部
62 洗浄液供給部
64 不活性ガス供給部
66 洗浄液供給管
68 不活性ガス供給管
70 制御部
72 入力部
74 演算部
76 出力部
80 電気通信回線
90 配管
90a 第1配管
90b 第2配管
90c 第3配管
100 塗布装置
120 インキ輸送部
130 インキ吐出部
Claims (9)
- 塗布法に用いられる有機化合物である発光材料を含む塗工液である原料インキを供給する原料インキ供給部と、
前記原料インキ供給部に接続されている第1配管と、
インキ攪拌機構を備え、前記第1配管により前記原料インキ供給部と接続されている攪拌槽と、
前記第1配管に設けられており、複数種類の原料インキそれぞれの前記撹拌槽への供給量を調節する供給調節部と、
前記供給調節部と電気通信回線により接続されており、複数種類の原料インキの混合比を決定し、該混合比に基づいて前記供給調節部の動作を制御する制御部と、
第2配管により前記攪拌槽に接続されているインキ輸送部、および第3配管により前記インキ輸送部に接続されているインキ吐出部を有する塗布装置と
を備える塗布システム。 - 前記供給調節部が、前記第1配管に設けられており、前記電気通信回線により前記制御部に接続されている流量測定部と、第1配管に設けられており、前記電気通信回線により前記制御部に接続されている調節部とを有する、請求項1に記載の塗布システム。
- 前記供給調節部が、前記第1配管に設けられており、前記電気通信回線により前記制御部に接続されている前バルブと、前記第1配管に設けられており、前記電気通信回線により前記制御部に接続されているダイヤフラム式定量ポンプと、前記電気通信回線により前記制御部に接続されている後バルブとを有する、請求項1に記載の塗布システム。
- 前記攪拌槽に洗浄液供給管により接続されている洗浄液供給部と、前記攪拌槽に不活性ガス供給管により接続されている不活性ガス供給部とを有する洗浄部をさらに備える、請求項1~3のいずれか1項に記載の塗布システム。
- 前記塗布装置により実施される塗布法が、スピンコート法、スリットダイ法、スプレー法またはキャピラリーコート法である、請求項1~4のいずれか1項に記載の塗布システム。
- 請求項1~5のいずれか1項に記載の塗布システムを用いる発光装置の製造方法において、
制御部が、要求インキデータを取得する工程と、
前記制御部が、標準インキデータ群を取得して、該標準インキデータ群および前記要求インキデータに基づいて、複数種類の原料インキの混合比を決定する工程と、
前記制御部が、決定された混合比に基づいて、攪拌槽に供給される複数種類の原料インキの量を決定する工程と、
前記制御部が、決定された量の原料インキをそれぞれ供給するために、供給調節部の動作を決定し、出力部に、該動作を実行するための設定信号を出力させる工程と、
前記供給調節部が、前記攪拌槽に、入力された設定信号に基づいて複数種類の原料インキそれぞれを決定された量ずつ供給する工程と、
前記攪拌槽内に設けられているインキ攪拌機構により、供給された複数種類の原料インキを攪拌して塗布用の混合インキを調製する工程と、
調製された前記混合インキを被塗布対象に塗布する工程と
を含む、発光装置の製造方法。 - 請求項6に記載の発光装置の製造方法において、
複数種類の前記原料インキの混合比を決定する工程が、
前記制御部が、3個以上の標準インキデータを含む標準インキデータ群と、前記要求インキデータとを対照するステップと、
前記制御部が、前記標準インキデータそれぞれの色度座標における座標と前記要求インキデータの色度座標における座標との間の距離を演算して距離データを取得するステップと、
前記制御部が、得られた前記距離データに基づいて、距離が短い前記距離データおよび対応する標準インキデータほど上位の順位となるように並べ替えるステップと、
前記制御部が、前記順位が第1位の第1座標および第2位の第2座標を通る第1直線の関係式を取得するステップと、
前記制御部が、前記標準インキデータ群のうちの第1座標および第2座標を除き最上位である第a位に対応する第a座標を、前記第1座標、前記第2座標および前記第a座標を互いに直線で結んでなる領域内に、前記要求インキデータの座標が含まれるように決定するステップと、
前記制御部が、決定された前記第a座標と前記要求インキデータの座標とを通る第2直線の関係式を取得するステップと、
前記制御部が、前記第1直線と、前記第2直線との交点の座標を取得するステップと、
前記制御部が、下記(1)および(2)の条件のうちの少なくとも一方を充足するか否かを判定するステップと、
(1)第a座標のx座標の値≧要求インキデータのx座標の値≧交点のx座標の値
(2)第a座標のx座標の値≦要求インキデータのx座標の値≦交点のx座標の値
前記制御部が、前記第1座標から前記交点の座標までの第1距離値および前記第2座標から前記交点の座標までの第2距離値を取得するステップと、
前記制御部が、前記第1距離値および第2距離値に基づいて、前記交点における前記原料インキの混合比を決定するステップと、
前記制御部が、前記第a座標から前記要求インキデータの座標までの第3距離値および前記要求インキデータの座標から前記交点の座標までの第4距離値を取得するステップと、
前記制御部が、前記第3距離値および前記第4距離値に基づいて、前記要求インキデータについての原料インキの混合比を決定するステップと
を含む、発光装置の製造方法。 - 前記混合インキを被塗布対象に塗布する工程が、スピンコート法、スリットダイ法、スプレー法またはキャピラリーコート法により行われる、請求項6または7に記載の発光装置の製造方法。
- 複数種類の混合インキを塗布して、複数種類の発光色を有する複数種類の発光装置を連続的に製造する、請求項6~8のいずれか1項に記載の発光装置の製造方法。
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