Organic EL display device and its manufacturing method

Abstract

The purpose of this invention is to provide an organic EL display device that can be manufactured using a simple method, comprising a pixel segmentation layer and spacers, which is a highly reliable flexible display device and can suppress external light reflection, as well as a method for manufacturing the same. The present invention provides an organic EL display device, which comprises a substrate having a first electrode, a pixel segmentation layer, and a spacer on a substrate, and further comprising an organic EL layer and a second electrode. The maximum value of the surface roughness (Ra1) of the pixel segmentation layer and the surface roughness (Ra2) of the spacer is set as Ramax, wherein Ramax is 1.0 nm or more and 50 nm or less.

Description

Technical Field

[0001] This invention relates to an organic EL display device having a complex number of display pixels arranged in a matrix and a method for manufacturing the same. Prior Technology

[0002] Organic EL (OLED) displays have garnered significant attention as the next generation of flat panel displays. Organic EL refers to the electroluminescence of an organic EL layer composed of organic compounds disposed between two electrodes. Therefore, a display device utilizing the light-emitting element of an organic EL is called an organic EL display device. Self-emissive organic EL displays can achieve wide viewing angles, high-speed response, and high-contrast image display. By using substrates such as thin glass or plastic resin, they can achieve thinness, lightness, and flexibility, hence their research and development have flourished in recent years. Flexible organic EL displays are expected to be applied in various fields, including bendable (flexible without breaking), rollable (rollable), and foldable (foldable).

[0003] However, such flexible organic EL display devices may experience delamination between the substrate and the organic EL layer due to manufacturing steps or usage methods such as bending or folding, resulting in reduced reliability of the organic EL display device (see, for example, Patent Document 1).

[0004] On the other hand, as a mobile device, the display device must also maintain display quality in various environments, both indoors and outdoors. In particular, in terms of suppressing external light reflection, there have been proposals for combinations with circular polarizers or blackening of the substrate (for example, see Patent Document 2). [Previous Technical Documents] [Patent Literature]

[0005] Patent Document 1: Japanese Patent Application Publication No. 2020-87935 Patent Document 2: Japanese Patent Application Publication No. 2004-281365 Summary of the Invention

[0006] (The problem the invention aims to solve)

[0007] However, the organic EL display device described in Patent Document 1, which aims to suppress peeling due to flexibility, has difficulties in setting materials or manufacturing conditions due to the characteristics of the spacer shape. This leads to problems such as the inability to process the pixel separation layer and the spacer together, resulting in reduced panel yield or significantly increased costs.

[0008] Furthermore, in the organic EL display device described in Patent Document 2, which blackens the first electrode or pixel segmentation layer for the purpose of suppressing external light reflection, although the suppression of external light reflection due to coloring can be expected to be somewhat achieved, the smoothness of the reflective surface still makes the suppression of external light reflection insufficient.

[0009] Therefore, the object of the present invention is to provide an organic EL display device comprising a pixel segmentation layer and spacers that can be manufactured by a simple method, which is a highly reliable organic EL display device as a flexible display device and can suppress external light reflection, and a method thereof. (Technical means to solve the problem)

[0010] The organic EL display device of the present invention comprises: a substrate having a first electrode, a pixel segmentation layer, and a spacer on a substrate; further comprising an organic EL layer and a second electrode, wherein, when the maximum value of the surface roughness (Ra1) of the pixel segmentation layer and the surface roughness (Ra2) of the spacer is set as Ramax, Ramax is 1.0 nm or more and 50 nm or less.

[0011] Furthermore, the manufacturing method of the organic EL display device of the present invention comprises: a substrate having a first electrode, a pixel dividing layer, and spacers on a substrate; and further comprising an organic EL layer and a second electrode; the manufacturing method of the organic EL display device includes a step of co-processing the pixel dividing layer and the spacers, and the photomask used for co-processing is a halftone photomask having a light-transmitting portion, a light-shielding portion, and a semi-light-transmitting portion. (Compared to the effectiveness of previous technologies)

[0012] The organic EL display device of the present invention can be manufactured in a simple manner, comprising a pixel dividing layer and spacers. The organic EL layer is not peeled off, and external light reflection can be suppressed by increasing the diffusion and reflection of light on the substrate. Simple Explanation of the Diagram

[0013] Figure 1 is a schematic cross-sectional view of the organic EL display device of the present invention. Figure 2 is a schematic cross-sectional view of a substrate according to an example of the present invention. Figure 3 is a schematic cross-sectional view of Ra1 and Ra2 of the present invention. Figure 4 is a schematic diagram of the push-out angle of the pixel segmentation layer of the present invention. Figure 5 is a schematic cross-sectional view of a typical organic EL display device. Figure 6 is a schematic diagram of the first electrode and halftone mask in an embodiment of the present invention. Figure 7 is a schematic diagram of the bending test of an embodiment of the present invention. Figure 8 is a schematic diagram of an organic EL display device according to an embodiment of the present invention. Figure 9 is a schematic diagram of the light-emitting element according to an embodiment of the present invention. Implementation

[0014] The following details the embodiments used to carry out the present invention (hereinafter referred to as "embodiments"). However, the present invention is not limited to the embodiments described below.

[0015] Organic EL Display Device The organic EL display device of the present invention has a plurality of display pixels formed in a matrix. Depending on the light emission direction of the organic EL layer, it can be broadly classified as top-emitting or bottom-emitting, without particular limitation. Furthermore, depending on the driving method, it can be broadly classified as a passive driving type, in which electrodes are divided into rows and columns and only the display pixels held by the electrodes emit light, and an active driving type, in which several TFTs are disposed on each display pixel and switched between them; other types are not particularly limited.

[0016] The organic EL display device of the present invention comprises: a substrate having a first electrode, a pixel segmentation layer, and a spacer on a substrate; further comprising an organic EL layer and a second electrode, wherein when the maximum value of the surface roughness (Ra1) of the pixel segmentation layer and the surface roughness (Ra2) of the spacer is set to Ramax, Ramax is 1.0 nm or more and 50 nm or less.

[0017] Figure 1 shows a schematic cross-sectional view of an organic EL display device according to an example of the present invention. In the organic EL display device, a first electrode 2 is provided on a substrate 1. On the substrate 1, a pixel separation layer 3 is provided in the region where the first electrode 2 is not present (hereinafter, the region on the substrate 1 where the first electrode 2 is not present is sometimes referred to as the gap of the first electrode), and further, spacers 4 are provided on the pixel separation layer. In the organic EL display device, this unit having a first electrode, a pixel separation layer, and spacers on a substrate is referred to as a substrate. Furthermore, an organic EL layer 5 and a second electrode 6 are provided on this substrate to form an organic EL display device.

[0018] <Substrate> In the organic EL display device of the present invention, the substrate is defined as a minimum unit comprising only the substrate 1 (described later), the first electrode 2, the pixel separation layer 3, and the spacer 4. If such a minimum unit is present, the substrate may also be further configured with wiring or TFTs 7, patterned antennas, and a planarization layer 8 (for example, the configuration shown in FIG. 2). In the present invention, all of the aforementioned wiring or TFTs 7, sensors, patterned antennas, and planarization layer 8 that form the substrate of the first electrode 2 are considered as part of the substrate 1.

[0019] Most of the wiring is connected to external machines via FPC (Flexible Printed Circuit) for driving purposes. Furthermore, besides TFT7, it can also include sensors such as cameras, ID or fingerprint readers, or illumination sensors, as well as patterned antennas for communication or power supply. In the substrate 1 integrating such multiple functions, a planarization layer 8 is preferably provided. By providing the planarization layer 8, the unevenness of the wiring or TFT7 is covered before the formation of the first electrode 2, thus planarizing the substrate 1. By planarizing the substrate 1, defects in the first electrode 2, pixel separation layer 3, and spacers 4 provided on the substrate can be prevented, resulting in a high-quality substrate. Figure 2 shows a schematic cross-sectional view of a substrate according to an example of the present invention.

[0020] <Substrate> In both Figure 1 and Figure 2, the substrate 1a, which is the substrate below the TFT7, can be appropriately selected from materials such as metal, glass, or resin film, which are suitable for supporting the display device or transporting it in subsequent steps. Especially when flexibility is required, resin film is preferred.

[0021] As the glass material, soda-lime glass or alkali-free glass can be used. The glass thickness should be sufficient to maintain mechanical strength. Regarding the glass material, it is preferable to have fewer dissolved ions from the glass, so alkali-free glass is preferred, but soda-lime glass with a shielding coating such as SiO2 can also be used.

[0022] For the purpose of superior light transmittance, the material of the resin film is preferably a resin material selected from polybenzoxazole resin, polyamide-imide resin, polyamide resin, polyamide resin, and parylene resin. The substrate may contain only these resin materials or a combination of several of them.

[0023] For example, in the case of forming a substrate using polyimide resin, a solution containing polyamide (including a portion of polyamide-modified polyamide) or soluble polyimide, which are precursors of polyimide resin, can be coated onto a support substrate and then fired to form the substrate.

[0024] Furthermore, since the aforementioned light-emitting elements are known to be relatively weak to oxygen or moisture, a barrier layer can also be appropriately incorporated into the substrate. Especially in the case of resin films, by using inorganic films in a laminate, a display device with high reliability can be obtained. Moreover, the substrate can also be one with wiring, TFTs (7), planarization layers (8), etc.

[0025] <First Electrode> In the case of bottom-emitting type, the first electrode 2 of the present invention must be a light-transmitting electrode, and in the case of top-emitting type, it must be a light-reflecting electrode.

[0026] For bottom-emitting types, conductive metal oxides such as transparent tin oxide, indium oxide, and indium tin oxide (ITO) can be used, or metals such as gold, silver, and chromium, inorganic conductive materials such as copper iodide and copper sulfide, and conductive polymers such as polythiophene, polypyrrole, and polyaniline, etc., without any particular limitation.

[0027] For top-emitting types, materials with high reflectivity for visible light and low resistivity above a certain film thickness are preferred. Furthermore, the material selection must also consider factors such as wet etching or cleaning, storage, and weather resistance under operating conditions. Ag or Ag-containing alloy films, especially, are useful due to their high reflectivity. Ag alloy films can use AgPdCu or AgTiCu, with Ag as the main component. When these Ag alloy films are laminated with oxide conductive films such as ITO or IZO, they are preferred because they achieve low contact resistance with the organic EL layer. Al or Al alloy films containing Al are also good as the first electrode for top-emitting types. Al-Ni alloy films containing 0.1~2 atomic% Ni are preferred because they have the same high reflectivity as pure Al. Other reflective metal films such as molybdenum (Mo) or tungsten (W) can also be used.

[0028] The resistance of the first electrode is not particularly limited as long as it can supply sufficient current for the light-emitting element to emit light. However, from the perspective of the power consumption of the light-emitting element, a low resistance is preferable. For example, ITO with a resistance of 300 Ω / □ or less can function as an electrode for the element. Currently, ITO with a resistance of around 10 Ω / □ can also be supplied, so it is particularly preferable to use a low-resistance material. The thickness of the first electrode can be arbitrarily selected according to characteristics such as transmittance or resistance value, and is usually used in the range of 100~300 nm.

[0029] The first electrode can be formed using known methods. For example, after forming a film using a vacuum film deposition method such as sputtering, patterning can be performed by etching using a photoresist.

[0030] <Pixel Split Layer> In the organic EL display device of the present invention, the pixel segmentation layer 3 is formed in the gap of the first electrode 2. By forming the pixel segmentation layer in the gap of the first electrode, display pixels can be segmented. That is, by patterning the pixel segmentation layer in the gap of the first electrode, the exposed portion of the first electrode is limited, so that only the opening of the pixel segmentation layer functions as a display pixel. Furthermore, by covering the periphery of the linear or island-shaped first electrode with the pixel segmentation layer, it also helps to prevent short circuits occurring at the edge of the first electrode or breakage of the second electrode, thereby improving the reliability of the display device. In addition, in the organic EL display device of the present invention, the pixel segmentation layer can also be formed outside the gap of the first electrode as needed.

[0031] In this invention, when the maximum value of the surface roughness (Ra1) of the pixel segmentation layer and the surface roughness (Ra2) of the spacer is set to Ramax, Ramax is 1.0 nm or more and 50 nm or less. More preferably, the surface roughness (Ra1) of the pixel segmentation layer is Ramax. Alternatively, both the surface roughness (Ra1) of the pixel segmentation layer and the surface roughness (Ra2) of the spacer can be Ramax.

[0032] Furthermore, in this invention, the atomic force microscope (AFM) used to measure the surface roughness is generally used from a vertical position relative to the substrate of the organic EL display device placed on a horizontal plane. Figure 3 shows the target ranges of Ra1 and Ra2. Therefore, in this invention, the so-called "surface roughness of the pixel segmentation layer" refers to the surface of the pixel segmentation layer that is in contact with the organic EL layer, which can be measured by AFM, that is, the surface roughness of the surface that is slightly parallel to the substrate.

[0033] Furthermore, since spacers are formed on the pixel segmentation layer, the portion without spacers becomes the interface with the organic EL layer. Conventionally, due to poor adhesion between the pixel segmentation layer and the organic EL layer, peeling is prone to occur, which is a significant issue, especially for flexible products. In this invention, by setting the surface roughness (Ra1) of the pixel segmentation layer to 1.0 nm or more, an anchoring effect can be obtained; preferably, it is 5.0 nm or more, and more preferably 20 nm or more, which improves the adhesion between the pixel segmentation layer and the organic EL layer.

[0034] Furthermore, regarding the surface roughness (Ra1) of the pixel separation layer, an anchoring effect can be achieved if it is 1.0 nm or greater. However, for the purpose of suppressing pinholes in the second electrode or defects in the sealing process described later, it is preferable to set it to 50 nm or less. Moreover, when improving adhesion by increasing Ra1, it is effective to ensure that the interface between the pixel separation layer and the organic EL layer is as large as possible. When Ra1 is greater than the surface roughness Ra2 of the spacer described later, i.e., Ra1 becomes Ramax, the area of ​​the interface between the substrate and the organic EL layer should preferably be 50% or more. This means that the pixel separation layer is 50% or more of the substrate surface area.

[0035] Furthermore, since the edge shape of the pixel segmentation layer can cause breakage in the second electrode, a gentle conical shape is preferred. Here, a conical shape refers to a state where the angle formed by the connection between the interface of the first electrode and the pixel segmentation layer, and the connection between the interface and the point on the surface of the pulled-out portion of the pixel segmentation layer where the film thickness is 50% of the maximum thickness of the pixel segmentation layer (hereinafter, this angle is sometimes referred to as the pull-out angle of the pixel segmentation layer) is less than 90 degrees. In this invention, to obtain a highly reliable display device that suppresses breakage in the second electrode, the pull-out angle of the pixel segmentation layer is preferably less than 60 degrees, and more preferably less than 50 degrees.

[0036] Figure 4 illustrates the pull-out angle of the pixel segmentation layer. In Figure 4, a first electrode 2 is provided on a substrate 1. A pixel segmentation layer 3 is provided in the gap of the first electrode 2, and a spacer 4 is further provided on the pixel segmentation layer. The angle (B) formed by the connection between the interface between the first electrode and the pixel segmentation layer and the point (point A) on the surface of the pulled-out portion of the pixel segmentation layer, where the film thickness is 50% of the maximum thickness of the pixel segmentation layer, is defined as the pull-out angle of the pixel segmentation layer.

[0037] The pixel separation layer is not limited to any known organic or inorganic material. From the viewpoint of easily adjusting surface roughness, the pixel separation layer is preferably a hardened film containing a photosensitive resin composition comprising an alkali-soluble resin. The pixel separation layer can be a single layer or multiple layers. For example, when the pixel separation layer is multiple layers, it is preferable that the surface slightly parallel to the substrate, which is the object of surface roughness measurement, is a hardened film containing a photosensitive resin composition comprising an alkali-soluble resin.

[0038] The photosensitive resin composition preferably contains (A) an alkali-soluble resin, (B) a photosensitizer, and (C) an organic solvent, and may further contain (D) a coloring material or (E) a repellent material. By combining an alkali-soluble resin containing (A) and a photosensitizer as the photosensitive resin composition, pattern processing utilizing photosensitivity can be performed. Furthermore, by containing (C) an organic solvent, a varnish-like state can be achieved, which can sometimes improve coatability. Moreover, by containing (D) a coloring material in the photosensitive resin composition, the pixel separation layer can be blackened. Furthermore, by containing (E) a repellent material, the pixel separation layer can be given repellency. By utilizing the differences in exposure sensitivity or dissolution rate between these (D) coloring materials or (E) repellent materials and (A) alkali-soluble resins, and through the step of using the halftone mask described later, the surface roughness of the pixel separation layer and the spacers can be increased, and the surface roughness of the pixel separation layer and the spacers can be adjusted separately, which is superior. The photosensitive resin composition may also further contain other components.

[0039] The pixel separation layer can be formed using known methods. Among these, wet coating is preferred because it allows for the uniform formation of a thin film on a large-size substrate. Examples of wet coating methods include spin coating, slot coating, dip coating, spray coating, and printing.

[0040] The thickness of the pixel segmentation layer is typically 0.3μm to 10μm, but there is no particular limitation as long as it is sufficient to cover the unevenness of the first electrode. Furthermore, the pixel segmentation layer must undergo patterning, and residue from the removal process can directly cause defects such as open circuits or black spots. Moreover, in order to support the structures on the covered second electrode in subsequent steps and ensure the strength of the display device, spacers must be fabricated on the pixel segmentation layer.

[0041] <(A) Alkali-soluble resin> The alkali solubility in this invention refers to the process of coating a silicon wafer with a solution of resin dissolved in γ-butyrolactone (GBL), pre-baking it at 120°C for 4 minutes to form a pre-baked film with a thickness of 10 μm ± 0.5 μm, immersing the pre-baked film in a 2.38 wt% tetramethylammonium hydroxide aqueous solution at 23°C ± 1°C for 1 minute, and then rinsing it with pure water. The resulting reduction in film thickness indicates a dissolution rate of 50 nm / min or higher.

[0042] (A) From the viewpoint of improving heat resistance, alkali-soluble resins are preferably those with an aromatic carboxylic acid structure. Furthermore, in this invention, the term "aromatic carboxylic acid structure" refers to a carboxylic acid structure that is directly covalently bonded to an aromatic ring.

[0043] As (A) alkali-soluble resin, it is preferably one or more of the group consisting of acrylic resins, phenolic resins, polysiloxane resins, cardo resins, polyimide resins, polyimide precursor resins, polybenzoxazole resins, and polybenzoxazole precursor resins.

[0044] Among these resins, considering both heat resistance and chemical resistance, (A) alkali-soluble resins are preferably those containing polyimide resins, polyimide precursor resins, polybenzoxazole resins, and / or polybenzoxazole precursor resins. High chemical resistance is preferable because the film reduction during wet etching of the pixel separation layer is smaller. Furthermore, polyimide precursor resins are particularly preferred due to low gas escape rates under high-temperature conditions. Moreover, from the viewpoint of improved alkali solubility, polyimide precursor resins with an amino acid structure are even more preferred.

[0045] <Silicon dioxide particles in the pixel segmentation layer> The pixel segmentation layer in the organic EL display device of the present invention preferably contains (a) silicon dioxide particles with a primary particle size of 5-30 nm (hereinafter sometimes referred to as component (a)). In addition to component (a), the pixel segmentation layer further preferably contains a (D) coloring material as described later. In this case, the (D) coloring material preferably contains an (D1) organic pigment, and even more preferably contains component (b) as the (D1) organic pigment as described later. Furthermore, component (a) preferably has a primary particle size of 5-30 nm and an aspect ratio (major axis / minor axis) of 1.0-1.5. By containing this component (a), the uniformity of the aperture width of the opening can be improved, thereby reducing brightness unevenness. Here, primary particle size refers to the major axis of the particle, and silicon dioxide particles with a primary particle size of 5-30 nm refer to those with a primary particle size in the range of 5-30 nm. The so-called "aspect ratio (major diameter / minor diameter)" refers to the value of the major diameter divided by the minor diameter in the primary diameter of silicon dioxide particles, rounded to the second decimal place.

[0046] The term "silica particles" here refers to particles containing 90% or more SiO2 by weight after water removal, particles composed of silica (silicic anhydride), particles composed of silica hydrate (hydrated silicic acid), and particles composed of quartz glass. The form in which hydrated silicic acid exists is not particularly limited; particles composed of orthosilicic acid, metasilicic acid, and / or disilicate acid are also equivalent to these so-called silica particles. The term "weight after water removal" refers to the weight of the particles minus the weight of the water contained within them.

[0047] However, in core-shell composite particles, surface treatment agents and coatings applied to particles that do not contain SiO2 as a core, such as particles composed of organic polymers, organic pigments, or inorganic pigments, which serve as a shell, do not affect the SiO2 content even if they contain SiO2. These are defined individually as not belonging to silicon dioxide particles. On the other hand, core-shell composite particles that contain SiO2 in the core and have a SiO2 content of 90% by weight or more after water removal are defined as belonging to silicon dioxide particles. That is, component (a) is filled as particles in a form dispersed in the pixel segmentation layer. The particle structure of component (a) is not particularly limited and may also have internal voids.

[0048] The aforementioned silicon dioxide particles, excluding those composed of silicon dioxide, silicon dioxide hydrates, and quartz glass, can be exemplified by silicon dioxide particles composed of a composite oxide of silicon and a metal, having a SiO2 content of 90% or more by weight after water removal. Examples of metals include zirconium, titanium, and cerium. Specifically, silicon dioxide particles containing hafnium atoms are defined as a mixture of silicon dioxide particles and hafnium atoms (hereinafter sometimes referred to as component (c)).

[0049] To further reduce the uneven brightness of organic EL display devices, it is preferable that (a) the component contains silicon dioxide particles with a primary particle size of 5-20 nm, and even more preferably, silicon dioxide particles with a primary particle size of 5-15 nm. Here, primary particles refer to the major axis of the silicon dioxide particles. It is even preferable that the component contains silicon dioxide particles with an aspect ratio of 1.0-1.3, and even more preferably, silicon dioxide particles with an aspect ratio of 1.0-1.2. Furthermore, when the aspect ratio is 1.0, it can be considered as perfectly spherical silicon dioxide particles.

[0050] Component (a) and silicon dioxide particles other than component (a) are observed by cutting thin sections of the pixel segmentation layer and spacer layer. Preferably, the smoothness of the section is improved by ion milling, and more preferably by pretreatment with focused ion beam (FIB) processing. The area located in the range of 0.2–0.8 μm from the outermost layer of the pixel segmentation layer or spacer layer towards the film depth is analyzed using transmission electron microscopy-energy dispersive X-ray spectroscopy (TEM-EDX). Elemental distribution analysis information allows for the identification and specific determination of the constituent elements of the particles. Transmission electron microscopy-electron energy loss spectroscopy (TEM-EELS) or scanning electron microscopy-energy dispersive X-ray spectroscopy (STEM-EDX) can also be used for analysis.

[0051] Specifically, images of the sample observed using a transmission electron microscope-energy dispersive X-ray spectroscopy (TEM-EDX) at 50,000x magnification were analyzed using an image resolution particle size analyzer, "Mac-View" (manufactured by MOUNTECH), to distinguish silicon dioxide particles belonging to component (a) from those not belonging to component (a). That is, 30 silicon dioxide particles were randomly selected from the TEM image in the pixel segmentation layer cross-section, and the major axis, minor axis, and aspect ratio of each selected particle were measured. Silicon dioxide particles with a major axis (nm) of 5–30 nm and an aspect ratio of 1.0–1.5 were defined as component (a). Furthermore, in the case where the minor axis and major axis of a single silicon dioxide particle are equal in the TEM image, i.e., it is a perfect circle, its diameter is considered the major axis. As representative values ​​representing the characteristics of silica particles belonging to component (a), the average value of the first particle size (i.e., the average value of the major diameter, rounded to the first decimal place) and the average value of the aspect ratio (i.e., the average value of the aspect ratio of each silica particle belonging to component (a), rounded to the second decimal place) are calculated. Here, SiO2 that has interfaces with the surfaces of particles composed of polymers, organic pigments, and / or inorganic pigments is excluded from the analysis. The major diameter and aspect ratio of silica particles contained in the spacer layer can also be determined using the same method.

[0052] Furthermore, the pixel segmentation layer of the organic EL display device of the present invention may further contain silicon dioxide particles that are not part of component (a), that is, silicon dioxide particles with a primary particle size of less than 5 nm or more than 30 nm, or silicon dioxide particles with an aspect ratio (major diameter / minor diameter) of more than 1.5. Examples of silicon dioxide particles that are not part of component (a) include "ADMAFINE" (registered trademark) SO-E2, SO-E4 (all of which are manufactured by Admatechs Corporation), KE-P10, and KE-S10 (all of which are manufactured by Nippon Shokubai Co., Ltd.).

[0053] The pixel segmentation layer of the organic EL display device of the present invention may further contain particles whose SiO2 content after water removal is less than 90% by weight and which are not silicon dioxide particles as described in this specification. Examples of particles not belonging to the aforementioned silicon dioxide particles include, for instance, the "ATLAS" (registered trademark) 100 (manufactured by CABOT Corporation), an organic-inorganic composite particle with a silicon dioxide:polymer ratio of 70:30 by weight, disclosed in Japanese Patent Application Publication No. 2018-97251.

[0054] The average primary particle size of the silicon dioxide particles contained in the pixel segmentation layer of the organic EL display device of the present invention, from the viewpoint of suppressing brightness unevenness, is preferably 5-30 nm, more preferably 5-25 nm. The average aspect ratio (major diameter / minor diameter) is preferably 1.0-1.3, more preferably 1.0-1.2. That is, even when the pixel segmentation layer of the organic EL display device of the present invention contains silicon dioxide particles that are not part of component (a), the average primary particle size of all the silicon dioxide particles contained therein is preferably 5-30 nm. Similarly, the average aspect ratio (major diameter / minor diameter) is preferably 1.0-1.3. Here, silicon dioxide particles include both component (a) and silicon dioxide particles that are not part of component (a). The so-called average primary particle size refers to the cross-section ranging from 0.2 to 0.8 μm in the direction of film depth, observed using transmission electron microscopy-energy dispersive X-ray spectroscopy (TEM-EDX) at a magnification of 50,000. Thirty images were randomly selected from the observed images using an image resolution particle size distribution measuring machine (Mac-View, MOUNTECH), and the average of the major diameters of all silicon dioxide particles was rounded to the first decimal place. The so-called "average aspect ratio (major diameter / minor diameter)" refers to the average of the 30 randomly selected images from the same image, calculated by dividing the major diameter by the minor diameter for each primary particle of all silicon dioxide particles, and rounded to the second decimal place. The term "silicon dioxide particles with an average primary diameter of 5-30 nm" refers to those with an average primary diameter in the range of 5-30 nm. The term "silicon dioxide particles with an average aspect ratio of 1.0-1.3" refers to those with an average aspect ratio in the range of 1.0-1.3.

[0055] The specific surface area of ​​component (a) with the corresponding primary particle size is preferably 50-500 m² / g, more preferably 200-400 m² / g. Here, specific surface area refers to the specific surface area measured by the BET method using nitrogen as the adsorbed gas. The surface of component (a) may be porous or non-porous, and may also have internal surface area.

[0056] The functional groups on the surface of component (a) can be, for example, reactive residues containing surface-modifying groups of vinyl unsaturated double bonds, silyl groups, alkoxysilyl groups, trialkylsilyl groups, and diphenylsilyl groups. More preferably, reactive residues containing surface-modifying groups of vinyl unsaturated double bonds are present to further reduce luminance unevenness. The term "reactive residues containing surface-modifying groups of vinyl unsaturated double bonds" refers to the residues remaining after the vinyl unsaturated double bonds of a surface-modifying group of vinyl unsaturated double bonds have undergone free radical polymerization by light and / or heat. Component (a) contains: silicon dioxide particles having reactive residues containing surface-modifying groups of vinyl unsaturated double bonds on the particle surface; the reactive residues containing surface-modifying groups of vinyl unsaturated double bonds preferably have the structure shown in formula (3) and / or the structure shown in formula (4). The reactive residues containing the surface-modifying group of the vinyl unsaturated double bond are preferably residues produced by free radical polymerization of compounds having two or more free radical polymerizable groups in the molecule, as described later.

[0057] [Chemistry 1]

[0058] In equation (3), R17 16 represents a hydrogen atom or a methyl group. R18 17 represents a divalent hydrocarbon group with 1 to 7 carbon atoms. j and k are integers, representing 0 or 1 independently, respectively. Among them, when j is 1, k is 1. ✽ 1 represents the bonding site between the atom and the carbon atom. ✽ 2 represents the bonding portion of silicon dioxide particles on the particle surface between oxygen atoms bonded to silicon atoms. R 19 18 represents alkyl groups with 1 to 3 carbon atoms. m and n are integers, where m represents 1 to 3 and n represents 0 to 2. Among them, m + n = 3 is satisfied.

[0059] [Chemistry 2]

[0060] In formula (4), R 20 19 represents a hydrogen atom or a methyl group. R 21 20 represents an alkyl group with 1 to 3 carbon atoms. r is an integer, representing 1 to 4. ✽ 3 represents the bonding site between the atom and the carbon atom. ✽ 4 represents the bonding portion of silicon dioxide particles on the particle surface between oxygen atoms bonded to silicon atoms.

[0061] The component (a) with the structure shown in formula (3) is introduced by introducing a surface modification group derived from an organic alkoxysilane compound having an ethylene unsaturated double bond group through a dehydration condensation reaction with the silanol group on the surface of silica particles. The ethylene unsaturated double bond group contained in the surface modification group can be obtained by free radical polymerization reaction by light and / or heat.

[0062] Examples of organoalkoxysilane compounds having vinyl unsaturated double bonds include vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, p-styryltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-propenyloxypropylmethyldimethoxysilane, 3-propenyloxypropylmethyldiethoxysilane, 3-propenyloxypropyltrimethoxysilane, 3-propenyloxypropyltrimethoxysilane, 3-propenyloxypropyltriethoxysilane, allyltrimethoxysilane, and allyltriethoxysilane.

[0063] The component (a) having the structure shown in formula (4) is a surface-modifying group derived from an isocyanate compound having an ethylene unsaturated double bond group, introduced by reacting with ethyl aminoformate between the silanol groups on the surface of silicon dioxide particles. The ethylene unsaturated double bond group contained in the surface-modifying group is obtained by free radical polymerization reaction by light and / or heat. Examples of isocyanate compounds having ethylene unsaturated double bonds include 2-methacryloxyethyl isocyanate, 2-acryloxyethyl isocyanate, and 2-(2-methacryloxyethyloxy)ethyl isocyanate.

[0064] Furthermore, by sequentially modifying the surface of silicon dioxide particles with surface-modifying groups derived from organic alkoxysilane compounds having ethylene unsaturated double bond groups and surface-modifying groups derived from isocyanate compounds having ethylene unsaturated double bond groups, component (a) with the structures shown in formula (3) and formula (4) of the reactive residues can be obtained.

[0065] For example, to improve the dispersion stability of component (a) in a negative photosensitive composition, it is preferable that component (a) further possesses a trialkylsilyl group, more preferably a trimethylsilyl group. The trimethylsilyl group is introduced into component (a) by using a trimethylsilylating agent to convert hydrogen atoms in the silanol groups on the surface of silica particles into trimethylsilyl groups. Examples of trimethylsilylating agents include hexamethyldisilazane and trimethylalkoxysilane, which can be introduced via deamination and dehydration condensation reactions, respectively. By improving the dispersion stability of component (a), luminance unevenness can sometimes be reduced more stably.

[0066] To further reduce luminance unevenness, component (a) is preferably composed of silicon dioxide particles containing sodium atoms. Examples of sodium atoms present are ions (Na+) and silanol salts (Si-ONa). The sodium atom content is preferably 100-5000 ppm by weight in component (a). Silicon dioxide particles containing sodium atoms can be synthesized under alkaline conditions by reacting a strongly alkaline sodium silicate (as a silicon source) with a strong mineral acid. Furthermore, the sodium atoms in the silicon dioxide particles can be detected using TEM-EDX at the center of the intersection of the major and minor axes in the cross-sectional image of the primary particles.

[0067] (a) The content of the component, in terms of suppressing uneven brightness, is preferably 1-50% by weight, more preferably 5-20% by weight, when calculated as SiO2, in the pixel separation layer. Similarly, for all silicon dioxide components in the pixel separation layer, the content is preferably 1-50% by weight, more preferably 7-30% by weight, when calculated as SiO2. Here, the content calculated as SiO2 refers to the content calculated by removing the moisture content from the silicon dioxide particles, which varies due to thermal history, according to the technical common sense of those skilled in the art.

[0068] In order to further reduce brightness unevenness, the pixel segmentation layer in the organic EL display device of the present invention preferably contains 1 to 50 ppm by weight of (c) hafnium atoms (hereinafter sometimes referred to as (c) component). More preferably, it contains 1 to 30 ppm by weight. As (c) component, it is preferably contained in the pixel segmentation layer in the form of inorganic particles containing hafnium atoms.

[0069] Examples of inorganic particles containing component (c) include hafnium oxide (HfO₂), composite oxides of hafnium and metals other than hafnium, solid solutions of hafnium oxide and metal oxides other than hafnium, hafnium oxynitride, composite oxynitrides of hafnium and metals other than hafnium, and solid solutions of hafnium oxynitrides of metals other than hafnium. From the viewpoint of superior effect in reducing brightness unevenness, hafnium oxide (HfO₂) or composite oxides of hafnium and metals other than hafnium are preferred, and composite oxides of zirconium and hafnium (ZrO₂-HfO₂) are even more preferred.

[0070] As inorganic particles containing component (c), commercially available materials that can be obtained in powder form can be used, such as hafnium oxide P, hafnium oxide R, hafnium oxide S (all manufactured by ATI METALS), and hafnium oxide microparticles (manufactured by the High Purity Chemical Research Institute). As another method, during the preparation of a pigment dispersion containing component (b) described below, microparticles generated by wet grinding of the surface of a grinding medium containing component (c) using mechanical energy are co-dispersed with component (b), thereby also containing component (c) in the final pixel separation layer.

[0071] (c) The composition was determined by cutting a portion of the pixel layer from the outermost layer towards the film depth in the range of 0.2–0.8 μm. This portion was then heated and ashed at 800 °C using an electric furnace, followed by decomposition with sulfuric acid, nitric acid, and hydrofluoric acid. The resulting solution, dissolved in dilute nitric acid, was used as the analytical sample, and quantification was performed using ICP (Inductively Coupled Plasma) luminescence spectrophotometry. A PS3520VDDII (manufactured by Hitachi High-Tech Science) was used as the analytical apparatus.

[0072] <(D) Coloring Materials> In cases where coloring is required from the perspective of light-shielding or anti-reflection, the photosensitive resin composition used in this invention preferably contains a (D) coloring material. Since the photosensitive resin composition contains a (D) coloring material, and the pixel separation layer contains a (D) coloring material, the effects described later can be obtained, which is therefore preferable. The (D) coloring material refers to a compound that absorbs light of a specific wavelength, particularly a compound that colors light by absorbing wavelengths of visible light (380~780nm). By containing a (D) coloring material, the hardened film obtained from the photosensitive resin composition can be colored, and light penetrating the hardened film of the photosensitive resin composition, or light reflected by the hardened film of the photosensitive resin composition, can be colored to the desired color, thus imparting colorability. Furthermore, light of the wavelengths absorbed by the (D) coloring material can be blocked from light penetrating the hardened film of the photosensitive resin composition, or light reflected by the hardened film of the photosensitive resin composition, thereby imparting light-shielding properties.

[0073] The content of the (D) coloring material used in this invention is preferably 1% by weight or more, more preferably 10% by weight or more, and even more preferably 15% by weight or more in the pixel splitting layer. By including the content within the above range, light-blocking properties, coloring properties, or tonal properties can be improved. On the other hand, the content is preferably 70% by weight or less, more preferably 65% ​​by weight or less, and even more preferably 60% by weight or less. If the content is within the above range, the sensitivity during exposure can be improved.

[0074] As (D) coloring materials, examples include known compounds such as (D1) organic pigments, (D2) inorganic pigments, or (D3) dyes that absorb wavelengths of visible light and color in the colors white, red, orange, yellow, green, blue, or purple. Two or more of these coloring materials can be used in combination, as can two or more colors. Combining two or more materials results in better pixel-segmentation layers that can be merged to achieve the effects described later. By combining two or more colors, light penetrating the hardened film of the photosensitive resin composition, or light reflected from the hardened film of the photosensitive resin composition, can be adjusted to the desired color coordinates, thereby improving tonal gradation.

[0075] By using (D1) organic pigments as (D) coloring materials, the transmission or absorption spectra of the hardened film of the photosensitive resin composition can be adjusted by utilizing the chemical structural changes or functional group conversion functions of (D1) organic pigments to allow light of a specific wavelength to pass through or block light, thereby improving the color gradability. Details of this type of (D1) organic pigment will be described later.

[0076] By using (D2) inorganic pigments as (D) coloring materials, the heat resistance and weather resistance of the hardened film of photosensitive resin composition can be improved due to the superior heat resistance and weather resistance properties of (D2) inorganic pigments. Examples of (D2) inorganic pigments include zirconium nitride, zirconium oxide, titanium oxide, barium carbonate, zinc oxide, zinc sulfide, lead white, calcium carbonate, barium sulfate, white carbon, aluminum white, silicon dioxide, kaolin clay, talc, bentonite, iron oxide red, molybdenum red, molybdenum orange, chromium cinnabar, lead yellow, cadmium yellow, yellow iron oxide, titanium yellow, chromium oxide, chrome green (Viridian), titanium cobalt green, cobalt green, cobalt chromium green, Victoria green, ultramarine, dark blue, cobalt blue, sky blue, cobalt silicon dioxide blue, cobalt zinc silicon dioxide blue, manganese violet, cobalt violet, graphite or silver-tin alloy, or microparticles, oxides, complex oxides, sulfides, sulfates, nitrates, carbonates, nitrides, carbides or oxynitrides of metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium or silver.

[0077] In order to make the surface roughness (Ra1) of the pixel segmentation layer 1.0 nm or more and 50 nm or less, it is preferable to disperse an inorganic pigment with a relatively high specific gravity, such as zirconium nitride. This is because, as will be described later, pigment precipitation is expected during development in the pixel segmentation layer corresponding to the halftone exposure area. Although inorganic pigments have issues such as pigment aggregation, thickening, and decreased sensitivity over time, by setting the acid equivalent of component (A) to 200 g / mol or more and 500 g / mol or less, the alkaline solubility of the exposed area, unexposed area, and halftone exposure area described later can be better adjusted. If the acid equivalent of component (A) is less than 200 g / mol, when obtaining, for example, a hardened film of a positive photosensitive resin composition, the alkaline solubility of the unexposed area becomes high, the difference in dissolution rate between the unexposed area and the exposed area is small, and the desired pattern cannot be formed. By setting the acid equivalent to 200 g / mol or higher, the solubility of the unexposed area can be suppressed, resulting in a pattern with less residue at the opening caused by the adhesion of dissolved substances from the unexposed area. Furthermore, by setting the acid equivalent of component (A) to 500 g / mol or lower, the dispersion and stabilization of zirconium nitride particles can be promoted, resulting in a photosensitive resin composition with excellent preservation stability.

[0078] Dyes (D3) refer to compounds that color an object through chemical adsorption or strong interaction between the dye's ionic groups or hydroxyl groups and other substituents on the object's surface structure. They are generally soluble in solvents. Furthermore, the coloring caused by dyes results in high tinting strength and high color development efficiency because each molecule adsorbs onto the object. Dyes can be classified as direct dyes, reactive dyes, sulfur dyes, vat dyes, acid dyes, metal-containing dyes, metal-containing acid dyes, basic dyes, mordant dyes, acid mordant dyes, disperse dyes, cationic dyes, or fluorescent whitening dyes, etc. From a materials science perspective, examples include anthraquinone dyes, azo dyes, azo dyes, phthalocyanine dyes, (poly)methine dyes, acetylene dyes, quinoline dyes, indigo dyes, indigo dyes, carbomon dyes, vat dyes, perylene dyes, pyrene dyes, triarylmethane dyes, or so on. While anthraquinone dyes, azo dyes, azo dyes, methine dyes, and triarylmethane dyes are preferred from the viewpoint of solubility and heat resistance in (C) organic solvents. Dyes.

[0079] In order to make the surface roughness (Ra1) of the pixel segmentation layer 1.0 nm or more and 50 nm or less, the preferred (D) coloring material is a salt-forming compound composed of acidic and basic dyes (D3-1). This is because by containing a salt-forming compound composed of acidic and basic dyes (D3-1), dye precipitation during development can be expected in the pixel segmentation layer corresponding to the halftone exposure area.

[0080] The term (D3-1) refers to a salt-forming compound composed of acidic and basic dyes, obtained by reacting acidic and basic dyes. It is a chemically stable compound resulting from the chemical (salt-forming) reaction between an acidic dye with an anionic dye ion and a basic dye with a cationic dye ion.

[0081] Acid dyes are compounds containing acidic substituents such as sulfonic acid groups or carboxyl groups in their molecules, or anionic water-soluble dyes that are salts of such compounds. Furthermore, acid dyes include those containing acidic substituents such as sulfonic acid groups or carboxyl groups and classified as direct dyes. From the viewpoint of reducing residue at the opening, acid dyes containing sulfonic acid groups are preferred. It is an acid dye. From the perspective that acid dyes can further reduce residue at the opening, it is preferable to use rhodamine-based acid dyes such as CI Acid Red 50, 52, and 289. Furthermore, from the perspective that rhodamine-based acid dyes can improve the blackness of the hardened film, it is preferable to use those containing CI Acid Red 52.

[0082] Basic dyes are compounds, or salts thereof, containing basic groups such as amine or imine groups in their molecules, which become cationic dyes in aqueous solutions. From the perspective of improving the blackness of the hardened film, basic dyes containing triarylmethane are preferred. From the perspective of further improving the blackness of the hardened film, triarylmethane basic dyes containing CI Basic Blue 7 and / or CI Basic Blue 26 are even more preferred.

[0083] Salt compounds of acid dyes and basic dyes can be synthesized using known methods. For example, aqueous solutions of acid dyes and basic dyes are prepared separately, and then slowly mixed with stirring to produce salt compounds of acid dyes and basic dyes as precipitates. These precipitates can be recovered by filtration to obtain the salt compounds. The obtained salt compounds are preferably dried at approximately 60-70°C.

[0084] Furthermore, in the photosensitive resin composition, the content of the salt-forming compound is set to 10 parts by weight or more relative to 100 parts by weight of the alkali-soluble resin (A), thereby achieving blackening; by setting it to 75 parts by weight or less, residue at the opening can be reduced. By containing salt-forming compounds within this range, the alkali solubility of the exposed, unexposed, and halftone exposed areas described later can be better adjusted.

[0085] Furthermore, when it is desired to improve the blackness of the hardened film, it is preferable to use a nonionic dye containing (D3-2) as a (D) coloring material.

[0086] (D3-2) Nonionic dyes refer to dyes other than acid dyes and basic dyes, and do not have an ionic structure.

[0087] Examples of nonionic dyes include azo-based nonionic dyes such as CI Disperse Orange 5, CI Disperse Red 58, CI Disperse Blue 165, and CI Solvent Red 18; and anthraquinone-based nonionic dyes such as CI Vat Blue 4, CI Disperse Red 22 and 60, CI Disperse Violet 26, 28, and 31, CI Disperse Blue 14, 56, and 60, CI Solvent Violet 13, 31, and 36, and CI Solvent Blue 35, 36, 45, 63, 78, 87, 97, 104, and 122.

[0088] Among them, anthraquinone-based nonionic dyes are preferred in terms of improving the blackness of the hardened film.

[0089] <(D1) Organic Pigments> Examples of (D1) organic pigments used as (D) coloring materials include phthalocyanine pigments, anthraquinone pigments, quinacrine pigments, pyranthrone pigments, dioxane pigments, thioindigo pigments, diketopyrrolopyrrole pigments, quinoline yellow pigments, threne pigments, indoline pigments, isoindoline pigments, isoindolineone pigments, benzofuranone pigments, perylene pigments, aniline pigments, azo pigments, methylene azo pigments, condensed azo pigments, carbon black, metal complex pigments, lake pigments, toner pigments, or fluorescent pigments. From the viewpoint of heat resistance, anthraquinone pigments, quinacrine pigments, pyranthrone pigments, diketopyrrolopyrrole pigments, benzofuranone pigments, perylene pigments, condensed azo pigments, and carbon black are preferred.

[0090] In this invention, the photosensitive resin composition used in forming the pixel segmentation layer preferably contains organic pigments in order to impart light-blocking properties to the pixel segmentation layer. Because the photosensitive resin composition contains organic pigments, the pixel segmentation layer becomes one containing organic pigments, thus achieving the effects described below, which is preferable. In this case, it is preferable to further contain organic black pigments and / or mixed organic black pigments (hereinafter sometimes referred to as component (b)) as (D1) organic pigments.

[0091] Examples of organic black pigments include benzodifuranone-based black pigments, perylene-based black pigments, and methylene azo-based black pigments.

[0092] Examples of benzodifuranone-based black pigments include the pigment disclosed in International Patent Publication No. 2009 / 010521. Commercially available benzodifuranone-based black pigments composed of compounds shown in formula (5) are preferably Irgaphor Black (registered trademark) S0100CF or Experimental Black 582 (both manufactured by BASF).

[0093] Examples of perylene-based black pigments include CI Pigment Black 31, CI Pigment Black 32, benzimidazole perylenetetracarboxylic acid or its derivatives, and the pigment disclosed in International Patent Publication No. 2005 / 078023. Commercially available products include Spectrasense Black S0084 (registered trademark), Spectrasense Black L0086, Spectrasense Black K0087, and Spectrasense Black K0088 (all manufactured by BASF).

[0094] Examples of methylene azo-based black pigments include those disclosed in U.S. Patent Publication No. 2002-121228. Commercially available examples include CHROMOFINEBLACK A1103 (manufactured by Daihatsu Seika Co., Ltd.).

[0095] Mixed organic black pigment refers to a pigment mixture containing (b-1) an organic pigment selected from organic yellow pigment, organic red pigment and organic orange pigment (hereinafter sometimes referred to as component (b-1)) and (b-2) an organic pigment selected from organic blue pigment and organic purple pigment (hereinafter sometimes referred to as component (b-2)), and the content of component (b-2) is 20% by weight or more relative to the total amount of component (b-1) and component (b-2).

[0096] Examples of organic yellow pigments include CI Pigment Yellow 24, 120, 138, 139, 151, 175, 180, 185, 181, 192, 193, and 194. Examples of organic orange pigments include CI Pigment Orange 13, 36, 43, 60, 61, 62, 64, 71, and 72. Examples of organic red pigments include CI Pigment Red 122, 123, 149, 178, 177, 179, 180, 189, 190, 202, 209, 254, 255, and 264. Examples of organic blue pigments include CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:6, 16, 25, 56, 57, 60, 61, 64, 65, 66, 75, 79, and 80. Examples of organic purple pigments include CI pigments 19, 23, 29, 32, and 37.

[0097] Of the components equivalent to component (b) above, in terms of reducing brightness unevenness, component (b) in the pixel separation layer of the organic EL display device of the present invention preferably contains an organic black pigment, which contains a compound and / or its isomers shown in formula (5) or formula (6). Component (b) in the pixel separation layer more preferably contains a compound or its isomers shown in formula (7). The compounds shown in formulas (5) to (7) can be synthesized by pigmentation through the reaction of 2,5-dihydroxy-1,4-phenylenediacetic acid with indigo or its derivatives under an acidic catalyst.

[0098] [Chemistry 3]

[0099] [Chemistry 4]

[0100] In formulas (5) and (6), R 22 1 to R 31 10 each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.

[0101] [Chemistry 5]

[0102] The component equivalent to component (b) can also be refined by known methods such as solvent salt milling and acid paste method in order to further suppress uneven brightness. In the case of refining benzodifuranone-based black pigments, the compound shown in formula (8) or its salt is coexisted and adsorbed on the pigment surface, thereby making it easier to suppress uneven brightness.

[0103] [Chemistry 6]

[0104] In equation (8), n and m represent integers, which are independent values ​​from 0 to 2. Among them, n+m≧1 is satisfied.

[0105] Furthermore, in the case where component (b) contains a benzodifuranone-based black pigment, in order to improve developability and suppress developing residue at the opening, it is preferable to have a silicon dioxide-containing coating layer on the surface of the pigment. The silicon dioxide contained in this coating layer is not component (a) as described above, but is considered to be a part of component (b).

[0106] (b) The content of the component is preferably 1% by weight or more, and more preferably 10% by weight or more, in the pixel separation layer for the purpose of achieving high light-blocking properties. For the purpose of reducing brightness unevenness, it is preferably 50% by weight or less, and more preferably 30% by weight or less.

[0107] Furthermore, in addition to component (b), if component (a) is further included, the content of component (a) relative to 100 parts by weight of component (b), calculated using SiO2, is preferably 20-70 parts by weight, more preferably 30-50 parts by weight. That is, in the pixel segmentation layer of the organic EL display device of the present invention, the content of component (a) relative to component (b), calculated using SiO2, is preferably 20-70 parts by weight.

[0108] <(E) Liquid-removing material> In the case of forming an organic EL layer by inkjet printing, it is preferable that the photosensitive resin composition used in this invention contains a repellent material. Known materials such as fluorinated polymers or fluorinated compounds containing silane compounds can be used, but it is preferable to use a repellent material having at least amide or ethyl carbamate groups. By having amide or ethyl carbamate groups, it is possible to improve the compatibility with the aforementioned alkali-soluble resin (A), reduce defects such as shrinkage, and improve the uniformity of the hardened film thickness, thereby reducing display defects in the display device.

[0109] As an example of liquid-repellent materials, 2-(perfluorobutyl)(meth)acrylate ethyl ester and 2-(perfluorohexyl)(meth)acrylate ethyl ester, which belong to the (meth)acrylate monomers containing perfluoroalkyl groups, are commercially available as "MEGAFAC (registered trademark)" RS-72-K, RS-72-A, RS-75, RS-76-E, RS-76-NS, RS-78, RS-90 (manufactured by DIC), etc.

[0110] Furthermore, preferred examples of (meth)acrylate monomers containing epoxy groups include glycidyl acrylate, glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether (4-HBAGE), 4-hydroxybutyl methacrylate glycidyl ether, acrylates having alicyclic epoxy groups, and methacrylates having alicyclic epoxy groups.

[0111] Liquid-repellent materials (E) containing amide or ethyl carbamate groups can also be copolymers of (meth)acrylic acid monomers with different functional groups. By copolymerizing (meth)acrylic acid monomers with different functional groups, a balance between liquid repellency and solubility can be easily obtained. Examples include (meth)acrylic acid esters containing hydroxyl groups, (meth)acrylic acid esters containing hydroxyl groups, (meth)acrylic acid esters containing alkoxy groups, (meth)acrylic acid esters containing block isocyanate groups, (meth)acrylic acid esters containing phenoxy groups, (meth)acrylic acid alkyl esters, and compounds containing vinyl groups. Examples of (meth)acrylic acid esters containing hydroxyl groups include 2-hydroxyethyl (meth)acrylic acid. Examples of (meth)acrylic acid esters containing hydroxyl groups include N-hydroxymethylacrylic acid. Examples of (meth)acrylic acid esters containing alkoxy groups include 3-methacryloxypropylmethyldimethoxysilane. Examples of (meth)acrylates containing block isocyanate groups include 2-(O-[1'-methylpropylamino]carboxyamino)ethyl methacrylate (Karenz MOI-BM: Showa Denko (Co., Ltd.; registered trademark)). Examples of (meth)acrylates containing phenoxy groups include 2-phenoxybenzyl acrylate and 3-phenoxybenzyl acrylate. Examples of (meth)acrylate alkyl esters include diluent monomers of unsubstituted or substituted alkyl (meth)acrylates having at least one of the following: unsubstituted, substituted with an amino group, a monoalkylamino group, a dialkylamino group, a hydrocarbon aromatic ring, or a heterocyclic ring, or having undergone cleavage addition of an anhydride to a hydroxyl group, such as alkyl acrylates. Examples of vinyl compounds include n-butyl vinyl ether.

[0112] The compounds contained in repellent materials (E) having amide or ethyl carbamate groups are usually copolymers. The copolymers containing the compounds in the repellent material (E) can be obtained by known polymerization methods. For example, copolymers can also be obtained by free radical polymerization, anionic polymerization, or plasma polymerization. Furthermore, they can be any of random copolymers, block copolymers, graft copolymers, or alternating copolymers. Free radical polymerization methods are listed here. For example, a predetermined amount of dimethyl (meth)acrylamide, a predetermined amount of fluorinated (meth)acrylate monomers, or, as needed, a predetermined amount of epoxy-containing (meth)acrylates, etc. Hydroxyl (meth)acrylates, hydroxyl-containing (meth)acrylamides, alkoxy-containing (meth)acrylates, block isocyanate-containing (meth)acrylates, phenoxy-containing (meth)acrylates, alkyl (meth)acrylates, and vinyl-containing compounds are randomly copolymerized in a suitable solvent with a free radical polymerization initiator to obtain a liquid-repellent material (E). A chain-moving agent may also be added during random copolymerization as needed. For example, tributyl-2-ethylhexanoate peroxide can be used as a free radical polymerization initiator. For example, dodecyl mercaptophosphate can be used as a chain-moving agent. Furthermore, an inert solvent such as cyclohexanone can be used as a solvent.

[0113] The weight-average molecular weight of the liquid-repellent material (E) containing amide or ethyl carbamate groups is preferably in the range of 1500 to 50000. By setting the molecular weight within this range, it is easier to dissolve in the solvent used in the photosensitive resin composition. Furthermore, by setting the molecular weight within this range, the defoaming properties of the photosensitive resin composition are increased, which is also preferable. From the viewpoint that 100 parts by weight of the liquid-repellent material (E) containing amide or ethyl carbamate groups easily and sufficiently exhibit liquid-repellent properties in the resulting cured film, it is preferably 0.1 parts by weight or more, more preferably 0.3 parts by weight or more. Furthermore, from the viewpoint that it is less likely to generate liquid repellency within the pixel and easier to obtain high durability, it is preferably 10 parts by weight or less, more preferably 5 parts by weight or less.

[0114] <spacer> In the organic EL display device of the present invention, the spacer 4 is disposed on the pixel separation layer. As a first objective, by providing the spacer, the contact area between the substrate and the vapor-deposited mask during the formation of the organic EL layer can be reduced, thereby suppressing particle generation during the process. As a result, the reduction in panel yield or the deterioration of the light-emitting element can be suppressed. Furthermore, as a second objective, as described above, in order to support the structure on the covered second electrode in subsequent steps and ensure the strength of the display device, the spacer must be fabricated on the pixel separation layer. The spacer must be patterned in the same way as the pixel separation layer; there is a possibility that residue from the removal section can directly cause defects such as open circuits or black spots. Moreover, the edge shape of the spacer can be a cause of breakage in the second electrode, therefore, a gentle push-pull shape and other processability are also required.

[0115] As a spacer, any material with the necessary mechanical or electrical properties can be used without particular limitation, and it is not limited to any known organic or inorganic material. However, from a processability perspective, a hardened film composed of photosensitive resin is preferred. Furthermore, by processing the same material as the pixel separation layer together, it is possible to increase panel yield or reduce costs by shortening the process time.

[0116] As mentioned above, the issue of delamination between the pixel segmentation layer and the organic EL layer also presents a challenge at the interface between the spacer and the organic EL layer. Therefore, in this invention, when the maximum value of the surface roughness (Ra1) of the pixel segmentation layer and the surface roughness (Ra2) of the spacer is set as Ramax, Ramax is 1.0 nm or more and 50 nm or less. Furthermore, it is more preferable that the surface roughness (Ra2) of the spacer is Ramax. Alternatively, both the surface roughness (Ra1) of the pixel segmentation layer and the surface roughness (Ra2) of the spacer can be Ramax. Furthermore, the surface roughness of the spacer, like that of the pixel segmentation layer, can be measured using atomic force microscopy (AFM).

[0117] Furthermore, since the spacer is formed on the outermost surface of the substrate, its surface becomes the interface with the organic EL layer. Conventionally, delamination easily occurs due to deterioration of the adhesion between the spacer and the organic EL layer, posing a significant problem, especially in flexible products. In this invention, by setting the surface roughness (Ra2) of the spacer to 1.0 nm or more, an anchoring effect can be obtained, preferably 5.0 nm or more, and more preferably 20 nm or more, thereby improving the adhesion between it and the organic EL layer. Furthermore, regarding the surface roughness (Ra2) of the spacer, if it is 1.0 nm or more, an anchoring effect can be obtained; however, for the purpose of suppressing pinholes in the second electrode or defects in the sealing step described later, it is preferably set to 50 nm or less. Furthermore, when improving adhesion by increasing Ra2, it is effective to ensure that the interface between the spacer and the organic EL layer is as large as possible. When Ra2 is greater than the surface roughness Ra1 of the pixel segmentation layer, i.e., Ra2 becomes Ramax, the area of ​​the interface between the substrate and the organic EL layer should preferably be more than 50% of the total area. This means that the spacer is more than 50% of the surface area of ​​the substrate.

[0118] When Ra1 or Ra2 is greater than 1.0 nm, in addition to the improved adhesion, it also suppresses external light reflection from the display device caused by the increased diffuse reflection of the substrate. Generally, when external light enters the substrate, two types of reflected light are generated on its surface: direct reflection and diffuse reflection. The sum of these two types constitutes the amount of reflected light, but the effect of direct reflection is greater than that of glare or reflection. That is, in order to maintain the display quality of the display device, it is effective to increase the diffuse reflection of the substrate and reduce the direct reflection. In other words, by increasing the surface roughness Ra1 or Ra2 of the pixel separation layer or spacers on the substrate surface to 1.0 nm or greater, the diffuse reflection of the substrate surface is increased, thereby ensuring the display quality of the display device.

[0119] Furthermore, if the absolute value of the difference between Ra1 and Ra2 is greater than 1.0 nm, more than two types of anchoring effects and improved adhesion can be obtained, which is even better.

[0120] Furthermore, since the edge shape of the spacer can cause the second electrode to break, a gentle push-pull shape is preferred. Here, the so-called push-pull shape refers to a state where the angle between the interface between the pixel dividing layer and the spacer, and the angle between the interface between the spacer and the push-pull portion of the spacer at a position where the maximum thickness of the spacer film is 50% of the thickness of the spacer, is less than 90 degrees.

[0121] The thickness of the spacer is typically 0.3μm to 10μm, and there are no particular limitations as long as it is sufficient to support the contact with the vapor-deposited mask or the structure on the second electrode.

[0122] <Organic EL Layer> In the organic EL display device of the present invention, the composition of the organic EL layer 5 is not particularly limited, and can be, for example, any one of (1) a hole transport layer / light-emitting layer, (2) a hole transport layer / light-emitting layer / electron transport layer, or (3) a light-emitting layer / electron transport layer. Furthermore, it can also be a tandem type, where the above-mentioned structures are multiple layers stacked via a charge-generating layer. The charge-generating layer is generally also called an electron extraction layer, connecting layer, intermediate layer, intermediate electrode, intermediate conductive layer, or intermediate insulating layer, and can be constructed using known materials. By adopting a tandem type, an improvement in luminous brightness or luminous lifetime can be expected, which is therefore preferable. Specific examples of series-connected structures include (4) hole transport layer / light emission layer / electron transport layer / charge generation layer / hole transport layer / light emission layer / electron transport layer, (5) hole injection layer / hole transport layer / light emission layer / electron transport layer / electron injection layer / charge generation layer / hole injection layer / hole transport layer / light emission layer / electron transport layer / electron injection layer, (6) hole transport layer / light emission layer / electron transport layer / charge generation layer / hole transport layer / light emission layer / electron transport layer / charge generation layer / hole transport layer / light emission layer / electron transport layer, etc., which are composed of a charge generation layer between the anode and the cathode.

[0123] Furthermore, the aforementioned layers can be either single layers or multiple layers, and can also be doped. Preferably, the electron transport layer and charge generation layer are metal-doped layers, which can improve electron transport capability or the ability to inject electrons into adjacent layers. In addition to the aforementioned layers, a protective layer (capping layer) can also be added, which can further improve luminous efficiency through optical interference effects. The thickness of each layer is selected considering its impact on the resistivity of the material or the light emission efficiency of the EL emission, and is generally chosen between 1 and 200 nm.

[0124] <Electric Void Transport Layer> The hole transport layer is formed, for example, by laminating or mixing one or more hole transport materials, or by using a mixture of hole transport materials and polymer binders. Alternatively, an inorganic salt such as ferric chloride (III) can be added to the hole transport material to form a hole transport layer. There are no particular limitations on the type of hole transport material; it is a thin film necessary for fabricating a light-emitting element, and it is a compound that can be injected into holes through an electrode that serves as the anode, thereby transporting holes. The hole transport layer can be a single layer or a multilayered structure.

[0125] Preferred examples of hole-carrying materials include triphenylamine derivatives such as 4,4'-bis(N-(3-methylphenyl)-N-phenylamino)biphenyl, 4,4'-bis(N-(1-naphthyl)-N-phenylamino)biphenyl, and 4,4',4”-triphenylamine (3-methylphenyl(phenyl)amino)triphenylamine; bis(N-allylcarbazole) and bis(N-alkylcarbazole) and other biscarbazole derivatives; pyrazoline derivatives; stilbene compounds; hydrazone compounds; benzofuran derivatives; thiophene derivatives; diazole derivatives; phthalocyanine derivatives; porphyrin derivatives; and polymer systems containing the above monomers in the side chains, such as polycarbonate or styrene derivatives, polythiophene, polyaniline, polyoxocyanate, polyvinylcarbazole, and polysilane.

[0126] <Emitting Layer> The light-emitting layer emits light by recombinizing injected electrons and holes. The ability to emit various colors of light by selecting the materials that constitute this light-emitting layer is a major characteristic of organic EL displays.

[0127] A light-emitting layer is a layer in which the light-emitting material is excited and emits light through the recombination energy caused by the collision of holes and electrons. The light-emitting layer can be a single layer or a plurality of layers stacked together, each formed by a light-emitting material (a host material and / or a dopant material). Each light-emitting layer can be composed of only one host material or one dopant material, or it can be composed of a combination of one or more host materials and one or more dopant materials. That is, in each light-emitting layer, only the host material or the dopant material emits light, or both the host material and the dopant material emit light together. From the viewpoint of efficiently utilizing electrical energy and obtaining light emission with high color purity, the light-emitting layer is preferably composed of a combination of a host material and a dopant material. The dopant material can be entirely contained in the host material or can be partially contained therein.

[0128] From the perspective of suppressing concentration quenching, the content of doped material in the light-emitting layer is preferably 30 parts by weight or less, and more preferably 20 parts by weight or less, relative to 100 parts by weight of the main material.

[0129] The light-emitting layer can be formed by the following methods: co-evaporation of the main material and the dopant material; or evaporation of the main material and the dopant material after pre-mixing them.

[0130] Examples of main materials constituting luminescent materials include compounds with condensed aromatic rings such as naphthalene, anthracene, phenanthrene, pyrene, benzo[a]benzene, triphenylene, perylene, benzo[a]acenaphthene, fentanyl, and indene. Two or more of these can also be used. Metal chelates are suitable as the main component used in triplet luminescence (phosphorescence) of the luminescent layer. (oxynoid) compounds, dibenzofuran derivatives, dibenzothiophene derivatives, carbazole derivatives, indolocarbazole derivatives, triphenylene derivatives, triphenylene derivatives, etc. Among them, compounds with anthracene or pyrene skeletons are preferred because they readily produce high-efficiency luminescence.

[0131] Examples of dopants constituting luminescent materials include condensation ring derivatives such as anthracene or pyrene, metal complexes such as tris(8-quinoline)aluminum, bis(styrene) derivatives such as bis(styrene)-anthracene derivatives or styrene-based benzene derivatives, tetraphenylbutadiene derivatives, dibenzofuran derivatives, carbazole derivatives, indole-carbazole derivatives, and polystyrene derivatives. For triplet luminescence (phosphorescence) of the luminescent layer, a metal complex containing at least one metal selected from the group consisting of iridium (Ir), rubidium (Ru), palladium (Pd), platinum (Pt), osmium (Os), and rhenium (Re) is preferred. The ligands constituting the metal complex can be appropriately selected based on the desired luminescence color, the performance of the organic EL display device, and the relationship with the host compound; preferably, they are nitrogen-containing aromatic heterocycles with a phenylpyridine backbone, a phenylquinoline backbone, or a carbapenem backbone. Specific examples include tris(2-phenylpyridine)iridium complex, bis(2-phenylpyridine)(acetone)iridium complex, and tetraethylporphyrin platinum complex. Two or more of these can also be used.

[0132] <Electron transport layer> The electron transport layer is a layer that transports electrons injected from the cathode to the light-emitting layer. To achieve a low driving voltage, the organic EL layer of this invention preferably contains an electron transport layer. For the electron transport layer, high electron injection efficiency and efficient transport of injected electrons are desirable. Therefore, the electron transport layer is preferably a substance with high electron affinity and mobility, excellent stability, and is less likely to become a trapping impurity during manufacturing and use. Especially when the film thickness is large, low molecular weight compounds are prone to film degradation due to crystallization, etc., so compounds with a molecular weight of 400 or higher are preferred. Furthermore, considering the balance between hole and electron transport, the electron transport layer preferably has the function of effectively preventing unrecombined holes from flowing from the anode to the cathode side. In this invention, a hole-blocking layer that efficiently prevents hole movement is also considered synonymous. The electron transport layer can be a single layer or a multilayer stack.

[0133] Examples of electron transport materials constituting the electron transport layer include condensed polycyclic aromatic derivatives of naphthalene and anthracene. Two or more of these can also be used. Among these, compounds with a heteroaromatic ring structure containing electron-accepting nitrogen are preferred for further reducing the driving voltage and achieving high-efficiency luminescence.

[0134] The term "electron-accepting nitrogen" refers to nitrogen atoms that have formed multiple bonds with neighboring atoms. Because nitrogen atoms have high electronegativity, these multiple bonds exhibit electron-accepting properties. Therefore, aromatic heterocyclic systems containing electron-accepting nitrogen possess high electron affinity. Electron transport materials containing electron-accepting nitrogen can further reduce the driving voltage because they readily accept electrons from cathodes with high electron affinity. Furthermore, the increased supply of electrons to the luminescent layer and the higher recombination probability result in improved luminous efficiency.

[0135] Examples of heteroaromatic rings containing electron-accepting nitrogen include triazine rings and pyridine rings. From the viewpoint of electron transport capability, it is preferable to use triazole derivatives such as N-naphthyl-2,5-diphenyl-1,3,4-triazole, dipyridine derivatives such as 2,5-bis(6'-(2',2”-dipyridyl))-1,1-dimethyl-3,4-diphenylsilole, and tripyridine derivatives such as 1,3-bis(4'-(2,2':6'2”-tripyridyl))benzene. Two or more of these may also be used.

[0136] Furthermore, compounds with a morpholine skeleton can be cited as examples of substances that meet the requirements of an electron transport layer. To obtain long-term stable luminescence and materials with superior thermal stability or thin film formation properties, compounds with a morpholine skeleton are preferably those whose substituents themselves have a three-dimensional structure, or whose three-dimensional structure is achieved through stereochemical reactions with the morpholine skeleton or adjacent substituents, or those in which multiple morpholine skeletons are linked. Moreover, in the case of multiple morpholine skeletons linked together, compounds containing conjugated bonds, substituted or unsubstituted aromatic hydrocarbons, or substituted or unsubstituted aromatic heterocycles in the linking units are even more preferred.

[0137] The electron transport material is not limited to a single compound with a phenobarbital skeleton; multiple of the aforementioned compounds may be used in combination, or one or more known electron transport materials may be mixed with the aforementioned compounds. Known electron transport materials are not particularly limited, and include, for example, quinoline ketone derivative metal complexes (represented by 8-hydroxyquinoline aluminum), benzoquinoline metal complexes, oxalool metal complexes, flavonol derivatives, perylene derivatives, perinone derivatives, naphthalene, coumarin derivatives, diazole derivatives, aldazine derivatives, bis(styrene) derivatives, piperazine derivatives, phenobarbital derivatives, quinoline derivatives, benzimidazole derivatives, triazole derivatives, quinoline derivatives, benzoquinoline derivatives, etc., but are not particularly limited. These electron transport materials can be used alone or in combination with different electron transport materials. Furthermore, compounds with nitrogen-containing aromatic heterocycles, such as phenobarbital derivatives and oligopyridine derivatives, may also be used. In particular, compounds with a morpholine skeleton, as described later, are preferred due to their superior electron transport capabilities.

[0138] The aforementioned electron transport materials can be used alone, or two or more of the aforementioned electron transport materials can be used in combination, or one or more other electron transport materials can be mixed into the aforementioned electron transport materials for use. Furthermore, the electron transport layer in this invention preferably contains a preform dopant material. Here, the preform dopant material is a compound that improves the electron injection barrier, making electron injection from the cathode or electron injection layer to the electron transport layer easier, thereby further enhancing the electrical conductivity of the electron transport layer. In this invention, the preform dopant material preferably contains one or more of the group consisting of alkali metals, alkaline earth metals, rare earth metals, inorganic salts of such metals, and complexes of such metals and organic compounds. The preform dopant material is preferred over metal monomers due to its ease of vacuum deposition and superior processability; and is more preferably a complex with organic compounds due to its ease of atmospheric processing and easy adjustment of the addition concentration.

[0139] <charge generation layer> The charge generation layer is generally composed of two layers. Specifically, a pn-junction type charge generation layer composed of an n-type charge generation layer and a p-type charge generation layer can be used. The aforementioned pn-junction type charge generation layer generates charge by applying a voltage to the organic EL layer, or separates the charge into holes and electrons, and injects these holes and electrons into the light-emitting layer via a hole transport layer and an electron transport layer. Specifically, it functions as an intermediate charge generation layer for the multiple light-emitting layers contained in the organic EL layer. The n-type charge generation layer supplies electrons to the light-emitting layer on the anode side, and the p-type charge generation layer supplies holes to the light-emitting layer on the cathode side. Therefore, the luminous brightness and luminous efficiency of the organic EL layer containing multiple light-emitting layers can be further improved, the driving voltage can be reduced, and the luminous lifetime of the organic EL layer can also be further improved. Therefore, in this invention, the organic EL layer preferably contains a charge generation layer. Furthermore, as will be described later, the charge generation layer in this invention preferably contains a pre-doped material, which preferably contains one or more of the group consisting of alkali metals, alkaline earth metals, rare earth metals, inorganic salts of such metals, and complexes of such metals and organic substances.

[0140] The aforementioned n-type charge generation layer is preferably composed of an n-type dopant material and a host material, which can be well-known materials. For example, alkali metals, alkaline earth metals, or rare earth metals can be used as the n-type dopant material. Furthermore, compounds with a morpholine backbone and nitrogen-containing aromatic heterocycles, such as oligopyridine derivatives, can be used as the host material. In particular, compounds with a morpholine backbone, as described later, exhibit superior properties as the host material for the aforementioned n-type charge generation layer, and are therefore preferred; combinations of these materials can also be used.

[0141] The aforementioned p-type charge generation layer is preferably composed of a p-type dopant material and a host material, which can be well-known materials. For example, as the p-type dopant material, tetrafluoro-7,7,8,8-tetracyanoquinone dimethane (F4-TCNQ), tetracyanoquinone dimethane derivatives, axialene derivatives, iodine, FeCl3, FeF3, SbCl5, etc., can be used. As the p-type dopant material, an axialene derivative is preferred. As the host material, an arylamine derivative is preferred.

[0142] <Compounds with a morpholine skeleton> In this invention, the electron transport layer and / or charge generation layer preferably contain a compound having a phytoline skeleton as shown in the following general formula (1).

[0143] [Chemistry 7]

[0144] Here, R1 to R8 may be the same or different, and are selected from hydrogen atoms, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, heteroaryl, and heterocyclic groups. Among them, at least one of R1, R3, R6, and R8 is selected from adamantyl, norethinyl, phenylvinyl, β-naphthyl, phenanthryl, and pyrene.

[0145] Furthermore, in this invention, the electron transport layer and / or charge generation layer preferably contain a compound having a phytoline skeleton as shown in the following general formula (2).

[0146] [Chemistry 8]

[0147] Here, R9 to R16 can be the same or different, and are selected from hydrogen atoms, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, heteroaryl, heterocyclic, and X1. At least one of R9 to R16 is X1. n represents a natural number from 2 to 6. X1 is a single bond, or an n-valent linking unit derived from any of benzene, anthracene, pyridine, ethylene, thiophene, furan, methylene, carbazole, cyclohexane, spirodiphenyl, triphenylamine, triphenylamine, and structures formed by combining these, used to link a complex cyanoline skeleton.

[0148] Among these substituents, alkyl refers to saturated aliphatic hydrocarbon groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, dibutyl, and tributyl, which may or may not have substituents. In the case of substitution, there are no particular limitations on the added substituents, and examples include alkyl, halogen, aryl, and heteroaryl groups, which will also be consistent with the following description. Furthermore, there is no particular limitation on the number of carbon atoms in the alkyl group; from the viewpoint of ease of acquisition or cost, it is preferably in the range of 1 to 20, more preferably 1 to 8. Furthermore, cycloalkyl refers to saturated alicyclic hydrocarbon groups such as cyclopropyl, cyclohexyl, noralkyl, and adamantyl, which may or may not have substituents. There is no particular limitation on the number of carbon atoms in the alkyl moiety; it is preferably in the range of 3 to 20. Furthermore, aralkyl refers to aromatic hydrocarbon groups derived from aliphatic hydrocarbons such as benzyl and phenylethyl; both aliphatic and aromatic hydrocarbons may be unsubstituted or substituted. Furthermore, alkenyl refers to unsaturated aliphatic hydrocarbon groups containing double bonds, such as vinyl, allyl, and butadienyl, which may be unsubstituted or substituted. Cycloalkenyl refers to unsaturated alicyclic hydrocarbon groups containing double bonds, such as cyclopentenyl, cyclopentadienyl, and cyclohexenyl, which may be unsubstituted or substituted. Alkynyl refers to unsaturated aliphatic hydrocarbon groups containing triple bonds, such as ethynyl, which may be unsubstituted or substituted. Alkoxy refers to aliphatic hydrocarbon groups via ether bonds, such as methoxy, which may be unsubstituted or substituted. Alkylthio is an alkoxy group where the oxygen atom in the ether bond is replaced by a sulfur atom. Aryletheryl refers to aromatic hydrocarbon groups via ether bonds, such as phenoxy, which may be unsubstituted or substituted. Arylthioetheryl is an arylether group where the oxygen atom in the ether bond is replaced by a sulfur atom. Furthermore, aryl refers to aromatic hydrocarbon groups such as phenyl, naphthyl, biphenyl, phenanthryl, triphenyl, and pyrene, which may be unsubstituted or substituted. Heterocyclic groups refer to aliphatic rings such as pyran rings, piperidine rings, and cyclic amides, which have atoms other than carbon atoms within the ring, and may or may not have substituents. The number of carbon atoms in the heterocyclic group is not particularly limited, but is preferably in the range of 2 to 20. Halogens refer to fluorine, chlorine, bromine, and iodine. Haloalkanes, haloalkenes, and haloynylenes refer to alkyl, alkenyl, and ynyl groups such as trifluoromethyl, where one or all of the above-mentioned alkyl, alkenyl, or ynyl groups are substituted with the above-mentioned halogens, and the remaining portion may be unsubstituted or substituted. Aldehydes, carbonyl groups, ester groups, aminomethyl groups, and amino groups include those substituted by aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and heterocycles, and further, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and heterocycles may be unsubstituted or substituted. The term "silicone" refers to a silicone compound group, such as trimethylsilyl, which may be unsubstituted or substituted. The term "siloxane" refers to a silicone compound via an ether bond, such as trimethylsiloxane, which may be unsubstituted or substituted. Furthermore, ring structures may also be formed with adjacent substituents. The formed ring structures may be unsubstituted or substituted.

[0149] Furthermore, by creating a three-dimensional structure through the substituent itself having a three-dimensional structure, or through stereochemical reaction with the morpholine skeleton or adjacent substituents, compounds containing the morpholine skeleton have low planarity and are not prone to crystallization, thus maintaining a good amorphous thin film state. The substituent itself having a three-dimensional structure refers to non-two-dimensional planar structures such as tertiary butyl, adamantyl, and norbutyl, exhibiting a large-volume three-dimensional structure, and can be unsubstituted or substituted. Furthermore, the substituents that create a three-dimensional structure through stereochemical reaction with the morpholine skeleton or adjacent substituents refer to α-naphthyl, phenanthrene, etc. Even if the substituent itself is planar, the substituent plane can appear as a different plane from the morpholine skeleton plane due to the stereochemical reaction between the substituent and the morpholine skeleton, or the stereochemical reaction between the substituent and adjacent substituents. These can be examined using molecular models or computational chemistry.

[0150] Furthermore, by linking multiple morpholine skeletons, compounds containing morpholine skeletons can be molecularized and their glass transfer temperature increased, making them less prone to crystallization and thus maintaining a good amorphous thin film state.

[0151] In the compound of general formula (1) of the present invention having a cyanoline skeleton, it is more preferable to introduce substituents at positions 2, 4, 7, and 9 of the cyanoline skeleton. These substituents are the same as those described above. Examples of the above-described compounds having a cyanoline skeleton include the structures described below, but are not limited thereto.

[0152] [Chemistry 9]

[0153] [Chemistry 10]

[0154] [Chemistry 11]

[0155] [Chemistry 12]

[0156] The main material of the electron transport layer and / or charge generation layer is not limited to a single compound with a morpholine skeleton. Multiple compounds with morpholine skeletons may be used in combination, or one or more known main materials may be used in combination with compounds with a morpholine skeleton. There are no particular limitations on the known main materials. It is known that condensation ring derivatives such as anthracene, phenanthrene, pyrene, perylene, and coumarin, as well as metal complexes of quinoline ketone derivatives represented by 8-hydroxyquinoline aluminum, benzo[a]azole derivatives, stilbene derivatives, benzo[a]thiazole derivatives, thiadiazole derivatives, thiophene derivatives, tetraphenylbutadiene derivatives, cyclopentadiene derivatives, benzo[a]azole derivatives, bis(styrene)-anthracene derivatives, or styrene-benzene derivatives, etc., can be used. In the polymer system, poly(styrene)-phenylene oxide derivatives, poly(p-phenylene) derivatives, and polythiophene derivatives can be used.

[0157] Furthermore, compounds with a cinnamon skeleton can also be used as dopants, but due to their superior electron transport capabilities, they are better suited as primary materials.

[0158] <Second Electrode> In this invention, the second electrode 6 must be a light-reflective electrode in the case of bottom-emitting type and a light-transmitting electrode in the case of top-emitting type.

[0159] For bottom-emitting types, materials with high reflectivity for visible light and low resistance at a certain film thickness or above are preferred. Ag or Ag alloy films containing Ag as the main component are useful due to their high reflectivity. Ag alloy films can use MgAg alloys, etc., with Ag as the main component. Furthermore, Al or Al alloy films containing Al as the main component are also good as the second electrode for bottom-emitting applications. AlCr alloy films containing Cr or AlNi alloy films containing Ni are preferred because they have the same high reflectivity as pure Al and can achieve low resistance.

[0160] For top-emitting types, transparent conductive metal oxides such as tin oxide, indium oxide, and indium tin oxide (ITO) can be used. However, to avoid damage to the organic EL layer, a thin film of MgAg alloy that can be fabricated by vapor deposition is preferred.

[0161] The resistance of the second electrode is not limited, as long as it can supply sufficient current for the light-emitting element to emit light, just like the first electrode. However, from the perspective of the power consumption of the light-emitting element, a low resistance is preferable. The electrode thickness can be arbitrarily selected according to characteristics such as transmittance or resistance value. However, for bottom-emitting type, it can be used between 100~300nm, and for top-emitting type, it can be used between 10~30nm.

[0162] Wiring, TFT In this invention, as described above, a driving circuit such as wiring or TFT7 is sometimes provided as a component of the substrate 1.

[0163] In the case of an organic EL display device that is an active-drive top-emitting type, the first electrode 2, which is an island-shaped part of the patterned material, is mostly connected to the TFT 7 that is pre-formed as part of the substrate 1.

[0164] As the semiconductor layer of a TFT, there are oxides such as a-Si (amorphous silicon), p-Si (polycrystalline silicon), microcrystalline silicon, and In-Ga-Zn-O, and LTPO (Low Temperature Polycrystalline Oxide) is also used in combination with p-Si. Generally, two types are used: a-Si TFT and p-Si TFT. a-Si TFT represents the low mobility index, but conversely, the manufacturing process is shorter and it can be used to manufacture large substrates, so it can be widely used in small to large displays. On the other hand, p-Si TFT has high mobility and driver circuits can be formed on the substrate. However, because the manufacturing steps are longer than a-Si and the manufacturing of large substrates is more difficult, it is mainly used in small and medium-sized displays. In particular, the p-Si in p-Si TFT is generally formed by using a-Si as a starting film and irradiating it with laser light, which melts and crystallizes instantaneously. Furthermore, in the a-Si TFT manufacturing process, the doping step of implanting phosphorus or boron into Si is not used. Threshold control of TFT characteristics can also be achieved by doping the Si film with impurities.

[0165] From a structural perspective, TFTs can be broadly classified into bottom-gate and top-gate types. For a-Si TFTs, bottom-gate is preferred, and for p-Si TFTs, top-gate is preferred. For example, in a top-gate type, the drain-side electrode and the source-side electrode are connected to the semiconductor layer, and the gate electrode is positioned above the semiconductor layer. TFTs are formed on a substrate by repeatedly performing thin film formation, patterning, etching, and cleaning steps. Known methods can be used to form TFTs. Furthermore, in a bottom-gate type, the gate electrode is placed on the bottom layer, with a semiconductor layer / insulating film above it, and then the source and drain electrodes are formed on the top layer. When the gate electrode is connected to the source and drain electrodes in a straight line, it forms an inverted triangle, which can also be called an "inverted staggered structure."

[0166] <Planning Layer> In cases where wiring or TFT7 is disposed within the substrate 1, particularly in active-drive types such as those shown in Figure 2, a planarization layer 8 is preferably used. By providing the planarization layer 8, the unevenness of the wiring or TFT7 can be covered and planarized. In this case, since the first electrode 2 is disposed on the planarization layer, the first electrode 2 and the wiring or TFT7 are preferably connected via contact holes formed in the planarization layer 8. The planarization layer 8 is not limited to any known organic or inorganic material; from a processability perspective, a hardened film containing a photosensitive resin composition is preferred. The planarization layer 8 can be formed using wet coating methods such as spin coating, slot coating, dip coating, spray coating, and printing, which are capable of uniformly forming thin films on large-size substrates.

[0167] The photosensitive resin composition preferably contains (A) an alkali-soluble resin, (B) a photosensitizer, and (C) an organic solvent, and may further contain (D) a coloring material. By combining (A) an alkali-soluble resin and (B) a photosensitizer as a photosensitive resin composition, pattern processing can be performed using photosensitivity. Furthermore, by containing (C) an organic solvent, a varnish-like state can be achieved, which can sometimes improve coatability. Moreover, by containing (D) a coloring material in the photosensitive resin composition, the planarization layer can be blackened. The photosensitive resin composition may also further contain other components.

[0168] Examples of materials that can be used as (A) alkali-soluble resins include acrylic resins, epoxy resins, polyamide resins, silicone resins, and precursors of these resins. The film thickness is sufficient to cover the uneven surface and is not particularly limited. In cases where coloring is required for light-blocking or anti-reflection purposes, it is preferable to include a suitable coloring material.

[0169] <Sealing layer> After the second electrode is formed, it is preferably sealed by the sealing layer 9 as shown in Figure 5. Since the light-emitting element of organic EL is considered to be relatively weak to oxygen or moisture, it is preferable to seal it in an environment with as little oxygen and moisture as possible in order to obtain a display device with high reliability. The component used for the sealing layer 9 is preferably selected from materials with high gas barrier properties, and is appropriately selected from glass, resin film, gas barrier film, etc., similar to the substrate 1. For example, as a gas barrier film, materials such as SiO2 (silicon oxide), SiN (silicon nitride), and SiON (silicon oxynitride) can be used. Furthermore, the sealing layer 9, which is made of resin materials such as acrylic resin and polysiloxane, can also be provided on the layer formed by materials such as SiO2 (silicon oxide), SiN (silicon nitride), and SiON (silicon oxynitride). In the case of a top-emitting display device, it is preferable to form it with a light-transmitting material.

[0170] Furthermore, the adhesive used in cases where bonding is required must also be one with high gas barrier properties. Commonly known adhesives such as two-component epoxy adhesives (XNR, manufactured by Nagase ChemteX) or organic device sealants (MOISTURECUT, manufactured by MORESCO) can be selected. Alternatively, a method of laser melting sintered glass at the periphery of the display device can be used.

[0171] Taking moisture into consideration, introducing a desiccant during the sealing process is also effective. Known desiccants include barium oxide or calcium oxide; higher moisture adsorption capacity is better, and there are no particular limitations.

[0172] <Polarization layer> The organic EL display device of the present invention preferably further includes a polarizing layer 10, as shown in FIG. 5. Specifically, a linear polarizing layer and a λ / 4 retardation layer are laminated to suppress the reflection of light incident on the display device from the outside. The linear polarizing layer is not particularly limited; for example, a film obtained by dyeing a polyvinyl alcohol-based film with iodine and then uniaxially stretching it is commonly used. The material constituting the λ / 4 retardation layer is not particularly limited, but a heat-resistant polyimide-based resin is preferred.

[0173] <Ultraviolet Absorption Layer> The organic EL display device of the present invention preferably further includes an ultraviolet absorption layer 11, as shown in FIG. 5. By including the ultraviolet absorption layer 11, degradation of the substrate or organic EL layer 5 caused by ultraviolet radiation can be suppressed, improving the reliability of the display device. The ultraviolet absorption layer 11 is preferably a layer that absorbs light with wavelengths below 320 nm, more preferably a layer that absorbs light with wavelengths below 360 nm, and even more preferably a layer that absorbs light with wavelengths below 420 nm. Since light with wavelengths above 420 nm overlaps with the blue light emitted for display, the ultraviolet absorption layer 11 preferably has high transmittance in the region above 420 nm. This is particularly effective when the organic EL display device of the present invention is used outdoors.

[0174] The ultraviolet absorbing layer 11 preferably contains resins such as polyimide resin, polyamine resin, polyamine-imide resin, polycarbonate resin, polyester resin, polyether resin, polyaryl ester resin, polyolefin resin, polyethylene terephthalate resin, polymethyl methacrylate resin, polyurethane resin, polyethylene resin, polyvinylidene chloride resin, alicyclic olefin polymer resin, acrylic polymer resin, and cellulose ester resin. It may also contain two or more types. More preferably, it is polyimide resin or polyamine resin.

[0175] The ultraviolet absorbing layer 11 may also contain ultraviolet absorbers. Examples of ultraviolet absorbers include diphenyl ketone compounds, diphenyl ketone oxide compounds, benzotriazole compounds, salicylate compounds, salicylates, acrylonitrile compounds, cyanoacrylate compounds, hindered amine compounds, triterpenoid compounds, nickel complex salt compounds, ultrafine titanium dioxide particles, metal complex salt compounds, and other known polymeric ultraviolet absorbers. Two or more of these may be present. Due to superior transparency, benzotriazole compounds and diphenyl ketone compounds are preferred, and benzotriazole compounds are even more preferred.

[0176] As a polymeric ultraviolet absorber, an example is the copolymerization of RUVA-93, a reactive ultraviolet absorber manufactured by Otsuka Chemical Co., Ltd., and acrylic monomers.

[0177] <Manufacturing Method of Organic EL Display Devices> The manufacturing method of the organic EL display device of the present invention is a manufacturing method of an organic EL display device having a substrate, an organic EL layer 5 and a second electrode 6. The substrate has a first electrode 2, a pixel segmentation layer 3 and a spacer 4 on a substrate 1. The manufacturing method of the organic EL display device includes a step of processing the pixel segmentation layer 3 and the spacer 4 together. The photomask used for processing together is a halftone photomask having a light-transmitting part, a light-shielding part and a semi-light-transmitting part.

[0178] One example of the manufacturing method of the organic EL display device of the present invention will be described using the case of manufacturing the top-emitting organic EL display device shown in FIG5 as an example.

[0179] First, wiring or TFTs 7 are formed on a substrate that is a resin film. As a step, in addition to the TFT formation steps such as the "gate electrode formation step", "gate insulating film formation step", "Si film formation step", and "source and drain electrode formation step", the configuration of wiring to ensure electrical connection can also be formed using known methods.

[0180] Next, the planarization layer 8 is coated into a film using a slot coating method and then heated to harden. At this time, contact holes are pre-formed for connecting the first electrode 2. If the material used for the planarization layer 8 is photosensitive, it is processed by photolithography; if it is non-photosensitive, it is processed by conventional etching using a resist material as a mask. This completes the substrate 1.

[0181] Next, AgPdCu and ITO are sequentially deposited on the substrate to form a first electrode 2, and patterning is performed to form the first electrode 2.

[0182] The method for manufacturing the organic EL display device of the present invention involves forming a pixel segmentation layer 3 in the gap of the first electrode 2, and then forming spacers 4 on the pixel segmentation layer. As a step, after coating the entire surface of the photosensitive resin, an opening is formed on the first electrode by photolithography, and the opening becomes a display pixel.

[0183] The manufacturing method of the organic EL display device of the present invention involves forming a pixel segmentation layer 3 and spacers 4 on the pixel segmentation layer together. The photomask used to process the pixel segmentation layer 3 and spacers 4 together must be a halftone photomask having a light-transmitting portion, a light-shielding portion, and a semi-transparent portion. Generally, in cases where photosensitivity is utilized, a full-tone photomask consisting of a light-shielding portion and a light-transmitting portion is used. However, the halftone photomask used in the present invention, for example, as shown in FIG. 6, has a pattern including a light-transmitting portion 12 and a light-shielding portion 14, and a semi-transparent portion 13 between the light-transmitting portion 12 and the light-shielding portion 14 with a lower transmittance than the light-transmitting portion 12 and a higher transmittance than the light-shielding portion 14. By using the halftone photomask for exposure, a pattern with a stepped shape can be formed after development and heat curing. Furthermore, when the photosensitive resin composition is positive, the exposed portion irradiated by the aforementioned light-transmitting portion exhibits alkali solubility and becomes an opening, while the unexposed portion, which is not irradiated by the aforementioned light-shielding portion, becomes a thick film, equivalent to the spacer 4. The halftone exposed portion irradiated by the aforementioned semi-transparent portion corresponds to the aforementioned pixel segmentation layer 3, which has a film thickness smaller than that of the spacer 4. Conversely, when the photosensitive resin composition is negative, the hardened portion irradiated by the aforementioned light-transmitting portion corresponds to the aforementioned spacer 4, and the halftone exposed portion irradiated by the aforementioned semi-transparent portion corresponds to the aforementioned pixel segmentation layer 3.

[0184] As will be described later, the halftone mask used in this invention preferably has a transmittance of 15% to 50% of the transmittance of the light-transmitting portion. When the transmittance of the light-transmitting portion is set to (%TFT), the transmittance of the semi-transparent portion (%THT) is preferably 15% or more of (%TFT), and more preferably 20% or more. If the transmittance of the semi-transparent portion (%THT) is within the above range, the exposure during the formation of the hardened pattern with a stepped shape can be reduced, and the tick time can be shortened. On the other hand, the transmittance of the semi-transparent portion (%THT) is preferably 50% or less of (%TFT), and more preferably 45% or less. If the transmittance of the semi-transparent portion (%THT) is within the above range, the thickness difference between the spacer 4 and the pixel dividing layer 3 can be sufficiently increased, thereby improving the reliability of the display device. Furthermore, if the transmittance of the semi-transparent portion is within the aforementioned range, sufficient exposure to reactive chemical rays will not be obtained in the semi-transparent portion during pattern processing of the photosensitive resin composition. After the development step following irradiation by the reactive chemical rays, a difference in surface roughness will occur between the pixel dividing layer 3 and the spacer 4. Thus, by creating a difference in the absolute value of the difference between the surface roughness Ra1 of the pixel dividing layer 3 and the surface roughness Ra2 of the spacer 4, two types of anchoring effects are achieved, as described above, resulting in improved adhesion. To effectively obtain the anchoring effect, the difference between Ra1 and Ra2 should preferably be at least 1.0 nm. In addition to the transmittance of the semi-transparent portion, Ra1 and Ra2 can also be adjusted by modifying the resin composition, which may contain coloring materials or repellent materials.

[0185] Furthermore, in addition to the steps of using the halftone mask described above, several methods such as mechanical grinding with abrasive materials, spraying or wet spraying with abrasive materials, plasma treatment or dry etching treatment such as RIE can also be used to adjust the surface roughness. In this invention, in order to make the absolute value of the difference between Ra1 and Ra2 greater than 1.0 nm, a halftone mask must also be used.

[0186] In the manufacturing method of the organic EL display device of the present invention, a cleaning step may be performed before the step of forming the organic EL layer 5 described later. Generally, since there is often residual contamination from previous steps such as photolithography on the surface of the first electrode, wet or dry cleaning is effective. For wet cleaning, methods such as immersion in organic solvents or surfactants, water, acid, alkali, etc., ultrasonic cleaning, and boiling cleaning can be selected. For dry cleaning, methods such as glow discharge treatment, plasma discharge treatment, and UV / ozone treatment can be selected. For dry cleaning using an oxygen environment, contaminants can be removed or the work function can be adjusted. By adjusting the characteristics of the first electrode 2, the carrier injection efficiency from the first electrode 2 to the adjacent organic EL layer 5 is increased, resulting in improved luminous efficiency and reliability as characteristics of the display device.

[0187] Next, the manufacturing method of the organic EL display device of the present invention includes the step of forming an organic EL layer 5. The hole transport layer or light-emitting layer, electron transport layer and other layers constituting the organic EL layer 5 can be formed by known methods, such as by mask evaporation or inkjet printing.

[0188] The so-called mask evaporation method is a method of patterning organic compounds by evaporating them using an evaporation mask. For example, a evaporation mask with the desired pattern as an opening is placed on the evaporation source side of a substrate and evaporation is performed. To obtain high-precision evaporation patterns, it is important to ensure that the evaporation mask with high flatness adheres tightly to the substrate. This can generally be achieved by applying tension to the evaporation mask or by using a magnet placed on the back of the substrate to ensure tight adhesion. Since particle generation caused by the contact between the substrate and the evaporation mask can reduce panel yield or degrade light-emitting elements, it is preferable to minimize and reduce the size of the spacers 4 in contact with the evaporation mask.

[0189] Methods for manufacturing vapor-deposited masks include etching, mechanical grinding, sandblasting, sintering, laser processing, the use of photosensitive resins, and electroforming. When fine patterns are required, etching or electroforming, which have superior processing precision, are preferred.

[0190] The more intricate the pattern, the more difficult the masking or inkjet coating process becomes. Therefore, it is required to use only the minimum amount of light-emitting layer needed to determine the color of the light emission. In this case, by making the hole transport layer or electron transport layer outside the light-emitting layer the same color, it is possible to coat the entire surface, thereby increasing the panel's yield or reducing its cost.

[0191] The method for manufacturing the organic EL display device of the present invention further includes a step of forming a second electrode 6. Known methods can be used for this formation, but vacuum evaporation is preferred to easily avoid deterioration or damage to the organic EL layer 5 that serves as the substrate.

[0192] In the method for manufacturing the organic EL display device of Figure 5, after the step of forming the second electrode 6, a sealing layer 9, a polarizing layer 10, and an ultraviolet absorption layer 11 are sequentially deposited. Each layer can be formed according to known methods, and the organic EL display device of Figure 5 is completed as described above. [Example]

[0193] The following examples illustrate the present invention, but the present invention is not limited to these examples.

[0194] In the following evaluations, those where the number of trials n was not recorded are evaluated based on n=1.

[0195] <Film thickness measurement and pull-out observation of pixel segmentation layer and spacer> The film thickness of the pixel segmentation layer and spacers in each embodiment and comparative example was measured using a surface roughness measuring machine (SURFCOM 1400D, Tokyo Seimitsu Corporation) based on the step difference between the pixel segmentation layer and spacers on the patterned substrate (100mm × 100mm). The pull-out was observed using a scanning electron microscope (SEM, S-3000N, Hitachi High-Technologies Corporation) on a cut cross-section of the patterned substrate.

[0196] <Surface roughness of pixel segmentation layer and spacer> The surface roughness of the pixel segmentation layer and spacers in each embodiment and comparative example is the arithmetic mean roughness (Ra) obtained from observations of the pixel segmentation layer and spacers on a patterned substrate (100mm × 100mm) using an atomic force microscope (AFM, Dimension Icon, Bruker). The observation conditions were set as follows: RTESP-300 probe, tapping mode, scan size 5µm□, scan rate 0.1Hz, and 1024 sample lines.

[0197] <Observation of silicon dioxide particles contained in the pixel segmentation layer> The silicon dioxide particles contained in the pixel segmentation layer in each embodiment and comparative example were measured using an image resolution particle size analyzer (Mac-View, manufactured by MOUNTECH) based on images observed by transmission electron microscopy-energy dispersive X-ray spectroscopy (TEM-EDX) at a magnification of 50,000. Specifically, 30 silicon dioxide particles (experiment number n = 30) were randomly selected from the cross-section of the pixel segmentation layer on a patterned substrate (100mm × 100mm) in the TEM image. The major axis, minor axis, and aspect ratio of each particle in the TEM image were measured. Silicon dioxide particles with a major axis (nm) of 5–30 nm and an aspect ratio of 1.0–1.5 were defined as component (a). Furthermore, in the case where the minor axis and major axis of a single silicon dioxide particle in the TEM image are equal, i.e., a perfect circle, its diameter was considered the major axis. The representative values ​​representing the characteristics of silicon dioxide particles belonging to component (a) are the average value of the first particle size, that is, the average value of the major diameter, rounded to the first decimal place, and the average value of the aspect ratio, that is, the average value of the aspect ratio of each silicon dioxide particle belonging to component (a), rounded to the second decimal place.

[0198] In Table 10, A represents the presence of component (a) and B represents the absence of component (a). The cross-sectional analysis results of Examples 23, 24, and 25, which contain component (a), are shown in Table 11.

[0199] <Measurement of Diffuse Reflection Light> The diffuse reflectance of the substrates in each embodiment and comparative example was measured on the surface of a patterned substrate (100mm × 100mm) where pixel separation layers and spacers were formed, using a spectrometer (CM-2600d, manufactured by Konica-Minolta Japan). The diffuse reflectance was measured at a wavelength of 550nm in the SCE mode, which is used to remove positive reflection. A higher diffuse reflectance was considered to be better at suppressing positive reflection, and was judged to have good characteristics.

[0200] <Adhesion Test> The adhesion test of the organic EL display devices in each embodiment and comparative example was conducted as shown in Figure 7. A 5mm diameter metal cylinder was fixed at the center of the side opposite to the surface where the light-emitting element was formed on the substrate (100mm × 100mm) where the light-emitting element was formed. Repeated bending operations were performed along this cylinder, ranging from an angle of 0° (when the substrate was flat) to an angle of 180° (when the cylinder was folded back). The bent portions were then observed using an optical microscope. Those exhibiting peeling after 1-100 bending operations were classified as having low adhesion (C), those after 101-1000 bending operations as having good adhesion (B), and those after 1001 bending operations or more as having high adhesion (A). Furthermore, the test was conducted 10 times (test number n = 10), and the result showing the minimum number of times peeling occurred was taken.

[0201] <Weathering Reliability Test> The weathering reliability test of the organic EL display devices in each embodiment and comparative example was conducted on the organic EL display devices manufactured in the following embodiments and comparative examples to confirm their condition after being placed at room temperature of 23°C and humidity of 45% for 24 hours. Ten display devices were tested (test number n = 10). If no corrosion was observed on the second electrode, the device was deemed to have good weathering reliability (A). If even one instance of corrosion was observed, it was deemed to have pinholes on the second electrode (B).

[0202] <Electrical Reliability Testing> The electrical reliability test of the organic EL display devices in each embodiment and comparative example was conducted by applying a voltage of 5V between two adjacent stripe-shaped first electrodes in the organic EL display devices manufactured in the embodiments and comparative examples described below, and measuring the current values ​​therebetween. The measurement was performed using a power meter (2400, manufactured by Keithley Instruments, Inc.). A lower current value indicates less leakage current, and is considered to indicate good performance. Furthermore, the test was conducted at 20 locations (test n = 20), and the average of the 10 locations after excluding the 5 largest and 5 smallest results was used.

[0203] <Luminous Properties Test> The light emission characteristics tests of the organic EL display devices in each embodiment and comparative example were conducted by applying a current of 10 mA / cm² to one light-emitting element with a selected pair of crossed first and second electrodes in the organic EL display devices described below, and measuring the voltage and luminance at that time. The voltage was measured using a power meter (2400, Keithley Instruments, Inc.), and the luminance was measured using a spectroradiometer (CS-1000, Konica Minolta).

[0204] <Design of the First Electrode and Halftone Mask> The designs of the first electrode and halftone mask in each embodiment and comparative example are shown in FIG. 6. As shown in FIG. 6a, the first electrode 2 is fabricated in a stripe pattern with 100 stripes of 60μm line width, 100μm spacing, and 10mm length at the center of the substrate 1 (100mm × 100mm). That is, the exposed portion of the substrate 1 is 40μm wide. In contrast, the positive halftone mask b is configured such that the light-shielding portion 14 serves as a spacer and the semi-transparent portion 13 serves as a pixel segmentation layer, with each line width adjusted at a spacing of 100μm. The negative halftone mask c is configured such that the light-transmitting portion 12 serves as a spacer and the semi-transparent portion 13 serves as a pixel segmentation layer, with each line width I and II adjusted. In any case, the pixel segmentation layer and the spacer are aligned as shown in FIG. 6 in such a way that they are positioned in the gap of the first electrode. In the completed substrate, linewidth I corresponds to the interface between the pixel separation layer and the organic EL layer, and linewidth II corresponds to the interface between the spacer and the organic EL layer.

[0205] <Preparation of Photosensitive Resin Composition> The photosensitive resin compositions R-1 to R-15 used in the various embodiments and comparative examples were formulated as follows. Furthermore, the names of the compounds used, when abbreviated, are as follows. BAHF: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane BFE: 1,2-bis(4-methoxyphenyl)ethane BIP-PHBZ:4,4',4”-Methylene pyrogallol (manufactured by Asahi Organics Co., Ltd.) BYK-333: Polysiloxane surfactant "BYK" (registered trademark) 333 (manufactured by BYK-Chemie). DAE: Diaminodiphenyl ether DFA: N,N-Dimethylformamide dimethyl acetal DMAA: N,N-dimethylacrylamide DPCA-60: Caprolactone 6-mol modified dinepentyltetraol hexaacrylate (a hexafunctional acrylate with 6 pentyleneoxy chains, manufactured by Nippon Kayaku Co., Ltd.) EL: Ethyl lactate FAMAC-6: 2-(perfluorohexyl) ethyl methacrylate GBL: γ-Butyrolactone GMA: Glycidyl methacrylate HA: a diamine compound containing hydroxyl groups HMOM-TPHAP: A compound having a phenolic hydroxyl group and substituents with a molecular weight of 40 or more at two ortho positions of the phenolic hydroxyl group, manufactured by Honshu Chemical Industry Co., Ltd.

[0206] [Chemistry 13]

[0207] KBM-403: 3-Epoxypropoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) MAP: 3-aminophenol; meta-aminophenol MBA: 3-Methoxy-n-Butyl Acetate MEK-ST-40: Silicon dioxide particle dispersion (manufactured by Nissan Chemical Industries, Ltd.). The solvent is methyl ethyl ketone (MEK). MEK-ST-L: Silicon dioxide particle dispersion (manufactured by Nissan Chemical Industries, Ltd.). The solvent is methyl ethyl ketone (MEK). MeTMS: Methyltrimethoxysilane NA: 5-Nordiene-2,3-dicarboxylic anhydride; Nadic anhydride TMOS: Tetramethoxysilane NCI-831: "ADEKA ARKLS" (registered trademark) NCI-831 (ADEKA (stock)) NMP: N-methyl-2-pyrrolidone ODPA: Bis(3,4-dicarboxyphenyl) ether dianhydride; oxydiphthalic acid dianhydride OSCAL-1421: Silica particle dispersion (manufactured by Nippon Chemi-Conductivity, Inc.). Solvent is isopropanol. PGME: Propylene Glycol Monomethyl Ether PGMEA: Propylene Glycol Monomethyl Ether Acetate PhTMS: Phenylacetyltrimethoxysilane S0100CF: Irgaphor Black (Registered Trademark) S0100CF SiDA: 1,3-bis(3-aminopropyl)tetramethyldisiloxane S-20000: SOLSPERSE (registered trademark) 20000 (polyether dispersant, manufactured by Lubrizol) TMSSucA: 3-Trimethoxysilylpropylsuccinic anhydride TrisP-PA: 1,1-bis(4-hydroxyphenyl)-1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethane (manufactured by Honshu Chemical Industry Co., Ltd.) WR-301: "ADEKA ARKLS" (registered trademark) WR-301 (manufactured by ADEKA (stock)) Karenz MOI-BM: Ethyl 2-(O-[1'-methylpropylamino]carboxamino)methacrylate Bisphenol AF: 2,2-bis(4-hydroxyphenyl)hexafluoropropane (Central Glass Corporation) 6FDA: 2,2-(3,4-dicarboxyphenyl)hexafluoropropane dianhydride; 4,4'-hexafluoropropane-2,2-diyl-bis(1,2-phthalic anhydride) Pigment dispersant 1: Pigment dispersant 1 (100% by weight solids) disclosed in Synthesis Example 2 of Japanese Patent Application Publication No. 2020 / 70352. It is a polymeric dispersant having a linear polyalkylamine structure and a polyether polymer chain.

[0208] <Synthesis Example 1: Synthesis of Polyimide Resin (PI-1)> Under a dry nitrogen stream, 31.13 g (0.085 mol; 77.3 mol relative to total amines and their derivatives), 1.24 g (0.0050 mol; 4.5 mol relative to total amines and their derivatives), 2.18 g (0.020 mol; 18.2 mol relative to total amines and their derivatives), and 150.00 g of NMP were weighed and dissolved in a three-necked flask. A solution containing 31.02 g (0.10 mol; 100 mol relative to total amines and their derivatives) of ODPA dissolved in 50.00 g of NMP was added, and the mixture was stirred at 20°C for 1 hour, followed by stirring at 50°C for 4 hours. Then, 15 g of xylene was added, and the mixture was azeotropically boiled with water and stirred at 150°C for 5 hours. After the reaction was complete, the reaction solution was added to 3 L of water, and the precipitated solid precipitate was filtered. The obtained solid was washed three times with water and then dried in a vacuum dryer at 80 °C for 24 hours to obtain polyimide resin (PI-1). The weight average molecular weight (Mw) of the obtained polyimide resin (PI-1) was 27,000, and the acid equivalent was 350.

[0209] <Synthesis Example 2: Synthesis of HA> Weigh 18.31 g (0.05 mol) of BAHF, 17.42 g (0.3 mol) of propylene oxide, and 100 mL of acetone and dissolve them. Add dropwise a solution of 20.41 g (0.11 mol) of 3-nitrobenzyl chloride dissolved in 10 mL of acetone. After the addition is complete, react at -15°C for 4 hours, then return to room temperature. Filter the precipitated white solid and dry it under vacuum at 50°C. Place 30 g of the resulting solid into a 300 mL stainless steel autoclave and disperse it in 250 mL of 2-methoxyethanol. Add 2 g of 5% palladium-carbon. Introduce hydrogen into the autoclave using a balloon and react at room temperature for 2 hours. After 2 hours, confirm that the balloon no longer shrinks. After the reaction is complete, filter to remove the palladium compound of the catalyst, then concentrate by vacuum distillation to obtain a diamine compound (HA) containing a hydroxyl group with the following structure.

[0210] [Chemistry 14]

[0211] <Synthetic Example 3: Synthesis of Polyimide Precursor Resin (PIP-1)> Under a dry nitrogen stream, 44.42 g (0.10 mol; relative to 100 mol of total carboxylic acids and their derivatives) and 150 g of NMP were weighed and dissolved in a three-necked flask. A solution containing 14.65 g (0.040 mol; relative to 32.0 mol of total amines and their derivatives), 18.14 g (0.030 mol; relative to 24.0 mol of total amines and their derivatives), and 1.24 g (0.0050 mol; relative to 4.0 mol of total amines and their derivatives) dissolved in 50 g of NMP was added to the solution. The mixture was stirred at 20 °C for 1 hour, followed by stirring at 50 °C for 2 hours. As a terminator, MAP 5.46 g (0.050 mol; 40.0 mol relative to the total amine and its derivatives) was dissolved in 15 g of NMP and stirred at 50 °C for 2 hours. Subsequently, a solution of DFA 23.83 g (0.20 mol) dissolved in 15 g of NMP was added. After the addition was complete, the mixture was stirred at 50 °C for 3 hours. After the reaction was complete, the reaction solution was cooled to room temperature and then added to 3 L of water. The precipitated solid was filtered to obtain the product. The obtained solid was washed three times with water and dried in a vacuum dryer at 80 °C for 24 hours to obtain polyimide precursor resin (PIP-1). The obtained polyimide precursor resin (PIP-1) had a weight average molecular weight (Mw) of 20,000 and an acid equivalent of 450.

[0212] <Synthesis Example 4: Synthesis of Polyimide Precursor Resin (PIP-2)> Under a dry nitrogen stream, 1.2 g (0.035 mol) of HA2, 7.0 g (0.035 mol) of DAE, and 1.2 g (0.005 mol) of SiDA obtained in Synthesis Example 2 were dissolved in 400 g of NMP. 1.0 g (0.10 mol) of ODPA3 was then added together with 50 g of NMP, and the mixture was stirred at 40 °C for 1 hour. Subsequently, 5.5 g (0.050 mol) of MAP was added, and the mixture was stirred at 40 °C for 1 hour. Then, a solution containing 8.3 g (0.07 mol) of DFA dissolved in 10 g of NMP was added. After the addition was complete, the mixture was stirred at 40 °C for 3 hours. After stirring, the solution was cooled to room temperature and then added to 3L of water to obtain a white precipitate. The precipitate was filtered and collected, washed three times with water, and then dried in a vacuum dryer at 50°C for 72 hours to obtain an alkali-soluble resin (PIP-2) composed of a polyimide precursor resin with an acid equivalent of 275 g / mol.

[0213] <Synthesis Example 5: Synthesis of Polyimide Precursor Resin (PIP-3)> The amount of DFA added in the same manner as in Synthesis Example 4 was set to 13.1 g (0.11 mol), and an alkali-soluble resin (PIP-3) composed of a polyimide precursor resin with an acid equivalent of 329 g / mol was obtained.

[0214] <Synthesis Example 6: Synthesis of Polyimide Precursor Resin (PIP-4)> The amount of DFA added in the same manner as in Synthesis Example 4 was set to 16.7 g (0.14 mol), and an alkali-soluble resin (PIP-4) composed of a polyimide precursor resin with an acid equivalent of 366 g / mol was obtained.

[0215] <Synthesis Example 7: Synthesis of Polybenzoxazole Resin (PBO-1)> In a 500 mL round-bottom flask filled with toluene and equipped with a Dean-Stark water separator and cooling tubes, 34.79 g (0.095 mol; 95.0 mol relative to total amines and their derivatives), 1.24 g (0.0050 mol; 5.0 mol relative to total amines and their derivatives), and 75.00 g of NMP were weighed and dissolved. A solution containing 19.06 g (0.080 mol; 66.7 mol relative to total carboxylic acids and their derivatives) of BFE dissolved in 25.00 g of NMP, and 6.57 g (0.040 mol; 33.3 mol relative to total carboxylic acids and their derivatives) of NA as a terminator was added. The mixture was stirred at 20 °C for 1 hour, followed by stirring at 50 °C for 1 hour. Subsequently, the mixture was heated and stirred at 200 °C or higher for 10 hours under nitrogen to carry out the dehydration reaction. After the reaction was complete, the reaction solution was added to 3 L of water, and the precipitated solid precipitate was filtered out. The obtained solid was washed three times with water and then dried in a vacuum dryer at 80 °C for 24 hours to obtain polybenzoxazole resin (PBO-1). The weight average molecular weight (Mw) of the obtained polybenzoxazole resin (PBO-1) was 25,000, and the acid equivalent was 330.

[0216] <Synthetic Example 8: Synthesis of Polybenzoxazole Precursor Resin (PBOP-1)> In a 500 mL round-bottom flask filled with toluene and equipped with a Dean-Stark water separator and cooling tubes, 34.79 g (0.095 mol; 95.0 mol relative to total amines and their derivatives), 1.24 g (0.0050 mol; 5.0 mol relative to total amines and their derivatives), and 70.00 g of NMP were weighed and dissolved. A solution containing 19.06 g (0.080 mol; 66.7 mol relative to total carboxylic acids and their derivatives) dissolved in 20.00 g of NMP was added to the flask. The mixture was stirred at 20 °C for 1 hour, followed by stirring at 50 °C for 2 hours.

[0217] Next, as a terminator, a solution containing 6.57 g of NA (0.040 mol; 33.3 mol relative to the total carboxylic acid and its derivatives) dissolved in 10 g of NMP was added, and the mixture was stirred at 50 °C for 2 hours. Subsequently, the mixture was stirred at 100 °C for 2 hours under nitrogen. After the reaction was complete, the reaction solution was added to 3 L of water, and the precipitated solid was filtered. The obtained solid was washed three times with water and then dried in a vacuum dryer at 80 °C for 24 hours to obtain polybenzoxazole precursor resin (PBOP-1). The obtained polybenzoxazole precursor resin (PBOP-1) had a weight-average molecular weight (Mw) of 20,000 and an acid equivalent of 330.

[0218] <Synthesis Example 9: Synthesis of Polysiloxane Resin Solution (PS-1)> A three-necked flask was filled with 23.84 g (35 mol%) of MeTMS, 49.57 g (50 mol%) of PhTMS, 3.81 g (5 mol%) of TMOS, and 76.36 g of PGMEA. Air was circulated through the flask at a rate of 0.05 L / min, and the mixture was stirred while being heated to 40°C in an oil bath. While continuing to stir the mixture, an aqueous solution of phosphoric acid (0.271 g dissolved in 28.38 g of water) was added dropwise over 10 minutes. After the addition was complete, the mixture was stirred at 40°C for 30 minutes to hydrolyze the silane compounds. After hydrolysis, a solution of 13.12 g (10 mol%) of TMS SucA (13.12 g dissolved in 8.48 g of PGMEA) was added. The bath temperature was then set to 70°C and stirred for 1 hour, after which the bath temperature was increased to 115°C. After heating began, the solution temperature reached 100°C in approximately one hour, and was then heated and stirred for 2 hours (internal temperature 100-110°C). The resulting resin solution was cooled in an ice bath, and then 2% by weight of anion exchange resin and cation exchange resin were added to the solution, respectively, and stirred for 12 hours. After stirring, the anion exchange resin and cation exchange resin were filtered off to obtain a polysiloxane resin solution (PS-1). The obtained polysiloxane resin had a weight-average molecular weight (Mw) of 4,200 and a carboxylic acid equivalent (acid equivalent) of 700 g / mol.

[0219] <Synthetic Example 10: Synthesis of a photosensitizer (diazidoquinone compound b-1)> Under a dry nitrogen stream, 21.22 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 36.27 g (0.135 mol) of 5-naphthoquinone sulfonyl chloride were dissolved in 450 g of 1,4-dimethylamine and allowed to reach room temperature. 15.18 g of triethylamine, mixed with 50 g of 1,4-dimethylamine, was added dropwise to the mixture, ensuring the reaction system did not exceed 35°C. The mixture was stirred at 30°C for 2 hours after the addition. The triethylamine salt was filtered, and the filtrate was added to water. The precipitate was then collected by filtration. This precipitate was dried using a vacuum dryer to obtain a photosensitizer (diazidoquinone compound b-1) with the following structure.

[0220] [Chemistry 15]

[0221] <Modulation of salt-forming compound d-1> In a separating flask, 9.25 g (0.018 mol) of CI Basic Blue 7 (a basic dye) and 200 g of pure water were added, and the mixture was stirred at 60 °C for 30 minutes. Then, an aqueous solution of 11.50 g (0.019.8 mol) of CI Acid Red 52 (an acid dye) dissolved in 120 g of pure water was added, and the mixture was stirred at 60 °C for 60 minutes. Afterward, heating was stopped, and the mixture was cooled to room temperature. Upon cooling to room temperature, the reaction solution was filtered to obtain a purple solid. This solid was dried under reduced pressure at 60 °C for 8 hours to obtain the salt-forming compound d-1.

[0222] <Modulation of salt-forming compound d-2> Following the same method as d-1, CI Basic Blue 7, which is a basic dye, was replaced with CI Basic Blue 26 to obtain the salt-forming compound d-2.

[0223] <Preparation of Pigment Dispersion 1> To 742.39 g of PGMEA (a solvent component), 15.00 g of S-20000 (a pigment dispersant with basic groups) was added, followed by 2.70 g of a PGMEA solution containing 1.00% by weight of 4-methylbenzenesulfonic acid. The mixture was then stirred for 1 hour at atmospheric pressure and 25°C, and then allowed to stand for 6 hours to allow the basic groups of S-20000 and the sulfonic acid groups of 4-methylbenzenesulfonic acid to form a salt. Next, 149.91 g of an alkali-soluble resin solution (a resin solution obtained by dissolving the above-mentioned PIP-1 in PGMEA to a solid content of 30% by weight, with 30.0% by weight of solids) was added. After stirring for 30 minutes, 90.00 g of a benzodifuranone-based black pigment with the structure described below was mixed and stirred for 20 minutes to obtain a pre-dispersion. The pre-dispersion was then transferred to a 0.4 mm thick container filled with a dispersion medium. Zirconia beads ("TORAYCERAM" (registered trademark), manufactured by Toray Industries, Inc.) were used in a bead mill at 75% volume and dispersed once. Then, a wet media dispersion was performed using a circulating method. After 30 minutes, every 10 minutes during the dispersion process, a sample of the pigment dispersion was extracted from the disperser's outlet and placed in a glass bottle container. The average dispersed particle size was measured using a laser diffraction / scattering particle size distribution measuring device (UPA150, manufactured by Microtrac Corporation). The pigment dispersion with an average dispersed particle size of 150 ± 10 nm (average diameter at 50% volume) and 300 ± 30 nm (average diameter at 90% volume) after 30 minutes was designated as "pigment dispersion 1".

[0224] [Chemistry 16]

[0225] <Preparation of Pigment Dispersion 2> Following the same procedure as "pigment dispersion 1", MBA was used instead of PGMEA to dissolve PIP-1 to prepare "pigment dispersion 2".

[0226] <Preparation of Pigment Dispersion 3> 200g of zirconium nitride particles (ZrN, manufactured by Nisshin Engineering Co., Ltd.) produced by thermoplasma method, 50g of polyimide precursor resin (PIP-1), and 1000g of γ-butyrolactone (GBL) were packed into a tank and stirred with a homogenizer for 20 minutes to obtain a pre-dispersion. The mixture was then packed with a 0.05mm... The prepared dispersion, supplied with 75% by volume of zirconia beads in a centrifuge-equipped disperser (Ultra Apex Mill, HIROSHIMA METAL & MACHINERY, Inc.), was dispersed at a rotation speed of 10 m / s for 3 hours to obtain a pigment dispersion with a solids concentration of 20% by weight and a colorant / resin (weight ratio) of 80 / 20. The composition is shown in Table 1.

[0227] [Table 1] Pigment dispersion Black dispersion (by weight) Coloring materials Alkali-soluble resins solvent Pigment Dispersion 3 ZrN (16) PIP-1 (4) GBL (80) Pigment Dispersion 4 ZrN (16) PIP-2 (4) GBL (80) Pigment Dispersion 5 ZrN (16) PIP-3 (4) GBL (80) Pigment Dispersion 6 ZrN (16) PIP-4 (4) GBL (80)

[0228] <Preparation of Pigment Dispersion 4> Pigment dispersion 4 was obtained by using the same method as pigment dispersion 3, by setting the added alkali-soluble resin as PIP-2.

[0229] <Preparation of Pigment Dispersion 5> Pigment dispersion 5 was obtained by using the same method as pigment dispersion 3, by setting the added alkali-soluble resin as PIP-3.

[0230] <Preparation of Pigment Dispersion 6> Pigment dispersion 6 was obtained by using the same method as pigment dispersion 3, but by setting the added alkali-soluble resin as PIP-4.

[0231] <Preparation of Pigment Dispersion 7> Add 30.00 g of pigment dispersant 1 to 770.00 g of PGMEA (a solvent), stir for 5 minutes, then add 100.00 g of ZCR-1569H and stir for 30 minutes. Next, add 100.00 g of SO100CF (component b) and stir for 30 minutes to obtain a pre-mixed solution. Transfer the pre-mixed solution to a container filled to a volume ratio of 75% by volume with a filler of 0.4 mm. A longitudinal bead mill, using a pulverizing media composed of a composite oxide (zirconia: hafnium oxide: iridium oxide: aluminum oxide = weight ratio 93.3:1.5:4.9:0.3, manufactured by Toray Industries, Inc.), was subjected to a first wet media dispersion treatment for 3 hours at a peripheral speed of 8 m / s using a circulation method. The solution was then fed into a container filled with 0.05 mm [amount missing] at a filling rate of 75% by volume. A longitudinal bead mill composed of a composite oxide grinding medium (zirconia: hafnium oxide: iridium oxide: aluminum oxide = weight ratio 93.3:1.5:4.9:0.3, manufactured by Toray Industries, Inc.) was used for a second wet media dispersion treatment at a circulation speed of 9 m / s for 6 hours. The mixture was then filtered through a 0.8 μm filter to prepare a pigment dispersion 1 with a solid content of 20.00% by weight. The weights of each raw material are shown in Table 2.

[0232] [Table 2] Pigment dispersion Mixing weight (g) Total (g) Pigment dispersion solid components (weight%) (b) Pigments dispersant resin solvent S0100CF Pigment Dispersant 1 ZCR-1569H PGMEA Pigment Dispersion 7 100.00 30.00 100.00 770.00 1000.00 20.00

[0233] <Modulation of photosensitive resin composition R-1> Under yellow light, in solvent (C) consisting of γ-butyrolactone (GBL) and ethyl lactate (EL) in a 1:1 weight ratio, the following were added in the amounts shown in Table 3: polyimide precursor resin PI-1 obtained as (A) alkali-soluble resin synthesis example 1, compound b-1 obtained as (B) photosensitizer synthesis example 10, compound d-1 as a salt-forming compound composed of acid dye and basic dye in (D) coloring material, CI solvent blue 45 as nonionic dye d-3, thermochromic compound f-1 (BIP-PHBZ) with the following structure, thermocrosslinking agent g-1 (HMOM-TPHAP) as other additives, compound h-1 (bisphenol AF) with phenolic hydroxyl groups, and adhesion modifier i-1 (KBM-403). The mixture was stirred until dissolved to prepare positive photosensitive resin composition R-1.

[0234] [Chemistry 17]

[0235] [Table 3] Photosensitive Tree lipid components Mixing weight (g) (A) Alkali soluble Sexual resin (B) Photosensitive agent (D) Coloring materials Thermal color development compound other (C) Solvent (D) Salt formation compound (D2) Non-isolated sub-dyes R-1 PI-1 (3.5g) b-1 (1.0g) d-1 (0.1g) d-3 (0.27g) f-1 (0.7g) g-1 (0.6g) h-1 (0.4g) i-1 (0.1g) GBL (10.0g) EL (10.0g) R-2 PI-1 (3.5g) b-1 (1.0g) d-2 (0.35g) d-3 (0.9g) R-3 PIP-1 (3.5g) b-1 (1.0g) d-2 (0.35g) d-3 (0.9g) R-4 PBO-1 (3.5g) b-1 (1.0g) d-2 (0.35g) d-3 (0.9g) R-5 PBOP-1 (3.5g) b-1 (1.0g) d-2 (0.35g) d-3 (0.9g) R-6 PI-1 (2.7g) PS-1 (0.8g) b-1 (1.0g) d-2 (0.35g) d-3 (0.9g)

[0236] <Preparation of photosensitive resin components R-2~R-6> Similar to the preparation of R-1, R-2 to R-6 are prepared according to the composition recorded in Table 3.

[0237] <Preparation of photosensitive resin component R-7> Under a yellow light, add 0.20g of NCI-831 (a photosensitizer) to 13.01g of PGMEA and stir for 3 minutes to dissolve it. Add 4.28g of alkali-soluble polyimide resin solution A (a resin solution obtained by dissolving PI-1 in PGMEA to a solid content of 30% by weight), 1.02g of alkali-soluble calomel resin solution A (amine value 0 (mgKOH / g), resin acid value 90 (mgKOH / g), solid content 44.2% by weight, PGMEA solution of alkali-soluble calomel resin with carboxyl groups as alkali-soluble groups) "ADEKA ARKLS" (registered trademark) WR-301 (manufactured by ADEKA (stock)), and 0.99g of DPCA-60, which belongs to compounds with two or more free radical polymerizable groups, and stir to obtain a blended solution. Mix this blended solution with 10.50g of pigment dispersion 1 sampled from the supernatant of a glass bottle container and stir for 30 minutes to obtain negative photosensitive resin composition R-7. The proportions of raw materials are shown in Table 4.

[0238] [Table 4] Photosensitive resin composition Mixing weight (g) (A) Alkali-soluble resin (B) Photosensitive agent (D) Coloring materials Having more than 2 free radicals Compounds with polymeric groups (C) Solvent R-7 Alkali-soluble polystyrene Amine resin solution A (4.28g) Alkali-soluble calorie Resin solution A (1.02g) NCI-831 (0.2g) Pigment Dispersion 1 (10.5g) DPCA-60 (0.99g) PGMEA (13.01g) R-8 Alkali-soluble polystyrene Amine resin solution B (4.28g) Alkali-soluble calorie Resin solution A (1.02g) NCI-831 (0.2g) Pigment Dispersion 2 (10.5g) DPCA-60 (0.99g) MBA (13.01g)

[0239] <Modification of Photosensitive Resin Composition R-8> Alkali-soluble polyimide resin solution B (a resin solution obtained by dissolving PI-1 in MBA to a solid content of 30% by weight) was used instead of alkali-soluble polyimide resin solution A, and pigment dispersion 2 was used instead of pigment dispersion 1. The negative photosensitive resin composition R-8 was prepared according to the same procedure as R-7. The proportions of the raw materials are shown in Table 4.

[0240] <Synthetic Example 11: Synthesis of Liquid-Repelling Materials (e-1) and (e-2)> 100 parts by weight of cyclohexanone were added to a 1000 mL reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen inlet. The mixture was heated to 110°C under nitrogen atmosphere. The temperature of the cyclohexanone was maintained at 110°C, and the monomer mixture solution shown in Table 5 was added dropwise over a constant rate for 2 hours to prepare the individual monomer solutions. After the addition was complete, the monomer solutions were heated to 115°C and reacted for 2 hours to obtain the liquid-dissolving materials (e-1) and (e-2).

[0241] [Table 5] (E) Liquid-repellent material (molecular weight) monomer Polymerization initiator Chain transfer agent solvent Acrylamides With perfluorinated groups Having epoxy groups other Tertiary butyl peroxide 2-Ethylhexanoate dodecyl mercapto Cyclohexanone DMAA FAMAC-6 GMA 3-Phenoxybenzyl acrylate e-1(4000) weight 65 7 25 3 1 2 200 e-2(3500) weight 82 4 14 - 1 2 200

[0242] <Synthetic Example 12: Synthesis of Phenolic Resin (j-1)> Under a dry nitrogen stream, 108.0 g (1.00 moles) of m-cresol, 75.5 g (0.93 moles) of 37% formaldehyde aqueous solution (formaldehyde), 0.63 g (0.005 moles) of oxalic acid dihydrate, and 264 g of methyl isobutyl ketone were packed into an oil bath and subjected to a polymerization-condensation reaction for 4 hours while the reaction solution was refluxed. Subsequently, the oil bath temperature was increased over 3 hours, and then the pressure inside the flask was reduced to 4.0 kPa–6.7 kPa to remove volatiles. The dissolved resin was then cooled to room temperature to obtain a phenolic varnish-type phenolic resin (j-1). The weight average molecular weight obtained by GPC was 3,500.

[0243] <Preparation of photosensitive resin components R-9 and R-10> Under a yellow light, the components were mixed according to the mixing ratio shown in Table 6 and stirred thoroughly at room temperature to dissolve them. The resulting solution was then filtered through a 1 μm pore size filter to obtain positive photosensitive resin compositions R-9 and R-10.

[0244] [Table 6] Photosensitive Tree lipid components (E) Liquid-repellent material (A) Alkali solubility resin Phenolic resin Crosslinking agent (B) Photosensitive agent (C) Organic solvents R-9 name e-1 PIP-1 j-1 HMOM-TPHAP b-1 PGMEA PGME weight 1 100 35 20 30 400 400 R-10 name e-2 PI-1 j-1 HMOM-TPHAP b-1 PGMEA PGME weight 5 100 35 20 30 400 400

[0245] <Modulation of Photosensitive Resin Composition R-11> To 93.8 g of pigment dispersion 3, 50.5 g of alkali-soluble resin (PIP-1), 17.0 g of diazidoquinone compound (b-1) as a photoacid generator, 13.6 g of phenolic compound (h-1, bisphenol AF), 0.2 g of polysiloxane surfactant (BYK-333), 105.0 g of GBL, and 720.0 g of PGME were added to obtain a positive photosensitive resin composition R-11 with a total solids concentration of 10% by weight and a pigment / resin (weight ratio) of 15 / 85. The composition is shown in Table 7.

[0246] [Table 7] Photosensitive Tree lipid components Composition (D) Coloring materials (A) Alkali-soluble resin (C) Solvent (B) Photosensitive agent surfactants Pigment dispersion Coloring materials type Acid equivalent (c-1) component (C) Ingredients (c-1) Component content (c-2) component W c2 / W c1 R-11 Pigment Dispersion 3 ZrN PIP-1 220g / mol GBL 20% by weight PGME 4.0 b-1 BYK-333 R-12 Pigment Dispersion 4 ZrN PIP-2 275g / mol GBL 20% by weight PGME 4.0 b-1 BYK-333 R-13 Pigment Dispersion 5 ZrN PIP-3 329g / mol GBL 20% by weight PGME 4.0 b-1 BYK-333 R-14 Pigment Dispersion 6 ZrN PIP-4 366g / mol GBL 20% by weight PGME 4.0 b-1 BYK-333

[0247] <Modulation of Photosensitive Resin Composition R-12> Following the same method as R-11, pigment dispersion 3, which was added as a pigment dispersion, was replaced with pigment dispersion 4, and PIP-1, which was used as an alkali-soluble resin, was replaced with PIP-2 to obtain positive photosensitive resin composition R-12. The composition is shown in Table 7.

[0248] <Modulation of Photosensitive Resin Composition R-13> Following the same method as R-11, pigment dispersion 3, which was added as a pigment dispersion, was replaced with pigment dispersion 5, and PIP-1, which was used as an alkali-soluble resin, was replaced with PIP-3 to obtain positive photosensitive resin composition R-13. The composition is shown in Table 7.

[0249] <Modulation of Photosensitive Resin Composition R-14> Following the same method as R-11, pigment dispersion 3, which was added as a pigment dispersion, was replaced with pigment dispersion 6, and PIP-1, which was used as an alkali-soluble resin, was replaced with PIP-4 to obtain positive photosensitive resin composition R-14. The composition is shown in Table 7.

[0250] <Preparation of Photosensitive Resin Composition R-15> Under yellow light, 10.0 g of polyimide precursor resin (PIP-1) (as (A) alkali-soluble resin) and 1.2 g of f-1 (as (B) photosensitizer) were added to 32.0 g of PGME and 8.0 g of GBL (as (C) organic solvents). The resulting solution was then diluted with water at 0.45 μm... The sample was filtered to obtain the positive photosensitive resin composition R-15.

[0251] <Modulation of Photosensitive Resin Composition R-16> Under yellow light, 0.38 g of OXE03, acting as a photopolymerization initiator, was added to a mixed solvent of 8.50 g of MBA and 16.16 g of PGMEA and stirred for 10 minutes to dissolve. Then, 1.88 g of MEK-ST-40, a silica particle dispersion and component (a), was added and stirred for 10 minutes to dissolve. Next, 4.61 g of ZAH-106, 0.45 g of TR4020G, 0.38 g of DPCA-60, and 0.97 g of GA-5060P were added and stirred for 30 minutes to obtain a transparent blend. 16.69 g of pigment dispersion 7 was mixed with this blend and stirred for 30 minutes to prepare a negative photosensitive resin composition R-16 with a solid content of 15.00% by weight. The mixing weights of each raw material are shown in Table 8.

[0252] [Table 8] Photosensitive Tree lipid components Mixing weight (g) total (g) Photosensitive resin The solid composition Partial composition (by weight) Pigment dispersion methacrylic acid Polyol resin (d) Components (a)Ingredients The molecule has more than two self Compounds with polymeric radicals Photopolymerization Initiator solvent Pigment Dispersion 7 ZAH-106 TR4020G MEK-ST-40 OSCAL-1421 MEK-ST-L DPCA-60 GA-5060P OXE03 MBA PGMEA R-16 16.69 4.61 0.45 1.88 - - 0.38 0.97 0.38 8.50 16.16 50.00 15.00 R-17 16.69 4.61 0.45 - 3.75 - 0.38 0.97 0.38 8.50 14.29 50.00 15.00 R-18 16.69 4.61 0.45 - - 2.50 0.38 0.97 0.38 8.50 15.54 50.00 15.00

[0253] <Preparation of photosensitive resin component R-17> Similar to the preparation of R-16, OSCAL-1421 was used instead of MEK-ST-40, and the negative photosensitive resin composition R-17 was prepared according to the preparation amounts shown in Table 8. The preparation weights of each raw material are shown in Table 8.

[0254] <Preparation of photosensitive resin component R-18> Similar to the formulation of R-16, MEK-ST-L was used instead of MEK-ST-40, and the negative photosensitive resin composition R-18 was formulated according to the formulation amounts shown in Table 8. The formulation weights of each raw material are shown in Table 8.

[0255] <Examples 1-25, Comparative Examples 1-3> The surface roughness of the pixel separation layer and spacer, the diffused and reflected light of the substrate, the adhesion of the organic EL display device, weather resistance reliability, electrical reliability, and luminous characteristics of each embodiment and comparative example are evaluated as follows.

[0256] First, in the center of a 100mm × 100mm PET substrate, AgPdCu (100nm) and crystalline ITO (10nm) are sequentially deposited using vacuum evaporation to form a first electrode, which is then etched into 100 stripes with a line width of 60μm, a spacing of 100μm, and a length of 10mm. That is, the exposed portion of the substrate is 40μm wide. The photosensitive resin compositions prepared according to the various embodiments and comparative examples shown in Table 9 are then coated using spin coating, and subsequently pre-baked on a 100°C heating plate for 2 minutes to form a film.

[0257] After UV exposure using the halftone photomask shown in Table 9, the film was developed with a 2.38% TMAH aqueous solution. For negative development, only the unexposed portions were dissolved; for positive development, only the exposed portions were dissolved. The film was then rinsed with pure water to obtain the pattern. Subsequently, it was cured in an oven at 250°C under nitrogen for 60 minutes to obtain a substrate with a pattern of pixel separation layers and spacers. Furthermore, by adjusting the spin-coating rotation speed, the thickness of the pixel separation layer and the thickness of the spacers were set to 1.5 μm in all examples and comparative examples.

[0258] Furthermore, in Comparative Example 1, a photomask without a semi-transparent portion, commonly known as a full-tone mask, was used to individually fabricate pixel separation layers and spacers. That is, after coating, pre-baking, exposure, development, and curing of the pixel separation layers, the spacers underwent coating, pre-baking, exposure, development, and curing processes. In Comparative Example 3, after curing, a plasma processing apparatus (SPC-100B+H, manufactured by Hitachi High-Technologies) was used for roughening in RIE mode, oxygen, 1000W, for 60 seconds.

[0259] The results of evaluating the surface roughness of the pixel segmentation layer and spacers and the diffused reflected light of the substrate under this condition are shown in Table 10.

[0260] Next, an organic EL layer is formed on the entire surface of the patterned substrate using vacuum evaporation. The vacuum level during evaporation is set to below 1 × 10⁻³ Pa, and the substrate is rotated relative to the evaporation source during the process. First, a 10 nm layer of compound (HT-1) as the hole injection layer and a 50 nm layer of compound (HT-2) as the hole transport layer are deposited. Next, as the light-emitting layer, a 40 nm thick layer is formed by depositing the main material compound (GH-1) and the dopant compound (GD-1) at a doping concentration of 10% by volume. Then, a 40 nm thick layer is formed by depositing the electron transport layer compound (ET-1) and LiQ at a volume ratio of 1:1. The hole injection layer, hole transport layer, light-emitting layer, and electron transport layer up to this point are referred to as the first light-emitting unit.

[0261] Next, 2 nm of LiQ will be deposited as the electron injection layer. The structure of the compound used as the organic EL layer is shown below.

[0262] [Chemistry 18]

[0263] [Chemistry 19]

[0264] Then, following the method of intersecting with the first electrode, Mg and Ag are vapor-deposited at a volume ratio of 10:1 for 10 nm to form a striped second electrode with a linewidth of 400 μm, a spacing of 500 μm, a length of 10 mm, and 20 stripes. Furthermore, the so-called film thickness is displayed by a crystal oscillator-type film thickness monitor.

[0265] Thus, an organic EL display device with 100 first electrodes, 20 second electrodes, and 200 equally intersecting light-emitting elements was completed. A schematic diagram of the organic EL display device of this embodiment is shown in Figure 8, and a schematic diagram of the light-emitting elements of the organic EL layer is shown in Figure 9, which omits the schematic diagram. Subsequently, the adhesion, weather resistance reliability, and electrical reliability of the organic EL display device were evaluated, and the results are shown in Table 10.

[0266] [Table 9-1] Photosensitive Tree lipid components (name) Photosensitive Tree lipid components (Photosensitivity) Light-transmitting part Penetration rate (%) %THT Penetration rate (%) shading part Penetration rate (%) HT mask I-line width (μm) Pixel segmentation Layer area ratio (%) HT mask II line width (μm) spacers Area ratio (%) opening Area ratio (%) Example 1 R-1 just 100 10 0 30 60 20 20 20 2 R-1 just 100 20 0 30 60 20 20 20 3 R-1 just 100 30 0 30 60 20 20 20 4 R-1 just 100 40 0 30 60 20 20 20 5 R-1 just 100 50 0 30 60 20 20 20 6 R-1 just 100 60 0 30 60 20 20 20 7 R-1 just 100 30 0 15 30 50 50 20 8 R-1 just 100 30 0 10 20 60 60 20 9 R-1 just 100 30 0 5 10 70 70 20 10 R-2 just 100 30 0 30 60 20 20 20 11 R-3 just 100 30 0 30 60 20 20 20 12 R-4 just 100 30 0 30 60 20 20 20 13 R-5 just 100 30 0 30 60 20 20 20 14 R-6 just 100 30 0 30 60 20 20 20 15 R-7 burden 100 30 0 30 60 20 20 20 16 R-8 burden 100 30 0 30 60 20 20 20 17 R-9 just 100 30 0 30 60 20 20 20 18 R-10 just 100 30 0 30 60 20 20 20

[0267] [Table 9-2] Photosensitive resin Composition (name) Photosensitive resin Composition (Photosensitivity) Light-transmitting part Penetration rate (%) %THT Penetration rate (%) shading part Penetration rate (%) HT mask I-line width (μm) Pixel segmentation Layer area ratio (%) HT mask II line width (μm) spacers Area ratio (%) opening Area ratio (%) Example 19 R-11 just 100 30 0 30 60 20 20 20 20 R-12 just 100 30 0 30 60 20 20 20 twenty one R-13 just 100 30 0 30 60 20 20 20 twenty two R-14 just 100 30 0 30 60 20 20 20 twenty three R-16 burden 100 30 0 30 60 20 20 20 twenty four R-17 burden 100 30 0 30 60 20 20 20 25 R-18 burden 100 30 0 30 60 20 20 20 26 R-1 just 100 30 0 30 60 20 20 20 27 R-1 just 100 30 0 30 60 20 20 20 28 R-1 just 100 30 0 30 60 20 20 20 29 R-1 just 100 30 0 30 60 20 20 20 30 R-1 just 100 30 0 30 60 20 20 20 31 R-1 just 100 30 0 30 60 20 20 20 32 R-1 just 100 30 0 30 60 20 20 20 33 R-1 just 100 30 0 30 60 20 20 20 Comparative example 1 R-15 just 100 - 0 30 60 20 20 20 2 R-15 just 100 30 0 30 60 20 20 20 3 R-15 just 100 30 0 30 60 20 20 20

[0268] [Table 10-1] Ra1 (nm) Ra2 (nm) Ra1-Ra2 (nm) Ramax (nm) Push angle (Spend) Dioxide Silicon particles diffusion Shot rate (%) tight adhesion Weather resistant reliability Electrically available Reliability (mA) Luminous properties Sex voltage (mV) Luminous properties Sexual luminance (cd / A) Example 1 15.5 15 0.5 15.5 40 B 13 B A 9.0E-06 12 30 2 20 15 5 20 40 B 14 A A 7.0E-06 12 30 3 30 15 15 30 40 B 15 And And 5.0E-06 12 30 4 35 15 20 35 40 B 16 And And 4.0E-06 12 30 5 40 15 25 40 40 B 17 And And 3.0E-06 12 30 6 45 15 30 45 40 B 18 And And 2.0E-06 12 30 7 30 15 15 30 40 B 14 And And 5.0E-06 12 30 8 30 15 15 30 40 B 12 A A 5.0E-06 12 30 9 30 15 15 30 40 B 10 B A 5.0E-06 12 30 10 30 15 15 30 40 B 15 A A 5.0E-06 12 30 11 30 15 15 30 40 B 15 A A 5.0E-06 12 30 12 30 15 15 30 40 B 15 And And 5.0E-06 12 30 13 30 15 15 30 40 B 15 And And 5.0E-06 12 30 14 30 15 15 30 40 B 15 And And 5.0E-06 12 30 15 45 20 25 45 45 B 20 And And 1.0E-06 12 30 16 45 20 25 45 45 B 20 And And 1.0E-06 12 30 17 30 15 15 30 40 B 15 A A 5.0E-06 12 30 18 30 15 15 30 40 B 15 A A 5.0E-06 12 30

[0269] [Table 10-2] Ra1 (nm) Ra2 (nm) Ra1-Ra2 (nm) Ramax (nm) Push angle (Spend) Dioxide Silicon particles diffusion reflectivity (%) tight adhesion Weather resistant reliability Electric reliability (mA) Luminous Sex voltage (mV) Luminous Brightness (cd / A) Actual example 19 40 15 twenty five 40 30 B 17 A A 3.0E-06 12 30 20 40 15 twenty five 40 30 B 17 A A 3.0E-06 12 30 twenty one 40 15 twenty five 40 30 B 17 A A 3.0E-06 12 30 twenty two 40 15 twenty five 40 30 B 17 A A 3.0E-06 12 30 twenty three 48 18 30 48 45 And 23 And And 1.0E-06 12 30 24 48 18 30 48 45 And 23 And And 1.0E-06 12 30 25 48 18 30 48 45 And 23 And And 1.0E-06 12 30 26 30 15 15 30 40 B 15 And And 5.0E-06 20 25 27 30 15 15 30 40 B 15 And And 5.0E-06 10 35 28 30 15 15 30 40 B 15 And And 5.0E-06 10 35 29 30 15 15 30 40 B 15 And And 5.0E-06 8 35 30 30 15 15 30 40 B 15 And And 5.0E-06 30 40 31 30 15 15 30 40 B 15 And And 5.0E-06 20 70 32 30 15 15 30 40 B 15 A A 5.0E-06 20 70 33 30 15 15 30 40 B 15 A A 5.0E-06 16 70 Comparative example 1 0.3 0.3 0 0.3 30 B 5 C A 5.0E-05 12 30 2 0.5 0.3 0.2 0.5 30 B 5 C A 5.0E-05 12 30 3 60 60 0 60 40 B 20 A B 2.0E-06 12 30

[0270] [Table 11] Example twenty three twenty four 25 Resin composition (name) R-16 R-17 R-18 Silicon dioxide particle dispersion containing component (a) MEK-ST-40 OSCAL-1421 MEK-ST-L Content (by weight%) of silicon dioxide particles in the silicon dioxide particle dispersion 40.00 20.00 30.00 In the examples and comparative examples The pixel segmentation layer Surface analysis results A considerable amount of silicon dioxide particles In (a) of the components Primary particle size distribution range (nm) - 10~20 20~30 Primary particle size (nm) (Average value of major diameter) 12 15 26 Distribution range of aspect ratio 1.0~1.1 1.2~1.3 1.0~1.2 Aspect Ratio (Average aspect ratio) 1.1 1.3 1.2 Sodium atom have have have Silicon dioxide particles {also including Not equivalent to (a) component} Primary particle size distribution range (nm) 10~15 10~20 20~60 Average primary particle size (nm) 12 15 40 Average aspect ratio 1.1 1.3 1.2

[0271] <Example 26> In the first light-emitting unit, except that LiQ was not used in the electron transport layer and only compound (ET-1) was used, the organic EL display device was fabricated in the same manner as in Example 1. The adhesion, weather resistance, electrical reliability, and light-emitting characteristics of the organic EL display device were evaluated. The conditions of the photosensitive resin composition and the photomask are shown in Table 9, and the evaluation results are shown in Table 10.

[0272] <Example 27> In the first light-emitting unit, except that LiQ was not used in the electron transport layer and only compound (ET-2) was used, the organic EL display device was fabricated in the same manner as in Example 1. The adhesion, weather resistance, electrical reliability, and light-emitting characteristics of the organic EL display device were evaluated. The conditions of the photosensitive resin composition and the photomask are shown in Table 9, and the evaluation results are shown in Table 10.

[0273] <Example 28> In the first light-emitting unit, except that LiQ was not used in the electron transport layer and only compound (ET-3) was used, the organic EL display device was fabricated in the same manner as in Example 1. The adhesion, weather resistance, electrical reliability, and light-emitting characteristics of the organic EL display device were evaluated. The conditions of the photosensitive resin composition and the photomask are shown in Table 9, and the evaluation results are shown in Table 10.

[0274] <Example 29> In the first light-emitting unit, except that LiQ was not used in the electron transport layer and only compound (ET-4) was used, the organic EL display device was fabricated in the same manner as in Example 1. The adhesion, weather resistance, electrical reliability, and light-emitting characteristics of the organic EL display device were evaluated. The conditions of the photosensitive resin composition and the photomask are shown in Table 9, and the evaluation results are shown in Table 10.

[0275] <Example 30> After obtaining the patterned substrate in the same manner as in Example 1, a first light-emitting unit is deposited as an organic EL layer. Subsequently, on the first light-emitting unit, compound (ET-1) and the doped material metallic Li are deposited at a deposition rate ratio of compound (ET-1):Li = 99:1 for 10 nm as an n-type charge generation layer. Then, compound (HT-1) is deposited for 10 nm as a p-type charge generation layer.

[0276] Next, an organic EL layer identical to the first light-emitting unit is formed in a series configuration after the charge generation layer. Then, a 2nm thick LiQ layer is deposited as the electron injection layer. Following this, Mg and Ag are deposited at a volume ratio of 10:1 for 10nm, intersecting with the first electrode, to form a striped second electrode with a linewidth of 400μm, a spacing of 500μm, a length of 10mm, and 20 stripes. The thickness is then displayed using a so-called film thickness monitoring crystal oscillator.

[0277] Thus, an organic EL display device with 200 light-emitting elements, including 100 first electrodes, 20 second electrodes, and their equal intersections, was completed. Subsequently, the adhesion, weather resistance, electrical reliability, and luminous characteristics of the organic EL display device were evaluated. The conditions of the photosensitive resin composition and the photomask are shown in Table 9, and the evaluation results are shown in Table 10.

[0278] <Example 31> Except that compound (ET-1) was replaced with compound (ET-2) in the n-type charge generation layer, the organic EL display device was fabricated in the same manner as in Example 30, and the adhesion, weather resistance, electrical reliability, and luminescence characteristics of the organic EL display device were evaluated. The conditions of the photosensitive resin composition and the photomask are shown in Table 9, and the evaluation results are shown in Table 10.

[0279] <Example 32> Except that compound (ET-1) was replaced with compound (ET-3) in the n-type charge generation layer, the organic EL display device was fabricated in the same manner as in Example 30, and the adhesion, weather resistance, electrical reliability, and luminescence characteristics of the organic EL display device were evaluated. The conditions of the photosensitive resin composition and the photomask are shown in Table 9, and the evaluation results are shown in Table 10.

[0280] <Example 33> Except that compound (ET-1) was replaced with compound (ET-4) in the n-type charge generation layer, the organic EL display device was fabricated in the same manner as in Example 30, and the adhesion, weather resistance, electrical reliability, and luminescence characteristics of the organic EL display device were evaluated. The conditions of the photosensitive resin composition and the photomask are shown in Table 9, and the evaluation results are shown in Table 10.

[0281] 1: Substrate 1a: Base 2: First electrode 3: Pixel segmentation layer 4: Spacer 5: Organic EL layer 6: Second electrode 7:TFT 8: Planarization layer 9: Sealing layer 10: Polarizing layer 11: Ultraviolet Absorption Layer 12: Light-transmitting section 13: Semi-transparent section 14:Light shielding part 15: Cylinder 16: Range of objects to be measured for Ra1 17: Scope of Ra2 Measurement 18: Organic EL display device 19: Light-emitting element

Claims

1. An organic EL display device comprising a substrate having a first electrode, a pixel separation layer, and spacers on a substrate, and further comprising an organic EL layer and a second electrode, wherein, When the maximum value of the surface roughness (Ra1) of the pixel segmentation layer and the surface roughness (Ra2) of the spacer is set to Ramax, Ramax is 1.0 nm or more and 50 nm or less; the absolute value of the difference between the surface roughness of the pixel segmentation layer and the surface roughness of the spacer is 1.0 nm or more.

2. The organic EL display device as claimed in claim 1, wherein, The surface roughness of the aforementioned pixel segmentation layer is called Ramax.

3. The organic EL display device as claimed in claim 2, wherein, Of the area of ​​the interface between the substrate and the organic EL layer, the area of ​​the interface between the pixel segmentation layer and the organic EL layer is 50% or more.

4. The organic EL display device as claimed in claim 1, wherein, The surface roughness of the aforementioned spacer is called Ramax.

5. The organic EL display device as claimed in claim 4, wherein, Of the area of ​​the interface between the substrate and the organic EL layer, the area of ​​the interface between the spacer and the organic EL layer is 50% or more.

6. An organic EL display device as described in any of claims 1 to 5, wherein, The aforementioned pixel segmentation layer contains silicon dioxide particles with a primary particle size of 5-30 nm.

7. An organic EL display device as described in any of claims 1 to 5, wherein, The aforementioned pixel segmentation layer system includes: a hardened film containing a photosensitive resin composition of an alkali-soluble resin.

8. The organic EL display device as claimed in claim 7, wherein, The aforementioned alkali-soluble resin contains one or more of the group consisting of acrylic resins, phenolic resins, polysiloxane resins, calomel resins, polyimide resins, polyimide precursor resins, polybenzoxazole resins, and polybenzoxazole precursor resins.

9. The organic EL display device as claimed in claim 7, wherein, The above-mentioned photosensitive resin composition contains coloring materials.

10. The organic EL display device as claimed in claim 7, wherein, The above-mentioned photosensitive resin composition contains a liquid-repellent material.

11. An organic EL display device as described in any of claims 1 to 5, wherein, The aforementioned organic EL layer system contains an electron transport layer and / or a charge generation layer.

12. The organic EL display device as claimed in claim 11, wherein, The aforementioned electron transport layer and / or charge generation layer contains bulk dopants.

13. The organic EL display device as claimed in claim 12, wherein, The aforementioned preform dopants are complexes of alkali metals and organic compounds.

14. The organic EL display device as claimed in claim 11, wherein, The above-mentioned electron transport layer and / or charge generation layer contains a compound with a phylloid skeleton as shown in the following general formula (1); [Chemical 1] (wherein, R1 to R8 may be the same or different, and are selected from hydrogen atoms, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, heteroaryl, heterocyclic; wherein at least one of R1, R3, R6, and R8 is selected from adamantyl, noryl, phenyl vinyl, β-naphthyl, phenanthryl, and pyrene).

15. The organic EL display device as claimed in claim 11, wherein, The above-mentioned electron transport layer and / or charge generation layer contains a compound with a cyanoline skeleton as shown in the following general formula (2); [Chemical 2] (here, R9 to R16 may be the same or different, and are selected from hydrogen atom, alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, heteroaryl, heterocyclic, X1; wherein at least one of R9 to R16 is X1; n represents a natural number from 2 to 6; X1 is a single bond, or an n-valent linking unit for connecting multiple cyanoline skeletons derived from any of benzene, anthracene, pyridine, ethylene, thiophene, furan, methylene, carbazole, cyclohexane, spirodiclofen, triphenylamine, triphenylamine and any structure formed by combining these).

16. A method for manufacturing an organic EL display device, which is a method for manufacturing the organic EL display device according to claims 1 to 15, and is a method for manufacturing an organic EL display device having a substrate having a first electrode, a pixel separation layer, and spacers on a substrate, and further having an organic EL layer and a second electrode, wherein, The above manufacturing method includes a step of processing the pixel segmentation layer and the spacer together. The photomask used for processing together is a halftone photomask having a light-transmitting part, a light-blocking part and a semi-light-transmitting part.

17. A method for manufacturing an organic EL display device as claimed in claim 16, wherein, The transmittance of the semi-transparent portion is 15% to 50% of the transmittance of the transparent portion.

Images