JP2006228578A - Color filter base plate for organic electroluminescent element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cheap color filter base plate for organic electroluminescent element preventing local deterioration of an organic EL element caused by local transmission of gas, capable of obtaining an excellent image display free from any fault like dark area. <P>SOLUTION: The color filter base plate for organic electroluminescent element is composed of a base material, a coloring layer formed into pattern shape on the base material, a gas barrier layer formed on the coloring layer, and a gas diffusion layer as a painted film formed on the gas barrier layer. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a color filter substrate for an organic electroluminescent element used in an organic electroluminescent (hereinafter abbreviated as EL) display device.

  In principle, an organic EL element has a structure in which a light emitting layer is sandwiched between an anode and a cathode. However, an organic EL display device capable of color display using an organic EL element is actually used. (1) a method of arranging light emitting layers that emit light of each of the three primary colors, (2) a color filter method that combines a light emitting layer that emits white light and a colored layer of the three primary colors, and (3) light emission that emits blue light. There is a color conversion method that combines a layer and a color conversion layer that converts blue to green and blue to red.

In the organic EL display device of the method (1), it is necessary to develop a light emitting material of each color, and since the material itself is an organic compound, there is a problem that resistance to patterning by photolithography is poor. Further, patterning in a dry process other than the photolithography method has a complicated process and has a problem in mass production.
Therefore, it is conceivable to utilize the organic EL display device of the color filter system (2) and the color conversion system (3).

  When manufacturing an organic EL display device of a color filter type, when organic EL elements are directly laminated on a color filter substrate, water vapor, oxygen, organic generated from an organic layer such as a colored layer or a planarizing layer of the color filter substrate A gas such as a monomer component or a low molecular component deteriorates the light emitting layer of the organic EL element, making it difficult to maintain light emission. The same applies to the case where an organic EL element is directly laminated on a color conversion substrate in a color conversion type organic EL display device. Therefore, conventionally, by providing a gas barrier layer between the color filter substrate and the organic EL element or between the color conversion substrate and the organic EL element, the components of the organic layer of the color filter substrate and the color conversion substrate are changed to the organic EL element. (See, for example, Patent Document 1).

  As the gas barrier layer, an inorganic oxide film is mainly formed by a vacuum film formation method such as a vacuum deposition method, a sputtering method, an ion plating method, a chemical vapor deposition (CVD) method or the like. However, if pinholes exist in these inorganic oxide films, the gas generated from the organic layers of the color filter substrate and the color conversion substrate is locally concentrated in the pinholes, and passes through the gas barrier layer to form the organic EL element. The organic EL element is deteriorated by reaching the light emitting layer. Such deterioration of the organic EL element causes a light emission failure portion (dark area), and becomes a factor of reducing the image quality. Therefore, the gas barrier layer needs to be a multilayer structure film made of the same material or different materials in order to prevent the occurrence of pinholes. However, when the gas barrier layer is a multilayer structure film, there is a problem that it is not preferable in terms of manufacturing cost, such as an increase in the number of processes and materials due to a plurality of film formations.

Japanese Patent No. 3247388

  The present invention has been made in view of the above problems, prevents local deterioration of the organic EL element due to the passage of local gas, and allows good image display without defects such as dark areas, Another object of the present invention is to provide an inexpensive color filter substrate for an organic EL element.

  In order to achieve the above object, the present invention is formed on a base material, a colored layer formed in a pattern on the base material, a gas barrier layer formed on the colored layer, and the gas barrier layer. And a color filter substrate for an organic electroluminescent element, comprising a gas diffusion layer which is a coating film.

  In the present invention, by providing the gas diffusion layer on the gas barrier layer, the gas generated from the colored layer or the like can be diffused, and it is possible to prevent the gas from being locally released. Therefore, when the organic EL display device using the color filter substrate for the organic EL element of the present invention, defects such as pinholes exist in the gas barrier layer, and even when the gas reaches the organic EL layer, Since local gas release can be prevented, local deterioration of the organic EL layer can be suppressed. As a result, the occurrence of defects such as dark spots and dark areas can be suppressed, and good image display can be achieved. In the present invention, since the gas diffusion layer is a coating film, it is possible to fill foreign substances, pinholes and the like on the gas barrier layer, and to improve the gas barrier properties of the gas barrier layer. Furthermore, in the present invention, since the gas generated from the colored layer or the like is diffused, there is no need to provide a gas barrier layer of a multilayer structure film that is expensive in order to complete the gas barrier property as in the prior art, An inexpensive organic EL display device can be provided.

  In the said invention, it is preferable that the said gas diffusion layer has low degassing property, heat resistance, and insulation. This is because the gas diffusion layer having a low degassing property can prevent gas from being generated from the gas diffusion layer itself. In addition, since the gas diffusion layer has heat resistance, a transparent electrode layer can be stably formed on the gas diffusion layer when an organic EL display device is produced using the color filter substrate for an organic EL element of the present invention. Because you can. Furthermore, because the gas diffusion layer has an insulating property, it is possible to avoid conduction with the transparent electrode layer.

  In this case, it is preferable that the gas diffusion layer contains an acrylic resin, an epoxy resin, or a polyimide resin. This is because a gas diffusion layer having the above-described properties can be obtained.

  In the present invention, the saturated water absorption rate of the gas diffusion layer is preferably 1.0% or less. When the saturated water absorption rate of the gas diffusion layer is in the above range, a pretreatment for removing moisture in the gas diffusion layer is performed when an organic EL display device is manufactured using the color filter substrate for an organic EL element of the present invention. This is because the manufacturing process can be simplified and the management of the color filter substrate for the organic EL element is facilitated.

  Furthermore, in the present invention, the thickness of the gas diffusion layer is preferably in the range of 0.2 μm to 5 μm. If the thickness of the gas diffusion layer is too thin, the gas generated from the colored layer or the like is difficult to diffuse. Conversely, if the thickness is too thick, the function of diffusing the gas hardly changes and the cost increases and the light transmittance decreases. Because there is a fear.

  Furthermore, in the present invention, the average surface roughness (Ra) of the gas diffusion layer is preferably in the range of 0.1 nm to 10.0 nm. If the average surface roughness (Ra) of the gas diffusion layer is within the above range, an electrode can be stably formed on the gas diffusion layer, and the color filter substrate for organic EL elements of the present invention is applied to an organic EL display device. This is because, when used, it is possible to suppress the occurrence of dark areas and to obtain a good image display.

  In the present invention, the gas barrier layer is preferably a single-layer or multilayer silicon nitride oxide film. This is because the silicon nitride oxide film hardly causes pinholes and protrusions and has a high gas barrier property.

  Furthermore, in the present invention, a planarization layer may be formed between the colored layer and the gas barrier layer. This is because the provision of the planarization layer can reduce the influence of forming a gas barrier layer or the like on the colored layer. Moreover, when it is set as an organic EL display apparatus using the color filter substrate for organic EL elements of this invention, generation | occurrence | production of the thickness nonuniformity at the time of forming a light emitting layer can be prevented.

  In the present invention, a light shielding portion may be formed between the colored layers on the substrate. This is because the provision of the light-shielding portion makes it possible to improve the contrast when an organic EL display device is formed using the color filter substrate for organic EL elements of the present invention.

  Furthermore, in the present invention, a color conversion layer may be formed between the colored layer and the gas barrier layer.

  The present invention also provides a color filter substrate for an organic EL element described above, a transparent electrode layer formed on a gas diffusion layer of the color filter substrate for an organic EL element, and formed on the transparent electrode layer, at least emitting light. An organic EL display device comprising an organic EL layer including a layer and a counter electrode layer formed on the organic EL layer.

  Since the organic EL display device of the present invention uses the above-described color filter substrate for an organic EL element, it is possible to suppress the release of gas generated from a colored layer or the like as described above. It is possible to prevent local degradation of the EL layer and suppress the occurrence of defects such as dark spots and dark areas. Therefore, an organic EL display device capable of displaying a good image can be obtained.

  According to the present invention, it is possible to suppress local gas passage by providing a gas diffusion layer as a coating film on the gas barrier layer. By using such a color filter substrate for an organic EL element according to the present invention, local deterioration of the organic EL layer is suppressed, and a highly reliable image display without dark spots or dark areas is possible. There is an effect that an organic EL display device can be obtained.

  Hereinafter, the color filter substrate for organic EL elements of the present invention and the organic EL display device using the same will be described in detail.

A. Color filter substrate for organic EL elements The color filter substrate for organic EL elements of the present invention includes a base material, a colored layer formed in a pattern on the base material, a gas barrier layer formed on the colored layer, It has a gas diffusion layer which is formed on the gas barrier layer and is a coating film.

FIG. 1 is a schematic cross-sectional view showing an example of a color filter substrate for an organic EL element of the present invention.
As shown in FIG. 1, a color filter substrate 10 for an organic EL element according to the present invention is obtained by sequentially laminating a colored layer 2, a planarizing layer 3, a gas barrier layer 4 and a gas diffusion layer 5 on a base material 1. . The colored layer 2 includes a red colored pattern 2R, a green colored pattern 2G, and a blue colored pattern 2B, and a black matrix 6 is formed between the colored colored patterns 2R, 2G, and 2B.

  The gas diffusion layer in the present invention has a function of diffusing gas. In general, the gas barrier layer is formed by a sputtering method, a chemical vapor deposition (CVD) method or the like, and it is technically possible to obtain a gas barrier layer free from foreign matters such as particles and pinholes by such a method. Have difficulty. Therefore, in the present invention, by providing a gas diffusion layer on the gas barrier layer, when the gas generated from the colored layer, the planarization layer, etc. passes through pinholes or the like existing in the gas barrier layer, it passes through the gas diffusion layer. In this case, the gas can be diffused and gas can be prevented from being released locally. Therefore, when an organic EL display device is formed using the color filter substrate for organic EL elements of the present invention, even if gas may reach the organic EL layer, local gas release can be prevented. Local degradation of the EL layer can be suppressed, and generation of defects such as dark spots and dark areas can be suppressed.

  In the present invention, since the gas diffusion layer is a coating film, a foreign substance, a pinhole, or the like on the gas barrier layer is filled by applying a gas diffusion layer forming coating liquid on the gas barrier layer when forming the gas diffusion layer. be able to. This can be expected to improve the gas barrier properties of the gas barrier layer.

As described above, in the present invention, by forming the gas diffusion layer, it is possible to prevent the local release of the gas generated from the colored layer and the like, and to improve the gas barrier property. When used, the occurrence of defects such as dark spots and dark areas can be suppressed. Therefore, an organic EL display device capable of displaying a good image can be obtained.
Further, the present invention diffuses the gas generated from the colored layer or the like as described above and prevents it from being locally released. Therefore, the present invention is expensive in order to complete the gas barrier property as in the prior art. It is not necessary to provide a gas barrier layer having a multilayer film, and an inexpensive organic EL display device can be provided.

Furthermore, in the present invention, since the gas diffusion layer is a coating film, the surface can be flattened. When an organic EL display device is formed using the color filter substrate for organic EL elements of the present invention, a transparent electrode layer, an organic EL layer, etc. are formed on the gas diffusion layer. Thus, a transparent electrode layer and an organic EL layer are formed, so that it is possible to form a uniform and dense transparent electrode layer and an organic EL layer having no thickness unevenness.
Hereinafter, each structure of the color filter substrate for organic EL elements of this invention is demonstrated.

1. Gas diffusion layer The gas diffusion layer used for this invention is formed on a gas barrier layer, and is a coating film. The “coating film” means one formed by a wet method, for example, one formed by coating using a coating solution.

  In the present invention, the gas diffusion layer preferably has a low degassing property. The degassing property refers to a property of desorbing (generating) gas from the gas diffusion layer by, for example, decomposing organic substances in the gas diffusion layer by heating the gas diffusion layer. This is because if the gas diffusion layer has a high degassing property, display defects may occur due to degassing from the gas diffusion layer.

Specifically, the degassing property of the gas diffusion layer is required to be lower than the degassing property of the colored layer, the color conversion layer, and the planarization layer. If the gas diffusion layer has a higher degassing property than a colored layer or the like, the gas generated from the gas diffusion layer itself causes dark spots, which has the effect of suppressing the generation of dark spots by diffusing the gas. It is because it cannot be obtained.
More specifically, the thermal weight loss rate (TGA) at 230 ° C. (temperature increase rate: 10 ° C./min) of the gas diffusion layer is preferably 10% or less.
The thermogravimetric reduction rate is a value measured by a differential thermal analysis (TG-DTA) apparatus.

In the present invention, the gas diffusion layer preferably has heat resistance. As described above, when an organic EL display device is produced using the color filter substrate for organic EL elements of the present invention, a transparent electrode layer or the like is formed on the gas diffusion layer. Therefore, the gas diffusion layer preferably has heat resistance. Specifically, the heat resistance of the gas diffusion layer may be about the same as or higher than the heat resistance of the colored layer. In general, the colored layer only needs to withstand about 230 ° C.
More specifically, as in the case described above, the thermal weight loss rate (TGA) at 230 ° C. of the gas diffusion layer is preferably 10% or less.

  Furthermore, in this invention, it is preferable that a gas diffusion layer has insulation. When an organic EL display device is produced using the color filter substrate for organic EL elements of the present invention, a transparent electrode layer, a light emitting layer, a counter electrode layer, and the like are sequentially formed on the gas diffusion layer. It is because there exists a possibility that it may conduct | electrically_connect when there is no insulation.

  In the present invention, the gas diffusion layer preferably has low hygroscopicity. This is because moisture absorbed or adsorbed in the gas diffusion layer causes dark spots. Further, if the gas diffusion layer has low hygroscopicity, the pretreatment for removing the moisture in the gas diffusion layer can be omitted when the organic EL display device is manufactured using the color filter substrate for organic EL elements of the present invention. And the manufacturing process can be simplified. Furthermore, management of the color filter substrate for organic EL elements becomes easy.

Specifically, the saturated water absorption rate of the gas diffusion layer is preferably 1.0% or less.
The saturated water absorption is obtained based on JIS K7209 by the Karl Fischer method. That is, (1) a sample object having a side of 50 mm is used as a measurement object, dried in a thermostat kept at 50 ° C. for 24 hours, allowed to cool in a desiccator, and then placed in pure water kept at a temperature of 23 ° C. After standing for a period of time, the sample piece is removed from the water. (2) The weight W1 of the sample after reaching the equilibrium state is measured. (3) This sample is heated to 200 ° C. under a dry nitrogen stream, and the water content W2 released thereby is quantified by the Karl Fischer method. (4) Calculate saturated water absorption by the following equation.
Saturated water absorption = 100 × W2 / (W1-W2) (%)

  As will be described later, a resin can be used as a material for forming the gas diffusion layer. However, if the number of polar groups contained per repeating unit of the resin is too large, the water absorption becomes too large, and the color for organic EL elements is increased. The amount of water contained in the filter substrate is increased, which causes a decrease in the performance of the organic EL display device. Therefore, in the present invention, as the material for forming the gas diffusion layer, a resin whose type and number of polar groups and other substituents are designed so that the saturated water absorption at 23 ° C. is 1.0% or less is used. Is preferred.

  Furthermore, the gas diffusion layer preferably has a dehydrating property. The dehydration property refers to the ease with which water is desorbed from the gas diffusion layer. If the gas diffusion layer has no dehydration property, that is, if the moisture is difficult to desorb, the pretreatment for removing the moisture in the gas diffusion layer can sufficiently remove the moisture. However, when an organic EL display device is manufactured using the color filter substrate for organic EL elements of the present invention or when the organic EL display device is used, there is a possibility that moisture is gradually desorbed from the gas diffusion layer. This is because it causes dark spots.

The gas diffusion layer preferably has low gas permeability. This is because the generation of dark spots can be suppressed due to the low permeability of gas desorbed from the colored layer or the like. The low gas permeability varies depending on the type of gas. For example, the water vapor permeability of the gas diffusion layer is preferably 1 g / m ² / day or less, more preferably 0.5 g / m ² / day. day or less, and most preferably 0.1 g / m ² / day or less. The oxygen diffusion rate of the gas diffusion layer is preferably 1 cc / m ² / day / atm or less, more preferably 0.5 cc / m ² / day / atm or less.

  The water vapor transmission rate is a value measured using a water vapor transmission rate measuring device (manufactured by MOCON, PERMATRAN-W 3/31: trade name) under the conditions of a measurement temperature of 37.8 ° C. and a humidity of 100% Rh. It is. The oxygen gas permeability is a value measured using an oxygen gas permeability measuring apparatus (manufactured by MOCON, OX-TRAN 2/20: trade name) under the conditions of a measurement temperature of 23 ° C. and a humidity of 90% Rh. It is.

  Further, the gas diffusion layer preferably has a light-transmitting property because light is extracted from the base material side when the organic EL display device is formed using the color filter substrate for organic EL elements of the present invention. Specifically, the light transmittance in the visible light region of the gas diffusion layer is preferably 60% or more, more preferably 80% or more, and most preferably 90% or more.

  In addition, the said light transmittance is an average value of the value measured using Shimadzu Corporation Corp. UV-3100 within the wavelength range of 380 nm-800 nm.

  The material for forming the gas diffusion layer used in the present invention is not particularly limited as long as it can be formed by a wet method. For example, polycarbonate resin, cyclic polyolefin resin, norbornene resin, 4-methylpentene resin, Polysulfone resin, polyethersulfone resin, polyarylate resin, polyethylene terephthalate resin, polyethylene naphthalate resin, polypropylene terephthalate resin, fluorine resin, polyurethane resin, polystyrene resin, polyethylene resin, polypropylene resin, polyvinyl chloride resin, polyester resin, acrylic Resin, polymethyl methacrylate resin, epoxy resin, epoxy resin, silicone resin, polyacrylate resin, melamine resin, phenol resin, alkyd resin, polyimide resin Resin such as polyimide amide resin, maleic acid resin, or cardo resin (including cardo acrylic resin and cardo epoxy resin); reactivity such as acrylate, methacrylate, polyvinyl cinnamate, or cyclized rubber Ionizing radiation curable resins having a vinyl group, especially electron beam curable resins or ultraviolet curable resins; sol-gel materials composed of polysiloxane oligomers; organic-inorganic hybrid materials composed of polysiloxane oligomers and organic polymers; Can be mentioned.

  Among these materials, those having the above-described properties such as low degassing property, heat resistance, insulating property, low hygroscopic property, dehydration property, low gas permeability, and light permeability are preferable. The above-described materials have at least heat resistance, insulating properties, and light transmittance.

  Among the materials described above, examples of the material having low degassing property include acrylic resin, epoxy resin, cardo resin, cyclic polyolefin resin, norbornene resin, silicone resin, polyimide resin, polysilazane, or organic-inorganic. Examples include hybrid materials.

  In addition, among the above-described materials, materials having relatively high heat resistance include, for example, cyclic polyolefin resin, norbornene resin, silicone resin, acrylic resin, epoxy resin, cardo resin, polyimide resin, polysilazane, or organic -An inorganic hybrid material etc. are mentioned.

  In addition, among the materials described above, examples of the material having dehydrating property include cyclic polyolefin resins, norbornene resins, and polyimide resins. Especially, cyclic polyolefin resin etc. are mentioned as a material which has low hygroscopicity. The cyclic polyolefin-based resin or norbornene-based resin has high heat resistance, low moisture absorption in the manufacturing process of the organic EL element color filter substrate, and the amount of moisture contained in the organic EL element color filter substrate is also low. As a result, dark spots and dark areas can be reduced.

  Further, among the materials described above, examples of the material having low gas permeability include an epoxy resin, a silicone resin, polysilazane, and an organic-inorganic hybrid material.

  Furthermore, among the materials described above, examples of materials having relatively high light transmission include acrylic resins, epoxy resins, polycarbonate resins, cyclic polyolefin resins, norbornene resins, 4-methylpentene resins, polysulfone resins, polysulfone resins, and the like. Ether sulfone resin, polyarylate resin, polyethylene terephthalate resin, polyethylene naphthalate resin, polypropylene terephthalate resin, fluorine resin, polyurethane resin, polystyrene resin, polyethylene resin, polypropylene resin, polyvinyl chloride resin, polyester resin, acrylic resin, poly Methyl methacrylate resin, epoxy resin, silicone resin, polyacrylate resin, melamine resin, phenol resin, alkyd resin, polyimide amide resin, maleic acid resin, cardo Resins, ionizing radiation-curable resin, a sol-gel materials, organic - inorganic hybrid materials, and the like. Acrylic resins or epoxy resins have high solubility in general-purpose solvents, are easily resisted into ionizing radiation curable resins, and can form a highly transparent gas diffusion layer. Thereby, it is possible to obtain sufficient transparency as a constituent member of the organic EL display device.

  Moreover, as a forming material of the gas diffusion layer used in the present invention, for example, any of a thermoplastic resin, a thermosetting resin, a photocurable resin, and the like can be used. Among these, a thermosetting resin or a photocurable resin is preferable, and a thermosetting resin is particularly preferable from the viewpoint that the effect of diffusing gas generated from the colored layer is high. On the other hand, from the viewpoint of patterning characteristics, a photocurable resin is preferably used.

  In the present invention, in view of the characteristics required for the gas diffusion layer, among the materials described above, acrylic resin, epoxy resin, cardo resin, cyclic polyolefin resin, norbornene resin, silicone resin, polyimide resin, Polysilazane or organic-inorganic hybrid material is particularly preferably used, and among these, acrylic resin, epoxy resin, or polyimide resin is preferably used.

  The film thickness of the gas diffusion layer is usually about 0.2 μm to 5 μm, preferably about 0.2 μm to 1.5 μm, although it depends on the uneven state of the underlying colored layer, gas barrier layer, and the like. This is because if the gas diffusion layer is too thin, the gas generated from the colored layer or the like is difficult to diffuse. On the other hand, if the film thickness of the gas diffusion layer is too thick, the function of diffusing the gas hardly changes and the cost increases, and the light transmittance may decrease.

  The average surface roughness (Ra) of the gas diffusion layer is such that when an organic EL display device is produced using the color filter substrate for organic EL elements of the present invention, a transparent electrode layer or organic layer is formed on the gas diffusion layer. Although it is not particularly limited as long as the EL layer can be stably formed, it is preferably in the range of 0.1 nm to 10.0 nm, more preferably in the range of 0.1 nm to 2.0 nm. It is. As long as the average surface roughness (Ra) of the gas diffusion layer is within the above range, when the color filter substrate for organic EL elements of the present invention is used in an organic EL display device, a uniform and dense transparent electrode is formed on the gas diffusion layer. This is because a layer can be formed and thickness unevenness in the organic EL layer can be suppressed. Thereby, generation | occurrence | production of a dark area can be suppressed and it becomes possible to obtain a favorable image display.

The average surface roughness (Ra) is a value measured in an observation range of 5 μm ² under the following conditions using a scanning probe microscope (SPM: D-3000, manufactured by Digital Instruments).
(Measurement condition)
Tapping mode Setting point: about 1.6 Scan line: 256
Frequency: 0.8Hz

  In the present invention, the gas diffusion layer may be formed at least on the colored layer. This is because the gas diffusion layer is provided for diffusing the gas generated from the colored layer or the like. Therefore, for example, as shown in FIG. 2A, the gas diffusion layer 5 may be formed on the entire surface of the base material 1. For example, as shown in FIGS. 2B and 2C, the gas diffusion layer 5 is patterned. It may be formed in a shape. Especially, it is preferable that the gas diffusion layer is formed in the whole surface of a base material at the point which can simplify a manufacturing process.

  The gas diffusion layer in the present invention is formed by a wet method in which the above-described materials are dispersed or dissolved in an appropriate solvent to prepare a gas diffusion layer forming coating solution, and this gas diffusion layer forming coating solution is applied. be able to.

  The viscosity of the gas diffusion layer forming coating solution used at this time is not particularly limited as long as it is a viscosity applicable to a wet method, but is usually about 5 cp to 100 cp.

  Further, as a method for applying the gas diffusion layer forming coating solution, a general wet method is used, for example, spin coating, die coating, slit coating, slot coating, bar coating, screen coating, bead coating, gravure coating, etc. The method is mentioned.

2. Gas barrier layer The gas barrier layer used in the present invention is formed between the colored layer and the gas diffusion layer. As the gas barrier layer used in the present invention, a transparent inorganic film is preferably used from the viewpoint of high gas barrier properties and production.

  The material used for the transparent inorganic film is not particularly limited as long as it can exhibit gas barrier properties. For example, oxides such as aluminum oxide, silicon oxide, and magnesium oxide; nitriding such as silicon nitride A nitride oxide such as silicon nitride oxide; Among these, silicon nitride oxide is preferable because pinholes and protrusions hardly occur and the gas barrier property is high.

  Further, the gas barrier layer may be a single layer or a multilayer. For example, when the gas barrier layer is a multilayer in which a plurality of silicon nitride oxide films are stacked, the gas barrier property can be further improved. Moreover, when a gas barrier layer is a multilayer, you may use a different material for each layer, respectively.

  The thickness of the gas barrier layer is not particularly limited, and differs depending on the base material to be used, the type of material used for the gas barrier layer, or whether the gas barrier layer is a single layer or a multilayer, and cannot be specified unconditionally. However, it is generally about 50 nm to 2 μm for the entire gas barrier layer. This is because if the thickness of the gas barrier layer is too thin, the gas barrier property may be insufficient, and if the thickness of the gas barrier layer is too thick, a phenomenon such as a crack due to the film stress of the thin film tends to occur.

  In the present invention, the gas barrier layer may be formed on at least the colored layer. This is because the gas barrier layer is provided to prevent the gas generated from the colored layer or the like from flowing out. Therefore, for example, as shown in FIGS. 2A and 2B, the gas barrier layer 4 may be formed on the entire surface of the base material 1. For example, as shown in FIG. It may be formed. At this time, when the gas barrier layer is formed in a pattern, the gas diffusion layer is usually formed in a pattern. Among the above, the gas barrier layer is preferably formed on the entire surface of the substrate in that the manufacturing process can be simplified.

  When the gas barrier layer is a transparent inorganic film, the method for forming the transparent inorganic film is not particularly limited as long as it is a film forming method that can be formed in a vacuum state. For example, sputtering, chemical vapor deposition ( CVD) method, ion plating method, vacuum deposition method such as electron beam (EB) deposition method and resistance heating method, laser ablation method and the like. Among these, considering the productivity of the color filter substrate for an organic EL element, the sputtering method, the ion plating method, and the CVD method are preferable, and the sputtering method is more preferable. This is because by using the sputtering method, a gas barrier layer having high productivity and excellent quality stability can be formed.

3. Colored layer The colored layer used in the present invention is usually one in which three colored patterns of a red colored pattern, a green colored pattern, and a blue colored pattern are regularly arranged. Each color coloring pattern of the colored layer may be provided for each opening when a light shielding portion is formed. For convenience, for example, a stripe is formed in the direction from the front side to the back side in FIG. It may be provided in a shape.

  Each color pattern of the colored layer contains a pigment or dye of each color and a binder resin.

  Examples of the pigment used in the red coloring pattern include perylene pigments, lake pigments, azo pigments, quinacridone pigments, anthraquinone pigments, anthracene pigments, and isoindoline pigments. These pigments may be used alone or in combination of two or more.

  Examples of pigments or dyes used in the green coloring pattern include phthalocyanine pigments such as halogen polysubstituted phthalocyanine pigments or halogen polysubstituted copper phthalocyanine pigments, triphenylmethane basic dyes, isoindoline pigments, and isoindolinone pigments. And pigments. These pigments or dyes may be used alone or in combination of two or more.

  Examples of the pigment used in the blue coloring pattern include copper phthalocyanine pigments, anthraquinone pigments, indanthrene pigments, indophenol pigments, cyanine pigments, dioxazine pigments and the like. These pigments may be used alone or in combination of two or more.

Moreover, transparent resin is used as binder resin used for each color coloring pattern.
When a printing method is used as a method for forming the colored layer, examples of the binder resin include polymethyl methacrylate resin, polyacrylate resin, polycarbonate resin, polyvinyl alcohol resin, polyvinyl pyrrolidone resin, hydroxyethyl cellulose resin, carboxymethyl cellulose resin, polychlorinated resin. Examples of the resin include vinyl resin, melamine resin, phenol resin, alkyd resin, epoxy resin, polyurethane resin, polyester resin, maleic acid resin, and polyamide resin.
In addition, when a photolithography method is used as a method for forming the colored layer, the binder resin is usually an ionizing radiation having a reactive vinyl group such as an acrylate, methacrylate, polyvinyl cinnamate, or cyclized rubber. A curable photosensitive resin is used, and it is particularly preferable to use an electron beam curable photosensitive resin or an ultraviolet curable photosensitive resin. When an ultraviolet curable photosensitive resin is used, a photopolymerization initiator is used alone or in combination with a binder resin. Further, when an ultraviolet curable photosensitive resin is used, a sensitizer, a coatability improver, a development improver, a crosslinking agent, a polymerization inhibitor, a plasticizer, a flame retardant, and the like may be used as necessary. .

  The pigment or dye content is preferably in the range of 5 to 50% by weight in each color coloring pattern. Further, the content of the binder resin is preferably in the range of 30 to 100 parts by weight with respect to 100 parts by weight of the pigment or dye.

  As a method for forming a colored layer, a pigment or dye is mixed, dispersed or solubilized in a binder resin to prepare a colored layer forming coating solution, and patterning is performed by a photolithography method using the colored layer forming coating solution. Or a method of patterning by a printing method using the colored layer forming coating solution.

  The thickness of the colored layer is about 1 μm to 3 μm.

4). Base material The base material used in the present invention is a support that supports a colored layer, a gas barrier layer, a gas diffusion layer, and the like, and is particularly limited as long as it has a function of protecting the colored layer and the like and is transparent. It is not a thing. Among them, a base material having a smooth surface is preferably used, and for example, a glass substrate or a plastic substrate is used. Specifically, a glass substrate containing alkali-free glass, soda lime glass, or the like, or a transparent plastic substrate such as polyimide or methacrylic acid resin can be used.

  Although it does not specifically limit as thickness of a base material, Usually, it is about 0.5 mm-1.5 mm.

  The base material may be further laminated with a hard coat layer for preventing scratches, an antistatic layer, an antifouling layer, an antireflection layer, an antiglare layer and the like on the observation side, if necessary. Or the function like a touch panel may be added to the said base material.

5. Flattening layer In the present invention, a flattening layer may be formed on the colored layer. At this time, in the case where a color conversion layer described later is provided, a planarization layer is formed on the color conversion layer. This flattening layer has a role of protecting the colored layer and the color conversion layer, and when the thickness of the colored layer and the color conversion layer is not constant, the surface of the layer is flattened to form a gas barrier layer. It is provided for the purpose of reducing the influence when forming the like. Further, when there is a level difference (surface irregularities) due to the configuration of the colored layer or the color conversion layer, the leveling layer eliminates the level difference and achieves leveling, and forms the organic EL layer when manufacturing the organic EL display device. It is a flattening action that prevents the occurrence of thickness unevenness during the process.

  As a material for forming the planarization layer used in the present invention, a transparent resin can be used. Specifically, a photocurable resin or a thermosetting resin having an acrylate-based or methacrylate-based reactive vinyl group can be used. In addition, as the transparent resin, polymethyl methacrylate, polyacrylate, polycarbonate, polyvinyl alcohol, polyvinyl pyrrolidone, hydroxyethyl cellulose, carboxymethyl cellulose, polyvinyl chloride resin, melamine resin, phenol resin, alkyd resin, epoxy resin, polyurethane resin, polyester resin A maleic acid resin, a polyamide resin, or the like can be used.

  As the method for forming the flattening layer, when the flattening layer forming coating liquid containing the transparent resin is a liquid, it is applied by spin coating, roll coating, cast coating, etc. In the case of a curable resin, there may be mentioned a method in which the resin is thermally cured as necessary after irradiation with ultraviolet rays, and in the case of a thermosetting resin, it can be directly heat cured after film formation. Moreover, when the transparent resin mentioned above is shape | molded in the film form, a planarization layer can be formed by sticking directly or via an adhesive.

  The thickness of such a planarization layer can be set to, for example, about 0.5 to 10 μm.

6). Light-shielding part In the present invention, a light-shielding part such as a black matrix may be formed between colored layers formed in a pattern on the substrate. The light shielding section is provided to partition the light emitting area for each pixel, prevent reflection of external light at the boundary between the light emitting areas, and increase the contrast of images and videos. Therefore, the light-shielding portion is not necessarily provided. However, in addition to improving the contrast, the light-shielding portion is formed when the colored layer, the color conversion layer, or the like is formed corresponding to the opening of the light-shielding portion. preferable. Further, when the organic EL display device is formed using the color filter substrate for the organic EL element of the present invention, the light shielding portion is formed because the light emitting layer and the like are formed corresponding to the opening of the light shielding portion. It is preferable.

  The light-shielding portion is usually formed of a black line, and is formed in a pattern shape having openings such as a matrix shape or a stripe shape. When an organic EL display device is formed using the color filter substrate for an organic EL element of the present invention, light emitted from the light emitting layer reaches the observation side via the opening of the light shielding portion.

  The light-shielding part used in the present invention may be insulating or non-insulating, but preferably has insulating properties. If the light-shielding part has an insulating property, even when the light-shielding part and the transparent electrode layer are in contact with each other when the organic EL element color filter substrate of the present invention is used to form an organic EL display device, the light-shielding part is shielded This is because it is possible to avoid electrical conduction between the portion and the transparent electrode layer.

  Examples of the material for forming the light-shielding portion having insulating properties include a resin composition containing a black colorant such as carbon black. Examples of the resin used in the resin composition include ionizing radiation curable resins having reactive vinyl groups such as acrylate-based, methacrylate-based, polyvinyl cinnamate, or cyclized rubber, particularly electron beam curable resins or An ultraviolet curable resin can be used. Also, for example, polymethyl methacrylate resin, polyacrylate resin, polycarbonate resin, polyvinyl alcohol resin, polyvinyl pyrrolidone resin, hydroxyethyl cellulose resin, carboxymethyl cellulose resin, polyvinyl chloride resin, melamine resin, phenol resin, alkyd resin, epoxy resin, polyurethane resin Examples thereof include a polyester resin, a maleic acid resin, and a polyamide resin.

Moreover, as a formation material of the light shielding part which does not have insulation, metals or metal oxides, such as chromium, are mentioned, for example. At this time, the light-shielding part having no insulating property may be a laminate of two layers of a CrO _x film (x is an arbitrary number) and a Cr film, and a CrO _x film with a further reduced reflectance. (X is an arbitrary number), a CrN _y film (y is an arbitrary number), and a three-layered Cr film may be laminated.

  As a method for forming a light-shielding portion having insulating properties, a method of applying the above resin composition on a substrate and patterning it by a photolithography method can be used. Also, a printing method or the like can be used.

  As a method for forming a light-shielding portion having no insulating property, a method of forming a thin film by a vapor deposition method, an ion plating method, a sputtering method, or the like, and patterning using a photolithography method can be used. Further, an electroless plating method or the like can also be used.

  The film thickness of the light-shielding portion is about 0.2 μm to 0.4 μm when formed by vapor deposition, ion plating, sputtering, or the like, and is about 0.2 μm when formed by coating or printing. It is about 5 μm to 2 μm.

7). Color Conversion Layer In the present invention, a color conversion layer may be formed between the colored layer and the gas barrier layer. At this time, for example, when the planarization layer 3 is provided as shown in FIG. 3, the color conversion layers 7 </ b> R, 7 </ b> G, and 7 </ b> B are formed between the colored layer 2 and the planarization layer 3.

  Similar to the colored layer, the color conversion layer may decompose the pigment contained in the color conversion layer to generate gas, which causes dark spots. In the present invention, since the gas diffusion layer is provided, the gas generated from the color conversion layer can be diffused, so that the generation of dark spots can be suppressed.

  The color conversion layer used in the present invention absorbs light emitted from the light-emitting layer of the organic EL element when the organic EL display device is formed using the color filter substrate for the organic EL element of the present invention, and is in a visible light region. It is a layer containing a fluorescent material that emits fluorescence, and is not particularly limited as long as the light from the light emitting layer can be blue, red, or green. The color conversion layer may be, for example, a layer that absorbs light from the light emitting layer and emits three colors of blue, red, and green fluorescence. When a blue light emitting layer is used, the color conversion layer is blue. It is also possible to be a layer that absorbs this light and emits red or green fluorescence. In the latter case, a transparent resin layer may be formed instead of the blue color conversion layer.

  As the color conversion layer, a layer in which a fluorescent dye that absorbs light from the light emitting layer and emits fluorescence is dispersed in a matrix resin is usually used.

  Examples of fluorescent dyes that absorb light in the blue to blue-green region emitted from the light emitting layer and emit fluorescence in the red region include rhodamine B, rhodamine 6G, rhodamine 3B, rhodamine 101, rhodamine 110, sulforhodamine, basic violet 11, Rhodamine dyes such as Basic Red 2, cyanine dyes such as 4-dicyanomethylene-2-methyl-6- (p-dimethylaminostillin) -4H-pyran, 1-ethyl-2- [4- (p- Examples thereof include pyridine dyes such as dimethylaminophenyl) -1,3-butadienyl] -pyridinium-perchlorate (pyridine 1), and oxazine dyes. Furthermore, various dyes (direct dyes, acid dyes, basic dyes, disperse dyes, etc.) can be used if they are fluorescent.

  Examples of fluorescent dyes that absorb blue to blue-green light emitted from the light emitting layer and emit green light include 3- (2′-benzothiazolyl) -7-diethylaminocoumarin (coumarin 6), 3- (2'-Benzimidazolyl) -7-N, N-diethylaminocoumarin (coumarin 7), 3- (2'-N-methylbenzimidazolyl) -7-N, N-diethylaminocoumarin (coumarin 30), 2, 3, 5 , 6-1H, 4H-tetrahydro-8-trifluoromethylquinolidine (9,9a, 1-gh) coumarin (coumarin 153) or the like, or coumarin dye-based basic yellow 51, and solvent Examples thereof include naphthalimide dyes such as yellow 11 and solvent yellow 116. Furthermore, various dyes (direct dyes, acid dyes, basic dyes, disperse dyes, etc.) can be used if they are fluorescent.

  Fluorescent dyes are pre-kneaded in polymethacrylic acid ester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer resin, alkyd resin, aromatic sulfonamide resin, urea resin, melamine resin, benzoguanamine resin, and a mixture of these resins. The pigment may be made into a fluorescent pigment. In addition, these fluorescent dyes and fluorescent pigments (hereinafter collectively referred to as fluorescent dyes together) may be used singly or in combination of two or more in order to adjust the hue of fluorescence. Good. In particular, since the conversion efficiency from blue to red is low, it is possible to increase the conversion efficiency by mixing the fluorescent dyes.

Examples of the matrix resin for dispersing the fluorescent dye include resins such as polymethyl methacrylate, polyacrylate, polycarbonate, polyvinyl alcohol, polyvinyl pyrrolidone, hydroxyethyl cellulose, and carboxymethyl cellulose.
In the case where the color conversion layer is patterned by photolithography, a photosensitive resin can be used as the matrix resin. Examples of the photosensitive resin include photocurable photosensitive resins having reactive vinyl groups such as acrylic acid, methacrylic acid, polyvinyl cinnamate, and cyclized rubber.
Furthermore, when a printing method is used as a method for forming the color conversion layer, an ink containing a matrix resin is used. Examples of the matrix resin used in this case include melamine resin, phenol resin, alkyd resin, epoxy resin, polyurethane resin, polyester resin, maleic acid resin, polyamide resin monomer, oligomer or polymer, or polymethyl methacrylate, polyacrylate And resins such as polycarbonate, polyvinyl alcohol, polyvinyl pyrrolidone, hydroxyethyl cellulose, and carboxymethyl cellulose.

  As a method for forming the color conversion layer, when the color conversion layer mainly contains a fluorescent dye, a method of forming a film by a vacuum deposition method or a sputtering method through a desired pattern mask is used. On the other hand, when the color conversion layer contains a fluorescent dye and a matrix resin, the fluorescent dye and the matrix resin are mixed, dispersed, or solubilized to prepare a color conversion layer forming coating solution. A method of applying a coating solution by a general coating method such as spin coating or roll coating, and patterning by a photolithography method, or a method of patterning by screen printing or the like using the coating solution for forming a color conversion layer. Used.

  The thickness of the color conversion layer is not particularly limited as long as the red conversion layer and the green conversion layer can sufficiently absorb the blue light emitted from the blue light emitting layer and emit fluorescence. . Specifically, it can be appropriately set in consideration of the fluorescent dye to be used, the concentration of the fluorescent dye, and the like, and can be about 5 to 15 μm, for example. Moreover, the thickness of each color conversion layer may differ.

8). Others As another aspect of the present invention, a colored layer or a colored layer and a color conversion layer are not formed, but only a color conversion layer may be formed. That is, the present invention includes a base material, a color conversion layer formed in a pattern on the base material, a gas barrier layer formed on the color conversion layer, and a coating film formed on the gas barrier layer. The present invention can also be applied to a color conversion substrate for organic EL elements characterized by having a certain gas diffusion layer.

B. Organic EL Display Device Next, the organic EL display device of the present invention will be described. The organic EL display device of the present invention is formed on the above-described color filter substrate for organic EL elements, the transparent electrode layer formed on the gas diffusion layer of the color filter substrate for organic EL elements, and the transparent electrode layer. And an organic EL layer including at least a light-emitting layer, and a counter electrode layer formed on the organic EL layer.

  FIG. 4 shows a schematic cross-sectional view of the organic EL display device of the present invention. As shown in FIG. 4, the organic EL display device 20 of the present invention includes a transparent electrode layer 11, an organic EL layer 12 including a light emitting layer, and a counter electrode layer on the gas diffusion layer 5 of the color filter substrate 10 for organic EL elements. 13 are sequentially formed. An insulating layer 14 is formed between the transparent electrode layers 11 formed in a pattern. In such an organic EL display device 20, when voltage is applied to the organic EL layer 12 including the light emitting layer sandwiched between the transparent electrode layer 11 and the counter electrode layer 13, light emission occurs at a predetermined position.

  According to the present invention, since the gas diffusion layer is formed on the gas barrier layer, the gas generated from the colored layer or the like diffuses when passing through the gas diffusion layer, so that the gas is locally released. Therefore, local deterioration of the organic EL layer can be prevented, and defects such as dark spots and dark areas can be suppressed. Moreover, since the gas diffusion layer is a coating film, pinholes and projections on the surface of the gas barrier layer can be filled, and it can be expected to improve the gas barrier property. Therefore, by using the above-described color filter substrate for an organic EL element, an organic EL display device capable of good image display can be obtained.

  Although not shown, the organic EL display device of the present invention may be sealed by laminating a sealing material on the counter electrode layer as necessary.

  The driving method of the organic EL display device of the present invention may be either a passive matrix method or an active matrix method.

  Hereinafter, each configuration of the organic EL display device of the present invention will be described. Since the color filter substrate for organic EL elements is the same as that described in the column “A. Color filter substrate for organic EL elements”, description thereof is omitted here.

1. Organic EL Layer The organic EL layer used in the present invention is composed of one or more organic layers including at least a light emitting layer. That is, the organic EL layer is a layer including at least a light emitting layer, and the layer configuration is a layer having one or more organic layers. Usually, when an organic EL layer is formed by a wet method by coating, it is often difficult to stack a large number of layers in relation to a solvent, so that it is often formed of one or two organic layers. However, it is possible to further increase the number of layers by devising an organic material so that the solubility in a solvent is different or by combining a vacuum deposition method.

Examples of the organic layer formed in the organic EL layer other than the light emitting layer include charge injection layers such as a hole injection layer and an electron injection layer. Furthermore, examples of the other organic layers include a charge transport layer such as a hole transport layer that transports holes to the light-emitting layer and an electron transport layer that transports electrons to the light-emitting layer. In many cases, it is formed integrally with the charge injection layer by imparting a charge transporting function. In addition, as an organic layer formed in the organic EL layer, it prevents holes or electrons from penetrating like a carrier block layer and further prevents diffusion of excitons and confines excitons in the light emitting layer. And a layer for increasing the recombination efficiency.
Hereinafter, each structure of such an organic EL layer will be described.

(1) Light emitting layer The light emitting layer used in the present invention may be composed of each color light emitting layer of a red light emitting layer, a green light emitting layer and a blue light emitting layer, or may be a white light emitting layer, It may be a blue light emitting layer. However, when a blue light emitting layer is used, a color conversion layer needs to be formed.

  The light emitting layer in the present invention has a function of emitting light by providing a recombination field between electrons and holes. Examples of the material for forming the light emitting layer generally include a dye-based light-emitting material, a metal complex-based light-emitting material, and a polymer-based light-emitting material.

  Examples of dye-based luminescent materials include cyclopentamine derivatives, tetraphenylbutadiene derivatives, triphenylamine derivatives, oxadiazole derivatives, pyrazoloquinoline derivatives, distyrylbenzene derivatives, distyrylarylene derivatives, silole derivatives, thiophene ring compounds, A pyridine ring compound, a perinone derivative, a perylene derivative, an oligothiophene derivative, an oxadiazole dimer, a pyrazoline dimer, and the like can be given.

  Examples of metal complex light emitting materials include aluminum quinolinol complex, benzoquinolinol beryllium complex, benzoxazole zinc complex, benzothiazole zinc complex, azomethylzinc complex, porphyrin zinc complex, europium complex, etc. Examples thereof include a metal complex having a rare earth metal such as Tb, Eu, or Dy, and having a oxadiazole, thiadiazole, phenylpyridine, phenylbenzimidazole, or quinoline structure as a ligand.

  Examples of the polymer light emitting material include polyparaphenylene vinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, polyacetylene derivatives, polyfluorene derivatives, or polyvinylcarbazole derivatives, or the above-described dye-based light emitting materials or metal complex systems. Examples thereof include those obtained by polymerizing a luminescent material.

  The above-described light emitting material can be doped for the purpose of improving the light emission efficiency or changing the light emission wavelength. Examples of the doping material include perylene derivatives, coumarin derivatives, rubrene derivatives, quinacridone derivatives, squalium derivatives, porphyrene derivatives, styryl dyes, tetracene derivatives, pyrazoline derivatives, decacyclene, phenoxazone, and the like.

  Although it does not specifically limit as thickness of a light emitting layer, For example, it can be set as about 5 nm-5 micrometers.

  The method for forming the light emitting layer is not particularly limited as long as it is a method capable of high-definition patterning. For example, vapor deposition method, printing method, inkjet method, spin coating method, casting method, dipping method, bar coating method, blade coating method, roll coating method, gravure coating method, flexographic printing method, spray coating method, and self-assembly method (Alternate adsorption method, self-assembled monolayer method) and the like. Among these, it is preferable to use a vapor deposition method, a spin coating method, and an ink jet method. Further, when the light emitting layer is patterned, it may be applied separately by a masking method for pixels having different light emission colors, or a partition may be formed between the light emitting layers. As a material for forming such a partition, a photocurable resin such as a photosensitive polyimide resin or an acrylic resin, a thermosetting resin, an inorganic material, or the like can be used. Furthermore, you may perform the process which changes the surface energy (wetting property) of the material which forms these partition walls.

(2) Hole injection layer In the present invention, a hole injection layer may be formed between the light emitting layer and the anode (transparent electrode layer or counter electrode layer). This is because by providing the hole injection layer, the injection of holes into the light emitting layer is stabilized and the light emission efficiency can be increased.

  As a constituent material of the hole injection layer used in the present invention, a material generally used for a hole injection layer of an organic EL element can be used. The constituent material of the hole injection layer may be any material that has either a hole injection property or an electron barrier property, and may be an organic material or an inorganic material.

  Specifically, the constituent material of the hole injection layer includes triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives. And styryl anthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, polysilane-based, aniline-based copolymers, or conductive polymer oligomers such as thiophene oligomers. Furthermore, examples of the constituent material of the hole injection layer include porphyrin compounds, aromatic tertiary amine compounds, and styrylamine compounds.

  Examples of the porphyrin compound include porphine, 1,10,15,20-tetraphenyl-21H, 23H-porphine copper (II), aluminum phthalocyanine chloride, copper octamethylphthalocyanine, and the like.

  Examples of the aromatic tertiary amine compound include N, N, N ′, N′-tetraphenyl-4,4′-diaminophenyl, N, N′-diphenyl-N, N′-bis- ( 3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine, 4- (di-p-tolylamino) -4 ′-[4 (di-p-tolylamino) styryl] stilbene, 3- Methoxy-4'-N, N-diphenylaminostilbenzene, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl, or 4,4 ', 4 "-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine and the like.

  The thickness of such a hole injection layer is not particularly limited, but can be, for example, about 5 nm to 5 μm.

(3) Electron Injection Layer In the present invention, an electron injection layer may be formed between the light emitting layer and the cathode (transparent electrode layer or counter electrode layer). This is because by providing the electron injection layer, the injection of electrons into the light emitting layer is stabilized and the light emission efficiency can be increased.

  As the constituent material of the electron injection layer used in the present invention, for example, nitro-substituted fluorene derivatives, anthraquinodimethane derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, heterocyclic tetracarboxylic anhydrides such as naphthaleneperylene, carbodiimide, Fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, or thiazole derivatives in which the oxygen atom of the oxadiazole ring of the oxadiazole derivative is substituted with a sulfur atom, quinoxaline known as an electron withdrawing group Examples thereof include quinoxaline derivatives having a ring, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum, phthalocyanine, metal phthalocyanine, or distyrylpyrazine derivatives.

  Although it does not specifically limit as thickness of the said electron injection layer, For example, it can be set as about 5 nm-5 micrometers.

2. Transparent electrode layer The transparent electrode layer used for this invention is formed on the gas diffusion layer of the color filter substrate for organic EL elements mentioned above. For example, as shown in FIG. 4, the transparent electrode layer 11 is formed in a stripe shape having a width corresponding to the width of the opening of the light shielding portion 6. In this case, the pitch of the striped transparent electrode layers 11 is the same as the pitch of the openings of the light shielding portion 6.

  The transparent electrode layer in the present invention is usually composed of a metal oxide thin film having transparency and conductivity. Examples of such a metal oxide include indium tin oxide (ITO), indium oxide, zinc oxide, and stannic oxide.

  As a method for forming such a transparent electrode layer, for example, a method of forming a thin film of metal oxide by vapor deposition or sputtering, and then patterning by photolithography is preferably used.

3. Counter Electrode Layer The counter electrode layer used in the present invention is an electrode facing the transparent electrode layer, and is formed on the organic EL layer including the light emitting layer.

The counter electrode layer in the present invention is usually composed of a metal, an alloy, or a mixture thereof having a work function as small as about 4 eV or less. Specifically, sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) mixture, indium, Or a lithium / aluminum mixture, a rare earth metal, etc. can be illustrated. More preferable examples include a magnesium / silver mixture, a magnesium / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al ₂ O ₃ ) mixture, or a lithium / aluminum mixture.

  As a method for forming such a counter electrode layer, a method of forming a thin film by an evaporation method or a sputtering method and then patterning by a photolithography method is preferably used.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

Hereinafter, the present invention will be specifically described using examples and comparative examples.
[Example 1]
(Formation of black matrix)
As a transparent substrate, soda glass (manufactured by Central Glass Co., Ltd.) having a thickness of 370 mm × 470 mm and a thickness of 0.7 mm was prepared. A thin film (thickness 0.2 μm) of oxynitride composite chromium was formed on this transparent substrate by sputtering. A photosensitive resist is applied on the oxynitride composite chrome thin film, mask exposure, development, and etching of the oxynitride composite chrome thin film are sequentially performed, and an 80 μm × 280 μm rectangular opening has a length of 100 μm in the short side direction. A black matrix arranged in a matrix at a pitch of 300 μm in the long side direction was formed.

(Formation of colored layer)
A photosensitive coating composition for forming colored patterns of each color of red, green, and blue was prepared. Condensed azo pigments (manufactured by Ciba Specialty Chemicals, Chromophthalred BRN) as red colorants, phthalocyanine green pigments (Lionol Green 2Y-301, manufactured by Toyo Ink Co., Ltd.), and blue as green colorants As the colorant, anthraquinone pigment (Ciba Specialty Chemicals, Chromophthal Blue A3R) was used. As the binder resin, an acrylic UV curable resin composition (acrylic UV curable resin 20%, acrylic UV curable resin monomer 20%, additive 5%, propylene glycol monomethyl ether acetate (PGMEA) 55%) Was used. A photosensitive paint for forming each color coloring pattern by blending 1 part of each colorant in a proportion of 10 parts of the acrylic UV curable resin composition (all parts are based on mass), thoroughly mixing and dispersing. A composition was obtained.

Each color coloring pattern was formed using the above-mentioned photosensitive coating composition for forming each color coloring pattern. That is, a photosensitive coating composition for forming a red coloring pattern was applied to the transparent base material on which the black matrix was formed by spin coating, and prebaked at 120 ° C. for 2 minutes. Then, it exposed using the photomask (integrated exposure amount 300mJ / cm < ² >), and developed with the developing solution (0.05% KOH aqueous solution). Next, post-baking is performed at 230 ° C. for 60 minutes to synchronize with the black matrix pattern, and a stripe-shaped red colored pattern having a width of 85 μm and a thickness of 1.5 μm is formed so that the width direction is in the short side direction of the opening of the black matrix. Was formed. Thereafter, the photosensitive coating composition for forming the green coloring pattern and the photosensitive coating composition for forming the blue coloring pattern are sequentially used to form the green coloring pattern and the blue coloring pattern. A colored layer arranged repeatedly in the direction was formed.

(Formation of color conversion layer)
Spin coating of blue conversion dummy layer forming coating liquid (manufactured by Fuji Hunt Electronics Technology Co., Ltd., transparent photosensitive resin composition, trade name: “Color Mosaic CB-701”) on which the black matrix and the colored layer are formed. This was applied by the method and prebaked at 100 ° C. for 5 minutes. Next, after patterning by photolithography, post baking was performed at 200 ° C. for 60 minutes. Thus, a striped blue conversion dummy layer having a width of 85 μm and a thickness of 10 μm was formed on the blue coloring pattern.

Next, an alkali-soluble negative photosensitive resist in which a green conversion phosphor (manufactured by Aldrich, Coumarin 6) is dispersed is used as a green conversion layer-forming coating solution. A stripe-shaped green conversion layer having a thickness of 85 μm and a thickness of 10 μm was formed.
Further, an alkali-soluble negative photosensitive resist in which a red-converting phosphor (Aldrich, Rhodamine 6G) is dispersed is used as a red-converting layer-forming coating solution. A striped red conversion layer having a thickness of 85 μm and a thickness of 10 μm was formed.

(Formation of planarization layer)
Next, a flattened layer formed by diluting an acrylate-based photocurable resin (manufactured by Nippon Steel Chemical Co., Ltd., trade name: “V-259PA / PH5”) with propylene glycol monomethyl ether acetate on the color conversion layer formed A coating solution was prepared, applied by spin coating, and prebaked at 120 ° C. for 5 minutes. Next, after patterning by photolithography, post baking was performed at 200 ° C. for 60 minutes to form a transparent flattening layer covering the entire color conversion layer with a thickness of 5 μm on the color conversion layer.

(Formation of gas barrier layer)
Next, a Si ₃ N ₄ target (3N) is used on the above planarized layer by sputtering to form an argon gas introduced amount: 40 sccm, RF power: 430 kW, substrate temperature: 100 ° C., and a thickness of 150 nm. A silicon oxynitride film was laminated to form a transparent gas barrier layer.

(Formation of gas diffusion layer)
Next, an epoxy thermosetting resin (manufactured by Nippon Steel Chemical Co., Ltd., trade name: “V-259EH / 210X6”) diluted with propylene glycol monomethyl ether acetate on the gas barrier layer is coated with a gas diffusion layer. A liquid was prepared, applied by spin coating, pre-baked at a temperature of 120 ° C. for 5 minutes, and then post-baked at 200 ° C. for 60 minutes to form a gas diffusion layer covering the entire transparent substrate. .

  As a result, a color filter substrate for an organic EL element was obtained.

(Formation of transparent electrode layer)
Next, an indium tin oxide (ITO) electrode film having a thickness of 150 nm is formed by ion plating on the gas diffusion layer of the color filter substrate for the organic EL element, and a photosensitive resist is applied on the ITO electrode film. Then, mask exposure, development, and etching of the ITO electrode film were performed to form a transparent electrode layer.

(Formation of auxiliary electrode)
Next, a chromium thin film (thickness 0.2 μm) is formed by sputtering on the entire surface of the gas diffusion layer so as to cover the transparent electrode layer, a photosensitive resist is applied on the chromium thin film, mask exposure, development Then, the chromium thin film was etched to form an auxiliary electrode. This auxiliary electrode was a striped pattern formed on the transparent electrode layer so as to run on the color conversion layer from the transparent substrate.

(Formation of insulating layer and partition wall)
Using a coating solution for forming an insulating layer obtained by diluting norbornene-based resin (ARTON, manufactured by JSR, Inc.) having an average molecular weight of about 100,000 with toluene, it is applied on the gas diffusion layer so as to cover the transparent electrode layer by spin coating. Then, baking (100 ° C., 30 minutes) was performed to form an insulating film (thickness 1 μm). Next, a photosensitive resist was applied on the insulating film, mask exposure, development, and etching of the insulating film were performed to form an insulating layer. This insulating layer was a stripe-like pattern (width 20 μm) intersecting the transparent electrode layer at a right angle, and was located on the black matrix.
Next, a partition wall coating (manufactured by Nippon Zeon Co., Ltd., photoresist, ZPN1100) was applied over the entire surface by spin coating so as to cover the insulating layer, and prebaked (70 ° C., 30 minutes). Then, it exposed using the predetermined | prescribed photomask, developed with the developing solution (Nippon-Zeon company make, ZTMA-100), and then post-baked (100 degreeC, 30 minutes). Thereby, the partition part was formed on the insulating layer. The partition wall had a shape with a height of 10 μm, a lower portion (insulating layer side) width of 15 μm, and an upper portion width of 26 μm.

(Formation of organic EL layer)
Next, an organic EL layer composed of a hole injection layer, a blue light emitting layer, and an electron injection layer was formed by vacuum deposition using the partition wall as a mask.
That is, first, 4,4 ′, 4 ″ -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine is 200 nm through a photomask having an opening corresponding to the image display region. By depositing 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl to a thickness of 20 nm to form a film, the partition wall becomes a mask pattern. The material for forming the hole injection layer passed only between the partition walls, and the hole injection layer was formed on the transparent electrode layer. Similarly, 4,4′-bis (2,2-diphenylvinyl) biphenyl was evaporated to 50 nm to form a blue light emitting layer. Thereafter, tris (8-quinolinol) aluminum was deposited to a thickness of 20 nm to form an electron injection layer. The organic EL layer thus formed exists between the partition walls as a stripe pattern having a width of 280 μm, and a dummy organic EL layer is formed on the upper surface of the partition wall with the same layer structure. It was done.

(Formation of counter electrode layer)
Next, magnesium and silver are simultaneously deposited by vacuum deposition (magnesium deposition rate) on the region where the partition wall is formed through a photomask having a predetermined opening wider than the image display region. = 1.3 to 1.4 nm / second, silver deposition rate = 0.1 nm / second). Thereby, the partition electrode portion was used as a mask to form a 200 nm-thick counter electrode layer made of a magnesium / silver compound on the organic EL layer. This counter electrode layer exists on the organic EL layer as a stripe pattern having a width of 280 μm, and a dummy counter electrode layer was also formed on the upper surface of the partition wall.

  The organic EL element was obtained by the above method.

(Organic EL display device)
The organic EL element was sealed to obtain an organic EL display device. By applying a voltage of DC 8.5V to the transparent electrode layer and the counter electrode layer of this organic EL display device at a constant current density of 10 mA / cm ² and driving them continuously, the transparent electrode layer and the counter electrode layer cross each other. The blue light emitting layer of the desired part to be made to emit light.
When an arbitrary 5 mm × 5 mm region of the light emitting part is observed with an optical microscope, a non-light emitting part of 10 μm or more is not observed, and there is no defect due to a dark area, and an organic EL display device capable of displaying a high-quality three primary color image was gotten.

[Example 2]
In Example 1, a color filter substrate for an organic EL device was produced in the same manner as in Example 1 except that the gas diffusion layer was formed as follows.

(Formation of gas diffusion layer)
A coating solution for forming a gas diffusion layer is prepared by diluting a norbornene-based resin having an average molecular weight of approximately 100,000 (manufactured by JSR, ARTON) with toluene, applied by spin coating, and prebaked at 80 ° C. for 5 minutes. After that, post baking was performed at 100 ° C. for 60 minutes to form a gas diffusion layer covering the entire transparent substrate.

  Using the color filter substrate for the organic EL element obtained in this manner, an organic EL display device was produced and made to emit light in the same manner as in Example 1. As a result, a high-quality image display that does not cause defects due to dark areas was obtained. Obtained.

[Comparative example]
An organic EL display device was produced in the same manner as in Example 1 except that the gas diffusion layer was not formed. By applying a direct current voltage of 8.5 V to the transparent electrode layer and the counter electrode layer of this organic EL display device at a constant current density of 10 mA / cm ² as in Example 1, the transparent electrode layer is continuously driven. The blue light emitting layer at a desired position where the counter electrode layer and the counter electrode layer intersect was caused to emit light.
In this organic EL display device, an arbitrary 5 mm × 5 mm region of the light emitting part was observed with an optical microscope, and when 10 μm or more non-light emitting parts were counted, an average of 15 to 30 non-light emitting parts were observed.

It is a schematic sectional drawing which shows an example of the color filter substrate for organic EL elements of this invention. It is a schematic sectional drawing which shows the other example of the color filter substrate for organic EL elements of this invention. It is a schematic sectional drawing which shows the other example of the color filter substrate for organic EL elements of this invention. It is a schematic sectional drawing which shows an example of the organic electroluminescent display apparatus of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Base material 2, 2R, 2G, 2B ... Colored layer 3 ... Planarization layer 4 ... Gas barrier layer 5 ... Gas diffusion layer 6 ... Light-shielding part 7R, 7B, 7G ... Color conversion layer 10 ... Color filter substrate for organic EL elements DESCRIPTION OF SYMBOLS 11 ... Transparent electrode layer 12 ... Organic EL layer 13 ... Counter electrode layer 20 ... Organic EL display apparatus

Claims (11)

  A substrate, a colored layer formed in a pattern on the substrate, a gas barrier layer formed on the colored layer, and a gas diffusion layer formed on the gas barrier layer and being a coating film A color filter substrate for an organic electroluminescent device characterized by the above.   The color filter substrate for an organic electroluminescent element according to claim 1, wherein the gas diffusion layer has low degassing properties, heat resistance, and insulating properties.   The color filter substrate for an organic electroluminescent element according to claim 1 or 2, wherein the gas diffusion layer contains an acrylic resin, an epoxy resin, or a polyimide resin.   4. The color filter substrate for an organic electroluminescent element according to claim 1, wherein a saturated water absorption rate of the gas diffusion layer is 1.0% or less. 5.   5. The color filter substrate for an organic electroluminescent element according to claim 1, wherein the thickness of the gas diffusion layer is in a range of 0.2 μm to 5 μm. .   6. The organic electro according to claim 1, wherein an average surface roughness (Ra) of the gas diffusion layer is in a range of 0.1 nm to 10.0 nm. Color filter substrate for luminescent element.   The color filter substrate for an organic electroluminescent element according to any one of claims 1 to 6, wherein the gas barrier layer is a single-layer or multilayer silicon nitride oxide film.   The color for organic electroluminescent elements according to any one of claims 1 to 7, wherein a planarizing layer is formed between the colored layer and the gas barrier layer. Filter substrate.   The color filter substrate for an organic electroluminescent element according to any one of claims 1 to 8, wherein a light shielding portion is formed between the colored layers on the base material.   The color filter substrate for organic electroluminescent elements according to any one of claims 1 to 9, wherein a color conversion layer is formed between the colored layer and the gas barrier layer.   The color filter substrate for organic electroluminescent elements according to any one of claims 1 to 10 and a transparent layer formed on a gas diffusion layer of the color filter substrate for organic electroluminescent elements. An organic layer comprising: an electrode layer; an organic electroluminescent layer formed on the transparent electrode layer and including at least a light emitting layer; and a counter electrode layer formed on the organic electroluminescent layer. Electroluminescent display device.

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