JP2006269227A - Multicolor light emitting device and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a multi-color light emitting device having high productivity, high quality and high accuracy, and capable of multi-color display suitable for use in a full color display, and a manufacturing method thereof.
A multicolor light emitting device including a colored substrate, at least three kinds of color filters and organic light emitting elements that are independently disposed on the colored substrate,
The colored substrate is disposed between the organic light emitting device and the color filter, transmits a part of the light emitted from the organic light emitting device, absorbs a part thereof, and emits light having a wavelength different from the absorbed wavelength. A featured multicolor light emitting device.
[Selection] Figure 1

Description

  The present invention relates to a multicolor light-emitting device having a color filter that has high productivity, high quality, high accuracy, and capable of multicolor display suitable for use in a full color display, and a method for manufacturing the same. The multicolor light emitting device can be used for display of an image sensor, a personal computer, a word processor, a television, an audio, a video, a car navigation, a telephone, a portable terminal, and an industrial measuring instrument.

  An electroluminescent element is known as an example of a light emitting element applied to a display device. An electroluminescent element is a thin-film self-luminous element and has excellent characteristics such as a low driving voltage, high resolution, and a high viewing angle. Therefore, various studies have been made for their practical use.

  As a method for producing a full color display using this electroluminescent element, 1) “three-color light emitting system” in which elements emitting light in red, green and blue are arranged by applying an electric field, and 2) emitting white light. "Color filter system" which makes red, green and blue light through a color filter that transmits light in a specific wavelength range, and 3) Absorbs near-ultraviolet light, blue light, blue-green light or white light and converts wavelength distribution A “color conversion method” has been proposed in which a color conversion dye that emits light in the visible region is used as a filter.

  Among these, in the above color filter system, a color filter is formed by adding a dye to a flexible substrate or adhering a dye film, and combining with a white light emitting EL element, red, green and Some have proposed taking out the blue color (see Patent Document 1).

JP 2003-36974 A JP 2000-243565 A JP-A-50-6410, JP-A 61-65226, JP-A 64-22987, JP-A-64-60671, JP-A-1-168911, JP 2004-75891 A JP 2002-187967 A JP-A-8-106006 JP-A-6-228440 JP 2004-66457 A JP 2002-37899 A JP 2004-151264 A Japanese Patent Laid-Open No. 5-134112 JP-A-7-218717 JP-A-7-306311 JP-A-5-119306 JP-A-7-104114 JP 7-48424 A JP-A-6-300910 JP 7-128519 A JP-A-8-279394 JP-A-9-330793 JP-A-8-27934 JP-A-5-36475 Monthly Display, Volume 3 Issue 7 (1997)

However, in the “three-color light emission method” of 1), the process is difficult to separate red, green, and blue, so it is difficult to increase the size. In addition, a circularly polarizing plate (transmittance of 50% or less) that prevents reflection of the metal electrode is required, and the cost increases, resulting in a large loss of efficiency.
In addition, as the “white + color filter method” of 2), there is a method of causing an EL element to emit white light (Patent Document 2), but this method has a problem that the current dependency of the emission spectrum of the EL element increases. As a result, the light emission balance is easily lost by driving, resulting in a problem of color shift. Therefore, the problem that a lifetime falls as a full-color organic electroluminescent display arises.

Furthermore, in the said patent document 1, although two examples are mentioned as a manufacturing method of a flexible substrate color filter, it has the same problem. That is, in the method of adhering the color filter film to the first flexible substrate, it is necessary to adhere red, green, and blue separately, and there is a problem that the process becomes complicated. In the second thermal transfer method, a dye is impregnated to form red, green, and blue color filters. In this method, since the dye is diffused and introduced into the film, the red, There is a problem that it is difficult to form green and blue patterns.
As a method for solving the problem of production efficiency and color, the “color conversion formula” in 3) above can be mentioned, but there is a tendency to increase the number of processes due to the process of the color conversion layer format, resulting in higher costs. There is a possibility that.
As described above, all the colorization methods proposed so far have problems. Accordingly, an object of the present invention is to solve the above-mentioned problems, and to provide a multicolor light emitting device capable of performing multicolor display with high productivity, high quality, high accuracy, and suitable for use in a full color display, and its It is to provide a manufacturing method.

The multicolor light emitting device of the present invention is a multicolor light emitting device comprising a colored substrate, at least three kinds of color filters and organic light emitting elements that are independently disposed on the colored substrate,
This colored substrate is disposed between the organic light emitting device and the color filter, transmits a part of the light emitted from the organic light emitting device, absorbs a part thereof, and emits light having a wavelength different from the absorbed wavelength. It is characterized by. At this time, the light from the organic light emitting element is blue to green, and preferably emits red light from the colored substrate. Further, in the present invention, the colored substrate having the function of the complementary color layer contains at least one organic fluorescent material in the colored substrate, whereby the substrate can be provided with the complementary color layer function by a simple dyeing method. . In addition, a layer for protecting the color filter may be further included.

  In addition, the multicolor light emitting device of the present invention includes a step of preparing a colored substrate, a step of disposing at least three kinds of color filters that are independently disposed on one surface of the colored substrate, and the colored substrate. And the step of disposing the organic light emitting device on the other surface of the substrate. At this time, a step of disposing a gas barrier layer can be provided before the step of disposing the organic light emitting element.

In the present invention, by adopting the configuration as described above, the thick film process for providing the color conversion layer in a pattern can be eliminated, so that the total number of manufacturing processes can be reduced. As a result, it is possible to manufacture a multicolor light emitting device with a high yield by a simple method with few manufacturing steps.
In addition, since the multicolor light emitting device of the present invention employs a colored substrate having the function of a complementary color layer, the thickness of the colored substrate itself can be increased and, as a result, used for coloring this colored substrate. Even when the concentration of the organic fluorescent material is low, sufficient optical density and color conversion intensity can be provided with high quality and high accuracy. Further, since a low concentration organic fluorescent material can be used for coloring, it is possible to prevent a decrease in efficiency due to concentration quenching.
Therefore, the multicolor light emitting device of the present invention has a cost aspect that the manufacturing process can be simplified and the productivity is high, and a decrease in initial efficiency can be suppressed by using a low-concentration complementary color layer dye. Both have the desired effect.

FIG. 1 shows a schematic cross-sectional view of a multicolor light emitting device which is one embodiment of the present invention.
In the multicolor light emitting device of the present embodiment, at least three kinds of color filters (red: 3, green: 4, blue: 5) and black matrix 2 that are independently arranged on one surface of the colored substrate 6 are provided. The protective layer 1 is laminated thereon. A gas barrier layer 7 and an organic light emitting element (transparent electrode 8, organic light emitting body 9, and reflective electrode 10) are stacked on the other surface of the colored substrate 6. The protective layer 1, the black matrix 2, and the gas barrier layer 7 may be optionally provided, but are preferably layers that are preferably provided. Hereinafter, each component will be described.

1. Colored substrate 6 having the function of a complementary color layer
The colored substrate 6 of the present invention has a function as a complementary color layer. As described later, for example, a colored substrate having a function of a complementary color layer can be produced by coloring the substrate with an organic fluorescent material.

1-1. Substrate Material The substrate used for the colored substrate 6 of the present invention has excellent visible light transmittance, and is not affected by the conditions (solvent, temperature, etc.) used in each process in the formation process of the multicolor light emitting device, and has dimensional stability. In particular, those that do not cause deterioration in the performance of the multicolor light emitting device are preferable. For example, glass, various plastics, or various films can be used.
Specific examples of the glass include silica glass, which is ordinary glass generally used as window glass, bottle glass, container glass, etc., soda / silica glass obtained by adding Na ₂ O to silica glass, and soda / silica glass. Examples thereof include soft glass such as soda-lime glass to which CaO, MgO, Al ₂ O ₃ , K ₂ O and the like are added, and lead glass containing PbO at a high concentration. Further, examples thereof include hard glasses such as borosilicate glass and aluminoborosilicate glass which have high corrosion resistance and are used in physics and chemistry instruments, medical instruments, and chemical containers.
Specific examples of plastic and film materials include polycarbonate (PC), polyethylene terephthalate (PET), polyethersulfone, polyvinyl butyral, polyphenylene ether, polyamide, polyetherimide, norbornene resin, acrylic resin, methacrylic resin, and isobutylene-anhydrous maleic acid. Thermoplastic resins such as acid copolymer resins and cyclic olefin resins; Thermosetting resins such as epoxy resins, phenol resins, urethane resins, vinyl ester resins, imide resins, urethane resins, urea resins, melamine resins; Alternatively, a polymer hybrid formed from a compound containing a trifunctional or tetrafunctional alkoxysilane and polystyrene, polyacrylonitrile, polycarbonate, or the like can be used.
In addition, a cured product obtained by photo-curing resin or photo-heat combination curable resin by light and / or heat treatment to generate radical species or ionic species to be polymerized or crosslinked to be insoluble and infusible can also be used. .

  Specifically, the cured product of the photocurable resin or photothermal combination curable resin is a composition comprising (1) an acrylic polyfunctional monomer and oligomer having a plurality of acroyl groups or methacryloyl groups, and a photo or thermal polymerization initiator. (2) A composition comprising a polyvinyl cinnamate ester and a sensitizer is dimerized by light or heat treatment to cause crosslinking. (3) A film of a composition comprising a chain or cyclic olefin and bisazide is light or heat treated to generate nitrene and crosslinked with the olefin, and (4) a monomer having an epoxy group and a photoacid A film of a composition comprising a generator is subjected to light or heat treatment to generate an acid (cation) and polymerized. In particular, the mixture of the acrylic polyfunctional monomer / oligomer and the initiator described in (1) can be patterned with high definition, and is preferable from the viewpoint of reliability such as solvent resistance and heat resistance.

1-2. Dye that gives the function of the complementary color layer The dye that gives the function of the complementary color layer to the substrate transmits a part of the light emitted from the organic light emitter of the organic light emitting element, absorbs a part thereof, and a wavelength different from the absorbed wavelength. It is a material having a function of emitting the light of, and having an inorganic or organic fluorescence or phosphorescence.
Examples of the inorganic phosphor material include inorganic phosphors described in Patent Documents 3 to 8 and the like. Specific inorganic phosphors include metal oxides represented by Y ₂ O ₂ S, Zn ₂ SiO ₄ , phosphates represented by Ca ₅ (PO ₄ ) ₃ Cl, ZnS, SrS, and CaS. As a crystal matrix, sulfides typified by, for example, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and other rare earth metal ions and Ag A combination of metal ions such as Al, Mn, and Sb as activators or coactivators can be used.

In the present invention, it is preferable to use an organic fluorescent material that absorbs blue to green light (400 to 550 nm) broadly and emits red fluorescence as the dye having a complementary color layer function. A material may be used independently and may be used in combination of 2 or more types.
Specific examples of red fluorescent materials include rhodamine dyes such as rhodamine B, rhodamine 6G, rhodamine 3B, rhodamine 101, rhodamine 110, sulforhodamine, basic violet 11, basic violet 2, and the like; cyanine dyes, 1-ethyl-2 Examples include pyridine dyes such as-[4- (p-dimethylaminophenyl) -13-butadienyl] -pyridium-perchlorate (pyridine 1); or oxazine dyes. Furthermore, various dyes (direct dyes, acid dyes, basic dyes, disperse dyes, etc.) can be used as long as they have absorptivity and fluorescence in an appropriate wavelength range.

  Further, as a means for adjusting the spectrum of white light output from the colored substrate, particularly the output red light, in addition to the red fluorescent material, a green fluorescent material may be added as a coloring matter having a complementary color layer function. it can. When the green fluorescent material is further added, an effect that conversion from blue light to green light and further conversion from green to red light can be performed efficiently is obtained.

  Specific green fluorescent materials include, for example, 3- (2′-benzothiazolyl) -7-diethylaminocoumarin (coumarin 6), 3- (2′-benzoimidazolyl) -7-N, N-diethylaminocoumarin (coumarin 7). 3- (2′-N-methyl-benzimidazolyl) -7-N, N-diethylaminocoumarin (coumarin 30), 2,3,5,6-1H, 4H-tetrahydro-8-trifluoromethylquinolizino ( 9,9a, 1-gh) Coumarin dyes such as coumarin (coumarin 153); or Basic Yellow 51 which is a coumarin dye dye; and Naphthalimide dyes such as Solvent Yellow 11 and Solvent Yellow 116. it can. Furthermore, various dyes (direct dyes, acid dyes, basic dyes, disperse dyes, etc.) can be used as long as they have absorptivity and fluorescence in an appropriate wavelength range.

  A preferred embodiment of the present invention converts a part of light emission of an organic luminescent material containing components in two wavelength ranges (blue to green) into red, and obtains white light containing components in three wavelength ranges as a whole. It is. Therefore, the type and amount of the organic fluorescent material having a color conversion function that can be used as a dye having the function of the complementary color layer are the emission spectrum of the organic light emitter, the absorption / fluorescence spectrum of each dye, and the film thickness of the substrate material. However, the sum of the portion that transmits through the colored substrate having the function of a complementary color layer of light from the organic light emitter and the amount of light emitted from the colored substrate is the target. It is possible to adjust the balance so as to obtain a white spectrum. As will be described later, in the present invention, a substrate material having a relatively thick film thickness can be used. In this case, since the additive concentration of a dye having a function of a complementary color layer can be lowered, high quality is achieved. -It can provide sufficient color conversion intensity with high accuracy.

1-3. Substrate Coloring Method As a substrate coloring method, a commonly used coloring method may be appropriately selected depending on the material used for the substrate. The “coloring method” refers to a method of coloring (including a method of dyeing) a substrate using the above-described dye that has the function of a complementary color layer, and any means is applicable.
Examples of the glass coloring method include a method of adding a metal ion, a non-metal ion, a metal colloid or the like to a commonly used glass material. Among these methods, it is general and preferable to use a method of adding metal ions.

  In addition, as a coloring method (including a dyeing method) for a film formed of plastic, various resins, etc., generally, a method using a colored resin as a raw material or a transparent film with heat in a later step The method of dyeing from both sides by applying pressure can be mentioned. Alternatively, a coating method that prints colors directly on the film may be used. In addition, organic glass coloring method by sublimation transfer method (see Patent Document 9), film coloring method by dye molecule injection method (see Patent Document 10), polysilane film dyeing method (see Patent Document 11), polyester A film dyeing method (see Patent Documents 12 and 13), a norbornene-based resin film coloring method (see Patent Document 14), and the like are disclosed, and these methods can be appropriately selected and used. In addition, a substrate colored (or dyed) by such a coloring (or dyeing) method can have partial coloring (or dyeing), surface coloring (or dyeing), or a concentration gradient.

The thickness of the colored substrate 6 of the present invention is not particularly limited, but the thickness of the colored substrate is from the point that when coloring the substrate, it can be colored using a low concentration of pigment. A relatively thick film is preferable. For a glass substrate, for example, it is preferably in the range of 30 μm to 100 μm, and for a plastic substrate, it is preferably in the range of 30 μm to 200 μm, for example. When it is thicker than the above range, impact resistance is inferior, winding becomes difficult during winding, and deterioration of gas barrier properties such as water vapor and oxygen may be observed. Moreover, when it is thinner within the above range, the mechanical suitability is poor, and the gas barrier property against water vapor, oxygen and the like is reduced.
As described above, the present invention can provide sufficient color conversion intensity with high quality and high accuracy even when the concentration of the dye having the function of the complementary color layer is lowered. In addition, since a low-concentration organic fluorescent material can be used for coloring, a multicolor light-emitting device that can prevent the decomposition of the dye that occurs when the concentration is high can be provided.
As described above, the present invention provides the colored substrate with the function of the complementary color layer by a simple dyeing method, and preferably emits blue to green light from the organic light-emitting element and red by the function of the complementary color layer of the colored substrate. By converting to light, it is possible to provide a multicolor light-emitting device that has high productivity, high quality, high accuracy, and capable of multicolor display suitable for use in a full color display, and a method for manufacturing the same.

2. Color filter and black matrix The color filter (3, 4, 5) used in the multicolor light emitting device of the present invention is a layer for transmitting a component in a desired wavelength range of light transmitted through a colored substrate having a complementary color layer. Yes, one or more layers may be provided. As the color filter, those for flat panel displays such as a liquid crystal display can be applied. In recent years, a pigment dispersion type color filter in which a pigment is dispersed in a photoresist has been widely used.

  In the configuration shown in FIG. 1, the color filters 3, 4, and 5 are color filters having transmission bands in different wavelength ranges. For example, the color filter 3 is a red color filter that transmits light in the red region (wavelength range of 600 nm or more), the color filter 4 is a green color filter that transmits light in the green region (wavelength region of 500 to 600 nm), and color The filter 6 may be a blue color filter that transmits light in a blue region (wavelength region of 400 to 550 nm).

  When the light emitting device is used as a display, each color filter is provided corresponding to the position of a pixel or subpixel defined by the arrangement of electrodes described later. Generally, a black matrix 2 that does not transmit light in the visible region is disposed in a gap formed between pixels or sub-pixels of each color filter. The black matrix 2 is effective for improving the contrast ratio of the multicolor light emitting device. The black matrix 2 in the present invention can be formed using a material commercially available for flat panel display applications.

3. Protective layer 1
The protective layer 1 of the color filter is disposed for the purpose of protecting the color filter and for the purpose of smoothing the film surface. For this reason, when forming this protective layer, it is necessary to select a process capable of disposing the protective layer so as not to deteriorate the function of the color filter by using a material that is highly visible light transmissive and does not deteriorate the color filter. is there.
The protective layer 1 has high transparency in the visible region (transmittance of 50% or more in the range of 400 to 700 nm), a glass transition temperature (Tg) of 100 ° C. or more, and a film hardness of pencil hardness of 2H or more. A coating film can be formed smoothly on the top, and it is formed from the material which does not reduce the function of the color filters 3-5. For example, a material in which an imide-modified silicone resin (see Patent Documents 15 to 17) and an inorganic metal compound (TiO, Al ₂ O ₃ , SiO _2, etc.) are dispersed in acrylic, polyimide, silicone resin, etc. (Patent Documents 18 and 19) Reference), epoxy-modified acrylate resin as UV curable resin (see Patent Document 20), resin having reactive vinyl group of acrylate monomer / oligomer / polymer, resist resin (see Patent Documents 21 to 24), sol-gel method Photocurable resins and / or thermosetting resins such as inorganic compounds (see Non-Patent Document 1 and Patent Document 25) and fluorine-based resins (see Patent Documents 24 and 26). When forming a gas barrier layer using these resin materials, the formation method is not particularly limited. For example, it can be formed by a conventional method such as a dry method (sputtering method, vapor deposition method, CVD method, etc.) or a wet method (spin coating method, roll coating method, casting method, etc.).

4). Gas barrier layer 7 (optional component)
The gas barrier layer 7 is a layer intended to prevent moisture and / or oxygen derived from a layer formed thereunder from reaching the organic light emitter and deteriorating the organic light emitter.
The gas barrier layer 7 has electrical insulation properties and barrier properties against gases and organic solvents, has high transparency in the visible range (transmittance of 50% or more in the range of 400 to 800 nm), and an electrode formed thereon As a hardness that can withstand the film forming conditions, a material having a film hardness of pencil hardness of 2H or more is preferably used. As such a material, for example, a material such as an inorganic oxide such as SiO _x , SiN _x , SiN _x O _y , AlO _x , TiO _x , TaO _x , ZnO _x, or inorganic nitride can be used. When the gas barrier layer 7 is formed using these inorganic materials, there is no particular limitation, and the gas barrier layer 7 can be formed by a conventional method such as a sputtering method, a CVD method, a vacuum deposition method, a dip method, or a sol-gel method. The gas barrier layer 7 may be a single layer of the above-described material, or may be a laminated structure of a plurality of layers formed from the above-described material.

  When the gas barrier layer 7 is provided in the multicolor light emitting device of this embodiment, it is necessary to consider the influence on the viewing angle characteristics. When the gas barrier layer 7 that is too thick is formed, the optical path length until the light emitted from the organic light-emitting body passes through the gas barrier layer 7 and reaches the colored substrate 6 having the function of the complementary color layer becomes long. As a result, when a multicolor light emitting device is viewed from an oblique direction, light leakage (optical crosstalk) to adjacent pixels or subpixels of another color occurs. Considering the display performance of a multicolor light emitting device as a display, it is required to sufficiently reduce the ratio of the light emission amount of adjacent pixels or subpixels due to optical crosstalk to the light emission amount of the original pixels or subpixels. The Considering this point, it is preferable that the film thickness of the gas barrier layer 7 (the total film thickness in the case of a multilayer structure) is 0.1 to 5 μm.

5. Electrode The organic light emitting device of the present invention includes an organic light emitting layer provided with an organic light emitter 9 sandwiched between an anode and a cathode. Among these, at least one of the anode and the cathode is preferably transparent in the wavelength range of visible light emitted from the organic light emitter 9, and emits this light through the transparent electrode to transmit light to the color filter. Is incident.
In the present invention, it is possible to use one of the transparent electrode 8 and the reflective electrode 10 as an anode and the other as a cathode, but it is desirable to use the transparent electrode 8 as an anode and the reflective electrode 10 as a cathode. Each of the transparent electrode 8 and the reflective electrode 10 may be formed from a plurality of stripe-shaped partial electrodes to perform passive matrix driving. In this case, the extending direction of the stripe-shaped partial electrode of the transparent electrode 8 intersects, preferably orthogonally, with the extending direction of the stripe-shaped partial electrode of the reflective electrode 10. Alternatively, a plurality of switching elements (such as TFTs) may be provided separately, and the reflective electrode 10 may be configured from a plurality of partial electrodes corresponding to the plurality of switching elements on a one-to-one basis to perform active matrix driving. . In this case, the transparent electrode 8 is formed as an integral electrode.

The transparent electrode 8 is formed by laminating conductive metal oxides such as SnO ₂ , In ₂ O ₃ , ITO, IZO, ZnO: Al using a sputtering method. The transparent electrode 8 preferably has a transmittance of 50% or more, more preferably 85% or more with respect to light having a wavelength of 400 to 800 nm. The transparent electrode 8 has a thickness of usually 50 nm or more, preferably 50 nm to 1 μm, more preferably 100 to 300 nm.

  The reflective electrode 10 is preferably formed using a highly reflective metal, amorphous alloy, or microcrystalline alloy. High reflectivity metals include Al, Ag, Mo, W, Ni, Cr, and the like. High reflectivity amorphous alloys include NiP, NiB, CrP, CrB, and the like. High reflectivity microcrystalline alloys include NiAl and the like. Alternatively, other alloys (for example, Mg / Ag alloy) containing the above-described highly reflective metal can be used. The reflective electrode 10 can be formed by any method known in the art such as vapor deposition or sputtering.

6). Organic Light Emitter The organic light emitter 9 is sandwiched between the transparent electrode 8 and the reflective electrode 10 and includes at least an organic light emitting layer. If necessary, it has a structure in which a hole injection layer, a hole transport layer, an electron transport layer, and / or an electron injection layer are interposed. More specifically, for example, the following structures are exemplified.

(1) Anode / organic light emitting layer / cathode (2) Anode / hole injection layer / organic light emitting layer / cathode (3) Anode / organic light emitting layer / electron injection layer / cathode (4) Anode / hole injection layer / organic Light emitting layer / electron injecting layer / cathode (5) Anode / hole injecting layer / hole transporting layer / organic light emitting layer / electron injecting layer / cathode In the above structures (1) to (5), the anode is preferably transparent. The electrode 8 and the cathode is preferably the reflective electrode 10.

  As a material for the hole injection layer, phthalocyanines (Pc) (including copper phthalocyanine (CuPc) and the like) or indanthrene compounds can be used.

  The hole transport layer can be formed using a material having a triarylamine partial structure, a carbazole partial structure, or an oxadiazole partial structure (eg, TPD, α-NPD, PBD, m-MTDATA, etc.).

  As the material for the electron injection layer, alkali metals such as Li, Na, K, or Cs, alkaline earth metals such as Ba and Sr, alloys containing them, rare earth metals, or fluorides of these metals may be used. Yes, but not limited to them. In the configuration of the present invention, a buffer layer may be provided to increase electron injection efficiency. The film thickness of the buffer layer can be appropriately selected in consideration of the driving voltage, transparency, and the like, but in a normal case, it is preferably 10 nm or less. Alternatively, an aluminum quinolinol complex doped with an alkali metal or an alkaline earth metal may be used.

Any known material can be used as the material of the organic light emitting layer. For example, in order to obtain light emission from blue to blue-green, for example, a condensed aromatic ring compound, a ring assembly compound, a metal complex (such as an aluminum complex such as Alq ₃ ), a styrylbenzene compound (4,4′-bis (diphenyl) (Vinyl) biphenyl (DPVBi), etc.), porphyrin-based compounds, benzothiazole-based, benzimidazole-based, benzoxazole-based fluorescent brighteners, and aromatic dimethylidin-based compounds are preferably used. Or you may form the organic light emitting layer which emits the light of a various wavelength range by adding a dopant to a host compound. Examples of host compounds include distyrylarylene compounds (for example, IDE-120 manufactured by Idemitsu Kosan Co., Ltd.), N, N′-ditolyl-N, N′-diphenylbiphenylamine (TPD), aluminum tris (8-quinolinolate) (Alq ₃ ). ) Etc. can be used. As dopants, perylene (blue purple), coumarin 6 (blue), quinacridone compounds (blue green to green), rubrene (yellow), 4-dicyanomethylene-2- (p-dimethylaminostyryl) -6-methyl- 4H-pyran (DCM, red), platinum octaethylporphyrin complex (PtOEP, red), or the like can be used.
In a preferred embodiment of the present invention, a part of light emission from blue to green is converted into red light in a colored substrate having the function of a complementary color layer, thereby sufficiently including components in three wavelength regions of red, green and blue. White light can be obtained.

Next, a method for producing a multicolor light emitting device of the present invention will be described below.
The method for producing a multicolor light emitting device of the present invention includes a step of preparing a colored substrate having a function of a complementary color layer, and at least three kinds of color filters that are independently arranged on one surface of the colored substrate. And a step of disposing an organic light emitting element on the other surface of the colored substrate.

That is, first, as described in “1. Colored substrate having function of complementary color layer”, a colored substrate having a function of complementary color layer is prepared. Next, as described in “2. Color filter and black matrix”, at least three kinds of color filters, preferably red, green, and blue color filters, are independently arranged on one surface of the colored substrate. Set up. In this case, the black matrix can be arranged arbitrarily, but is preferably arranged. Moreover, it is preferable to provide a protective layer for the color filter.
Further, an organic light emitting element is disposed on the other surface of the colored substrate according to a normal method as described above. At this time, a step of disposing a gas barrier layer can be provided before the step of disposing the organic light emitting element.

  Note that either the step of arranging the color filter and the step of arranging the organic light emitting element may be performed first.

  The present invention will be further described below with reference to specific examples, but the present invention is not limited by the description of these examples.

  An example of applying the patterning method of the present invention will be described below with reference to the drawings.

[Example 1]
(Production of substrate having complementary color layer function)
Rhodamine B (48 g), which is a fluorescent dye, was dissolved in 1 L of an ethanol-water mixed solvent (composition ratio, 5: 1). Next, the dyeing bath containing this solution was heated to 80 ° C. In this solution, an acrylic resin film (a resin composition composed of 94 parts by weight of an oil-containing ring skeleton bismethacrylate and 6 parts by weight of an oil-containing ring skeleton bismonoacrylate: a film thickness of 50 μm) is prepared. It was immersed for 1 hour to obtain a dyed film substrate.

(Color filter)
On the film substrate, a black matrix material (CK-7001: manufactured by FUJIFILM Electronics Materials), a red color filter material (CR-7001: manufactured by FUJIFILM Electronics Materials), and a green color filter material (CG-7001: FUJIFILM Materials). A black matrix and color filters (red, green, and blue) were formed using a blue color filter material (CB-7001: manufactured by Fujifilm Electronics Materials) and a blue color filter material. The thickness of the green color filter was 2 μm, and the thicknesses of the other layers were 1 μm.

  Each color filter was formed so that a set of pixels in which red, green, and blue sub-pixels were aligned in the horizontal direction was used as a pixel. The size of each subpixel is 300 μm in length × 100 μm in width, and the interval between adjacent subpixels is 30 μm in the vertical direction and 10 μm in the horizontal direction. Accordingly, one pixel has dimensions of 300 μm in length × 320 μm in width, and the interval between adjacent pixels is 30 μm in the vertical direction and 10 μm in the horizontal direction. In this embodiment, 50 pixels in the vertical direction and 50 pixels in the horizontal direction are arranged to form a total of 2500 pixels.

(Protective layer)
Photopolymerizable resin V259PA / P5 (Nippon Steel Chemical Co., Ltd.) was dissolved to obtain a coating solution. And this coating liquid was apply | coated to the said color filter upper surface using the photolithographic method, and the protective layer with a film thickness of 2 micrometers was obtained.

(Gas barrier layer)
Next, a SiO ₂ film having a thickness of 0.5 μm was deposited on the protective layer by sputtering to form a gas barrier layer. An RF-planar magnetron type apparatus was used as the sputtering apparatus, and SiO ₂ was used as the target. Ar was used as the sputtering gas, and the substrate temperature during formation was set to 80 ° C.

(Organic phosphor)
Next, an electrode and an organic light emitter were formed in a layer configuration of anode / hole injection layer / hole transport layer / organic light emitting layer / electron injection layer / cathode.

  First, a transparent electrode (ITO) was deposited on the entire lower surface of the film substrate by sputtering. Next, after applying a resist agent “OFRP-800” (manufactured by Tokyo Ohka Kogyo Co.) on ITO, patterning was performed by a photolithography method to obtain an anode having a stripe pattern having a width of 105 μm, a pitch of 110 mm, and a film thickness of 100 nm.

Next, the substrate on which the anode was formed was mounted in a resistance heating vapor deposition apparatus, and a hole injection layer, a hole transport layer, an organic light emitting layer, and an electron injection layer were sequentially formed without breaking the vacuum. During film formation, the internal pressure of the vacuum chamber was reduced to 1 × 10 ⁻⁴ Pa. As the hole injection layer, copper phthalocyanine (CuPc) having a thickness of 100 nm was stacked. As the hole transport layer, 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (α-NPD) having a thickness of 20 nm was stacked. Then, 4,4′-bis (2,2′-diphenylvinyl) biphenyl (DPVBi) having a thickness of 30 nm was laminated as the organic light emitting layer. Then, as the electron injection layer, a laminate of aluminum complexes such as Alq ₃ having a thickness of 20 nm.

  After that, using a mask that can obtain a stripe pattern having a width of 0.3 mm and a pitch of 0.33 mm gap perpendicular to the anode (ITO) line, Mg / Ag (weight ratio 10/1) without breaking the vacuum Was deposited to obtain an electrode having a thickness of 200 nm.

  Finally, the obtained laminate is moved into a glove box in a dry nitrogen atmosphere (both oxygen concentration and moisture concentration is 10 ppm or less), and sealed using sealing glass and a UV curable adhesive, and the light emitting device is mounted. Obtained. The structure of the multicolor light emitting device thus obtained is shown in FIG.

[Comparative Example 1]
(Color filter)
As a transparent substrate, on the same acrylic resin film substrate (645 mm × 845 mm × 1.1 mm) as used in Example 1 (transparent substrate 11), a black matrix material (CK-7001: manufactured by FUJIFILM Electronics Materials) ), Red color filter material (CR-7001: manufactured by FUJIFILM Electronics Materials), green color filter material (CG-7001: manufactured by FUJIFILM Electronics Materials), and blue color filter material (CB-7001: FUJIFILM Electronics Materials) Black matrix 2 and color filters (red, green and blue) were formed. The thickness of the green color filter was 2 μm, and the thickness of the other layers was 1 μm.

  Each color filter was formed so that a set of pixels in which red, green, and blue sub-pixels were aligned in the horizontal direction was used as a pixel. The size of each subpixel is 300 μm in length × 100 μm in width, and the interval between adjacent subpixels is 30 μm in the vertical direction and 10 μm in the horizontal direction. Accordingly, one pixel has dimensions of 300 μm in length × 320 μm in width, and the interval between adjacent pixels is 30 μm in the vertical direction and 10 μm in the horizontal direction. In this embodiment, 50 pixels in the vertical direction and 50 pixels in the horizontal direction are arranged to form a total of 2500 pixels.

(Distribution of fluorescence conversion layer)
Next, a fluorescence conversion layer was disposed on the transparent substrate provided with the black matrix and the color filter. That is, as described below, the green fluorescence conversion layer was disposed on the green color filter (13), and the red fluorescence conversion layer was disposed on the red color filter (12). Note that no fluorescence conversion layer is disposed on the blue color filter (14).

(A) Arrangement of green fluorescence conversion layer Coumarin 6 (0.7 parts by weight), which is a fluorescent dye, was dissolved in 120 parts by weight of propylene glycol monoethyl acetate (PEGMA) as a solvent. To this solution, 100 parts by weight of a photopolymerizable resin “V259PA / P5” (Nippon Steel Chemical Co., Ltd.) was added and dissolved to obtain a coating solution. This coating solution is applied on a transparent substrate provided with the above color filter by using a spin coating method, and patterned by a photolithographic method, and a line width of 0.134 mm and a pitch of 1.. A line pattern of 016 mm and a film thickness of 8 μm was obtained.

(B) Arrangement of red fluorescence conversion layer Coumarin 6 (0.6 parts by weight), rhodamine 6G (0.3 parts by weight), and basic violet 11 (0.3 parts by weight), which are fluorescent dyes, are used as propylene glycol as a solvent. It was dissolved in 120 parts by weight of monoethyl acetate (PEGMA). To this solution, 100 parts by weight of a photopolymerizable resin V259PA / P5 (Nippon Steel Chemical Co., Ltd.) was added and dissolved to obtain a coating solution. This coating solution is applied on a transparent substrate provided with the above color filter by using a spin coating method, and patterned by a photolithographic method, and a line width of 0.134 mm and a pitch of 1.. A line pattern of 016 mm and a film thickness of 8 μm was obtained.

(Preparation of planarization layer) (not shown in FIG. 2)
On these green fluorescence conversion layer and red fluorescence conversion layer (fluorescence conversion filter), a UV curable resin (epoxy-modified acrylate) is applied as a flattening layer using a spin coating method and irradiated with a high-pressure mercury lamp. A layer having a thickness of 8 μm was formed. At this time, the pattern of the fluorescence conversion filter was not deformed, and the upper surface of the planarization layer was flat.

(Gas barrier layer) (not shown in FIG. 2)
Next, a SiO ₂ film having a thickness of 0.5 μm was deposited on the planarizing layer by sputtering to form a gas barrier layer. An RF-planar magnetron type apparatus was used as the sputtering apparatus, and SiO ₂ was used as the target. Ar was used as the sputtering gas, and the substrate temperature during formation was set to 80 ° C.

(Organic phosphor)
On the gas barrier layer as described above, in the same manner as in Example 1, a layer structure of anode / hole injection layer / hole transport layer / organic light emitting layer / electron injection layer / cathode was used. A phosphor was formed. Finally, sealing was performed in the same manner as in Example 1 to obtain a multicolor light emitting device. The structure of the conventional multicolor light emitting device thus obtained is shown in FIG.

  All pixels of the multicolor light emitting devices of Example 1 and Comparative Example 1 obtained as described above were caused to emit light, and the chromaticity (x, y) in the CIE XYZ color system of the light emission was measured. Table 1 shows the obtained lighting characteristics. The red, blue and green backlights were turned on under the same conditions. The brightness (lighted white) was compared as Comparative Example 1.

  As described above, in Example 1 of the present invention, the same chromaticity and luminance ratio as in Comparative Example 1 were obtained. That is, the multicolor light emitting device of the present invention manufactured by a method that does not require a thick film process for providing a color conversion layer in a pattern is a multicolor light emitting device manufactured by a conventional manufacturing method having a thick film process. It was confirmed that the device showed the same high quality and high accuracy as the device.

It is typical sectional drawing which shows an example of the structure of the multicolor light emitting device of embodiment of this invention. It is typical sectional drawing which shows an example of the structure of the conventional type (color conversion system) multicolor light-emitting device.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Protective layer 2 Black matrix 3 Red color filter 4 Green color filter 5 Blue color filter 6 Substrate having the function of a complementary color layer 7 Gas barrier layer 8 Anode 9 Organic light emitter 10 Cathode 11 Transparent substrate 12 Red fluorescence conversion layer + red color filter 13 Green fluorescence conversion layer + green color filter 14 Blue color filter

Claims (5)

A multi-color light emitting device comprising a colored substrate, at least three kinds of color filters and organic light emitting elements arranged independently on the colored substrate,
The colored substrate is disposed between the organic light emitting element and the color filter, transmits a part of light emitted from the organic light emitting element, absorbs a part thereof, and emits light having a wavelength different from the absorbed wavelength. A multicolor light emitting device characterized by emitting.   The multicolor light emitting device according to claim 1, wherein light from the organic light emitting element is blue to green, and red light is emitted by the colored substrate.   The multicolor light-emitting device according to claim 1, wherein the colored substrate contains at least one kind of organic fluorescent material in the colored substrate.   A step of preparing a colored substrate, a step of disposing at least three kinds of color filters independently disposed on one surface of the colored substrate, and an organic light emitting device disposed on the other surface of the colored substrate. A process for providing a multicolor light emitting device. Preparing a colored substrate, disposing at least three kinds of color filters on one surface of the colored substrate, disposing a gas barrier layer on the other surface of the colored substrate, And a step of disposing an organic light emitting element on the gas barrier layer in order.

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