JP2006066285A - Color filter substrate for organic electroluminescent element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inexpensive color filter substrate for organic EL element which enables a good image display without defects such as dark spot etc. and also to provide an organic EL display device. <P>SOLUTION: The color filter for an organic EL element comprises a substrate, a colored layer patterned on the substrate, a first transparent electrode layer formed on the colored layer, and a second transparent electrode layer which is formed on the first transparent electrode layer and has barrier properties. The second transparent electrode is characterized in that it is a coated film. <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 display device capable of color display.

  Organic electroluminescent (hereinafter abbreviated as “organic EL”) elements have high luminous efficiency such as high luminance emission even when the applied voltage is less than 10 V, and can emit light with a simple element structure. Therefore, application to an image display device is expected, and research is actively conducted. In particular, the organic EL element has high visibility due to self-coloring, is different from a liquid crystal display in that it is an all-solid-state display, has excellent impact resistance, is less affected by temperature changes, and has a large viewing angle. In recent years, it has been put to practical use as a light emitting element in an image display device.

  What is important in putting an organic EL element into practical use as a light-emitting element in an image display device is that the organic EL element has a fine display function and long-term stability. However, some organic EL elements have a drawback that when they are driven for a certain period, the light emission characteristics such as current-luminance characteristics are remarkably deteriorated.

  A typical cause of the deterioration of the light emission characteristics is the growth of light emission defect points called dark spots. This dark spot is considered to be caused by oxidation or aggregation of constituent materials of each layer constituting the organic EL element due to oxygen or moisture in the organic EL element. The growth of the dark spot proceeds not only during energization (during driving) but also during storage, and in an extreme case spreads over the entire light emitting surface. The growth is particularly accelerated by (1) oxygen or moisture present around the organic EL element, (2) affected by oxygen or moisture present as an adsorbate in each layer, and (3) the organic EL element. It is considered that it is also affected by moisture adsorbed on the parts used at the time of production or moisture permeation at the time of production.

  In addition, a gas generated by decomposition of a pigment contained in a colored layer, a color conversion layer, or the like that constitutes the organic EL element at the time of heating during the production of the organic EL element also causes a dark spot.

  As a technique for preventing the moisture, oxygen and gas from entering the organic EL layer, a method of providing a transparent barrier layer such as a transparent inorganic film or a resin film has been proposed (see, for example, Patent Documents 1 to 5).

  However, the transparent inorganic film is generally formed by a sputtering method, a CVD method, or the like, and it is technically difficult to obtain a transparent inorganic film free from foreign matters such as particles and pinholes by such a method. For this reason, the transparent inorganic film has insufficient moisture resistance and gas barrier properties for preventing deterioration of the organic EL element. Therefore, a method of increasing the gas barrier property by increasing the film thickness of the transparent inorganic film is employed, but there is a problem that the cost becomes very high.

  In addition, when a resin film is used as the transparent barrier layer, dark spots due to pinholes can be prevented, but the resin film expands and contracts due to thermal expansion, etc., so when forming a transparent electrode layer or a colored layer There is a problem that displacement occurs and pixel reduction occurs from the end of the transparent electrode layer.

  Further, if there are irregularities due to the patterned colored layer, it becomes difficult to maintain the barrier property of the transparent barrier layer. Therefore, when providing a transparent barrier layer, the colored layer is usually between the colored layer and the transparent barrier layer. A resin protective layer is provided for flattening the unevenness caused by. However, this resin protective layer is made of a resin, and there is a problem that pixel shrinkage due to thermal expansion occurs as in the case of the resin film.

JP 2002-1000046 A JP 2002-117976 A JP 2002-134268 A JP 2002-175880 A JP 2002-184578 A

  The present invention has been made in view of the above problems, and provides an inexpensive color filter substrate for an organic EL element and an organic EL display device which can display a good image without defects such as dark spots. The main purpose.

  In order to achieve the above object, the present invention provides a substrate, a colored layer formed in a pattern on the substrate, a first transparent electrode layer formed on the colored layer, and the first transparent electrode layer. A color filter substrate for an organic electroluminescent element having a second transparent electrode layer formed thereon and having a barrier property, wherein the second transparent electrode layer is a coating film A color filter substrate is provided.

  According to the present invention, since the second transparent electrode layer is a coating film, even when there are defects such as pinholes in the first transparent electrode layer, the second transparent electrode layer is formed on the first transparent electrode layer at the time of formation. By applying the second transparent electrode layer forming coating solution, defects such as pinholes can be blocked. For this reason, it can prevent that the gas generated from the colored layer etc. flows out from defects, such as a pinhole of the 1st transparent electrode layer, and used the color filter substrate for organic EL elements of the present invention for the organic EL display device. In this case, it is possible to suppress the occurrence of dark spots. Further, by providing the second transparent electrode layer on the first transparent electrode layer, the outflow of gas from the colored layer or the like can be prevented as described above. Therefore, in order to obtain gas barrier properties, the thickness is increased by sputtering or CVD. It is not necessary to provide a transparent barrier layer made of an insulating inorganic material for the film, and the manufacturing cost can be reduced. Furthermore, even if irregularities exist due to the patterned colored layer, the barrier properties of the first transparent electrode layer and the second transparent electrode layer are not greatly affected. Therefore, there is no need to provide a resin protective layer, and pixel reduction or the like does not occur due to the expansion and contraction of the resin due to thermal expansion.

  The present invention also provides a substrate, a colored layer formed in a pattern on the substrate, a first transparent electrode layer formed on the colored layer, and a first layer formed on the first transparent electrode layer. An organic electroluminescent element color filter substrate having two transparent electrode layers, wherein the second transparent electrode layer closes a pinhole existing in the first transparent electrode layer. A color filter substrate for an electroluminescent device is provided.

  According to the present invention, since the second transparent electrode layer closes the pinhole existing in the first transparent electrode layer, the gas generated from the colored layer or the like is prevented from flowing out from the pinhole of the first transparent electrode layer. Can be prevented. For this reason, when the color filter substrate for organic EL elements of the present invention is used in an organic EL display device, it is possible to suppress the occurrence of dark spots. Further, as described above, there is an advantage that it is not necessary to provide a conventional transparent barrier layer or resin protective layer.

  In the said invention, it is preferable that at least any one of the said 1st transparent electrode layer and the said 2nd transparent electrode layer is formed so that the said colored layer whole surface formed in pattern shape may be covered. If the entire surface of the colored layer is covered with at least one of the first transparent electrode layer and the second transparent electrode layer, that is, if the colored layer is not exposed, the outflow of gas generated from the colored layer is more effective. This is because it can be prevented.

  In the present invention, an inorganic layer having a barrier property may be formed between the colored layer and the first transparent electrode layer. According to the present invention, since the colored layer surface can be flattened by providing the inorganic layer, the occurrence of dark areas can be suppressed. Moreover, it is because the adhesive force of a 1st transparent electrode layer and a colored layer can be improved by providing an inorganic layer. Furthermore, since the inorganic layer having the barrier property, the first transparent electrode layer, and the second transparent electrode layer having the barrier property are sequentially laminated on the colored layer, the outflow of gas generated from the colored layer or the like This is because the entry of oxygen, water vapor, etc. can be further prevented.

  In the said invention, it is preferable that at least any one of the said 1st transparent electrode layer, the said 2nd transparent electrode layer, and the said inorganic layer is formed so that the said colored layer whole surface formed in pattern shape may be covered. . If the entire surface of the colored layer is covered with at least one of the first transparent electrode layer, the second transparent electrode layer, and the inorganic layer, that is, if the colored layer is not exposed, the outflow of gas generated from the colored layer It is because it can prevent more effectively.

  Moreover, in said case, it is preferable that the average surface roughness (Ra) of the said 2nd transparent electrode layer exists in the range of 10 to 100cm. When the average surface roughness (Ra) of the second transparent electrode 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, generation of dark areas is suppressed. Because you can.

  Furthermore, in the above case, the inorganic layer is preferably conductive. This is because, if the inorganic layer has conductivity, the inorganic layer can be integrated with the first transparent electrode layer and the second transparent electrode layer and function as an electrode, so that the electrical resistance can be reduced. .

  Furthermore, in the above case, the inorganic layer preferably contains fine particles having an average particle diameter in the range of 1 nm to 10 nm. Due to the size effect peculiar to the fine particles, the firing temperature of the coating liquid for forming the inorganic layer containing the fine particles can be lowered compared to the normal firing temperature at the time of forming the inorganic layer. This is because firing is possible.

  In the present invention, the second transparent electrode layer preferably contains fine particles having an average particle diameter in the range of 1 nm to 10 nm. Fine particles having an average particle size that is too small are difficult to produce. On the other hand, if the average particle size of the particles is too large, it may be difficult to close defects such as pinholes in the first transparent electrode layer. This is because a decrease in firing temperature due to the effect cannot be expected.

  In the above invention, the fine particles are preferably fine particles of indium tin oxide (ITO). This is because ITO is preferably used as the second transparent electrode layer.

  The fine particles may be at least one fine particle selected from the group consisting of Au, Ag, Cu, Pt, Sn, Zn, In, Pb, Al, and oxides thereof.

  In the present invention, a light shielding portion may be formed on the substrate and between the colored layers. This is because providing a light-shielding portion such as a black matrix can improve contrast when an organic EL display device is formed using the color filter substrate for organic EL elements of the present invention.

  At this time, it is preferable that the light shielding portion has an insulating property. This is because, since the light shielding part has insulating properties, it is possible to prevent the light shielding part and the first transparent electrode layer from conducting even when the light shielding part is in contact with, for example, the first transparent electrode layer.

  In the present invention, a color conversion layer may be formed on the colored layer and between the colored layer and the first transparent electrode layer.

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

  According to the present invention, since the above-described color filter substrate for an organic EL element is used, the occurrence of defects such as dark spots can be suppressed, and an organic EL display device capable of good image display can be obtained. Further, since it is not necessary to provide a thick transparent barrier layer as in the prior art, an organic EL display device can be provided at low cost.

  According to the present invention, by providing the second transparent electrode layer, which is a coating film, on the first transparent electrode layer, defects such as pinholes existing in the first transparent electrode layer can be closed, so that a colored layer or the like It is possible to prevent the outflow of gas generated from the gas and the entry of water vapor, oxygen, and the like. Thereby, when the color filter substrate for organic EL elements of the present invention is used in an organic EL display device, generation of dark spots can be suppressed, and good image display can be achieved. In addition, since good barrier properties can be obtained by the first transparent electrode layer and the second transparent electrode layer, there is no need to provide a thick transparent barrier layer as in the prior art, and the cost can be reduced.

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

A. First, the color filter substrate for organic EL elements of the present invention will be described. The color filter substrate for an organic EL element of the present invention can be divided into two embodiments depending on the configuration of the second transparent electrode layer. Each embodiment will be described below.

1. 1st embodiment The 1st embodiment of the color filter substrate for organic EL elements of the present invention includes a substrate, a colored layer formed in a pattern on the substrate, and a first transparent electrode formed on the colored layer. A color filter substrate for an organic electroluminescent element, comprising: a layer; and a second transparent electrode layer having a barrier property formed on the first transparent electrode layer, wherein the second transparent electrode layer is a coating film It is characterized by being.

The color filter substrate for organic EL elements of this embodiment will be described with reference to the drawings.
FIG. 1 is a schematic cross-sectional view showing an example of a color filter substrate for an organic EL element of this embodiment. As shown in FIG. 1, a color filter substrate 10 for an organic EL element according to this embodiment has a colored layer 2, a first transparent electrode layer 3, and a second transparent electrode layer 4 sequentially formed in a pattern on a substrate 1. It has been done.

  In general, indium tin oxide (ITO), indium zinc oxide (IZO) or the like is used for the transparent electrode layer, and such a transparent electrode layer is a gas generated from water vapor, oxygen, a colored layer, a color conversion layer, or the like. It has a certain degree of barrier property. However, the transparent electrode layer is generally formed by a sputtering method or a vacuum evaporation method, and it is technically difficult to obtain a transparent electrode layer free from foreign matters such as particles or pinholes by the sputtering method or the vacuum evaporation method. Therefore, the transparent electrode layer formed by the sputtering method or the vacuum deposition method has defects on the manufacturing surface, microscopic structural defects, and the like. For this reason, when used for an organic EL display device, it is necessary to block defects such as foreign matter and pinholes existing in the transparent electrode layer. This is because the gas generated from the colored layer, the color conversion layer, etc. flows out from the defects such as pinholes existing in the transparent electrode layer, or water vapor or oxygen enters, which causes dark spots. is there.

  Therefore, in this embodiment, by providing the second transparent electrode layer 4 which is a coating film on the first transparent electrode layer 3, a barrier property is obtained with respect to the gas generated from the colored layer 2 and the like, water vapor and oxygen. be able to. Since the 2nd transparent electrode layer 4 in this embodiment is a coating film, even if it is a case where the defect in a manufacturing surface, a micro structural defect, etc. exist in the 1st transparent electrode layer 3, the 1st transparent electrode layer The defect can be corrected by applying the second transparent electrode layer-forming coating solution on 3. That is, in the process of applying and drying the second transparent electrode layer forming coating solution, the second transparent electrode layer forming coating solution penetrates into, for example, pinholes existing in the first transparent electrode layer 3, so Can be blocked.

  As described above, in this embodiment, the second transparent electrode layer 4 is a coating film, thereby preventing the gas generated from the colored layer 2 and the like from flowing out from the pinholes and the like of the first transparent electrode layer 3. it can. In addition, entry of water vapor, oxygen, or the like can be prevented. Thereby, when the color filter substrate for organic EL elements of this embodiment is used for an organic EL display device, it is possible to display a good image without dark spots.

  Further, in this embodiment, by providing the second transparent electrode layer on the first transparent electrode layer, it is possible to obtain a barrier property against the gas generated from the colored layer and the like, and water vapor and oxygen. Since there is no need to provide a thick transparent barrier layer by sputtering or CVD, the cost can be reduced.

  Furthermore, since the barrier properties of the first transparent electrode layer and the second transparent electrode layer are not greatly affected even if there are irregularities due to the colored layer, it is not necessary to provide a resin protective layer for planarization, and thermal expansion The pixel reduction or the like does not occur due to the expansion and contraction of the resin.

  In the present embodiment, for example, if the first transparent electrode layer 3 and the second transparent electrode layer 4 are formed on the colored layer 2 as shown in FIG. In particular, it is preferable that at least one of the first transparent electrode layer and the second transparent electrode layer is formed so as to cover the entire colored layer formed in a pattern. This is because if the entire surface of the colored layer is covered with at least one of the first transparent electrode layer and the second transparent electrode layer, outflow of gas generated from the colored layer can be more effectively prevented.

  The first transparent electrode layer and the second transparent electrode layer may be formed so that at least one of them covers the entire colored layer formed in a pattern. For example, as shown in FIG. It is preferable that both the layer 3 and the second transparent electrode layer 4 are formed so as to cover the entire surface of the colored layer 2 formed in a pattern. This is because the outflow of gas generated from the colored layer can be more effectively prevented.

Here, “forming so as to cover the entire surface of the colored layer” means that the entire surface and side surfaces of the colored layer are covered and the colored layer is not exposed. For example, as shown in FIG. The case where the 1st transparent electrode layer 3 and the 2nd transparent electrode layer 4 are formed so that neither surface of the colored layer 2 may be exposed is said.
Hereafter, each structure of such a color filter substrate for organic EL elements is demonstrated.

(1) 2nd transparent electrode layer The 2nd transparent electrode layer used for this embodiment is a coating film formed on the 1st transparent electrode layer mentioned below, has barrier properties, and is formed by application. .

  The barrier property of the second transparent electrode layer used in this embodiment is not limited as long as it can close defects such as pinholes in the first transparent electrode layer described later.

  In the present embodiment, since the two layers of the second transparent electrode layer and the first transparent electrode layer only have to function as an electrode, the conductivity of the second transparent electrode layer can function independently as an electrode. It is not necessary to have such a sheet resistance value. Specifically, the sheet resistance value of the second transparent electrode layer may be about 100Ω / □ to 10000Ω / □, and preferably in the range of 100Ω / □ to 1000Ω / □.

  Here, the sheet resistance value is a value measured by a four-probe method using Mitsubishi Chemical Corporation Loresta-GP (MCP-T600).

The second transparent electrode layer used in this embodiment is not particularly limited as long as it has the above-described properties and can be formed by coating. Specifically, indium tin oxide (ITO), Indium zinc oxide (IZO), antimony tin oxide (ATO), aluminum zinc oxide (AZO), indium oxide, tin oxide, zinc oxide, cadmium oxide, gallium oxide, In ₂ O ₃ (ZnO) _m , InGaO ₃ (ZnO) _m, can be mentioned metal oxides such as CaWO _4. Also, Au, Ag, Cu, Pt, Sn, Zn, Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, V, Cr, Mn, Fe, Co, Ni, Ga, Rb, Sr, Y, Zr, Nb, Pb, Mo, Cd, In, Sb, Cs, Ba, La, Hf, Ta, W, Ti, Pb, Bi, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Examples thereof include conductive metals such as Tb, Dy, Ho, Er, Tm, Yb, and Lu, and oxides thereof. Among these, ITO is preferable. Further, at least one selected from the group consisting of Au, Ag, Cu, Pt, Sn, Zn, In, Pb, Al, and oxides thereof is also preferable.

  At this time, the material used for the second transparent electrode layer may be the same as or different from the material used for the first transparent electrode layer described later, but is preferably the same. If the materials used for the first transparent electrode layer and the second transparent electrode layer are the same, after forming the first transparent electrode layer and the second transparent electrode layer on the entire surface of the substrate on which the colored layer is formed, for example, This is because two layers can be patterned simultaneously using the same etching solution. As a result, the manufacturing process can be simplified.

  Further, even when the materials used for the first transparent electrode layer and the second transparent electrode layer are different, if the film thickness of the second transparent electrode layer is relatively thin, two layers are formed using the same etching solution. Patterning may be possible at the same time. This differs depending on the material used. For example, when an ITO film having a thickness of 150 nm is formed as the first transparent electrode layer and an Ag film having a thickness of 5 nm is formed as the second transparent electrode layer, Both the ITO film and the Ag film can be patterned at the same time using an etching solution for the ITO film.

  In the present embodiment, the second transparent electrode layer preferably contains fine particles having an average particle diameter in the range of 1 nm to 10 nm. This is because the fine particles have an average particle size smaller than a defect such as a pinhole in the first transparent electrode layer, and can effectively close the defect such as a pinhole. Further, due to the size effect peculiar to the fine particles, the firing temperature of the second transparent electrode layer forming coating liquid containing the fine particles at the time of forming the second transparent electrode layer can be lowered compared to the normal firing temperature, This is because firing at a temperature lower than the heat resistant temperature of the colored layer becomes possible.

  Examples of such fine particles include the metal oxides, conductive metals, and conductive metal oxide fine particles described above. In this embodiment, in particular, the fine particles are preferably fine particles of indium tin oxide (ITO). This is because ITO is preferably used as the second transparent electrode layer. Further, at least one kind of fine particles selected from the group consisting of Au, Ag, Cu, Pt, Sn, Zn, In, Pb, Al and oxides thereof are also preferable.

  The average particle size of the fine particles may be any as long as it can block defects such as pinholes in the first transparent electrode layer, and is specifically in the range of 0.5 nm to 50 nm, preferably 1 nm. Within the range of -10 nm. If the average particle size is too small, it is difficult to produce. On the other hand, if the average particle size of the fine particles is too large, it may be difficult to block defects such as pinholes in the first transparent electrode layer. This is because a decrease in firing temperature due to the size effect cannot be expected.

  Here, the average particle diameter is generally used to indicate the particle size of the particles, and in the present invention, is a value measured by a laser method. The laser method is a method of measuring an average particle size, a particle size distribution, and the like by dispersing particles in a solvent and thinning and calculating scattered light obtained by applying a laser beam to the dispersion solvent. The average particle size is a value measured using a particle size analyzer Microtrac UPA Model-9230 manufactured by Leeds & Northrup as a particle size measuring device by a laser method.

  Since the second transparent electrode layer containing such fine particles is formed by applying and sintering a second transparent electrode layer forming coating solution containing fine particles, as will be described later, the second transparent electrode layer is made of fine particles. It is thought to be a thing. Therefore, the content of fine particles contained in the second transparent electrode layer is assumed to be about 100%.

  The fact that the second transparent electrode layer contains the fine particles can be confirmed by a scanning electron microscope (SEM) observation photograph (magnification: 50,000 times or more). At this time, first, the interface between the first transparent electrode layer and the second transparent electrode layer is confirmed, and in the second transparent electrode layer, if a granular shape melted by firing at the time of forming the second transparent electrode layer is confirmed, Suppose that it contains fine particles.

  Moreover, when the color filter substrate for organic EL elements of this embodiment is used for an organic EL display device, it is preferable that the second transparent electrode layer has light transmittance because light is extracted from the substrate side. As the light transmittance of the second transparent electrode layer, the light transmittance in the visible light region is preferably 60% or more, more preferably 80% or more, and particularly preferably 90% or more.

  Here, 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.

  Furthermore, the film thickness of the second transparent electrode layer is not particularly limited as long as it satisfies the above-described barrier property, conductivity, and light transmittance. Specifically, the film thickness is within the range of 5 nm to 2000 nm. And preferably within a range of 50 nm to 500 nm. This is because if the film thickness of the second transparent electrode layer is too thick, the light transmittance may be lowered, or peeling from the first transparent electrode layer may occur. Furthermore, since the second transparent electrode layer is provided on the outermost surface of the color filter substrate for the organic EL element of the present embodiment, if the thickness of the second transparent electrode layer is too thick, the resistance of the terminal connection portion may be increased. Because there is. On the other hand, if the film thickness of the second transparent electrode layer is too thin, it is difficult to block pinholes and the like existing in the first transparent electrode layer.

  In addition, when the above-described conductive metals or their oxides are used as the second transparent electrode layer, light transmittance is impaired if the thickness of the second transparent electrode layer is too thick. A thinner one is preferred. Specifically, it is preferably in the range of 5 nm to 50 nm.

  The second transparent electrode layer used in this embodiment is a coating film. The “coating film” means a film formed by a wet method, for example, a film formed by coating using a coating liquid.

  Here, the transparent electrode layer is generally formed by a sputtering method or a vacuum deposition method. Whether the second transparent electrode layer is formed by coating or formed by a sputtering method or a vacuum deposition method can be confirmed by, for example, a scanning electron microscope (SEM) observation photograph. If it is formed by application, for example, as shown in FIG. 3A, the first transparent electrode layer forming coating liquid for forming the second transparent electrode layer 4 has a level of first transparent. It is considered that the pinhole PH is substantially flattened because the second transparent electrode layer forming coating solution enters the pinhole PH of the electrode layer 3. On the other hand, if formed by sputtering or the like, for example, as shown in FIG. 3B, the pinhole PH of the transparent electrode layer 23 cannot be sufficiently blocked by the sputtering film 24 and flattened. Can not. Thus, if the pinhole of the first transparent electrode layer is almost completely closed and flattened, it can be said that the second transparent electrode layer is formed by coating.

  In this embodiment, a coating method is used as a method for forming the second transparent electrode layer, and examples thereof include a method using a sol-gel method and a method using a second transparent electrode layer forming coating solution containing fine particles. It is done. When using the sol-gel method, the second transparent electrode layer can be formed by applying a second transparent electrode layer-forming coating solution on the first transparent electrode layer, heating it, and causing a polycondensation reaction. In the method using fine particles, the second transparent electrode layer can be formed by applying a second transparent electrode layer-forming coating solution onto the first transparent electrode layer and sintering it. Further, as a patterning method for the second transparent electrode layer, a photolithography method is usually used.

In the present embodiment, it is particularly preferable that the second transparent electrode layer is formed by a method using a coating solution for forming a second transparent electrode layer containing fine particles. As described above, the fine particles can effectively block the pinholes, and further, due to the size effect unique to the fine particles, the colored layer can be baked at the heat resistant temperature or lower when the second transparent electrode layer is formed. .
Hereinafter, the formation method of the 2nd transparent electrode layer using the coating liquid for 2nd transparent electrode layer formation containing such microparticles | fine-particles is demonstrated.

The method for forming the second transparent electrode layer using the coating liquid for forming the second transparent electrode containing fine particles used in this embodiment is divided into two modes depending on the constituent material of the second transparent electrode layer. Can do. The first aspect is a case where the second transparent electrode layer is a conductive layer made of a metal oxide, and the second aspect is that the second transparent electrode layer is at least any one of a conductive metal and a conductive metal oxide. This is a case of a conductive metal layer made of either of them.
Hereinafter, the description will be made separately for each aspect.

(I) 1st aspect The formation method of the 2nd transparent electrode layer of this aspect is for conductive layer formation containing the microparticles | fine-particles of the metal which are contained in the metal oxide or the metal particle | grains contained in the said metal oxide. A dispersion is prepared, and the dispersion for forming a conductive layer is applied on the first transparent electrode layer, and the atmosphere is an oxygen gas or ozone gas atmosphere at atmospheric pressure or a plasma atmosphere of a gas obtained by adding oxygen gas or ozone gas to an inert gas. It is fired at 150 ° C. to 250 ° C., and is oxidized and sintered simultaneously to form a conductive layer made of a metal oxide.

  According to this aspect, by baking at a predetermined temperature in an oxidizing atmosphere, oxidation and sintering proceed simultaneously, and a conductive layer can be formed. At this time, since the fine particles are densely sintered at a temperature much lower than the firing temperature of a general conductive layer, the colored layer can be fired at a temperature lower than the heat resistant temperature.

As a metal oxide in this aspect, what is necessary is just what can form the 2nd transparent electrode layer which has the barrier property, electroconductivity, and light transmittance mentioned above, for example, an indium oxide, a tin oxide, a zinc oxide, Cadmium oxide, gallium oxide, In ₂ O ₃ (ZnO) _m , InGaO ₃ (ZnO) _m , CaWO ₄ , indium tin oxide (ITO), tin oxide antimony (ATO), indium zinc oxide (IZO), and zinc aluminum oxide (AZO) metal oxide. Among these, ITO, ATO, IZO, zinc oxide, tin oxide, and CaWO ₄ are preferable, and ITO is particularly preferable. Examples of the fine particles used in this embodiment include metal fine particles contained in the metal oxide, and alloy fine particles made of a metal contained in the metal oxide.

  The conductive layer forming dispersion used in this embodiment is obtained by dispersing the fine particles in a solvent. The solvent to be used may be appropriately selected depending on the fine particles to be used. For example, alcohols such as methanol, ethanol, propanol, isopropyl alcohol and butanol, glycols such as ethylene glycol; ketones such as acetone, methyl ethyl ketone and diethyl ketone; acetic acid Esters such as ethyl, butyl acetate and benzyl acetate; ether alcohols such as methoxyethanol and ethoxyethanol; ethers such as dioxane and tetrahydrofuran; acid amides such as N, N-dimethylformamide; aromatics such as toluene and xylene Hydrocarbons; and the like. Furthermore, water can also be used.

  What is necessary is just to select the usage-amount of the said solvent suitably according to the microparticles to be used so that it may be easy to apply and a desired film thickness can be obtained. For example, the fine particles may be contained in the range of 1 to 50 wt% with respect to the solvent. Preferably it exists in the range of 10-40 wt%. This is because if the content of the fine particles is too small, it is difficult to close defects such as pinholes in the first transparent electrode layer. On the other hand, if the content of the fine particles is too large, the fluidity is lowered, which also makes it difficult to close defects such as pinholes in the first transparent electrode layer, and further the flatness of the surface of the second transparent electrode layer is reduced. This is because it may be damaged.

  Examples of the method for applying the dispersion for forming a conductive layer include spin coating, spray coating, inkjet method, dip coating, roll coating, and screen printing.

  In addition, after applying the conductive layer forming dispersion, the temperature is much lower (150 to 250 ° C.) than the temperature (generally 500 to 700 ° C.) required to sinter the fine particles alone in an oxidizing atmosphere. ), And a film is formed by simultaneously performing oxidation and sintering to obtain a conductive layer.

  The firing temperature is in the range of 150 to 250 ° C. This is because if the firing temperature is too low, it may not sinter sufficiently, and if the firing temperature is too high, problems will occur in the production process.

  Examples of the oxidizing atmosphere include a plasma atmosphere such as an atmospheric pressure oxygen gas or ozone gas atmosphere or an atmospheric pressure plasma of a gas obtained by adding an oxygen gas or an ozone gas to an inert gas such as a rare gas such as helium.

  Moreover, after apply | coating the dispersion liquid for conductive layer formation, before baking, you may dry the apply | coated dispersion liquid for conductive layer formation at predetermined | prescribed temperature.

  Furthermore, although oxidation and sintering are performed simultaneously in an oxidizing atmosphere, it is preferable to perform ultraviolet irradiation at the same time. More effective in terms of time reduction and low temperature. Also, so-called plasma sintering using atmospheric pressure plasma or the like can be used.

(Ii) Second Aspect A method for forming a second transparent electrode layer according to this aspect comprises applying a dispersion for forming a conductive metal layer containing fine particles of a conductive metal on the first transparent electrode layer, It sinters at 180-250 degreeC, and forms the electroconductive metal layer which consists of at least any one of an electroconductive metal and an electroconductive metal oxide.

  According to this aspect, since the fine particles are densely sintered at a temperature much lower than the firing temperature of a general conductive metal layer, firing at a temperature lower than the heat resistant temperature of the colored layer is possible.

  In this embodiment, since the second transparent electrode layer is formed using fine particles of conductive metal, as described above, if the film thickness of the second transparent electrode layer is too thick, the light transmittance is impaired. It is necessary to form such that the thickness is relatively thin. The specific film thickness is as described above.

  As the conductive metal fine particles used in this embodiment, at least one fine particle of Ag, Sn, and Zn is preferable, but in addition, Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc V, Cr, Mn, Fe, Co, Ni, Ga, Rb, Sr, Y, Zr, Nb, Cu, Pb, Mo, Cd, In, Sb, Cs, Ba, La, Hf, Ta, W, Ti , Pb, Bi, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu can also be used. Among these, fine particles of Ag, Sn, Zn, In, Cu, and Pb are preferable in order to lower the sintering temperature.

  The conductive metal layer forming dispersion is obtained by dispersing the conductive metal fine particles in a solvent. The solvent, the amount of the solvent used, and the coating method of the conductive metal layer forming dispersion are the same as those of the conductive layer forming dispersion described in the first aspect.

  In addition, after applying the conductive metal layer forming dispersion, the temperature is much lower than the temperature (generally 400 to 600 ° C.) required to sinter the conductive metal fine particles alone in the atmosphere ( A conductive metal layer is obtained by sintering at 180 to 250 ° C. and forming a film.

  In this aspect, the conductive metal may be somewhat oxidized during the manufacturing process of the conductive metal layer. For this reason, since the conductive metal layer may contain fine particles of a conductive metal oxide, it is made of at least one of a conductive metal and a conductive metal oxide.

  The firing temperature is in the range of 180 to 250 ° C. This is because if the firing temperature is too low, it may not sinter sufficiently, and if the firing temperature is too high, problems will occur in the production process.

(2) 1st transparent electrode layer Next, the 1st transparent electrode layer used for this embodiment is demonstrated. The 1st transparent electrode layer used for this embodiment is formed on the coloring layer mentioned below.

  As the first transparent electrode layer, those generally used as the transparent electrode layer of the organic EL element can be used, and ITO is preferably used.

  In addition, when the color filter substrate for organic EL elements of this embodiment is used in an organic EL display device, light is extracted from the substrate side, and thus has the same light transmittance as the second transparent electrode layer described above. It is preferable.

  Further, the film thickness of the first transparent electrode layer is not particularly limited, but specifically, it can be set within a range of 50 nm to 500 nm, and preferably within a range of 100 nm to 200 nm. This is because if the film thickness of the first transparent electrode layer is too thick, the light transmittance may be reduced, or peeling from the substrate may occur. On the other hand, if the thickness of the first transparent electrode layer is too thin, desired electrical characteristics may not be obtained.

  Further, as described above, the sheet resistance value of the first transparent electrode layer may be such that the two layers of the first transparent electrode layer and the second transparent electrode layer integrally function as an electrode. / □ to about 50Ω / □, preferably within the range of 10Ω / □ to 30Ω / □.

  In addition, about the measuring method of the said sheet resistance value, it is the same as that of the method described in the term of the said 2nd transparent electrode layer.

  The 1st transparent electrode layer used for this embodiment can be formed using the formation method of a general transparent electrode layer. Examples of the method for forming the first transparent electrode layer include a sputtering method and a vacuum deposition method.

(3) Inorganic layer In this embodiment, as shown in FIG. 4, for example, an inorganic layer 5 having a barrier property may be formed between the colored layer 2 and the first transparent electrode layer 3.

  According to this embodiment, by providing the inorganic layer, the unevenness of the colored layer and the foreign matter existing on the colored layer can be repaired. If there are irregularities in the colored layer, the irregular shape is also reflected in the first transparent electrode layer formed on the colored layer, and the organic EL element color filter substrate of this embodiment is applied to the organic EL display device. When used, defects due to electrostatic breakdown or the like are likely to occur in the thin organic EL layer. Such a defective portion becomes a defective portion (dark area), which causes a reduction in display quality. For this reason, it is preferable to provide an inorganic layer to planarize the colored layer surface.

  Moreover, since the said 1st transparent electrode layer is formed by sputtering method or a vacuum evaporation method as mentioned above, adhesiveness with a colored layer may not be enough. In this embodiment, by providing the inorganic layer, the adhesion between the first transparent electrode layer and the colored layer can be improved, and the first transparent electrode layer can be prevented from peeling from the colored layer. .

  Furthermore, when an inorganic layer is provided, an inorganic layer having a barrier property, a first transparent electrode layer, and a second transparent electrode layer having a barrier property are sequentially laminated on the colored layer. Thereby, the barrier property with respect to the gas generated from the colored layer or the like, and water vapor or oxygen can be enhanced.

  In addition, when the organic EL element color filter substrate of the present embodiment is used in an organic EL display device, light is extracted from the substrate side, and thus the inorganic layer preferably has light transmittance. It is preferable to have the same light transmittance as the second transparent electrode layer described above.

The inorganic layer used in this embodiment is not particularly limited as long as it has the above-described properties and can planarize the colored layer surface, but there are two preferred embodiments. The 1st of a preferable aspect is a case where an inorganic layer is a barrier layer generally used for an organic EL element (3rd aspect). Moreover, the 2nd of a preferable aspect is a case where an inorganic layer is a coating film (4th aspect).
Hereinafter, each aspect will be described.

(I) 3rd aspect The inorganic layer of this aspect is a barrier layer generally used for an organic EL element. In this aspect, the barrier property of the color filter substrate for organic EL elements can be enhanced by providing a general barrier layer.

  The material used for the barrier layer of this embodiment may be any material generally used for organic EL elements. For example, silicon oxide, silicon oxynitride, aluminum oxide, titanium oxide, tantalum oxide, zinc oxide, magnesium oxide, tin oxide Inorganic oxides such as indium oxide alloys; inorganic nitrides such as silicon nitride, aluminum nitride, titanium nitride, and silicon carbonitride; metals such as aluminum, silver, tin, chromium, nickel, and titanium;

  Among the above materials, silicon oxide or silicon oxynitride is preferable. This is because these materials have good adhesion to the colored layer and the first transparent electrode layer. Such a silicon oxide thin film can be formed using an organosilicon compound as a raw material. Specific examples of the organosilicon compound include 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane, vinyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, trimethylsilane, diethylsilane, and propylsilane. , Phenylsilane, vinyltriethoxysilane, tetramethoxysilane, phenyltriethoxysilane, methyltriethoxysilane, octamethylcyclotetrasiloxane and the like. Among the organosilicon compounds, tetramethoxysilane (TMOS) and hexamethyldisiloxane (HMDSO) are preferably used. This is because these are excellent in handleability and vapor deposition film characteristics.

  Further, the barrier layer may be a single layer, or a plurality of layers may be laminated in order to improve the barrier property. Moreover, as a combination in the case of stacking, the same kind or different kinds may be used.

  Such a barrier layer can be formed by, for example, a sputtering method, a CVD method, a vacuum deposition method, a dip method, or the like.

  The thickness of the barrier layer is not particularly limited as long as it has a barrier property against the gas generated from the colored layer and the like, water vapor and oxygen, and satisfies the above-described light transmittance. The material is selected as appropriate. Usually, it exists in the range of 5 nm-5000 nm, Preferably it exists in the range of 5 nm-500 nm. Further, when aluminum oxide or silicon oxide is used, it is more preferably in the range of 10 nm to 300 nm. This is because when the thickness of the barrier layer is too thin, the barrier property is reduced. On the other hand, if the thickness of the barrier layer is too large, cracks or the like may occur during the formation of the barrier layer, and the light transmittance may decrease.

  In this aspect, it is preferable that at least one of the first transparent electrode layer, the second transparent electrode layer, and the barrier layer is formed so as to cover the entire colored layer formed in a pattern. If the entire surface of the colored layer is covered with at least one of the first transparent electrode layer, the second transparent electrode layer, and the barrier layer, the outflow of gas generated from the colored layer can be more effectively prevented. Because.

  Here, the first transparent electrode layer and the second transparent electrode layer need to be patterned, but the barrier layer does not need to be particularly patterned. For this reason, if the barrier layer is formed on the entire surface of the substrate, the entire colored layer can be covered with at least the barrier layer.

  Further, the first transparent electrode layer, the second transparent electrode layer, and the barrier layer may be formed so as to cover the entire colored layer in which at least one of them is formed in a pattern. For example, as shown in FIG. It is preferable that all of the barrier layer 5, the first transparent electrode layer 3 and the second transparent electrode layer 4 are formed so as to cover the entire surface of the colored layer 2 formed in a pattern. This is because the outflow of gas generated from the colored layer can be more effectively prevented.

(Ii) Fourth Aspect The inorganic layer of this aspect is a coating film. In this embodiment, even when a defect such as a pinhole exists in the first transparent electrode layer, the inorganic layer and the second transparent electrode layer are coating films, and therefore the pin that penetrates from the inorganic layer to the surface of the second transparent electrode layer Generation of defects such as holes can be prevented. For this reason, the outflow of gas generated from the colored layer or the like can be prevented, and intrusion of oxygen, water vapor, or the like can be prevented.

  The inorganic layer of this embodiment preferably has conductivity. This is because, if the inorganic layer has conductivity, the inorganic layer can be integrated with the first transparent electrode layer and the second transparent electrode layer and function as an electrode, so that the electrical resistance can be reduced. .

  The conductivity of the inorganic layer only needs to have a sheet resistance value comparable to that of the second transparent electrode layer described above.

The material used for such an inorganic layer is not particularly limited as long as it can be formed by coating and has conductivity, and examples thereof include a material used for the second transparent electrode layer. Specifically, indium oxide, tin oxide, zinc oxide, cadmium oxide, gallium oxide, In ₂ O ₃ (ZnO) _m , InGaO ₃ (ZnO) _m , CaWO ₄ , indium tin oxide (ITO), tin oxide antimony (ATO) ), Indium zinc oxide (IZO), zinc oxide aluminum (AZO), and other metal oxides. Also, Au, Ag, Cu, Pt, Sn, Zn, Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, V, Cr, Mn, Fe, Co, Ni, Ga, Rb, Sr, Y, Zr, Nb, Pb, Mo, Cd, In, Sb, Cs, Ba, La, Hf, Ta, W, Ti, Pb, Bi, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Examples thereof include conductive metals such as Tb, Dy, Ho, Er, Tm, Yb, and Lu, and oxides thereof. Among these, ITO is preferable. Further, at least one selected from the group consisting of Au, Ag, Cu, Pt, Sn, Zn, In, Pb, Al, and oxides thereof is also preferable.

  At this time, the material used for the inorganic layer may be the same as or different from the material used for the first transparent electrode layer and the second transparent electrode layer, but is preferably the same. If the materials used for the inorganic layer, the first transparent electrode layer, and the second transparent electrode layer are the same, three layers of the inorganic layer, the first transparent electrode layer, and the second transparent electrode layer are formed on the entire surface of the substrate on which the colored layer is formed. This is because, for example, three layers can be simultaneously patterned using the same etching solution.

  In this embodiment, the inorganic layer preferably contains fine particles having an average particle diameter in the range of 1 nm to 10 nm. Due to the size effect peculiar to the fine particles, the firing temperature of the inorganic layer-forming coating liquid containing the fine particles during the formation of the inorganic layer can be lowered as compared with the normal firing temperature, and the heat resistance temperature of the colored layer or less. This is because firing is possible.

The fine particles are the same as those described in the above-mentioned section of the second transparent electrode layer, and thus description thereof is omitted here.
Moreover, about the film thickness of an inorganic layer, it is the same as that of the said 2nd transparent electrode layer.

  In this aspect, it is preferable that at least one of the first transparent electrode layer, the second transparent electrode layer, and the inorganic layer is formed so as to cover the entire colored layer formed in a pattern. If the entire surface of the colored layer formed in a pattern is covered with at least one of the first transparent electrode layer, the second transparent electrode layer, and the inorganic layer, the outflow of gas generated from the colored layer is more effective. It is because it can prevent.

  In such a case, the first transparent electrode layer, the second transparent electrode layer, and the inorganic layer may be formed so as to cover the entire colored layer in which at least one of them is formed in a pattern, for example, FIG. It is preferable that all of the inorganic layer 5, the first transparent electrode layer 3, and the second transparent electrode layer 4 are formed so as to cover the entire colored layer 2 as shown in FIG. This is because the outflow of gas generated from the colored layer can be more effectively prevented.

  The inorganic layer of this embodiment is a coating film formed by coating. Whether the inorganic layer is formed by coating can be confirmed by the method described in the section of the second transparent electrode layer.

  In this embodiment, a coating method is used as a method of forming the inorganic layer, and examples thereof include a method using a sol-gel method and a method using a coating liquid for forming an inorganic layer containing fine particles. In addition, as a patterning method for the inorganic layer, a photolithography method is usually used.

  In this embodiment, it is particularly preferred that the inorganic layer is formed by a method using an inorganic layer forming coating solution containing fine particles. This is because, as described above, the fine particles effectively block the pinholes, and due to the size effect unique to the fine particles, the colored layer can be fired at a temperature lower than the heat resistant temperature when the inorganic layer is formed. Furthermore, the inorganic layer formed using such an inorganic layer forming coating solution containing fine particles also has an advantage of good adhesion to the colored layer and the first transparent electrode layer.

  In addition, about the formation method of an inorganic layer, since it is the same as the formation method of the 2nd transparent electrode layer mentioned above, description is abbreviate | omitted here.

(4) Characteristics of the first transparent electrode layer, the second transparent electrode layer, and the inorganic layer In this embodiment, by providing the second transparent electrode layer that is a coating film on the first transparent electrode layer, from the colored layer or the like. A barrier property against the generated gas, water vapor and oxygen can be obtained. As the barrier property when the first transparent electrode layer and the second transparent electrode layer are provided, the oxygen gas permeability is 1 cc / m ² / day / atm or less, particularly 0.5 cc / m ² / day / It is preferable that it is atm or less. Further, the water vapor transmission rate is preferably 1 g / m ² / day or less, particularly preferably 0.5 g / m ² / day or less.

Further, in this embodiment, by providing an inorganic layer between the colored layer and the first transparent electrode layer, the barrier property against gas from oxygen, water vapor, colored layer, etc. can be made high. In this case, as a barrier property when the inorganic layer, the first transparent electrode layer, and the second transparent electrode layer are provided, the oxygen gas permeability is 1 cc / m ² / day / atm or less, particularly 0.5 cc / m ^2. / Day / atm or less, and particularly preferably 0.1 cc / m ² / day / atm or less. The water vapor transmission rate of ^1g / m 2 / day or less, preferably 0.5g ^/ m 2 ^/ day or less, preferably not more than particular 0.1g ^/ m 2 ^/ day.

  When the oxygen gas permeability and the water vapor permeability are in the above-described ranges, the barrier property can be made high, and the color filter substrate for the organic EL element of this embodiment can be obtained from oxygen, water vapor, a colored layer, or the like. This is because it can be suitably used for an organic EL element having a member that is weak against the gas.

  Here, the oxygen gas permeability was measured using an oxygen gas permeability measuring device (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. Value. 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.

  In addition, as described above, when the organic EL element color filter substrate of the present embodiment is used in an organic EL display device, since the organic EL layer is formed on the second transparent electrode layer, generation of dark areas is suppressed. Therefore, the surface of the second transparent electrode layer is preferably flat. In particular, when the inorganic layer is provided, the colored layer surface can be flattened, and thus the second transparent electrode layer surface can be flattened. Specifically, the average surface roughness (Ra) of the second transparent electrode layer is preferably in the range of 10 to 500 mm, more preferably in the range of 10 to 100 mm. When the average surface roughness (Ra) of the second transparent electrode layer is within the above-described range, when the color filter substrate for an organic EL element of this embodiment is used in an organic EL display device, generation of dark areas is suppressed. This is because a good image display can be obtained.

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

(5) Colored layer Next, the colored layer used for this embodiment is demonstrated. The colored layer used in this embodiment is formed in a pattern on the substrate.

  The colored layer used in the present embodiment changes the color tone of white light emitted from the light emitting layer of the organic EL display device when the organic EL display device is formed using the organic EL element color filter substrate of the present embodiment. Or a layer for further adjusting the color tone of light transmitted through a color conversion layer described later. In general, the colored layer is formed as a blue, red, or green colored layer. When a color conversion layer is provided, blue, red, and green colored layers are formed at positions corresponding to the colors of the color conversion layer, respectively. By forming such a colored layer, when the color filter substrate for organic EL elements of this embodiment is used in an organic EL display device, it is possible to achieve high-purity color development and high color reproducibility. can do.

  As a material for forming the colored layer, pigments and binder resins that can be generally used for color filters can be used.

  Specifically, examples of the pigment used in the red colored layer include perylene pigments, lake pigments, azo pigments, quinacridone pigments, anthraquinone pigments, anthracene pigments, isoindoline pigments, and the like. . These pigments may be used alone or in combination of two or more.

  Examples of the pigment used for the green colored layer include halogen polysubstituted phthalocyanine pigments, halogen polysubstituted copper phthalocyanine pigments, triphenylmethane basic dyes, isoindoline pigments, and isoindolinone pigments. be able to. These pigments may be used alone or in combination of two or more.

  Furthermore, examples of the pigment used in the blue colored layer include copper phthalocyanine 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.

  The pigment is usually contained in the red, green or blue colored layer within a range of 5 to 50% by weight.

  The binder resin used for the colored layer is preferably a transparent resin having a visible light transmittance of 50% or more, such as polymethyl methacrylate, polyacrylate, polycarbonate, polyvinyl alcohol, polyvinyl pyrrolidone, hydroxyethyl cellulose, carboxymethyl cellulose, and the like. Can be mentioned.

  As a method for forming the colored layer, a general method for forming a color filter, such as a photolithography method or a mask vapor deposition method, can be used.

(6) Light Shielding Part In this embodiment, the light shielding part 6 may be formed on the substrate 1 and between the colored layers 2 as shown in FIG. This is because by providing a light blocking portion such as a black matrix, the contrast can be improved when an organic EL display device is formed using the color filter substrate for organic EL elements of the present embodiment.

The light shielding portion used in this embodiment may have insulating properties or may not have insulating properties. When the light shielding part has insulating properties, examples of the material for forming the light shielding part include a resin containing a black colorant. Moreover, when the light shielding part does not have insulating properties, examples of the material for forming the light shielding part include chromium. At this time, the light shielding portion, CrO _x film (x is an arbitrary number) may be one and the Cr film is two-layered, also, CrO _x film (x is any with reduced more reflectivity Number), a CrN _y film (y is an arbitrary number), and three layers of Cr films may be laminated.

  In this embodiment, when at least one of the first transparent electrode layer and the second transparent electrode layer is formed so as to cover the entire colored layer formed in a pattern, or the first transparent electrode layer, When at least one of the second transparent electrode layer and the inorganic layer is formed so as to cover the entire surface of the colored layer formed in a pattern, it is preferable that the light shielding part has an insulating property. For example, in FIG. 5, since the first transparent electrode layer 3 and the second transparent electrode layer 4 are formed so as to cover the entire surface of the colored layer 2, the first transparent electrode layer 3 and the second transparent electrode layer 4, The light shielding part 6 is in contact. In this case, if the light-shielding part 6 does not have insulating properties, that is, has electrical conductivity, the light-shielding part 6 and the first transparent electrode layer 3 and the second transparent electrode layer 4 are electrically connected to each other. This is because, in an organic EL display device using an EL element color filter substrate, when a signal is applied to the first transparent electrode layer, the signals of the adjacent first transparent electrode layers may not be operated independently. .

  The light shielding part using a resin containing a black colorant can be formed in a pattern by a photolithography method by applying a resin composition containing a black colorant on a substrate.

  In addition, the light-shielding portion using a metal such as chromium is formed into a pattern using a photolithography method by forming a thin film of metal, metal oxide, metal nitride, or the like by sputtering or vacuum deposition. be able to. Alternatively, it can be formed using an electroless plating method, a printing method, or the like.

  The thickness of the light shielding portion is about 0.2 μm to 0.4 μm when formed by sputtering or vacuum vapor deposition, and about 0.5 μm to 2 μm when formed by coating or printing. is there.

  In the present embodiment, when the light shielding portion is formed using, for example, a resin containing a black colorant, gas may be generated from the resin or the like. An inorganic barrier layer may be provided on the part. Examples of the inorganic barrier layer include a silicon oxide film and a silicon nitride film that are generally used as an inorganic barrier layer of an organic EL element.

  Here, since the resin containing the black colorant used in the light shielding part may have a light shielding property, sufficient heat treatment can be performed unlike the colored layer. For this reason, a degassing component can be removed at the time of light shielding part formation. Therefore, it is considered that there is a low possibility that gas is generated from the light-shielding part during the heating for producing the color filter substrate for the organic EL element.

  In addition, when the light shielding portion does not have insulating properties, an insulator layer can be provided on the light shielding portion. Thereby, it can prevent that a 1st transparent electrode layer or a 2nd transparent electrode layer and a light shielding part conduct | electrically_connect.

(7) Color Conversion Layer In this embodiment, for example, as shown in FIG. 6, the color conversion layer 7 is formed on the colored layer 2 and between the colored layer 2 and the first transparent electrode layer 3. It may be.

  Like the colored layer, the color conversion layer may decompose the pigment contained in the color conversion layer to generate gas, which may cause dark spots. In this embodiment, the color conversion layer is on the color conversion layer. By providing the first transparent electrode layer and the second transparent electrode layer, barrier properties can be obtained not only for the gas generated from the colored layer but also for the gas generated from the color conversion layer.

  Therefore, when a color conversion layer is provided, as in the case of the colored layer, at least one of the first transparent electrode layer and the second transparent electrode layer is formed in a pattern on the color conversion layer. It is preferably formed so as to cover the entire surface of the formed color conversion layer. If the entire surface of the color conversion layer is covered with at least one of the first transparent electrode layer and the second transparent electrode layer, the outflow of gas generated from the color conversion layer can be more effectively prevented. is there.

  The first transparent electrode layer and the second transparent electrode layer may be formed so as to cover the entire surface of the color conversion layer in which at least one of them is formed in a pattern, but the first transparent electrode layer and the second transparent electrode Both layers are preferably formed so as to cover the entire surface of the color conversion layer. This is because the outflow of gas generated from the colored layer can be more effectively prevented.

  When an inorganic layer is provided, at least one of the inorganic layer, the first transparent electrode layer, and the second transparent electrode layer is formed so as to cover the entire surface of the color conversion layer formed in a pattern. In particular, it is preferable that all of the inorganic layer, the first transparent electrode layer, and the second transparent electrode layer are formed so as to cover the entire surface of the color conversion layer formed in a pattern.

  The color conversion layer used in this embodiment 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 this embodiment, and is visible. It is a layer containing a fluorescent material that emits light region 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 emits fluorescence of three colors of blue, red, and green. When a blue light emitting layer is used, a transparent resin is used instead of the blue color conversion layer. A layer may be formed.

  The color conversion layer usually contains an organic fluorescent dye that absorbs light from the light emitting layer and emits fluorescence, and a matrix resin.

  The fluorescent dye used in the color conversion layer absorbs light in the near ultraviolet region or visible region emitted from the light emitting layer, particularly light in the blue or blue-green region, and emits visible light having different wavelengths as fluorescence. Usually, since a blue light emitting layer is used as the light emitting layer, it is preferable to use at least one fluorescent dye that emits fluorescence in the red region, and it is combined with one or more fluorescent dyes that emit fluorescence in the green region. It is preferable.

  That is, when a light emitting layer that emits light in the blue or blue-green region is used as the light source, if light from the light emitting layer is passed through a simple red colored layer to obtain light in the red region, the wavelength of the red region is originally Because there is little light, it becomes very dark output light. Therefore, by converting the light in the blue or blue-green region from the light emitting layer into the light in the red region by the fluorescent dye, the light in the red region having sufficient intensity can be output.

  On the other hand, the light in the green region may be output by converting the light from the light emitting layer into the light in the green region by another fluorescent dye, similarly to the light in the red region. Alternatively, when the light emission of the light emitting layer sufficiently includes light in the green region, the light from the light emitting layer may be simply output through the green colored layer. Further, regarding the light in the blue region, the light of the light emitting layer may be converted and output using a fluorescent dye, but it is preferable to output the light of the light emitting layer through a simple blue colored layer.

  Examples of fluorescent dyes that absorb light in the blue to blue-green region emitted from the light emitting layer and emit red region fluorescence include rhodamine B, rhodamine 6G, rhodamine 3B, rhodamine 101, rhodamine 110, sulforhodamine, basic violet 11, Rhodamine dyes such as Basic Red 2, cyanine dyes, pyridine dyes such as 1-ethyl-2- [4- (p-dimethylaminophenyl) -1,3-butadienyl] -pyridinium perchlorate (pyridine 1), Or an oxazine pigment | dye etc. are mentioned. 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.

  The fluorescent dye is contained in the color conversion layer in an amount of 0.01 to 5% by weight, more preferably 0.1 to 2% by weight, based on the weight of the color conversion layer. If the fluorescent dye content is too low, sufficient wavelength conversion cannot be performed. On the other hand, if the fluorescent dye content is too high, the color conversion efficiency may decrease due to effects such as concentration quenching. is there.

  In addition, as a matrix resin used for the color conversion layer, photocurable or photothermal combination type curable resin (resist) is subjected to light and / or heat treatment to generate radical species or ionic species to be polymerized or crosslinked, Insoluble and infusible materials can be used, and in order to perform patterning of the color conversion layer, the photocurable or photothermal combination type curable resin is soluble in an organic solvent or an alkali solution in an unexposed state. Is desirable.

  Such a photocurable or photothermal combination type curable resin includes (1) a composition comprising an acrylic polyfunctional monomer and oligomer having a plurality of acroyl groups and methacryloyl groups, and a photo or thermal polymerization initiator, (2) A composition comprising a polyvinylcinnamic acid ester and a sensitizer, (3) a composition comprising a chain or cyclic olefin and bisazide, and (4) a composition comprising a monomer having an epoxy group and an acid generator, etc. Including. In particular, the composition comprising the acrylic polyfunctional monomer and oligomer (1) and photo or thermal polymerization initiator is capable of high-definition patterning and has high reliability such as solvent resistance and heat resistance. To preferred. As described above, the matrix resin is formed by applying light and / or heat to the photocurable or photothermal combination type curable resin.

  The photopolymerization initiator, sensitizer, and acid generator that can be used in the color conversion layer are preferably those that initiate polymerization by light having a wavelength that is not absorbed by the fluorescent dye contained therein. In the color conversion layer, when the resin itself in the photocurable or photothermal combination type curable resin can be polymerized by light or heat, it is possible to add no photopolymerization initiator and thermal polymerization initiator. It is.

  As a method for forming the color conversion layer, a general method for forming a color filter, such as a photolithography method or a vapor deposition method, can be used.

(8) Substrate Next, the substrate used in this embodiment will be described. The substrate used in this embodiment is preferably transparent in order to extract light from the substrate side when an organic EL display device is formed using the color filter substrate for organic EL elements of this embodiment. Moreover, it is preferable that a board | substrate has solvent resistance and heat resistance, and is excellent in dimensional stability. This is because it is possible to stabilize the colored layer, the first transparent electrode layer, the second transparent electrode layer, and the like on the substrate.

  As such a transparent substrate, for example, a glass plate or a film or sheet formed of an organic material can be used.

  In this embodiment, when a glass plate is used as the transparent substrate, it is not particularly limited as long as it is highly transmissive to visible light. For example, an unprocessed glass plate may be used. It may be a processed glass plate or the like. As such a glass plate, both alkali glass and alkali-free glass can be used. However, in this embodiment, when impurities are a problem, for example, alkali-free glass such as Pyrex (registered trademark) glass is used. It is preferable to use glass. In addition, the type of the processed glass plate is appropriately selected according to the use of the color filter substrate for the organic EL element of the present embodiment. And those that have been applied.

  The thickness of such a glass plate is preferably in the range of 20 μm to 2 mm. In particular, when used as a flexible substrate, it is preferably in the range of 20 μm to 200 μm, and when used as a rigid substrate. Is preferably in the range of 200 μm to 2 mm.

  Organic materials used as transparent substrates include polyarylate resin, polycarbonate resin, crystallized polyethylene terephthalate resin, polyethylene terephthalate resin, polyethylene naphthalate resin, UV curable methacrylic resin, polyether sulfone resin, polyether ether ketone. Examples thereof include resins, polyetherimide resins, polyphenylene sulfide resins, polyimide resins and the like.

  Further, as the transparent substrate, for example, the above-described organic material, for example, cyclic polyolefin resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), poly (Meth) acrylic resins, polycarbonate resins, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyamide resins such as various nylons, polyurethane resins, fluorine resins, acetal resins, cellulose resins, polyethers Two or more types can be used in combination with a sulfone resin or the like.

  When a transparent substrate is formed using the organic material as described above, the thickness of the substrate is preferably in the range of 10 μm to 500 μm, more preferably in the range of 50 to 400 μm, and particularly preferably in the range of 100 to 300 μm. . This is because if the thickness of the substrate is too thick, the impact resistance is inferior, the winding becomes difficult at the time of winding, and the barrier property may be deteriorated. Moreover, if the film thickness of the substrate is too thin, the mechanical suitability is poor and the barrier property may be lowered.

  In this embodiment, the substrate is preferably used after being cleaned. As a cleaning method, it is preferable to perform ultraviolet light irradiation treatment using oxygen, ozone, etc., plasma treatment, argon sputtering treatment, or the like. This is because moisture and oxygen are not adsorbed, and dark spots can be reduced and the life of the organic EL element can be extended.

(9) Manufacturing method of color filter substrate for organic EL element Next, an example of the manufacturing method of the color filter substrate for organic EL element of this embodiment is demonstrated.
First, a composite chromium oxynitride film is formed on a substrate by sputtering, for example, and patterned by photolithography to form a black matrix. Further, a colored layer is formed by applying a photosensitive coating for a colored layer on the substrate on which the black matrix is formed by, for example, a spin coating method and patterning by using a photolithography method. Next, an ITO film is formed on the colored layer by, for example, a sputtering method, and a dispersion for forming a conductive layer containing fine particles of an In alloy containing Sn is applied onto the ITO film by a spin coating method and baked. Thus, a conductive film is formed. Furthermore, the first transparent electrode layer and the second transparent electrode layer are formed by simultaneously patterning the ITO film and the conductive film using a photolithography method. Thereby, the color filter substrate for organic EL elements of this embodiment can be produced.

2. Second Embodiment Next, a second embodiment of the color filter substrate for an organic EL element of the present invention will be described.
A second embodiment of the color filter substrate for an organic EL element of the present invention includes a substrate, a colored layer formed in a pattern on the substrate, a first transparent electrode layer formed on the colored layer, A color filter substrate for an organic electroluminescent device having a second transparent electrode layer formed on the first transparent electrode layer, wherein pinholes existing in the first transparent electrode layer are formed on the second transparent electrode layer. Is characterized by being blocked.

  In this embodiment, for example, as shown in FIG. 3A, since the second transparent electrode layer 4 closes the pinhole PH existing in the first transparent electrode layer 3, a colored layer, a color conversion layer, etc. It is possible to obtain a barrier property against the gas generated from the water, water vapor and oxygen. Thereby, when the color filter substrate for organic EL elements of this embodiment is used for an organic EL display device, it is possible to display a good image without dark spots.

  In addition, it can confirm with the scanning electron microscope (SEM) observation photograph that the 2nd transparent electrode layer has block | closed the pinhole which exists in a 1st transparent electrode layer, for example. For example, as shown in FIG. 3A, if the pinhole PH existing in the first transparent electrode layer 3 is closed by the second transparent electrode layer 4, the pinhole PH is considered to be substantially flattened. On the other hand, as shown in FIG. 3B, for example, when the second transparent electrode layer 24 does not block the pinhole PH existing in the first transparent electrode layer 23, the pinhole PH cannot be flattened. . Thus, in the present invention, the state in which the pinhole of the first transparent electrode layer is substantially flattened is referred to as the second transparent electrode layer closing the pinhole.

  In addition, about each structure of the color filter substrate for organic EL elements, since it is the same as that of what was described in the said 1st embodiment, description here is abbreviate | omitted.

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 the organic EL element color filter substrate described above, the organic EL layer formed on the second transparent electrode layer of the organic EL element color filter substrate and including at least a light emitting layer, and the above And a counter electrode layer formed on the organic EL layer.

  According to the present invention, since the above-described color filter substrate for an organic EL element is used, the occurrence of defects such as dark spots can be suppressed, and an organic EL display device capable of good image display can be obtained. Moreover, in the color filter substrate for organic EL elements, since the barrier property is obtained by the first transparent electrode layer and the second transparent electrode layer, it is not necessary to provide a thick transparent barrier layer as in the conventional case, and the cost can be reduced. I can plan.

FIG. 7 shows an example of the organic EL display device of the present invention. As shown in FIG. 7, the organic EL display device of the present invention is formed in a pattern on the above-described color filter substrate 10 for organic EL elements and the second transparent electrode layer 4 of the color filter substrate 10 for organic EL elements. The organic EL layer 11 and the counter electrode layer 12 formed on the organic EL layer 11 are provided. An insulating layer 13 is formed on the second transparent electrode layer 4 and between the organic EL layers 11. The insulating layer 13 is a layer provided to prevent the second transparent electrode layer 4 and the counter electrode layer 12 from contacting each other. Further, a partition wall portion 14 is formed on the insulating layer 13. The portion where the organic EL layer 11 is formed is an image display area.
Hereinafter, each configuration of such an organic EL display device will be described.

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 has a function of emitting light by providing a recombination field of electrons and holes. As the material for forming the light emitting layer, a dye-based light-emitting material, a metal complex-based light-emitting material, or a polymer-based light-emitting material can be generally used.

  Examples of dye-based light emitting materials include cyclopentadiene derivatives, tetraphenylbutadiene derivatives, triphenylamine derivatives, oxadiazole derivatives, pyrazoloquinoline derivatives, distyrylbenzene derivatives, distyrylarylene derivatives, silole derivatives, thiophene ring compounds, pyridine rings Examples thereof include compounds, perinone derivatives, perylene derivatives, oligothiophene derivatives, trifumanylamine derivatives, coumarin derivatives, oxadiazole dimers, pyrazoline dimers, and the like.

Metal complex light emitting materials include aluminum quinolinol complex, benzoquinolinol beryllium complex, benzoxazole zinc complex, benzothiazole zinc complex, azomethyl zinc complex, porphyrin zinc complex, europium complex, iridium metal complex, platinum metal complex, etc. The metal has Al, Zn, Be, Ir, Pt, etc., or a rare earth metal such as Tb, Eu, Dy, etc., and the ligand has an oxadiazole, thiadiazole, phenylpyridine, phenylbenzimidazole, quinoline structure, etc. A metal complex etc. can be mentioned. Specifically, tris (8-quinolinol) aluminum complex (Alq ₃ ) can be used.

  Furthermore, as the polymer light emitting material, polyparaphenylene vinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, polyacetylene derivatives, polyvinylcarbazole, polyfluorenone derivatives, polyfluorene derivatives, polyquinoxaline derivatives, polydialkylfluorene derivatives, And copolymers thereof. Moreover, what polymerized the said pigment-type luminescent material and metal complex type | system | group luminescent material is also mentioned.

  Among the above, the light emitting material used in the present invention is preferably a metal complex light emitting material or a polymer light emitting material, and more preferably a polymer light emitting material. Of the polymer light emitting materials, a conductive polymer having a π-conjugated structure is preferable. Examples of the conductive polymer having such a π-conjugated structure include polyparaphenylene vinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, polyacetylene derivatives, polyfluorenone derivatives, polyfluorene derivatives, polyquinoxaline derivatives as described above. , Polydialkylfluorene derivatives, and copolymers thereof.

  The thickness of the light emitting layer is not particularly limited as long as it can provide a function of emitting light by providing a recombination field between electrons and holes, and can be, for example, about 1 nm to 200 nm. .

  Further, a dopant that emits fluorescence or phosphorescence may be added to the light emitting layer for the purpose of improving the light emission efficiency and changing the light emission wavelength. Examples of such dopants include perylene derivatives, coumarin derivatives, rubrene derivatives, quinacridone derivatives, squalium derivatives, porphyrin derivatives, styryl dyes, tetracene derivatives, pyrazoline derivatives, decacyclene, phenoxazone, quinoxaline derivatives, carbazole derivatives, fluorene derivatives, and the like. Can be mentioned.

  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) Charge injection / transport layer In the present invention, a charge injection / transport layer may be formed between the second transparent electrode layer and the light-emitting layer, or between the light-emitting layer and the counter electrode layer. The charge injection and transport layer here has a function of stably transporting charges from the first transparent electrode layer and the second transparent electrode layer or the counter electrode layer to the light emitting layer. By providing the transport layer between the second transparent electrode layer and the light-emitting layer, or between the light-emitting layer and the counter electrode layer, injection of charges into the light-emitting layer is stabilized, and the light emission efficiency can be increased.

  Examples of the charge injection transport layer include a hole injection transport layer that transports holes injected from the anode into the light emitting layer, and an electron injection transport layer that transports electrons injected from the cathode into the light emitting layer. Hereinafter, the hole injection / transport layer and the electron injection / transport layer will be described.

(I) Hole Injecting and Transporting Layer The hole injecting and transporting layer used in the present invention is either a hole injecting layer for injecting holes into the light emitting layer or a hole transporting layer for transporting holes. The hole injection layer and the hole transport layer may be laminated, or a single layer having both the hole injection function and the hole transport function may be used.

  The material used for the hole injecting and transporting layer is not particularly limited as long as it can stably transport holes injected from the anode into the light emitting layer. In addition to the exemplified compounds, phenylamine, starburst amine, phthalocyanine, vanadium oxide, molybdenum oxide, ruthenium oxide, aluminum oxide and other oxides, amorphous carbon, polyaniline, polythiophene, polyphenylene vinylene derivatives, etc. may be used. it can. Specifically, bis (N- (1-naphthyl-N-phenyl) benzidine (α-NPD), 4,4,4-tris (3-methylphenylphenylamino) triphenylamine (MTDATA), poly 3, 4-ethylenedioxythiophene-polystyrene sulfonic acid (PEDOT-PSS), polyvinyl carbazole (PVCz), etc. are mentioned.

  The thickness of the hole injecting and transporting layer is not particularly limited as long as the hole injecting holes from the anode and transporting the holes to the light emitting layer is sufficiently exhibited. It is preferable to be in the range of 5 nm to 1000 nm, especially in the range of 10 nm to 500 nm.

(Ii) Electron Injection / Transport Layer The electron injection / transport layer used in the present invention may be either an electron injection layer for injecting electrons into the light emitting layer or an electron transport layer for transporting electrons. A layer and an electron transport layer may be laminated, or a single layer having both an electron injection function and an electron transport function may be used.

  The material used for the electron injection layer is not particularly limited as long as the material can stabilize the injection of electrons into the light emitting layer. In addition to the compounds exemplified as the light emitting material of the light emitting layer, Aluminum lithium alloy, lithium fluoride, strontium, magnesium oxide, magnesium fluoride, strontium fluoride, calcium fluoride, barium fluoride, aluminum oxide, strontium oxide, calcium, polymethyl methacrylate, sodium polystyrene sulfonate, lithium, cesium, Alkali metals, alkali metal halides, alkali metal organic complexes, and the like, such as cesium fluoride, can be used.

  In addition, the thickness of the electron injection layer is not particularly limited as long as the electron injection function is sufficiently exerted.

On the other hand, the material used for the electron transport layer is not particularly limited as long as it is a material capable of transporting electrons injected from the first transparent electrode layer and the second transparent electrode layer or the counter electrode layer into the light emitting layer. For example, bathocuproin, bathophenanthroline, phenanthroline derivative, triazole derivative, oxadiazole derivative, or tris (8-quinolinol) aluminum complex (Alq ₃ ) can be used.

  Furthermore, as an electron injecting and transporting layer composed of a single layer having both an electron injecting function and an electron transporting function, a metal doped layer in which an alkali metal or an alkaline earth metal is doped on an electron transporting organic material is formed. This can be used as an electron injecting and transporting layer. Examples of the electron-transporting organic material include bathocuproin, bathophenanthroline, and phenanthroline derivatives. Examples of the metal to be doped include Li, Cs, Ba, and Sr.

2. Next, the counter electrode layer used in the present invention will be described. The counter electrode layer is an electrode facing the first transparent electrode layer and the second transparent electrode layer, and generally a metal is used. Specifically, magnesium alloy (MgAg etc.), aluminum alloy (AlLi, AlCa, AlMg etc.), aluminum, alkaline earth metal (Ca etc.), alkali metal (K, Li etc.), etc. are mentioned.

  The counter electrode layer can be formed using a general electrode layer forming method, and examples thereof include a sputtering method and a vacuum deposition method.

3. Insulating Layer In the present invention, for example, as shown in FIG. 7, an insulating layer 13 may be formed between the organic EL layers 11. This insulating layer is formed in a pattern as a non-display area.

  Examples of the material for forming the insulating layer used in the present invention include a photocurable resin such as an ultraviolet curable resin, a thermosetting resin, and the like. Such an insulating layer can be formed using a resin composition containing the above resin. As a patterning method, a general method such as a photolithography method or a printing method can be 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 (Sn surface polished product manufactured by Central Glass Co., Ltd.) having a thickness of 370 mm × 470 mm and a thickness of 0.7 mm was prepared. After cleaning this transparent substrate according to a regular method, a thin film (thickness 0.2 μm) of oxynitride composite chromium is formed by sputtering on the entire surface of one side of the transparent substrate, and a photosensitive resist is applied on the thin film of composite oxynitride chrome nitride, Mask exposure, development, and etching of the composite chromium oxynitride thin film were performed to form a black matrix having rectangular openings of 84 μm × 284 μm in a matrix at a pitch of 100 μm.

(Formation of colored layer)
A photosensitive coating composition for forming colored layers of three colors of red, green and blue was prepared. As a red colorant, a condensed azo dye (Chromophthalred BRN manufactured by Ciba Geigy), as a green colorant, a phthalocyanine green pigment (Lionol Green 2Y-301 manufactured by Toyo Ink Co., Ltd.), and as a blue colorant Each anthraquinone pigment (Chromophthal Blue A3R manufactured by Ciba Geigy) was used, polyvinyl alcohol (10% aqueous solution) was used as the binder resin, and 1 part of each colorant was added to 10 parts of the polyvinyl alcohol aqueous solution (all parts in all). (Based on mass), and sufficiently mixed and dispersed. To 100 parts of the resulting solution, 1 part of ammonium dichromate is added as a cross-linking agent, and a photosensitive coating composition for forming colored layers of each color. Got.

  A colored layer of each color was formed using the above-described photosensitive coating composition for forming each colored layer sequentially. That is, a photosensitive coating composition for forming a red colored layer was applied to the transparent substrate on which the black matrix was formed by spin coating, and prebaked at 100 ° C. for 5 minutes. Then, it exposed using the photomask and developed with the developing solution (0.05% KOH aqueous solution). Next, post-baking is performed at 200 ° C. for 60 minutes to synchronize the opening with the black matrix pattern, and a band-shaped red colored layer having a width of 85 μm and a thickness of 1.5 μm is formed. It was formed so as to be in the short side direction. Thereafter, a photosensitive coating composition for forming a green colored layer and a photosensitive coating composition for forming a blue colored layer are sequentially used to form a green colored layer and a blue colored layer, thereby forming a three-color pattern. A colored layer in which the colored layers were repeatedly arranged in the width direction was formed.

(Formation of barrier layer)
Furthermore, a SiON thin film having a thickness of 300 nm was formed by a sputtering method so as to cover the entire colored layer, thereby forming a barrier layer.

(Formation of first transparent electrode layer)
An ITO film having a thickness of 150 nm was formed on the barrier layer by sputtering.

(Formation of second transparent electrode layer)
An In alloy fine particle containing 5% of Sn was dispersed in n-butyl acetate so as to have a concentration of 5% by weight to prepare a dispersion for forming a conductive layer. The conductive layer forming dispersion is applied by spin coating on the ITO film, and then baked at 250 ° C. for 10 minutes in an atmospheric pressure oxygen gas atmosphere (oxygen gas concentration: 100 vol%). Thus, a conductive film having a thickness of 150 nm was formed. This conductive film was a transparent and uniform film. In addition, it was confirmed that the defects (pinholes) generated when the ITO film was formed were covered with the conductive film and the defects were corrected.

(Patterning of first transparent electrode layer and second transparent electrode layer)
A photosensitive resist is applied to the ITO film and the conductive film, mask exposure, development, etching of the ITO film and the conductive film are performed, and the first transparent electrode layer and the second transparent electrode layer are patterned (width 100 μm). , Space 20 μm).

(Formation of insulating layer and partition wall)
Using a coating solution for an insulating layer obtained by diluting norbornene-based resin (ARTON manufactured by JSR) having an average molecular weight of about 100,000 with toluene, the first transparent electrode layer and the second transparent electrode layer are covered by a spin coating method. 2 After coating on the transparent electrode layer, 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 is a stripe pattern (width 20 μm) that intersects the first transparent electrode layer at a right angle, and is located on the black matrix.

  Next, the partition wall coating material (photoresist ZPN1100 manufactured by Nippon Zeon Co., Ltd.) 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 partition wall photomask, developed with the developing solution (ZTMA-100 by Nippon Zeon Co., Ltd.), and 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)
Using the partition wall as a mask, 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.

  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. The partition wall becomes a mask pattern by depositing the film to a thickness and then depositing 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl to a thickness of 20 nm. The hole injection layer material passed only between the partition walls, and a hole injection layer was formed on the second transparent electrode layer. Similarly, 4,4′-bis (2,2-diphenylvinyl) biphenyl was deposited to a thickness of 50 nm to form a blue light emitting layer. Thereafter, tris (8-quinolinol) aluminum was deposited to a thickness of 20 nm to form a film, thereby forming an electron injection layer. The organic EL layer thus formed is present between the partition walls as a strip pattern having a width of 280 μm, and a dummy organic EL layer having a similar layer structure was formed on the upper surface of the partition wall.

(Formation of counter electrode layer)
Next, aluminum is vapor-deposited on the region where the partition wall is formed through a photomask having a predetermined opening wider than the image display region (aluminum vapor deposition rate = 1.3). (About 1.4 nm / second). Thus, the counter electrode layer (back electrode layer, thickness 200 nm) made of aluminum was formed on the organic EL element layer using the partition wall as a mask. This counter electrode layer was formed on the organic EL layer as a belt-like 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. Moreover, the organic EL element was sealed to obtain an organic EL display device.

[Example 2]
In the same manner as in Example 1, a black matrix, a colored layer, and a barrier layer were formed on a transparent substrate.

(Formation of first transparent electrode layer)
An ITO film having a thickness of 150 nm was formed on the barrier layer by sputtering. Further, a photosensitive resist was applied on the ITO film, mask exposure, development, and etching were performed to form a first transparent electrode layer in a pattern (width 100 μm, space 20 μm).

(Formation of second transparent electrode layer)
A dispersion liquid for forming a conductive metal layer was prepared by dispersing Ag fine particles in n-butyl acetate so as to have a concentration of 1%. This conductive metal layer forming dispersion was applied by spin coating on the ITO film and dried. Next, an Ag film having a thickness of 5 nm was formed by baking at 250 ° C. for 10 minutes in the atmosphere to obtain a conductive metal film. This conductive metal film was a transparent and uniform film. In addition, it was confirmed that the defects (pinholes) generated when the first transparent electrode layer was formed were covered with the conductive metal film and the defects were corrected.

  Further, a photosensitive resist was applied on the conductive metal film, mask exposure, development, and etching were performed to form a second transparent electrode layer in a pattern (width 100 μm, space 20 μm).

(Production of organic EL element)
Next, in the same manner as in Example 1, an insulating layer, a partition wall, an organic EL layer, and a counter electrode layer were formed to obtain an organic EL element. Moreover, the organic EL element was sealed to obtain an organic EL display device.

[Example 3]
In the same manner as in Example 1, a black matrix and a colored layer were formed on a transparent substrate.

(Formation of inorganic layer)
An In alloy fine particle containing 5% of Sn was dispersed in n-butyl acetate so as to have a concentration of 5% by weight to prepare a dispersion for forming a conductive layer. The dispersion for forming a conductive layer was applied by spin coating on the colored layer, and then baked at 250 ° C. for 10 minutes in an atmospheric pressure oxygen gas atmosphere (oxygen gas concentration: 100 vol%). Thus, a conductive film having a thickness of 150 nm was formed. This conductive film was a transparent and uniform film.

(Formation of first transparent electrode layer)
An ITO film having a thickness of 150 nm was formed on the inorganic layer by sputtering.

(Formation of second transparent electrode layer)
The conductive layer forming dispersion used in the formation of the inorganic layer is applied by spin coating on the ITO film, and then an atmospheric pressure oxygen gas atmosphere (oxygen gas concentration: 100% by volume) The film was baked at 250 ° C. for 10 minutes to form a conductive film having a thickness of 150 nm. This conductive film was a transparent and uniform film. In addition, it was confirmed that the defects (pinholes) generated when the ITO film was formed were covered with the conductive film and the defects were corrected.

(Patterning of inorganic layer, first transparent electrode layer and second transparent electrode layer)
A photosensitive resist is applied to the laminated film in which the conductive film, the ITO film, and the conductive film are laminated, mask exposure, development, etching of the ITO film and the conductive film is performed, and the inorganic layer, the first transparent electrode The layer and the second transparent electrode layer were formed in a pattern (width 100 μm, space 20 μm).

(Production of organic EL element)
Next, in the same manner as in Example 1, an insulating layer, a partition wall, an organic EL layer, and a counter electrode layer were formed to obtain an organic EL element. Moreover, the organic EL element was sealed to obtain an organic EL display device.

[Example 4]
In the same manner as in Example 1, a black matrix and a colored layer were formed on a transparent substrate.

(Formation of color conversion layer)
A coating liquid for forming a blue color conversion layer (dummy layer) is formed on the black matrix and the colored layer (transparent photosensitive resin composition trade name; “Color Mosaic CB-701” manufactured by Fuji Hunt Electronics Technology Co., Ltd.). It apply | coated by the spin coat method and prebaked for 5 minutes at 100 degreeC. Next, after patterning by photolithography, post-baking was performed at 200 ° C. for 60 minutes. Thereby, a band-like blue conversion layer (dummy layer) having a width of 85 μm and a thickness of 10 μm was formed on the blue colored layer.

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

(Formation of hard coat layer)
Next, after the color conversion layer is formed, a hard coat layer is formed by diluting an acrylate-based thermosetting resin (product name of Nippon Steel Chemical Co., Ltd .; “V-259PA / PH5”) with propylene glycol monomethyl ether acetate. The coating solution is applied by spin coating, and pre-baked at 120 ° C. for 5 minutes. Then, the whole surface is exposed to an irradiation dose of 300 mJ with ultraviolet rays. After the exposure, post-baking is performed at 200 ° C. for 60 minutes. And a transparent hard coat layer having a thickness of 5 μm was formed so as to cover the entire color conversion layer.

(Production of organic EL element)
Next, a barrier layer, a first transparent electrode layer, a second transparent electrode layer, an insulating layer, a partition wall, an organic EL layer and a counter electrode layer are formed on the hard coat layer in the same manner as in Example 1. Thus, an organic EL element was obtained. Moreover, the organic EL element was sealed to obtain an organic EL display device.

[Comparative Example 1]
In Example 1, the organic EL element was produced like Example 1 except not having formed the 2nd transparent electrode layer. Moreover, the organic EL element was sealed to obtain an organic EL display device.

[Comparative Example 2]
In Example 4, the organic EL element was produced like Example 1 except not having formed the 2nd transparent electrode layer. Moreover, the organic EL element was sealed to obtain an organic EL display device.

[Evaluation]
A voltage of DC 8.5 V is applied to the first transparent electrode layer and the counter electrode layer of the organic EL display devices of Examples 1 to 4 and Comparative Examples 1 and ^{2 at} a constant current density of 10 mA / cm ² to drive continuously. Thus, the blue light-emitting layer at a desired portion where the first transparent electrode layer and the counter electrode layer intersect was caused to emit light. The light emitting area of this organic EL display device is 6 mm □, and the organic EL display device was subjected to a storage test at a temperature of 85 ° C. and a relative humidity of 60%. ) Evaluation was made by observation.
As a result, dark spots were generated in the organic EL display device of Comparative Example 1. Further, pixel reduction was observed in the organic EL display device of Comparative Example 2. On the other hand, in the organic EL display devices of Examples 1 to 4, generation of dark spots was not recognized, and excellent durable display characteristics were shown. In addition, in the organic EL display devices of Examples 1 to 3, no pixel reduction was 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 explanatory drawing for demonstrating a 2nd transparent electrode layer. 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 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 ... Substrate 2 ... Colored layer 3 ... 1st transparent electrode layer 4 ... 2nd transparent electrode layer 5 ... Inorganic layer 6 ... Light-shielding part 7 ... Color conversion layer 10 ... Color filter substrate for organic EL elements 11 ... Organic EL layer 12 ... Counter electrode layer 13 ... Insulating layer 14 ... Partition wall PH ... Pinhole

Claims (15)

  A substrate, a colored layer formed in a pattern on the substrate, a first transparent electrode layer formed on the colored layer, and a second transparent layer formed on the first transparent electrode layer and having a barrier property A color filter substrate for an organic electroluminescent element, comprising: an electrode layer, wherein the second transparent electrode layer is a coating film.   A substrate, a colored layer formed in a pattern on the substrate, a first transparent electrode layer formed on the colored layer, and a second transparent electrode layer formed on the first transparent electrode layer A color filter substrate for an organic electroluminescent element, wherein the second transparent electrode layer closes a pinhole existing in the first transparent electrode layer. Color filter substrate.   3. At least one of the first transparent electrode layer and the second transparent electrode layer is formed so as to cover the entire surface of the colored layer formed in a pattern. The color filter substrate for organic electroluminescent elements described in 1.   The color filter for organic electroluminescent elements according to claim 1 or 2, wherein an inorganic layer having a barrier property is formed between the colored layer and the first transparent electrode layer. substrate.   5. The at least one of the first transparent electrode layer, the second transparent electrode layer, and the inorganic layer is formed so as to cover the entire surface of the colored layer formed in a pattern. The color filter substrate for organic electroluminescent elements described in 1.   6. The color filter substrate for an organic electroluminescent element according to claim 4, wherein an average surface roughness (Ra) of the second transparent electrode layer is in a range of 10 to 100 mm.   The said inorganic layer has electroconductivity, The color filter substrate for organic electroluminescent elements of any one of Claim 4-6 characterized by the above-mentioned.   8. The organic electroluminescent device according to claim 4, wherein the inorganic layer contains fine particles having an average particle diameter in the range of 1 nm to 10 nm. Color filter substrate.   The organic electroluminescence according to any one of claims 1 to 8, wherein the second transparent electrode layer contains fine particles having an average particle diameter in the range of 1 nm to 10 nm. Color filter substrate for cent element.   The color filter substrate for an organic electroluminescent element according to claim 8, wherein the fine particles are fine particles of indium tin oxide (ITO).   The said fine particle is at least 1 sort (s) of fine particle selected from the group which consists of Au, Ag, Cu, Pt, Sn, Zn, In, Pb, Al, and those oxides, The claim 8 or Claim characterized by the above-mentioned. Item 10. A color filter substrate for an organic electroluminescent device according to Item 9.   The color filter substrate for an organic electroluminescent element according to any one of claims 1 to 11, wherein a light-shielding portion is formed on the substrate and between the colored layers. .   The color filter substrate for an organic electroluminescent element according to claim 12, wherein the light shielding part has an insulating property.   14. A color conversion layer is formed on the colored layer and between the colored layer and the first transparent electrode layer, wherein the color conversion layer is formed. The color filter substrate for organic electroluminescent elements described in 1. It forms on the 2nd transparent electrode layer of the color filter board | substrate for organic electroluminescent elements in any one of Claim 1-14, and the said color filter board | substrate for organic electroluminescent elements. An organic electroluminescent display device comprising: an organic electroluminescent layer including at least a light emitting layer; and a counter electrode layer formed on the organic electroluminescent layer.

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