Organic EL display device

Abstract

The present invention relates to an organic EL display device having high long-term reliability and bending reliability. The organic EL display device of the present invention is an organic EL display device having a substrate having a first electrode and a pixel division layer, an organic EL layer, and a second electrode on a substrate, and is detected by time-of-flight secondary ion mass spectrometry in a range of 20 nm to 100 nm from the surface of the pixel division layer toward the substrate. 75 C4H 12 N + Ion intensity average (I TMA-1 ) is 10.2 × 10 -4 Below 1.0×10 -4 That's all.

Description

[Technical field]

[0001] The present invention relates to an organic electroluminescence display device. [Background technology]

[0002] 2. Description of the Related Art Many products using organic electroluminescence (hereinafter, "organic EL") display devices have been developed as display devices having thin displays, such as smartphones, tablet PCs, and televisions.

[0003] In general, an organic EL display device has a driving circuit, a planarization layer, a first electrode, a pixel division layer, a light-emitting layer, and a second electrode on a substrate, and can emit light by applying a voltage between the opposing first and second electrodes or by passing a current between them. Of these, photosensitive resin compositions that can be patterned by ultraviolet irradiation are generally used as materials for the planarization layer and the pixel division layer. Among these, photosensitive resin compositions using polyimide-based or polybenzoxazole-based resins are preferably used because they have high heat resistance and generate little gas components from the cured product, and therefore can provide a highly reliable organic EL display device (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2002-91343 A Summary of the Invention [Problem to be solved by the invention]

[0005] On the other hand, the demand for high reliability of organic EL display devices is getting stricter every year, and materials for the planarization layer and pixel division layer are required to have long-term reliability without any decrease in luminance or pixel shrink after reliability tests under accelerated conditions such as high temperature, high humidity, and light exposure. Here, pixel shrink refers to the phenomenon in which luminance decreases from the edge of a pixel or the pixel does not light up.

[0006] Furthermore, in recent years, flexible organic EL display devices formed on a resin film substrate have been actively developed. Flexible organic EL display devices have bendable parts and / or parts that are fixed in a bent state in their structure, and bending stress may be applied or is applied to the planarizing layer and pixel division layer at these bent parts. In flexible organic EL display devices that include such bent parts, bending operations may cause peeling between the substrate and the organic EL layer, which may result in a decrease in the bending reliability of the organic EL display device. Here, bending reliability refers to the phenomenon in which the luminance of light emitted from the edge of a pixel decreases or the pixel does not light up due to bending operations.

[0007] The materials proposed in the above-mentioned patent documents are not sufficient to meet the recent requirements for long-term reliability and bending reliability. In view of the above problems, the present invention aims to provide an organic EL display device having high long-term reliability and bending reliability. [Means for solving the problem]

[0008] In order to solve the above problems, the organic EL display device of the present invention has the following configuration. [1] An organic EL display device having a substrate having a first electrode, a pixel division layer, an organic EL layer, and a second electrode on a substrate, the organic EL layer being detected by time-of-flight secondary ion mass spectrometry in a range of 20 nm to 100 nm from the surface of the pixel division layer toward the substrate. 75 C 4 H 12 N + Ion intensity average (I TMA-1 ) is 10.2 × 10 -4 Below 1.0×10 -4 This is the organic EL display device. [2] In the organic EL display device, the detection is performed by time-of-flight secondary ion mass spectrometry in a range of 101 nm or more and 300 nm or less from the surface of the pixel division layer toward the substrate. 75 C 4 H12 N + Ion intensity average (I TMA-2 ) is 5.0×10 -4 The organic electroluminescence display device according to [1] below. [3] In the organic EL display device, the detection is performed by time-of-flight secondary ion mass spectrometry in a range of 20 nm to 300 nm from the surface of the pixel division layer toward the substrate. 31 CF + Ion intensity average (I CF ) is 0.5 × 10 -4 The organic electroluminescence display device according to the following [1] or [2]. [4] The organic electroluminescence display device according to any one of [1] to [3], wherein the pixel division layer contains polyimide and / or polybenzoxazole, and the polyimide and / or polybenzoxazole has a structure represented by formula (1).

[0009] [ka]

[0010] (In formula (1), X 1 is a non-cyclic divalent hydrocarbon group having 4 to 10 carbon atoms, R 1 each independently represents a hydrocarbon group having 1 to 4 carbon atoms or a hydroxyl group, and each a independently represents an integer of 0 to 4. [5] X in the above formula (1) 1 is a structure represented by formula (2).

[0011] [ka]

[0012] (In formula (2), R 2 and R 3 are each independently a non-cyclic hydrocarbon group having 1 to 9 carbon atoms or a hydrogen atom, and * indicates the point of attachment to the aromatic ring. 2 and R 3 The total number of carbon atoms is 3 to 9. [6] The pixel division layer has a wavelength of 1365 cm in an infrared spectrum measured by a Fourier transform infrared spectrophotometer (FT-IR). -1 Over 1385cm -1 The organic electroluminescence display device according to any one of [1] to [5], wherein an index A, which has a maximum in the following range and indicates the amount of imide structures present in the pixel dividing layer, is 0.10 or more and 1.10 or less: Index A=(1365cm -1 Over 1385cm -1 Maximum below 1590cm -1 over 1610cm -1 Maximum value below (Note that the maximum value used in the above index A is the intensity value at the absorption maximum measured by FT-IR.) [7] The pixel division layer has a wavelength of 1040 cm in an infrared spectrum measured by FT-IR. -1 More than 1060cm -1 The organic electroluminescence display device according to any one of [1] to [6], wherein the organic electroluminescence display device has a maximum in the following range, and an index B showing the amount of benzoxazole structures present relative to the amount of imide structures present in the pixel dividing layer is 0.20 or more and 2.50 or less: Index B=(1040cm -1 More than 1060cm -1 Maximum below 1365cm -1 Over 1385cm -1 Maximum value below (However, the maximum value used in the above index B is the intensity value at the absorption maximum measured by FT-IR.) [8] The organic electroluminescence display device according to any one of [1] to [7], wherein the pixel dividing layer further contains a compound derived from a thermal acid generator. [9] The organic electroluminescence display device according to any one of [1] to [8], wherein the pixel dividing layer further contains a compound derived from a phenolic hydroxyl group-containing resin.

[10] The organic electroluminescence display device according to [9], wherein the phenolic hydroxyl group-containing resin is polyhydroxystyrene or a polyhydroxystyrene / polystyrene copolymer. Effect of the Invention

[0013] It is possible to obtain an organic EL display device that does not experience a decrease in luminance or pixel shrinkage due to long-term storage or bending operations and that has high long-term reliability and bending reliability. [Brief description of the drawings]

[0014] [Figure 1] FIG. 2 is a cross-sectional view of a TFT substrate on which a planarizing layer and a pixel dividing layer are formed. [Diagram 2] FIG. 2 is a schematic diagram of a substrate of an organic EL display device. [Diagram 3] FIG. 2 is a schematic diagram of a base material of an organic EL display device used in a bending reliability test according to an embodiment of the present invention. [Figure 4] FIG. 1 is a schematic diagram of a bending reliability test according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] The present invention will be described in detail with reference to the embodiment. However, the present invention should not be limited to the embodiment described below.

[0016] The organic EL display device of the present invention is an organic EL display device having a substrate having a first electrode and a pixel division layer, an organic EL layer, and a second electrode on a substrate, and is detected by time-of-flight secondary ion mass spectrometry in a range of 20 nm to 100 nm from the surface of the pixel division layer toward the substrate. 75 C 4 H 12 N + Ion intensity average (I TMA-1 ) is 10.2 × 10 -4 Below 1.0×10 -4 That's all.

[0017] As a result of intensive research, the inventors of the present invention have found that the ion beams detected from the pixel division layer by time-of-flight secondary ion mass spectrometry 75 C 4 H 12 N + Ion intensity average (I TMA-1) to 10.2 x 10 -4 It has been found that the long-term reliability of an organic EL display device can be improved by the following. TMA-1 It was determined that this is due to tetramethylammonium ions (TMA) contained in the pixel division layer, and that the TMA in the pixel division layer gasifies during long-term reliability testing and seeps into the inside of the pixel, causing a decrease in luminance from the edge of the pixel or pixel shrinkage. The pixel division layer is in contact with the edge of the pixel, and during long-term reliability testing, the gasified components move into the pixel division layer through the area in contact with the pixel division layer, and further seep into the inside of the pixel, causing pixel shrinkage. Therefore, in order to improve the long-term reliability of organic EL display devices, it is necessary to quantitatively manage the amount of TMA contained in the pixel division layer, and the I TMA-1 They also found that time-of-flight secondary ion mass spectrometry, which can detect

[0018] From the viewpoint of improving the long-term reliability of organic EL displays, TMA-1 is 10.2 x 10 -4 More preferably, it is 9.6×10 or less. -4 Less than 8.4×10, more preferably -4 Less than 7.2 × 10 -4 By setting the content to the range below, a decrease in luminance and pixel shrinkage do not occur, and it becomes possible to provide an organic EL display device with sufficient long-term reliability.

[0019] Furthermore, in the organic EL display device, the light emitting diode is detected by a time-of-flight secondary ion mass spectrometry in a range of 101 nm or more and 300 nm or less from the surface of the pixel division layer toward the substrate. 75 C 4 H 12 N + Ion intensity average (I TMA-2 ) to 5.0×10 -4 By setting the following, it is possible to further improve long-term reliability. TMA-2 is the amount of TMA ions in the inner layer of the pixel division layer. I TMA-1 With the above range, I TMA-2 5.0×10-4 By satisfying the following, it is possible to dramatically improve the long-term reliability of the organic EL display device.

[0020] From the viewpoint of improving the long-term reliability of organic EL displays, TMA-2 is 5.0 x 10 -4 Preferably, the value is less than or equal to 3.0×10 -4 Less than 2.0×10, more preferably -4 The following is particularly preferably 1.0×10 -4 The lower limit is not particularly limited, but is preferably 0.001×10 -4 That's all.

[0021] On the other hand, TMA-1 to 1.0×10 -4 It has also been found that by satisfying the above, the bending reliability of the organic EL display device can be improved and sufficient bending reliability can be imparted to the organic EL display device. TMA-1 is 1.0 × 10 -4 That is 3.6 x 10 -4 More preferably, 4.5×10 -4 More preferably, 4.9×10 -4 More preferably, 5.4×10 -4 More than 6.0×10, most preferably -4 That's all.

[0022] Deterioration in the bending reliability of organic EL display devices is often caused by peeling between the pixel division layer and the organic EL dye. Although the reason for this is unclear, it is believed that the inclusion of TMA improves the adhesion between the pixel division layer and the organic EL dye, making them less likely to peel off, improving bending reliability.

[0023] <Organic EL display device> The organic EL display device of the present invention is an organic EL display device having at least a first electrode, a substrate having a pixel division layer, an organic EL layer, and a second electrode on a substrate. The organic EL display device of the present invention can also be an organic EL display device having a plurality of pixels formed on a matrix. The driving method of the organic EL display device is roughly classified into a passive matrix type in which electrodes are divided into columns and rows and only pixels sandwiched between the electrodes are made to emit light, and an active matrix type in which several TFTs are provided for each pixel and switched, but is not particularly limited thereto. The active matrix type organic EL display device has a TFT (thin film transistor) on a substrate and wiring located on the side of the TFT and connected to the TFT, a planarization layer on the driving circuit so as to cover the unevenness, a first electrode, a pixel division layer, an organic EL layer, and a second electrode on the planarization layer.

[0024] FIG. 1 shows a cross-sectional view of an organic EL display device provided on a substrate 1. On the substrate 1, bottom-gate or top-gate TFTs 2 are provided in a matrix. A TFT insulating layer 3 is formed to cover the TFTs 2. A wiring 4 connected to the TFTs 2 is provided under the TFT insulating layer 3. On the TFT insulating layer 3, a contact hole 6 for opening the wiring 4 and a planarization layer 5 for filling the contact hole 6 are provided. An opening is provided in the planarization layer 5 so as to reach the contact hole 6 of the wiring 4. A first electrode 7 is formed on the planarization layer 5 in a state of being connected to the wiring 4 through the contact hole 6. A pixel division layer 8 is formed to cover the periphery of the first electrode 7. An organic EL layer 9 and a second electrode 10 are further formed thereon. This organic EL display device may be a top-emission type that emits emitted light from the opposite side of the substrate 1, or a bottom-emission type that extracts light from the substrate 1 side.

[0025] <Organic EL display device: substrate> In the organic EL display device of the present invention, the substrate is made up of the above-mentioned base material 1, first electrode 7, and pixel division section 8 as a minimum unit. If the substrate has such a minimum unit, it may further have wiring as a driving circuit, TFT 2, sensors and pattern antennas, flattening layer 5, etc. However, in the present invention, wiring, TFT, sensors and pattern antennas, flattening layer, etc., which are the underlayer of the first electrode, are all treated as part of the substrate. In addition, in a substrate that integrates multiple functions such as a camera, ID and fingerprint reading, illuminance sensors, and pattern antennas for communication and power supply, in addition to TFT, it is preferable to provide a flattening layer. By providing a flattening layer, unevenness of wiring, TFT, etc. can be covered before the first electrode is formed, and the substrate can be flattened. By flattening the substrate, defects in the first electrode and pixel division layer provided on the substrate can be prevented, and a high-quality substrate can be obtained.

[0026] 1 can be appropriately selected from materials suitable for supporting a display device and transporting it in a later process, such as metal, glass, resin film, etc. When flexibility is required, a resin film is preferable.

[0027] As the glass, soda-lime glass, non-alkali glass, etc. can be used. The thickness of the glass is sufficient as long as it is thick enough to maintain mechanical strength. As for the glass material, it is preferable that the glass has a small amount of ions eluted therefrom, so non-alkali glass is preferable. SiO 2 It is also possible to use soda lime glass coated with a barrier coating such as SiO 2 .

[0028] The material of the resin film is preferably a resin material selected from polybenzoxazole resin, polyamideimide resin, polyimide resin, polyamide resin, and poly(p-xylylene) resin, because of its excellent light transmittance. The substrate may contain these resin materials alone or in combination.

[0029] For example, when forming the substrate from a polyimide resin, the substrate can be formed by applying a solution containing a polyamic acid resin (including a partially imidized polyamic acid) which is a precursor of the polyimide resin, or a soluble polyimide resin, to a supporting substrate and baking the applied solution.

[0030] In addition, since the above-mentioned light-emitting element is known to be vulnerable to oxygen and moisture, a gas barrier layer may be appropriately provided as a component of the substrate. In particular, when the substrate is a resin film, a highly reliable display device can be obtained by laminating an inorganic thin film thereon.

[0031] <Organic EL display device: first electrode> The first electrode 7 in the present invention must be a light-transmitting electrode in the case of a bottom emission type, and a light-reflective electrode in the case of a top emission type.

[0032] For a bottom emission type, for example, conductive metal oxides such as transparent tin oxide, indium oxide, and indium tin oxide (ITO), metals such as gold, silver, and chromium, inorganic conductive substances such as copper iodide and copper sulfide, and conductive polymers such as polythiophene, polypyrrole, and polyaniline can be used, but are not particularly limited thereto.

[0033] For top emission type, a material that shows high reflectance of visible light at a certain film thickness and low electrical resistance is preferable. Furthermore, material selection is required in terms of wet etching and cleaning in the subsequent process, and weather resistance in the storage and use environment. In particular, Ag or Ag alloy films mainly containing Ag are useful because of their high reflectance. Ag alloy films can be made of AgPdCu or AgTiCu, etc., which contain Ag as the main component. It is preferable to laminate these Ag alloy films with oxide conductive films such as ITO films and IZO films, because low contact resistance with the organic EL layer can be achieved. In addition, Al or Al alloy films mainly containing Al are also good as the first electrode of the top emission type. An Al-Ni alloy film containing 0.1 to 2 atomic % of Ni is preferable because it has a high reflectance comparable to that of pure Al. In addition, reflective metal films such as molybdenum (Mo) and tungsten (W) can also be used.

[0034] The first electrode can be formed by a known method, for example, by forming a film by a vacuum film forming method such as sputtering, and then patterning the film by etching using a photoresist.

[0035] <Organic EL display device: second electrode> In the present invention, the second electrode 6 must be a light-reflective electrode in the case of a bottom emission type, and must be a light-transmitting electrode in the case of a top emission type.

[0036] For bottom emission, a material that exhibits high visible light reflectance and low electrical resistance above a certain film thickness is preferred, and Ag or an Ag alloy film mainly containing Ag is useful because of its high reflectance. As the Ag alloy film, an MgAg alloy containing Ag as the main component can be used. In addition, an Al or an Al alloy film mainly containing Al is also good as a second electrode for bottom emission. An AlCr alloy film containing Cr and an AlNi alloy film containing Ni are preferred because they have a high reflectance comparable to that of pure Al and can achieve low electrical resistance.

[0037] For top emission, for example, conductive metal oxides such as transparent tin oxide, indium oxide, indium tin oxide (ITO) can be used. In order to avoid damage to the organic EL layer, a thin film of MgAg alloy that can be produced by vapor deposition is preferable.

[0038] The resistance of the second electrode is not limited as long as it can supply a sufficient current for the light emission of the light emitting element, as with the first electrode. From the viewpoint of the power consumption of the light emitting element, it is desirable to have a low resistance. The thickness of the electrode can be selected arbitrarily according to the characteristics such as transmittance and resistance value. For a bottom emission type, a thickness between 100 and 300 nm can be used, and for a top emission type, a thickness between 10 and 30 nm can be used.

[0039] <Organic EL display device: wiring, TFT> In the present invention, as described above, the base material 1 may include wiring and a driving circuit such as the TFT 2.

[0040] The semiconductor layer of a TFT may be a-Si (amorphous silicon), p-Si (polycrystalline silicon), microcrystalline silicon, oxides such as In-Ga-Zn-O, or LTPO (Low Temperature Polycrystalline Oxide) using p-Si and oxides in combination. Generally, two types of TFTs are used: a-SiTFT and p-SiTFT. Although a-SiTFTs have low mobility, which is an index of the ease of electron movement, the manufacturing process is relatively short and they can be manufactured on large substrates, so they can be used in a wide range of displays from small to large. On the other hand, p-SiTFTs have high mobility and driver circuits can be formed on the substrate. The manufacturing process is longer than a-Si and manufacturing is difficult on large substrates, so it is preferable to use them mainly for small and medium-sized displays. In particular, p-Si in p-SiTFTs can be formed by irradiating laser light onto a-Si as a starting film, and instantly melting and crystallizing it. Furthermore, there is a process called doping, which is not used in the manufacturing process of a-Si TFTs, in which phosphorus or boron is implanted into Si, and the threshold value of the TFT characteristics may be controlled by doping the Si film with impurities.

[0041] <Organic EL display device: Organic EL layer> The configuration of the organic EL layer 9 in the present invention is not particularly limited, and may be, for example, any of (1) hole transport layer / light emitting layer, (2) hole transport layer / light emitting layer / electron transport layer, and (3) light emitting layer / electron transport layer. Furthermore, the above configuration may be a tandem type in which a plurality of layers are laminated via a charge generating layer. The tandem type is preferable because it is expected to improve the luminance and the luminescence life. The thickness of each layer is preferably 1 nm to 200 nm, taking into consideration the resistance value of each layer material and the effect on the extraction efficiency of EL emission.

[0042] <Organic EL display device: Organic EL layer (light-emitting layer)> The light-emitting layer is a layer in which a light-emitting material is excited by recombination energy due to collision of holes and electrons, and emits light. The light-emitting layer may be a single layer or a laminate of multiple layers, each of which is formed from a light-emitting material (host material and / or dopant material).

[0043] The light-emitting layer can be formed by a method of co-evaporating a host material and a dopant material, or a method of previously mixing a host material and a dopant material and then vapor-depositing the mixture.

[0044] Examples of host materials constituting the light-emitting layer include compounds having condensed aryl rings such as naphthalene, anthracene, phenanthrene, pyrene, chrysene, naphthacene, triphenylene, perylene, fluoranthene, fluorene, and indene. Two or more of these may be used. As hosts used when the light-emitting layer emits triplet light (phosphorescence), metal chelated oxinoid compounds, dibenzofuran derivatives, dibenzothiophene derivatives, carbazole derivatives, indolocarbazole derivatives, triazine derivatives, and triphenylene derivatives are preferably used. Among these, compounds having an anthracene skeleton or a pyrene skeleton are more preferable because they are more likely to emit light with high efficiency.

[0045] Examples of dopant materials constituting the light-emitting material include condensed ring derivatives such as anthracene and pyrene, metal complex compounds such as tris(8-quinolinolato)aluminum, bisstyryl derivatives such as bisstyryl anthracene derivatives and distyrylbenzene derivatives, tetraphenylbutadiene derivatives, dibenzofuran derivatives, carbazole derivatives, indolocarbazole derivatives, and polyphenylenevinylene derivatives. As a dopant material used when the light-emitting layer performs triplet emission (phosphorescence emission), a metal complex compound containing at least one metal selected from the group consisting of iridium (Ir), ruthenium (Ru), palladium (Pd), platinum (Pt), osmium (Os), and rhenium (Re) is preferable. The ligand constituting the metal complex compound can be appropriately selected based on the required emission color, organic EL display device performance, and relationship with the host compound. The ligand constituting the metal complex compound preferably has a nitrogen-containing aromatic heterocycle such as a phenylpyridine skeleton, a phenylquinoline skeleton, or a carbene skeleton. Specific examples include tris(2-phenylpyridyl)iridium complex, bis(2-phenylpyridyl)(acetylacetonate)iridium complex, tetraethylporphyrin platinum complex, etc. Two or more of these may be used.

[0046] <Organic EL display device: Organic EL layer (electron transport layer)> The electron transport layer is a layer that transports electrons injected from the cathode to the light emitting layer. In order to achieve a low driving voltage, the organic EL layer of the present invention preferably includes an electron transport layer.

[0047] Known electron transport materials include, but are not limited to, quinolinol derivative metal complexes typified by 8-hydroxyquinoline aluminum, benzoquinoline metal complexes, tropolone metal complexes, flavonol metal complexes, perylene derivatives, perinone derivatives, naphthalene, anthracene, coumarin derivatives, oxadiazole derivatives, aldazine derivatives, bisstyryl derivatives, pyrazine derivatives, phenanthroline derivatives, quinoline derivatives, benzimidazole derivatives, triazole derivatives, quinoxaline derivatives, and benzoquinoline derivatives.

[0048] Among these, compounds having a heteroaryl ring structure containing electron-accepting nitrogen are preferred because they can reduce the driving voltage and provide highly efficient light emission. The electron-accepting nitrogen referred to here means a nitrogen atom that forms a multiple bond with an adjacent atom. Since the nitrogen atom has high electronegativity, such a multiple bond has an electron-accepting property. Therefore, aromatic heterocycles containing electron-accepting nitrogen have high electron affinity. Electron transport materials having electron-accepting nitrogen can easily accept electrons from a cathode having high electron affinity, so that the driving voltage can be further reduced. In addition, the supply of electrons to the light-emitting layer increases, and the recombination probability increases, improving the light-emitting efficiency.

[0049] Examples of heteroaryl rings containing electron-accepting nitrogen include triazine rings and pyridine rings. As compounds having these heteroaryl ring structures, triazole derivatives such as N-naphthyl-2,5-diphenyl-1,3,4-triazole, bipyridine derivatives such as 2,5-bis(6'-(2',2"-bipyridyl))-1,1-dimethyl-3,4-diphenylsilole, and terpyridine derivatives such as 1,3-bis(4'-(2,2':6'2"-terpyridinyl))benzene are preferably used from the viewpoint of electron transport ability.

[0050] <Organic EL display device: Organic EL layer (charge generating layer)> The charge generation layer generally consists of a double layer, and specifically, a pn junction type charge generation layer consisting of an n-type charge generation layer and a p-type charge generation layer can be used. The pn junction type charge generation layer generates charges or separates charges into holes and electrons by applying a voltage in the organic EL layer, and injects these holes and electrons into the light emitting layer via the hole transport layer and the 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 present on the anode side, and the p-type charge generation layer supplies holes to the light emitting layer present on the cathode side. Therefore, the luminance 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 life of the organic EL layer can also be further improved. For these reasons, it is preferable that the organic EL layer in the present invention contains a charge generation layer. Furthermore, as described later, it is preferable that the charge generation layer in the present invention contains a donor dopant material. The donor dopant material preferably contains one or more elements selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals, inorganic salts of these metals, and complexes of these metals with organic substances.

[0051] The n-type charge generating layer is preferably made of an n-type dopant material and a host material, and these can be known materials. For example, an alkali metal, an alkaline earth metal, or a rare earth metal can be used as the n-type dopant material. In addition, a compound having a phenanthroline skeleton and a compound having a nitrogen-containing aromatic heterocycle such as an oligopyridine derivative can be used as the host material.

[0052] The p-type charge generating layer is preferably made of a p-type dopant material and a host material, and these can be known materials. For example, the p-type dopant material can be tetrafluorene-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ), a tetracyanoquinodimethane derivative, a radialene derivative, iodine, FeCl3, FeF3, SbCl5, etc. The p-type dopant material is preferably a radialene derivative.

[0053] <Organic EL display device: Organic EL layer (hole transport layer)> The hole transport layer is formed, for example, by a method of laminating or mixing one or more types of hole transport materials, or a method of using a mixture of a hole transport material and a polymer binder. The hole transport layer may also be formed by adding an inorganic salt such as iron (III) chloride to the hole transport material. The hole transport material is not particularly limited as long as it is a compound that can form a thin film required for the production of a light-emitting device, can inject holes from an electrode that serves as an anode, and can transport holes. The hole transport layer may be a single layer or a laminate of multiple layers.

[0054] Suitable examples of the hole transport material 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"-tris(3-methylphenyl(phenyl)amino)triphenylamine; biscarbazole derivatives such as bis(N-allylcarbazole) and bis(N-alkylcarbazole); heterocyclic compounds such as pyrazoline derivatives, stilbene compounds, hydrazone compounds, benzofuran derivatives, thiophene derivatives, oxadiazole derivatives, phthalocyanine derivatives, and porphyrin derivatives; and, in the case of polymers, polycarbonates and styrene derivatives having the above-mentioned monomers in their side chains, polythiophenes, polyanilines, polyfluorenes, polyvinylcarbazoles, and polysilanes.

[0055] <Organic EL display device: flattening layer> In particular, when wiring and TFT2 are provided on the substrate 1 of FIG. 1, as in the case of an active driving type, it is preferable to use the planarization layer 5. By providing the planarization layer, the unevenness of the wiring and TFT2 can be covered and planarized. In this case, since the first electrode 7 is provided on the planarization layer, it is preferable that the first electrode 7 and the wiring and TFT2 are connected through a contact hole formed in the planarization layer 5. The planarization layer 5 is not limited to either a known organic material or an inorganic material, but preferably contains a cured film of a photosensitive resin composition from the viewpoint of processability. The planarization layer 5 can be applied by a wet coating method such as a spin coating method, a slit coating method, a dip coating method, a spray coating method, or a printing method that can uniformly form a thin film on a large-sized substrate.

[0056] <Organic EL display device: pixel division layer> The pixel division layer is a layer that has the role of dividing pixels, and has the purpose of opening the organic EL layer 9 forming portion and dividing it into pixels. That is, the pixel division layer must be patterned to form an opening, and the pixel opening, which is the removed portion, functions as a display pixel. The pixel division layer also has the purpose of electrically insulating adjacent pixels, and needs to be an insulating organic or inorganic material, and is not limited to either, but is preferably a cured film of a photosensitive resin composition from the viewpoint of pattern processing.

[0057] The pixel division layer of the present invention is TMA-1 is 10.2 × 10 -4 Below 1.0×10 -4 As described above, it is possible to achieve both long-term reliability and bending reliability.

[0058] Above I TMA-1 to 10.2 x 10 -4 Below 1.0×10 -4 Methods for achieving the above include the following methods 1 to 3. TMA-1 to 10.2 x 10 -4 Below 1.0×10 -4The method for achieving the above is not particularly limited, but since method 1 may have a detrimental effect on the storage stability of the photosensitive resin composition due to the anion component contained in the TMA compound, method 2 or method 3 is preferred. Furthermore, method 3 is particularly preferred from the viewpoint of simplifying the manufacturing process. That is, in the organic EL display device of the present invention, the pixel dividing layer has a wavelength of 1365 cm in the infrared spectrum measured by a Fourier transform infrared spectrophotometer (FT-IR). -1 Over 1385cm -1 It is preferable that the pixel dividing layer has a maximum in the following range, and index A, which indicates the amount of imide structures present in the pixel dividing layer, is 0.10 or more and 1.10 or less.

[0059] [Method 1] Method 1 is to add a TMA compound to a photosensitive resin composition used to form a pixel division layer, and form the pixel division layer using the photosensitive resin composition, thereby obtaining I TMA-1 to 10.2 x 10 -4 Below 1.0×10 -4 More specifically, the amount of TMA remaining in the pixel division layer after curing is adjusted by adding a TMA compound to a photosensitive resin composition used to form the pixel division layer and adjusting the amount of TMA added, thereby obtaining a pixel division layer having a TMA content in the range of I. TMA-1 to 10.2 x 10 -4 Below 1.0×10 -4 The above range can be satisfied. Specific examples of the TMA compound include tetramethylammonium hydroxide, tetramethylammonium chloride, and tetramethylammonium bromide.

[0060] [Method 2] Method 2 is TMA-1 is 10.2 × 10 -4 After forming the pixel division layer, the pixel division layer is washed with an acidic aqueous solution. TMA-1 to 10.2 x 10 -4 Below 1.0×10 -4 This is a method to keep the range above. More specifically, I TMA-1 is 10.2 × 10 -4The pixel division layer after hardening was immersed in an acidic aqueous solution for 2 minutes and then rinsed with distilled water to reduce the TMA ions in the pixel division layer and to obtain the I TMA-1 to 10.2 x 10 -4 Below 1.0×10 -4 The cleaning method using an acidic aqueous solution can be, for example, spraying, paddle washing, or immersion. The acidic aqueous solution is preferably a weak acid having a pH of 3.0 or more and less than 6.0. If a strong acid having a pH of less than 3.0 is used, the cleaning action becomes too strong, and the I TMA-1 Specifically, it is preferable to use an aqueous solution of oxalic acid, sulfurous acid, phosphoric acid, nitrous acid, hydrofluoric acid, methanoic acid, benzoic acid, acetic acid, formic acid, carbonic acid, or the like, adjusted to have a pH within the above range.

[0061] [Method 3] Method 3 is a method for determining whether the ion exchange reaction is carried out at 1365 cm in an infrared spectrum measured by a Fourier transform infrared spectrophotometer (FT-IR). -1 Over 1385cm -1 The method has a maximum in the following range, and sets index A, which indicates the amount of imide structures present in the pixel division layer, to 0.10 or more and 1.10 or less. Index A=(1365cm -1 Over 1385cm -1 Maximum below 1590cm -1 over 1610cm -1 (maximum value below) (Note that the maximum value used in the above index A is the intensity value at the absorption maximum measured by FT-IR.) This method is a method in which TMA ions in a tetramethylammonium hydroxide (TMAH) aqueous solution used in a development process after pattern exposure of a photosensitive resin composition are penetrated into a film during the same process, and by setting the index A within the above range, the penetration of TMA ions becomes appropriate, and as a result, the I TMA-1 to 10.2 x 10 -4 Below 1.0×10 -4In the infrared spectrum measured by a Fourier transform infrared spectrophotometer (FT-IR), -1 Over 1385cm -1 Absorption originating from the imide structure occurs in the following range, and the pixel division layer must contain an imide structure in method 3. Furthermore, the index A is an index that substantially indicates the amount of the imide structure contained in the pixel division layer, and a method for making index A 0.10 or more and 1.10 or less can be achieved by making the pixel division layer contain an imide structure and setting the amount of the imide structure within a specific range.

[0062] In addition, the pixel division layer of the present invention is TMA-2 to 5.0×10 -4 Long-term reliability can be improved by the following: TMA-2 to 5.0×10 -4 Examples of the method for reducing the amount of the fluorine-containing compound include, but are not limited to, the following methods.

[0063] Detected by time-of-flight secondary ion mass spectrometry in a range of 20 nm to 300 nm from the surface of the pixel division layer toward the substrate. 31 CF + Ion intensity average (I CF ) to 0.5 × 10 -4 The method is as follows. CF 0.5×10 -4 By setting the concentration to below 100%, the penetration of TMA ions during development is suppressed, resulting in a reduction in the I TMA-2 to 5.0×10 -4 That is, in the organic EL display device, the following can be achieved: 31 CF + Ion intensity average (I CF ) is 0.5 × 10 -4 More specifically, it is preferable that the photosensitive resin composition used to form the pixel dividing layer does not contain fluorine atoms. The lower limit is not particularly limited, but is preferably 0.001×10 -4 That's all.

[0064] <Pixel division layer: Imide> The pixel division layer of the present invention preferably contains an imide structure. When the pixel division layer of the present invention contains a specific amount of an imide structure, TMA-1 In order to improve the long-term reliability and the bending reliability, the pixel division layer is preferably analyzed by FT-IR to determine whether the pixel division layer contains polyimide. -1 Over 1385cm -1 Since the pixel division layer has a maximum in the following range, it can be judged by the presence or absence of the maximum. In addition, in the present invention, an index A indicating the amount of imide structures present in the pixel division layer is defined. TMA-1 In order to improve long-term reliability, the index A is preferably 1.10 or less, more preferably 1.00 or less, even more preferably 0.80 or less, and particularly preferably 0.60 or less. TMA-1 is set as a specific range, and from the viewpoint of improving folding reliability, index A is preferably 0.10 or more, more preferably 0.20 or more, further preferably 0.30 or more, and particularly preferably 0.40 or less. Index A=(1365cm -1 Over 1385cm -1 Maximum below 1590cm -1 over 1610cm -1 Maximum value below (Note that the maximum value used in the above index A is the intensity value at the absorption maximum measured by FT-IR.) The method of making the index A 0.10 or more and 1.10 or less can be achieved by adjusting the amount of imide structures contained in the photosensitive resin composition used to form the pixel division layer. More specifically, the pixel division layer can be formed using a photosensitive resin composition in which the molar amount of imide structures contained in 1 g of all the components excluding the solvent constituting the photosensitive resin composition is 0.2 mmol / g or more and 0.9 mmol / g or less. The molar amount (mmol / g) of imide structures contained in 1 g of all the components excluding the solvent constituting the photosensitive resin composition can be calculated from the value of the imide structures contained in 1 g of all the components excluding the solvent constituting the photosensitive resin composition.

[0065] By increasing the blending amounts of components other than polyimide contained in the polyimide-based photosensitive resin composition, such as polybenzoxazole and a phenolic hydroxyl group-containing resin described below, the molar amount of the imide structure can be set to 0.2 mmol / g or more and 0.9 mmol / g or less using the calculated value of the molar amount of the imide structure, and as a result, the index A can be set to 0.10 or more and 1.10 or less.

[0066] <Pixel division layer: benzoxazole> The pixel division layer of the present invention preferably contains a benzoxazole structure. When the pixel division layer of the present invention contains a benzoxazole structure, the numerical value of the index A of the pixel division layer can be efficiently reduced. As a method for determining whether the pixel division layer contains a benzoxazole structure, for example, a method of analyzing the pixel division layer by FT-IR can be mentioned. When the pixel division layer contains a benzoxazole structure, a benzoxazole structure is detected at 1040 cm in an infrared spectrum measured by FT-IR. -1 More than 1060cm -1Since it has a maximum in the following range, it can be judged by the presence or absence of a maximum. In addition, in the present invention, an index B indicating the amount of benzoxazole structure present in the pixel division layer is defined. The index B is an index indicating the amount of imidazole structure present relative to the amount of imide structure present, and by setting the numerical value of the index to a specific range, the crack resistance of the organic EL display device can be improved. From the viewpoint of improving the crack resistance of the organic EL display device, the index B is preferably 0.20 or more, more preferably 0.30 or more, even more preferably 0.40 or more, and particularly preferably 0.50 or more. From the viewpoint of balancing long-term reliability, the index B is preferably 2.50 or less, more preferably 2.00 or less, even more preferably 1.80 or less, and particularly preferably 1.50 or less. Index B=(1040cm -1 More than 1060cm -1 Maximum below 1365cm -1 Over 1385cm -1 Maximum value below (However, the maximum value used in the above index B is the intensity value at the absorption maximum measured by FT-IR.)

[0067] That is, in the organic EL display device of the present invention, the pixel dividing layer has a wavelength of 1040 cm in the infrared spectrum measured by FT-IR. -1 More than 1060cm -1 It is preferable that the index B, which has a maximum in the following range and indicates the amount of benzoxazole structures present relative to the amount of imide structures present in the pixel dividing layer, is 0.20 or more and 2.50 or less.

[0068] Although the reason is unclear, it is speculated that by setting the ratio of the imide structure and the oxazole structure contained in the pixel division layer within a specific range, the intermolecular interactions between the imide structure and the oxazole structure are not too strong, and the brittleness caused by the too strong intermolecular interactions is alleviated, and as a result, the pixel division layer can be given appropriate flexibility and the crack resistance is improved. As a method for making the index B 0.20 or more and 2.50 or less, the addition ratio of the polyimide and / or polyimide precursor, the polybenzoxazole and / or polybenzoxazole precursor, and other components can be adjusted to make the index B 0.20 or more and 2.50 or less.

[0069] <Pixel division layer: Compound derived from phenolic hydroxyl group-containing resin> The pixel division layer of the present invention preferably contains a compound derived from a phenolic hydroxyl group-containing resin. In order for the pixel division layer to contain a compound derived from a phenolic hydroxyl group-containing resin, the photosensitive resin composition used to form the pixel division layer must substantially contain a phenolic hydroxyl group-containing resin. By containing a phenolic hydroxyl group-containing resin in the photosensitive resin composition, the content of the imide structure in the photosensitive resin composition can be relatively reduced, and the amount of TMA penetrating into the pixel division layer during the development process after the pattern exposure of the photosensitive resin composition in the process of forming the pixel division layer can be controlled. As a result, the amount of TMA ions remaining in the pixel division layer after curing can be reduced, making it easier to improve long-term reliability. In addition, the phenolic hydroxyl group-containing resin is likely to form a crosslinked structure with the crosslinking agent described later, making it easier to improve the crack resistance of the pixel division layer. As a method for measuring whether the pixel division layer contains a compound derived from a phenolic hydroxyl group-containing resin, for example, the pixel division layer can be pyrolyzed at 600 ° C. and then the components are measured by gas chromatography using pyrolysis GC / MS.

[0070] The content of the compound derived from the phenolic hydroxyl group-containing resin is preferably 1% by mass or more and 50% by mass or less in 100% by mass of the pixel dividing layer.

[0071] <Pixel division layer: Compound derived from thermal acid generator> The pixel division layer of the present invention preferably contains a compound derived from a thermal acid generator. In order for the pixel division layer to contain a compound derived from a thermal acid generator, the photosensitive resin composition used to form the pixel division layer must substantially contain a thermal acid generator. When the photosensitive resin composition contains a thermal acid generator, acid is generated in the curing step of the pixel division layer, which makes it easier to thermally decompose the TMA ions contained in the pixel division layer, and as a result, the amount of TMA ions remaining in the pixel division layer after curing can be reduced, making it easier to improve long-term reliability.

[0072] The content of the compound derived from the thermal acid generator is preferably 0.1% by mass to 10% by mass in 100% by mass of the pixel division layer. If the content is 0.1% by mass to 10% by mass, the effect of thermally decomposing the TMA ions contained in the pixel division layer can be easily obtained.

[0073] <Photosensitive resin composition for forming pixel dividing layer> Next, the photosensitive resin composition used for forming the pixel dividing layer of the present invention will be described.

[0074] The pixel division layer of the present invention is preferably a cured film of a photosensitive resin composition that can be patterned. From the viewpoint of pattern processability and reliability, the photosensitive resin composition used to form the pixel division layer of the present invention can be obtained by dissolving an alkali-soluble resin, a quinone diazide compound, a thermal acid generator, a thermal crosslinking agent, an organic solvent, an adhesion improver, a surfactant, a colorant, and the like.

[0075] Next, the components contained in the photosensitive resin composition used to form the pixel division layer of the present invention will be described. The photosensitive resin composition used to form the pixel division layer of the present invention can contain resins such as polyimide, polybenzoxazole, phenolic hydroxyl group-containing resin, polymer obtained by polymerizing radical polymerizable monomer, cardo resin, and polysiloxane, which will be described later, and among these, it is preferable to use an alkali-soluble resin.

[0076] In the present invention, alkali-soluble means that a dissolution rate calculated from the reduction in film thickness when a solution of a resin dissolved in γ-butyrolactone is applied onto a silicon wafer and prebaked at 120° C. for 4 minutes to form a prebaked film with a film thickness of 10 μm±0.5 μm, the prebaked film is immersed in a 2.38 mass % aqueous solution of tetramethylammonium hydroxide at 23±1° C. for 1 minute, and then rinsed with pure water is 50 nm / min or more.

[0077] <Photosensitive resin composition: polyimide> In order for the pixel division layer to have an imide structure, it essentially means that the photosensitive resin composition used to form the pixel division layer contains a polyimide and / or a polyimide precursor, and these can be synthesized by known methods.

[0078] In the case of a polyimide precursor, a polyamic acid can be synthesized, for example, by a method of reacting a tetracarboxylic dianhydride with a diamine compound at low temperature, while a polyamic acid ester can be synthesized, for example, by a method of reacting a tetracarboxylic dianhydride with a diamine compound at low temperature and then partially esterifying the amide acid structure with N,N-dimethylformamide dimethyl acetal or the like, a method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol and then reacting it with an amine in the presence of a condensing agent, a method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol and then converting the remaining dicarboxylic acid into an acid chloride and reacting it with an amine, or the like.

[0079] Polyimide can be obtained, for example, by heating the polyamic acid or polyamic acid ester obtained by the above-mentioned method in an organic solvent or by dehydrating and ring-closing the polyamic acid or polyamic acid ester through a chemical treatment with an acid or base.

[0080] Specific examples of the acid dianhydride used as a raw material for polyimide and / or polyimide precursor include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxy ... Examples of the tetracarboxylic acid dianhydride include aromatic tetracarboxylic acid dianhydrides such as bis(3,4-dicarboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 2,3,5,6-pyridine tetracarboxylic acid dianhydride, 3,4,9,10-perylene tetracarboxylic acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, and 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorene dianhydride, as well as aliphatic tetracarboxylic acid dianhydrides such as butane tetracarboxylic acid dianhydride and 1,2,3,4-cyclopentane tetracarboxylic acid dianhydride, and tetracarboxylic acid dianhydrides having the structure shown below. Two or more of these may be used.

[0081] [ka]

[0082] R 4 is an oxygen atom, SO 2 , cyclo ring, C(CF 3 ) 2 , C(CH3 ) 2 or a hydrocarbon group. 5 ~R 8 each independently represents a hydrogen atom or a hydroxyl group.

[0083] Specific examples of diamines used as raw materials for polyimides, polyimide precursors, and copolymers containing them include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, Examples of the aromatic ring include fluorene, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-di(trifluoromethyl)-4,4'-diaminobiphenyl, 9,9-bis(4-aminophenyl)fluorene, and compounds in which at least a portion of the hydrogen atoms in these aromatic rings are substituted with alkyl groups or halogen atoms, as well as aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, and diamines having the structures shown below. Two or more of these may be used.

[0084] [ka]

[0085] R 9 , R 12 is an oxygen atom, SO 2 , cyclo ring, C(CF 3 ) 2 , or C(CH 3 ) 2or a hydrocarbon group. 10 , R 11 , R 13 ~R 20 each independently represents a hydrogen atom or a hydroxyl group.

[0086] In the present invention, polyimide is defined as a resin having an imide bond in the main chain. In addition, when a polyimide contains a polybenzoxazole structural unit and / or a polybenzoxazole precursor structural unit in addition to a polyimide structural unit and / or a polyimide precursor structural unit, the polyimide is considered to be a polyimide.

[0087] <Photosensitive resin composition: Polybenzoxazole> In order for the pixel dividing layer to have a benzoxazole structure, it essentially means that the photosensitive resin composition used to form the pixel dividing layer contains polybenzoxazole and / or a polybenzoxazole precursor, and these can be synthesized by known methods.

[0088] In the case of polybenzoxazole precursors, they can be produced by condensation reaction of bisaminophenol compounds with dicarboxylic acids. Specifically, there is a method of reacting a dehydration condensation agent such as dicyclohexylcarbodiimide (DCC) with an acid and adding a bisaminophenol compound to the reaction, or a method of dropping a solution of dicarboxylic acid dichloride into a solution of a bisaminophenol compound to which a tertiary amine such as pyridine has been added.

[0089] Polybenzoxazole can be obtained, for example, by heating the polybenzoxazole precursor obtained by the above-mentioned method in an organic solvent or by subjecting it to a chemical treatment with an acid or base for dehydration and ring closure.

[0090] Examples of dicarboxylic acids used as raw materials for benzoxazole and / or benzoxazole precursors include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, and triphenyl dicarboxylic acid. Examples of tricarboxylic acids include trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, and biphenyl tricarboxylic acid. Examples of tetracarboxylic acids include pyromellitic acid, 3,3',4,4'-biphenyl tetracarboxylic acid, 2,3,3',4'-biphenyl tetracarboxylic acid, 2,2',3,3'-biphenyl tetracarboxylic acid, 3,3',4,4'-benzophenone tetracarboxylic acid, 2,2',3,3'-benzophenone tetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)propane, 2,2-bis(2,3-dicarboxyphenyl)propane, and 2,2-bis( Examples of the tetracarboxylic acid include aromatic tetracarboxylic acids such as 3,4-dicarboxyphenyl)hexafluoropropane, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane, 1,1-bis(3,4-dicarboxyphenyl)ethane, 1,1-bis(2,3-dicarboxyphenyl)ethane, bis(3,4-dicarboxyphenyl)methane, bis(2,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 9,9-bis(3,4-dicarboxyphenyl)fluorene, and 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorene, and aliphatic tetracarboxylic acids such as butanetetracarboxylic acid and 1,2,3,4-cyclopentanetetracarboxylic acid. Two or more of these may be used.

[0091] In order to improve the storage stability of the photosensitive resin composition, it is preferable to cap the main chain ends of one or more alkali-soluble resins selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, and copolymers thereof with a terminal capping agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, a monoactive ester compound, etc. For the purpose of improving the chemical resistance of the cured resin obtained by baking, a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound having at least one alkenyl group or alkynyl group can also be used as the terminal capping agent.

[0092] The content of the terminal blocking agent such as monoamine, acid anhydride, acid chloride, monocarboxylic acid, etc. is preferably 1 mol% or more, more preferably 5 mol% or more, based on the total of all monomer components constituting the resin (100 mol%), from the viewpoint of improving storage stability. Also, from the viewpoint of obtaining a resin with good film properties, the content is preferably 40 mol% or less, more preferably 30 mol% or less, based on the total of all monomer components constituting the resin (100 mol%). A plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.

[0093] <Photosensitive resin composition: polyimide and polybenzoxazole> In the present invention, it is preferable that the pixel division layer contains polyimide and / or polybenzoxazole, and the polyimide and / or polybenzoxazole has a structure represented by formula (1). TMA-2 can be lowered and even I TMA-1 can also be made lower.

[0094] [ka]

[0095] In formula (1), X 1 is a non-cyclic divalent hydrocarbon group having 4 to 10 carbon atoms, R 1each independently represents a hydrocarbon group having 1 to 4 carbon atoms or a hydroxyl group, and each a independently represents an integer of 0 to 4.

[0096] X 1 X is a non-cyclic divalent hydrocarbon group having 4 to 10 carbon atoms. 1 By making is a non-cyclic divalent hydrocarbon group having 4 to 10 carbon atoms, the hydrophobicity of the polyimide and / or polybenzoxazole is improved, and the penetration of TMA ions can be efficiently suppressed. On the other hand, if a cyclic structure is included, it is not preferable because it is three-dimensionally bulky and TMA ions tend to penetrate into the pixel division layer during the development process.

[0097] In particular, X in the formula (1) 1 It is preferable that the structure represented by formula (2) is used. This can improve hydrophobicity more efficiently, and further, I TMA-2 can be lowered.

[0098] [ka]

[0099] In formula (2), R 2 and R 3 are each independently a non-cyclic hydrocarbon group having 1 to 9 carbon atoms or a hydrogen atom, and * indicates the point of attachment to the aromatic ring. 2 and R 3 The total number of carbon atoms is 3 to 9.

[0100] X 1 Specific examples of the structure of R include, but are not limited to, the following structures. 2 and R 3 From the viewpoint of easily increasing the solvent solubility of the polyimide and the polybenzoxazole, it is preferable that the structures are different from each other.

[0101] [ka]

[0102] <Photosensitive resin composition: phenolic hydroxyl group-containing resin> In order for the pixel division layer to contain a compound derived from a phenolic hydroxyl group-containing resin, this essentially means that the photosensitive resin composition used to form the pixel division layer contains a phenolic hydroxyl group-containing resin, and these can be synthesized by known methods.

[0103] The phenolic hydroxyl group-containing resin in the present invention is a resin having a phenolic hydroxyl group or a naphthol structure as a constituent unit, and examples thereof include polyhydroxystyrene resins, novolak resins, resol resins, triphenol-type phenolic resins, and biphenylenemethylene-type phenolic resins, but are not limited to these.

[0104] The polyhydroxystyrene resin can be obtained, for example, by addition polymerization of a phenol derivative having an unsaturated bond by a known method. Examples of the phenol derivative having an unsaturated bond include hydroxystyrene, dihydroxystyrene, allylphenol, coumaric acid, 2'-hydroxychalcone, resveratrol, and 4-hydroxystilbene, and two or more of these may be used. In addition, it may be a copolymer with a monomer that does not contain a phenolic hydroxyl group, such as styrene.

[0105] Novolak resins, resol resins, and benzyl ether type phenolic resins can be obtained by polycondensation of phenols and aldehydes by known methods.

[0106] Examples of phenols include phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2,4,5-trimethylphenol, methylene bisphenol, methylene bis(p-cresol), resorcin, catechol, 2-methylresorcin, 4-methylresorcin, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichlorophenol, m-methoxyphenol, p-methoxyphenol, p-butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3-diethylphenol, 2,5-diethylphenol, p-isopropylphenol, α-naphthol, β-naphthol, etc. Two or more of these may be used.

[0107] Examples of aldehydes include formalin, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde, etc. Two or more of these may be used.

[0108] The biphenylenemethylene type phenolic resin can be obtained by polycondensation of the above-mentioned phenols with bischloromethylbiphenyl.

[0109] Among these, the pixel division layer I TMA-1 From the viewpoint of easily lowering the temperature, polyhydroxystyrene, polyhydroxystyrene / polystyrene copolymer, and biphenylenemethylene type phenolic resin are preferred. TMA-1 From the viewpoint of further reducing the viscosity, polyhydroxystyrene and polyhydroxystyrene / polystyrene copolymers are more preferred. The phenolic hydroxyl group-containing resin is more preferably polyhydroxystyrene or polyhydroxystyrene / polystyrene copolymer.

[0110] <Photosensitive resin composition: other resins> The photosensitive resin composition used to form the pixel dividing layer of the present invention may also contain a polymer obtained by polymerizing a radical polymerizable monomer, a cardo resin, and a polysiloxane, as long as the effects of the present invention are not impaired.

[0111] As the polymer obtained by polymerizing a radical polymerizable monomer, a polymer obtained by radical polymerization of (meth)acrylic acid or a (meth)acrylic acid ester is preferable. As the (meth)acrylic acid ester, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, cyclopropyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cyclohexenyl (meth)acrylate, 4-methoxycyclohexyl (meth)acrylate, 2-cyclopropyloxycarbonylethyl (meth)acrylate, 2-cyclopentyloxycarbonylethyl (meth)acrylate, 2-cyclohexyloxycarbonyl (meth)acrylate, Known acrylates such as ethyl, 2-cyclohexenyloxycarbonylethyl (meth)acrylate, 2-(4-methoxycyclohexyl)oxycarbonylethyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, tetracyclodecanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, adamantyl (meth)acrylate, adamantylmethyl (meth)acrylate, and 1-methyladamantyl (meth)acrylate can be used. Here, (meth)acrylic acid is a general term for methacrylic acid and acrylic acid, and the same applies to compounds in this specification including the above series of compounds. Aromatic vinyl compounds such as styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, and α-methylstyrene may be copolymerized with the above (meth)acrylic acid or (meth)acrylic acid ester. In addition, an ethylenically unsaturated double bond group can be introduced by addition reaction of an epoxy compound having an ethylenically unsaturated double bond group with (meth)acrylic acid.

[0112] Cardo resins include resins having a cardo structure, i.e., a skeleton structure in which two ring structures are bonded to a quaternary carbon atom constituting a ring structure. A typical cardo structure is one in which two aromatic rings are bonded to the 9-position of a fluorene ring. Specific examples of skeleton structures in which two ring structures are bonded to a quaternary carbon atom constituting a ring structure include a bisarylfluorene skeleton, a bisphenolfluorene skeleton, and a bisaminophenylfluorene skeleton. The skeleton may have an epoxy group, an acrylic group, or a methacrylic group as a substituent. Cardo resins are formed by polymerizing a skeleton having this cardo structure through a reaction between functional groups bonded to it. Cardo resins have a structure (cardo structure) in which a main chain and a bulky side chain are connected by one element, and have a ring structure in a direction almost perpendicular to the main chain. Specific examples of monomers having a cardo structure include resins such as bis(glycidyloxyphenyl)fluorene type epoxy resins, and bisphenols containing a cardo structure, such as 9,9-bis(4-hydroxyphenyl)fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene. A cardo resin is a polymer obtained by polymerizing a monomer having a cardo structure, but it may also be a copolymer with other copolymerizable monomers.

[0113] Examples of polysiloxanes include siloxane resins obtained by hydrolyzing one or more organosilanes selected from tetrafunctional organosilanes, trifunctional organosilanes, bifunctional organosilanes, and monofunctional organosilanes (these may be referred to as monomers of siloxane resins) and partially condensing them by a dehydration reaction. Partial condensation by a dehydration reaction may also be simply referred to as partial condensation. Specific examples of organosilanes include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, and tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, 1-(p-hydroxyphenyl)trimethoxysilane, and the like. diphenyl)ethyltrimethoxysilane, 2-(p-hydroxyphenyl)ethyltrimethoxysilane, 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyltrimethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,Trifunctional silanes such as 4-epoxycyclohexyl)ethyltriethoxysilane, [(3-ethyl-3-oxetanyl)methoxy]propyltrimethoxysilane, [(3-ethyl-3-oxetanyl)methoxy]propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic acid, 1-naphthyltrimethoxysilane, 1-naphthyltriethoxysilane, 1-naphthyltri-n-propoxysilane, 2-naphthyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxy Examples of the organosilanes include bifunctional silanes such as silane, dimethyldiacetoxysilane, di-n-butyldimethoxysilane, diphenyldimethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, di(1-naphthyl)dimethoxysilane, and di(1-naphthyl)diethoxysilane, and monofunctional silanes such as trimethylmethoxysilane, tri-n-butylethoxysilane, (3-glycidoxypropyl)dimethylmethoxysilane, and (3-glycidoxypropyl)dimethylethoxysilane. Two or more of these organosilanes may be used. In addition, silicate compounds such as Methyl Silicate 51 manufactured by Fuso Chemical Industry Co., Ltd. and M Silicate 51 manufactured by Tama Chemical Industry Co., Ltd. may be copolymerized.

[0114] Polysiloxane is synthesized by hydrolysis and partial condensation of polysiloxane monomers such as organosilanes. Here, partial condensation refers to leaving some Si-OH in the obtained polysiloxane, rather than condensing all Si-OH in the hydrolyzate. A general method can be used for hydrolysis and partial condensation. For example, an organic solvent, water, and optionally a catalyst are added to an organosilane mixture, and the mixture is heated and stirred at 50 to 150°C for about 0.5 to 100 hours. During stirring, hydrolysis by-products (alcohols such as methanol) and condensation by-products (water) may be removed by distillation, if necessary.

[0115] The catalyst used for hydrolysis and partial condensation of polysiloxane monomers such as organosilane is not particularly limited, but acid catalyst or base catalyst is preferably used.Specific examples of acid catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acid or its anhydride, acidic cation exchange resin, etc.Specific examples of base catalyst include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, sodium hydroxide, potassium hydroxide, alkoxysilane having amino group, basic anion exchange resin, etc.

[0116] <Photosensitive resin composition: thermal acid generator> In order for the pixel dividing layer to contain a compound derived from a thermal acid generator, the photosensitive resin composition used to form the pixel dividing layer must substantially contain the thermal acid generator.

[0117] A thermal acid generator is sufficient if it has the function of generating an acid when heated, and the definition of a thermal acid generator also includes compounds that have the function of generating an acid when exposed to light such as ultraviolet light in addition to heat. However, quinone diazide compounds are defined as not being included in the category of thermal acid generators even if they generate an acid when heated.

[0118] Examples of the thermal acid generator include sulfonium salts, sulfonic acid esters, etc. Two or more of these may be contained.

[0119] The acid generated from the thermal acid generator is preferably a strong acid, for example, an arylsulfonic acid such as p-toluenesulfonic acid or benzenesulfonic acid, an alkylsulfonic acid such as methanesulfonic acid, ethanesulfonic acid or butanesulfonic acid, or camphorsulfonic acid.

[0120] Among thermal acid generators, it is preferable to use a thermal acid generator having a sulfonate structure, because it has a high effect of improving long-term reliability. Examples of thermal acid generators having a sulfonate structure include compounds obtained by sulfonating a compound containing an alcoholic hydroxyl group or a compound containing a phenolic hydroxyl group with methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, octane sulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, camphorsulfonic acid, or the like. Examples of compounds containing an alcoholic hydroxyl group include methanol, ethanol, propanol, and butanol, and examples of phenolic hydroxyl groups include phenol, cresol, and naphthol. Examples of dihydric alcohol compounds include methanediol, ethanediol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, and decanediol. Specific examples of trihydric or higher alcohol compounds include propanetriol, butanetriol, pentanetriol, hexanetriol, heptanetriol, octanetriol, nonanetriol, decanetriol, pentaerythritol, etc. Specific examples of polyhydric phenol compounds include dihydroxybenzene, trihydroxybenzene, tetrahydroxybenzene, etc.

[0121] Examples of thermal acid generators that generate acid when exposed to light such as ultraviolet light in addition to heat include "Irgacure" PAG103 and PAG121 (trade names, manufactured by BASF Japan Ltd.), PA-411, PA-480 (trade names, manufactured by Heraeus K.K.), PAI-01, PAI-101, PAI-106, PAI-1001, PAI-1002, PAI-1003, and PAI-1004 (trade names, manufactured by Midori Examples of such antibacterial agents include SP-082, SP-601, SP-606, SP-607, SP-612 (trade names, manufactured by ADEKA CORPORATION), NIT, MIN, ILP-110, ILP-110N, ILP-118, ILP-113, PA-223, PA-298 (trade names, manufactured by Heraeus K.K.), NAI-105, NAI-106, NAI-109 (trade names, manufactured by Midori Chemical Co., Ltd.), and the like.

[0122] <Photosensitive resin composition: quinonediazide compound> The photosensitive resin composition used for forming the pixel division layer of the present invention preferably contains a quinone diazide compound for the purpose of imparting pattern processability. By containing a quinone diazide compound, an acid is generated in the light-irradiated portion, and the solubility of the light-irradiated portion in an alkaline aqueous solution is increased, and a positive relief pattern in which the light-irradiated portion dissolves can be obtained. Examples of the quinone diazide compound include a polyhydroxy compound to which a sulfonic acid of quinone diazide is bonded via an ester bond, a polyamino compound to which a sulfonic acid of quinone diazide is bonded via a sulfonamide bond, and a polyhydroxypolyamino compound to which a sulfonic acid of quinone diazide is bonded via an ester bond and / or a sulfonamide bond. It is preferable that 50 mol % or more of the functional groups of these polyhydroxy compounds or polyamino compounds are substituted with quinone diazide. The photosensitive resin composition may also contain two or more quinone diazide compounds.

[0123] Among the quinone diazide compounds, naphthoquinone diazide sulfonic acid ester compounds are preferably used, and can be synthesized by esterification reaction between a compound having a phenolic hydroxyl group and a naphthoquinone diazide sulfonic acid compound, and can be synthesized by a known method. By using these naphthoquinone diazide sulfonic acid ester compounds, resolution, sensitivity, and residual film rate are further improved.

[0124] The compounds having a phenolic hydroxyl group used herein include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenetris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, Examples of compounds include TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (trade name, manufactured by Asahi Organic Chemical Industry Co., Ltd.), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, and BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.). As naphthoquinone diazide sulfonic acid ester compounds, those in which naphthoquinone diazide-4-sulfonic acid or naphthoquinone diazide-5-sulfonic acid is introduced via an ester bond can be mentioned as preferred examples, but other compounds can also be used.

[0125] Naphthoquinone diazide sulfonic acid-4-ester compounds have absorption in the i-line region of a mercury lamp and are suitable for i-line exposure, while naphthoquinone diazide-5-sulfonic acid ester compounds have absorption extending to the g-line region of a mercury lamp and are suitable for g-line exposure. The pixel division layer of the present invention can contain both naphthoquinone diazide-4-sulfonic acid ester compounds and naphthoquinone diazide-5-sulfonic acid ester compounds, can contain naphthoquinone diazide sulfonic acid ester compounds in which a naphthoquinone diazide-4-sulfonyl group and a naphthoquinone diazide-5-sulfonyl group are used in combination in the same molecule, or can contain a mixture of naphthoquinone diazide-4-sulfonic acid ester compounds and naphthoquinone diazide-5-sulfonic acid ester compounds.

[0126] <Photosensitive resin composition: thermal crosslinking material> The photosensitive resin composition used to form the pixel division layer of the present invention may contain a thermal crosslinking agent. The thermal crosslinking agent refers to a compound having a thermally reactive functional group such as a methylol group, an alkoxymethyl group, an epoxy group, or an oxetanyl group. The thermal crosslinking agent crosslinks the resin or other additive components, and can improve the chemical resistance and heat resistance of the pixel division layer.

[0127] Examples of thermal crosslinking agents having a methylol group and / or an alkoxymethyl group include DML-PC, DML-PEP, DMOM-PC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, and HMOM Examples of such compounds include -TPHAP, HMOM-TPPA (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A (all trade names, manufactured by Asahi Yukizai Co., Ltd.), "NIKALAC" (registered trademark) MX-290, MX-280, MX-270, MX-279, MW-100LM, MX-750LM (all trade names, manufactured by Sanwa Chemical Co., Ltd.), and each of these compounds is available from the respective companies mentioned above.

[0128] Examples of epoxy group-containing resins include "Epicoat" (registered trademark) 807, 828, 1002, 1750, 1007, YX8100-BH30, E1256, E4250, and E4275 (all trade names, manufactured by Japan Epoxy Co., Ltd.), "Epiclon" (registered trademark) EXA-4880, EXA-4822, EXA-9583, HP4032, and HP4770 (all trade names, manufactured by Dainippon Ink and Chemicals, Inc.), and "Epolite" (registered trademark) 40E, 100E, 200E, 400E, 70P, 200P, 400P, 1500NP, 80MF, and 400 0, 3002, 1708A, 1608F (all trade names, manufactured by Kyoeisha Chemical Co., Ltd.), "Denacol" (registered trademark) EX-212L, EX-214L, EX-216L, EX-252, EX-850L, EX-201-IM, EX-321L, EX-614B, EX-313, EX-512, EX-321L, EX-810, EX-861, EX-211 (all trade names, manufactured by Nagase ChemteX Corporation), GAN, GOT (all trade names, manufactured by Nippon Kayaku Co., Ltd.), "Celloxide" (registered trademark) 2021P (trade name, manufactured by Daicel Corporation), "RIKARESIN" (registered trademark) DME-100, BEO-60E (all trade names, manufactured by New Japan Chemical Co., Ltd.), "TBIS" (registered trademark) -GG, -RXG, -BNEG (trade name, manufactured by Taoka Chemical Co., Ltd.), VG3101L (trade name, manufactured by Printec Co., Ltd.), "TEPIC" (registered trademark) -S, -L, -VL, -FL, -UC (all trade names, manufactured by Nissan Chemical Industries, Ltd.), "Epiclon" N660, N695, HP7200 (all trade names, manufactured by Dainippon Ink and Chemicals, Inc.), NC6000, EPPN502H, NC3000 (all trade names, manufactured by Dai Nippon Ink and Chemicals, Inc.), Examples of such antibacterial agents include "Epotohto" (registered trademark) YH-434L (trade name, manufactured by Tohto Kasei Co., Ltd.), EHPE-3150 (trade name, manufactured by Daicel Corporation), MA-DGIC (trade name, manufactured by Shikoku Kasei Co., Ltd.), "Epocalic" (registered trademark) THI-DE, DE-102, DE-103 (all trade names, manufactured by ENEOS Corporation), "Showfree" (registered trademark) CDMDG (trade name, manufactured by Showa Denko K.K.), and "Epogose" (registered trademark) BD, NPG, HD (trade names, manufactured by Yokkaichi Chemical Co., Ltd.), each of which is available from the respective companies.

[0129] Examples of oxetane compounds include OXT-121, OXT-221, OX-SQ-H, OXT-191, PNOX-1009, RSOX (all trade names, manufactured by Toa Gosei Co., Ltd.), "Ethanacol" (registered trademark) OXBP, and OXTP (all trade names, manufactured by Ube Industries, Ltd.), each of which is available from the respective companies.

[0130] Examples of the bismaleimide compound include 1,2-bis(maleimide)ethane, 1,3-bis(maleimide)propane, 1,4-bis(maleimide)butane, 1,5-bis(maleimide)pentane, 1,6-bis(maleimide)hexane, 2,2,4-trimethyl-1,6-bis(maleimide)hexane, N,N'-1,3-phenylenebis(maleimide), 4-methyl-N,N'-1,3 N,N'-1,4-phenylene bis(maleimide), 3-methyl-N,N'-1,4-phenylene bis(maleimide), 4,4'-bis(maleimide)diphenylmethane, 3,3'-diethyl-5,5'-dimethyl-4,4'-bis(maleimide)diphenylmethane, or 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane.

[0131] Examples of the isocyanate compound include aromatic polyisocyanates such as 4,4'-methylenebis(phenylene isocyanate) (MDI) and tolylene diisocyanate (TDI); aliphatic polyisocyanates such as hexamethylene diisocyanate (HDI), trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, pentamethylene diisocyanate and lysine diisocyanate; and alicyclic polyisocyanates such as isophorone diisocyanate (IPDI) and 4,4'-methylenebis(cyclohexyl isocyanate) (H12MDI).

[0132] Examples of the blocked isocyanate compound include compounds obtained by blocking the above-mentioned isocyanate compound with a blocker such as oxime, lactam, pyrazole, etc., and the crosslinking temperature can be easily adjusted. The content of the thermal crosslinking agent is preferably 1 to 30% by mass based on the total amount of the photosensitive resin composition excluding the organic solvent and water.

[0133] <Photosensitive resin composition: organic solvent> The photosensitive resin composition used for forming the pixel dividing layer of the present invention preferably contains an organic solvent, which can make the composition into a varnish state and improve the coatability.

[0134] The organic solvent may be a polar aprotic organic solvent such as γ-butyrolactone, an ether such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tetrahydrofuran, or dioxane, a ketone such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, or diacetone alcohol, an ethylene glycol monomethyl ether acetate, an ethylene glycol monoethyl ether ... Organic solvents such as esters such as ethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, 3-methoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, methyl acetoacetate, and ethyl acetoacetate, aromatic hydrocarbons such as toluene and xylene, and amides such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide can be used alone or in combination.

[0135] The amount of the organic solvent used is not particularly limited, but is preferably 100 to 3000 parts by mass, more preferably 150 to 2000 parts by mass, based on 100 parts by mass of the total amount of the photosensitive resin composition excluding the organic solvent and water. The proportion of organic solvents having a boiling point of 180° C. or higher to the total amount of organic solvents is preferably 20% by mass or less, more preferably 10% by mass or less. By keeping the proportion of organic solvents having a boiling point of 180° C. or higher to 20% by mass or less, the amount of outgassing from the cured product can be kept low, and as a result, the reliability of the organic EL device can be improved.

[0136] <Photosensitive resin composition: adhesion improver> The photosensitive resin composition used in the formation of the pixel division layer of the present invention can contain an adhesion improver. Examples of adhesion improvers include silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane, titanium chelate agents, aluminum chelate agents, and compounds obtained by reacting aromatic amine compounds with alkoxy group-containing silicon compounds. Two or more of these may be contained. By containing these adhesion improvers, when developing a photosensitive resin film, it is possible to improve the adhesion of the silicon wafer, ITO, SiO 2 The adhesion improver can improve adhesion to the underlying substrate such as silicon nitride. Also, the resistance to oxygen plasma and UV ozone treatments used for cleaning, etc. The content of the adhesion improver is preferably 0.1 to 10 mass % based on the total amount of the photosensitive resin composition excluding organic solvents and water.

[0137] <Photosensitive resin composition: surfactant> The photosensitive resin composition used in the formation of the pixel division layer of the present invention may contain a surfactant for the purpose of improving wettability with the substrate as necessary. Commercially available compounds can be used as the surfactant. Specifically, silicone surfactants include the SH series, SD series, and ST series of Toray Dow Corning Silicone Co., Ltd., the BYK series of BYK Japan Co., Ltd., the KP series of Shin-Etsu Silicone Co., Ltd., the Disform series of Nippon Oil & Fats Co., Ltd., and the TSF series of Toshiba Silicone Co., Ltd.; fluorine surfactants include the "Megafac (registered trademark)" series of Dainippon Ink Mfg. Co., Ltd., the Fluorard series of Sumitomo 3M Co., Ltd., the "Surflon (registered trademark)" series and "Asahi Guard (registered trademark)" series of Asahi Glass Co., Ltd., the EF series of Shin Akita Kasei Co., Ltd., and the Polyfox series of OmNova Solutions Co., Ltd.; and surfactants consisting of acrylic and / or methacrylic polymers include the Polyflow series of Kyoeisha Chemical Co., Ltd., and the "Disparon (registered trademark)" series of Kusumoto Chemical Co., Ltd., but are not limited thereto.

[0138] The content of the surfactant is preferably 0.001 to 1% by mass based on the total amount of the photosensitive resin composition excluding the organic solvent and water.

[0139] <Photosensitive resin composition: Coloring material> The photosensitive resin composition used to form the pixel division layer of the present invention may contain a colorant as necessary. The colorant refers to an organic pigment, an inorganic pigment, or a dye. The colorant is preferably an organic pigment and / or an inorganic pigment.

[0140] Examples of organic pigments include diketopyrrolopyrrole pigments, azo pigments such as azo, disazo, or polyazo, phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine, or metal-free phthalocyanine, anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavanthrone, anthranthrone, indanthrone, pyranthrone, or violanthrone, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, threne pigments, benzofuranone pigments, or organometallic complex pigments.

[0141] Examples of inorganic pigments include titanium oxide, zinc oxide, zinc sulfide, white lead, calcium carbonate, precipitated barium sulfate, white carbon, alumina white, kaolin clay, talc, bentonite, black iron oxide, cadmium red, red iron oxide, molybdenum red, molybdate orange, chrome vermilion, yellow lead, cadmium yellow, yellow iron oxide, titanium yellow, chromium oxide, viridian, titanium cobalt green, cobalt green, cobalt chrome green, Victoria green, ultramarine, Prussian blue, cobalt blue, cerulean blue, cobalt silica blue, cobalt zinc silica blue, manganese violet, and cobalt violet.

[0142] Dyes include, for example, azo dyes, anthraquinone dyes, condensed polycyclic aromatic carbonyl dyes, indigoid dyes, carbonium dyes, phthalocyanine dyes, methine or polymethine dyes.

[0143] The content of the colorant is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, based on the total amount of the photosensitive resin composition excluding the organic solvent and water, from the viewpoint of obtaining necessary colorability for the cured product. Also, from the viewpoint of obtaining good storage stability, the content is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less, based on the total amount of the photosensitive resin composition excluding the organic solvent and water.

[0144] <Time-of-flight secondary ion mass spectrometry> Here, the time-of-flight secondary ion mass spectrometry technique will be described in detail.

[0145] Time-of-flight secondary ion mass spectrometry is commonly called TOF-SIMS (Time-Of-Flight Secondary Ion Mass Spectrometry). TOF-SIMS is an analytical method in which pulsed primary ions are irradiated onto the surface of a solid sample in a high vacuum, and the secondary ions emitted from the solid are mass-separated using a velocity distribution according to mass, with light ions being fast and heavy ions being slow. A mass spectrum of the top surface of the sample can be obtained by measuring this time-of-flight distribution. A sputter ion gun can be used in conjunction with this TOF-SIMS analysis to perform TOF-SIMS analysis while sputtering in the depth direction, thereby obtaining a mass spectrum in the depth direction.

[0146] The ion intensity in the present invention is the secondary ion intensity released per irradiated primary ion, which is calculated by dividing the ion intensity obtained by measurement by the number of primary ion irradiations (also called the dose) during the measurement. 75 C 4 H 12 N + Ion intensity average (I TMA-1 )teeth, 75 C 4 H 12 N + The ion intensity is measured in a range of 20 nm to 100 nm from the surface of the pixel division layer toward the substrate. 75 C 4 H 12 N + The average ionic strength.

[0147] The measurement conditions in the TOF-SIMS analysis in the present invention are shown below. It is preferable to perform the analysis under the following conditions. Etching ion species: Ar-GCIB Etching ion acceleration voltage: 10 kV Primary ion species: Bi3 2+ Primary ion charge: 2 Primary ion acceleration voltage: 30 kV Primary ion current value: 0.1pA Cycle time: 140μsec Number of primary ions per pulse: 43.7 (Primary ion current value x cycle time / elementary charge: 1.602 x 10 -19 / primary ion valence) = (0.1 × 10 -12 )×(140×10 -6 ) / (1.602×10 -19 ) / (2)=43.7 Number of integrations per measurement point: 65536 Dose: 2863923.2 (Number of primary ion irradiations per pulse) × (Number of integrations per measurement point) = 43.7 × 65536 = 2863923.2 Secondary ion polarity: positive Antistatic: Irradiation with electron beam from flood gun (electron gun) 75 C 4 H 12 N + ion( 13 CC 3 H 12 N + ) mass number: 75 31 CF + Mass number of ion: 31.

[0148] Next, the analysis portion of the pixel division layer will be described. 75 C 4 H 12 N + Ion intensity average (I TMA-1 ) is detected by time-of-flight secondary ion mass spectrometry in a range of 20 nm to 100 nm from the pixel division layer surface toward the substrate. 75 C 4 H 12 N +It is an average ion intensity value and is essentially meant to analyze the surface area of ​​the pixel division layer.

[0149] Obtained by time-of-flight secondary ion mass spectrometry of the pixel division layer 75 C 4 H 12 N + Ion intensity average (I TMA-2 ) is detected by time-of-flight secondary ion mass spectrometry in the range of 101 nm to 300 nm from the pixel division layer surface toward the substrate. 75 C 4 H 12 N + This is the average ion intensity value, and essentially means analyzing the inner layer region of the pixel division layer.

[0150] When analyzing the pixel division layer of an organic EL display device, it is preferable to perform TOF-SIMS analysis on the surface of the cured product in a region 2 μm or more away from the pixel opening edge in the planar direction. The region 2 μm or less away from the pixel opening edge in the planar direction may have a film thickness of 100 nm or less, and in that case, mass spectrum information of the lower layer components other than the pixel division layer may be mixed.

[0151] Information on the direction from the surface of the cured material to the inside obtained by TOF-SIMS analysis is usually obtained by converting the sputtering time to the distance from the surface of the object to the inside. Methods for converting the sputtering time to the distance from the surface of the object to the inside include, for example, a method of converting the time to distance based on the relationship between the film thickness of the pixel division layer measured in advance and the sputtering time from the surface of the cured material to the inside of the cured material, or a method of interrupting the acquisition of a profile during TOF-SIMS analysis, measuring the distance from the surface to the inside of the obtained analysis crater with a stylus film thickness meter, and calculating the sputtering rate in the pixel division layer in advance.

[0152] For example, when analyzing a pixel division layer of an organic EL display device using the above-mentioned TOF-SIMS, it is necessary to expose the surface of the pixel division layer. An example of a method for exposing the surface of a cured product will be described below, but the exposure method is not limited to the following.

[0153] As a method for exposing the surface of the pixel division layer, for example, a sputtering gun of argon, cesium, oxygen, gallium, etc. can be used to remove the upper part of the surface of the desired pixel division layer, thereby exposing the surface of the pixel division layer.

[0154] Alternatively, as an exposure method using chemical etching, both or one of the electrodes sandwiched above and below the pixel dividing layer can be dissolved with an acid or alkali to create gaps above and below the cured product, and the laminate can be peeled off to expose the surface of the cured product.

[0155] Furthermore, a substrate in which a member existing above the organic EL layer of an organic EL display device is mechanically peeled off to expose a pixel division layer with an organic EL layer, and the remaining organic EL layer is washed with an organic solvent such as tetrahydrofuran, if necessary, can be analyzed by the above-mentioned method.

[0156] <Fourier transform infrared spectrophotometer (FT-IR)> Next, a method for analyzing the pixel division layer using a Fourier transform infrared spectrophotometer (FT-IR) will be described.

[0157] FT-IR is a method for detecting chemical bonds and lattice vibrations excited by absorbing infrared rays, and is suitable for obtaining qualitative analysis of functional groups and information on chemical structures. Measurement modes such as transmission and ATR (total reflection) can be selected depending on the measurement location and the form of the sample, but are not particularly limited. In the present invention, the statement that a maximum exists means that the peak intensity has a maximum within a specified wavenumber range. In addition, a method for calculating the peak intensity is preferably a method in which a baseline is drawn from one end of a specified wavenumber range to the other end, and the peak intensity from the maximum point at the maximum wavenumber to the baseline is calculated in terms of intensity calculation accuracy.

[0158] The measurement conditions in the FT-IR analysis in the present invention are shown below. It is preferable to perform the analysis under the following conditions. Light source: Globar (SiC) Detector: DLaTGS Resolution: 4cm -1 Number of times accumulated: 256 Attached equipment: Thunderdome single reflection ATR, incident angle 45°, Ge prism used.

[0159] <Manufacturing method for organic EL display device> An example of a method for manufacturing an organic EL display device of the present invention will be described using the case of manufacturing the organic EL display device of Fig. 1 as an example. First, wiring and TFT 2 are provided on substrate 1, which is a resin film. In addition to TFT formation steps such as "gate electrode formation step," "gate insulating film formation step," "Si film formation step," and "source and drain electrode formation step," wiring is also provided to ensure electrical connection, and all of these steps can be formed using known methods.

[0160] Next, the planarization layer 5 is formed by coating using a spin or slit coating method, and then cured by heating. At this time, a contact hole is provided for the purpose of connection with the first electrode 7. If the material used for the planarization layer 5 is a photosensitive resin composition, this can be achieved by photolithography, and if it is non-photosensitive, this can be achieved by general etching using a resist material as a mask.

[0161] Subsequently, AgPdCu and ITO are successively formed on the flattening layer 5 and then patterned to form the first electrode 7 .

[0162] Next, a method for producing the pixel division layer 8 will be described taking as an example a method in which a photosensitive resin film made of a photosensitive resin composition is formed, exposed to light, developed, and then heat-treated.

[0163] First, a photosensitive resin film made of a photosensitive resin composition is formed on the first electrode 7. Examples of methods for forming the photosensitive resin film include spin coating, slit coating, dip coating, spray coating, and printing. After coating, a reduced pressure drying process is performed as necessary. The reduced pressure drying speed depends on the vacuum chamber volume, vacuum pump capacity, and pipe diameter between the chamber and the pump, but it is preferable to set the conditions such that the pressure inside the vacuum chamber is reduced to 40 Pa after 60 seconds without a coated substrate.

[0164] After coating or drying under reduced pressure, the coating film is generally heated and dried. This process is also called pre-baking. A hot plate, oven, infrared rays, etc. are used for drying. When using a hot plate, the coating film is heated directly on the plate or held on a jig such as a proxy pin placed on the plate. The heating time is preferably from one minute to several hours. The heating temperature varies depending on the type and purpose of the coating film, but from the viewpoint of promoting solvent drying during pre-baking, it is preferably 80°C or higher, and more preferably 90°C or higher. On the other hand, from the viewpoint of reducing the progress of curing during pre-baking, it is preferably 150°C or lower, and more preferably 140°C or lower.

[0165] The photosensitive resin film can be patterned. For example, the photosensitive resin film can be exposed to actinic radiation through a photomask having a desired pattern, and then developed to form a desired pattern.

[0166] Examples of the actinic radiation used for exposure include ultraviolet light, visible light, electron beams, and X-rays. In the present invention, it is preferable to use i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) from a mercury lamp. When the film has positive photosensitivity, the exposed area dissolves in the developer.

[0167] After exposure, in the case of a positive type, the exposed area is removed with a developer to form a desired pattern. Tetramethylammonium hydroxide is used as the developer. Development methods include spray, paddle, immersion, and ultrasonic methods.

[0168] Next, the pattern formed by development is preferably rinsed with distilled water. Alternatively, alcohols such as ethanol and isopropyl alcohol, or esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to the distilled water for rinsing.

[0169] Next, the developed photosensitive resin film is heat-treated to obtain a pixel division layer. The heat treatment temperature is preferably 180°C or higher, more preferably 200°C or higher, even more preferably 230°C or higher, and particularly preferably 250°C or higher, from the viewpoint of further reducing the amount of outgas generated from the cured film. On the other hand, from the viewpoint of improving the film toughness of the cured film, it is preferably 500°C or lower, more preferably 450°C or lower. In this temperature range, the temperature may be raised stepwise or continuously. The heat treatment time is preferably 30 minutes or more, from the viewpoint of further reducing the amount of outgas. Also, from the viewpoint of improving the film toughness of the cured film, it is preferably 3 hours or less. For example, a method of heat treatment at 150°C and 250°C for 30 minutes each, or a method of heat treatment while linearly increasing the temperature from room temperature to 300°C over 2 hours, etc. can be mentioned.

[0170] The atmosphere during the heat treatment is preferably a low oxygen concentration of less than 5%, from the viewpoint of improving the long-term reliability of the cured film and suppressing a decrease in luminance during continuous high-temperature operation, particularly when used in an organic EL display device. Examples of inert gases for achieving an oxygen concentration of less than 5% include nitrogen and argon. The oxygen concentration in the inert gas atmosphere is preferably less than 5%, more preferably less than 1%, even more preferably less than 0.5%, and particularly preferably less than 0.01%.

[0171] Subsequently, each layer constituting the organic EL layer 9, such as a hole transport layer, a light emitting layer, and an electron transport layer, can be formed by a known method, for example, a vacuum deposition method or an inkjet method.

[0172] The mask deposition method, which is one of the vacuum deposition methods, is a method of depositing an organic compound by using a deposition mask to form a pattern. For example, a method of depositing a deposition mask with a desired pattern as an opening on the deposition source side of a substrate. In order to obtain a highly accurate deposition pattern, it is important to make a deposition mask with high flatness adhere to the substrate. In general, a technique of applying tension to the deposition mask or a technique of adhering the deposition mask to the substrate by a magnet placed on the back of the substrate can be used. Examples of methods for manufacturing a deposition mask include an etching method, mechanical polishing, a sandblasting method, a sintering method, a laser processing method, the use of a photosensitive resin, and an electroforming method. When a fine pattern is required, it is preferable to use an etching method or an electroforming method, which have excellent processing accuracy.

[0173] The organic EL display device of the present invention further comprises a second electrode 10. A known method can be used for the formation of the second electrode 10, but a vacuum deposition method is preferred since it is easy to avoid deterioration or damage of the underlying organic EL layer 9.

[0174] <Method for producing photosensitive resin composition> The photosensitive resin composition used in the manufacture of the pixel division layer of the present invention can be obtained, for example, by dissolving an alkali-soluble resin, a quinone diazide compound, and, if necessary, an organic solvent, a thermal crosslinking agent, a thermal acid generator, an adhesion improver, a surfactant, a colorant, inorganic particles, etc.

[0175] Examples of dissolving methods include stirring and heating. When heating, the heating temperature is preferably set within a range that does not impair the performance of the photosensitive resin composition, and is usually room temperature to 80°C. The order of dissolving each component is not particularly limited, and for example, a method of dissolving compounds in order starting from the least soluble compound can be used. For components that are prone to generating bubbles when dissolved by stirring, such as surfactants and some adhesion improvers, the components can be added last after dissolving the other components, thereby preventing insufficient dissolution of the other components due to the generation of bubbles.

[0176] The obtained photosensitive resin composition is preferably filtered using a filter to remove dust and particles. The filter pore size is, for example, 0.5 μm, 0.2 μm, 0.1 μm, 0.07 μm, 0.05 μm, 0.02 μm, etc., but is not limited thereto. The material of the filter includes polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), etc., and polyethylene and nylon are preferred. EXAMPLES

[0177] The present invention will be described below with reference to examples, but the present invention is not limited to these examples. The photosensitive resin compositions in the examples were evaluated by the following methods.

[0178] (1)TOF-SIMS analysis <Creating the pixel division layer> Figure 2 shows a schematic diagram of the base material used. First, a 100 - nm ITO transparent conductive film was formed on the entire surface of a 38×46 - mm non - alkaline glass base material 11 by sputtering and etched to form the first electrode 12. At the same time, an auxiliary electrode 13 was also formed to take out the second electrode. The obtained base material was ultrasonically cleaned with "Semicoclean 56" (trade name, manufactured by Furuchi Chemical Co., Ltd.) for more than 10 minutes and then washed with ultrapure water. Next, the photosensitive resin composition according to each of the following examples and comparative examples was applied to the entire surface of this base material by spin - coating and pre - baked on a hot plate at 120 °C for 2 minutes. Using a parallel - light mask aligner (PLA - 501F manufactured by Canon Inc.) on this film with an ultra - high - pressure mercury lamp as the light source (a mixed line of g - line, h - line, and i - line), it was UV - exposed through a photomask. Then, it was developed with a 2.38 - mass% TMAH aqueous solution to dissolve only the exposed part, and then rinsed with pure water. The obtained patterned base material was cured in an inert oven (CLH - 21CD - S manufactured by Koyo Thermo Systems Co., Ltd.) at the temperature described in each of the examples and comparative examples for 60 minutes in a nitrogen atmosphere. In this way, pixel - dividing layers 14 with openings having a width of 50 μm and a length of 260 μm were arranged with a pitch of 155 μm in the width direction and a pitch of 465 μm in the length direction, and each opening exposed the first electrode. The pixel - dividing layer was formed limited to the effective area of the base material. In this way, a pixel - dividing layer with an aperture ratio of 18% was provided in a base - material effective area that was a square with a side length of 16 mm, and the thickness of the pixel - dividing layer was about 2.0 μm. Further, for the examples and comparative examples described as "yes" in the "acid cleaning" row in Tables 1 and 2, the cured pixel - dividing layer was immersed in various acidic aqueous solutions for 2 minutes or 10 minutes, and then rinsed with distilled water for acid cleaning. Carbonic acid (weak acid) and hydrochloric acid (strong acid) were used for acid cleaning, and acidic aqueous solutions adjusted to pH values of 4.7 and 1.0 respectively were used.

[0179] <Positive secondary ion detection by TOF - SIMS depth - profile analysis> For the pixel - dividing layer part of the obtained base material with a pixel - dividing layer, TOF - SIMS depth - profile analysis was performed using the following device, and secondary ions generated during TOF - SIMS depth - profile analysis were measured. Device: TOF.SIMS5 (manufactured by ION - TOF) Etching ion species: Ar-GCIB Etching ion acceleration voltage: 10 kV Primary ion species: Bi 3 2+ Primary ion charge: 2 Primary ion acceleration voltage: 30 kV Primary ion current value: 0.1pA Cycle time: 140μsec Number of primary ions per pulse: 43.7 (Primary ion current value x cycle time / elementary charge: 1.602 x 10 -19 / primary ion valence) = (0.1 × 10 -12 )×(140×10 -6 ) / (1.602×10 -19 ) / (2)=43.7 Number of integrations per measurement point: 65536 Dose: 2863923.2 (Number of primary ions per pulse) x (Number of integrations per measurement point) = 43.7 x 65536 = 2863923.22 Secondary ion polarity: positive Antistatic: Irradiation with electron beam from flood gun (electron gun) 75 C 4 H 12 N + ion( 13 CC 3 H 12 N + ) mass number: 75 31 CF + Ion mass number: 31.

[0180] The results obtained in this analysis 75 C 4 H 12 N + The ion intensity value was divided by the dose amount to calculate the value obtained for a thickness direction range of 20 nm to 100 nm from the pixel division layer surface toward the substrate. 75 C 4 H 12 N +Regarding the ionic strength, within the same range 75 C 4 H 12 N + The average value of ionic strength (I TMA-1 ) was calculated.

[0181] Using the measured value of the etching crater depth of the thickness in this analysis, the etching rate was calculated to obtain the thickness information.

[0182] (2) FT-IR analysis <Measurement of infrared spectrum by FT-IR and calculation of each index> The pixel division layer described in the above (1) TOF-SIMS analysis <fabrication of pixel division layer> was analyzed by FT-IR. Apparatus: FT-IR TENSOR2 (manufactured by Bruker) Light source: Globar (SiC) Detector: DLaTGS Resolution: 4 cm -1 Number of integrations: 256 times Accessory device: Standard dome single reflection ATR, incident angle 45°, using Ge prism.

[0183] (3) Long-term reliability test <Long-term reliability evaluation> After performing nitrogen plasma treatment as a pretreatment on the substrate described in the above (1) TOF-SIMS analysis <fabrication of pixel division layer>, the organic EL layer 15 was formed by vacuum evaporation method. The degree of vacuum during evaporation was 1×10 -3 Pa or less, and the substrate was rotated with respect to the evaporation source during evaporation. First, 10 nm of compound (HT-1) was evaporated as a hole injection layer, and 50 nm of compound (HT-2) was evaporated as a hole transport layer. Next, compound (GH-1) as a host material and compound (GD-1) as a dopant material were evaporated to a thickness of 40 nm so that the doping concentration became 10%. Next, compound (ET-1) and compound (LiQ) were laminated to a thickness of 40 nm at a volume ratio of 1:1 as an electron transport material. The structures of the compounds used in the organic EL layer are shown below.

[0184] [ka]

[0185] Next, a compound (LiQ) was evaporated to a thickness of 2 nm, and then Mg and Ag were evaporated to a thickness of 60 nm in a volume ratio of 1:10 to form a second electrode 16. Finally, a cap-shaped glass plate was attached using an epoxy resin adhesive in a low-humidity nitrogen atmosphere to seal the device, and four light-emitting devices, each of which was a rectangle with a side length of 5 mm, were fabricated on one substrate. The film thickness referred to here is the value displayed on a quartz crystal oscillator film thickness monitor.

[0186] The organic EL display device thus fabricated was stored in an air atmosphere at 100°C, and the organic EL display device was taken out every 100 hours and subjected to a current of 10 mA / cm 2 The long-term reliability (unit: hours) was defined as the minimum time for the light-emitting area after long-term storage to become 50 or less when the initial light-emitting area before the reliability test was taken as 100, and the minimum time was determined as being less than 450 hours, with the characteristic (E), 450 hours or more but less than 500 hours as characteristic (D), 500 hours or more but less than 550 hours as characteristic (C), 550 hours or more but less than 600 hours as characteristic (B), 600 hours or more but less than 650 hours as characteristic (A), 650 hours or more but less than 700 hours as characteristic (S), 700 hours or more but less than 750 hours as characteristic (S+), 750 hours or more but less than 800 hours as characteristic (S++), and 800 hours or more as characteristic (S+++).

[0187] (4) Bending reliability test <Bending reliability evaluation> AgPdCu (100 nm) and ITO (10 nm) were deposited as a first electrode in the center of a 100 mm x 100 mm polyimide film Kapton 100H (trade name, manufactured by DuPont Toray Co., Ltd.) by vacuum sputtering, and etched into 100 stripes with a line width of 60 μm, a pitch of 100 μm, and a length of 10 mm. In other words, the exposed portion of the substrate was 40 μm wide. A photosensitive resin composition according to each example and comparative example was applied by spin coating, and then prebaked on a hot plate at 120° C. for 2 minutes to form a film.

[0188] This film was exposed to UV light through a stripe pattern photomask, then developed with a 2.38% by mass TMAH aqueous solution, and only the exposed area was dissolved, followed by rinsing with pure water to obtain a pattern. Then, the film was cured for 60 minutes in an oven at 250°C under a nitrogen atmosphere to obtain a substrate with a pixel division layer pattern. In addition, the film thickness of the pixel division layer was set to 1.5 μm in all examples and comparative examples by adjusting the rotation speed in the spin coating method.

[0189] An organic EL layer was formed on the obtained substrate with a pattern of pixel division layers in the same manner as described in the above-mentioned <Reliability Evaluation>. Furthermore, 20 stripe-shaped second electrodes, each having a line width of 400 μm, a pitch of 500 μm, and a length of 10 mm, were formed by depositing Mg and Ag at a volume ratio of 10:1 to a thickness of 10 nm so as to intersect with the first electrodes. The film thickness referred to here is the value displayed on a quartz crystal oscillation film thickness monitor. In this manner, an organic EL display device was completed, which has 100 first electrodes, 20 second electrodes, and 200 light-emitting elements intersecting with each other. A schematic diagram of the organic EL display device of this embodiment is shown in FIG. 3.

[0190] As shown in FIG. 4, a metal cylinder with a diameter of 5 mm was fixed to the center of the opposite side of the substrate (100 mm×100 mm) on which the light-emitting element was formed, and the substrate was repeatedly folded along the cylinder in a range from an embrace angle of 0° (substrate is flat) to an embrace angle of 180° (folded back by the cylinder), and the folded portion was observed with an optical microscope. The substrate was judged to have low bending reliability (characteristic (E)) when the organic EL layer peeled off from the substrate after 1 to 49 bending operations, characteristic (D) when the organic EL layer peeled off after 50 to 99 bending operations, characteristic (C) when the organic EL layer peeled off after 100 to 499 bending operations, characteristic (B) when the organic EL layer peeled off after 500 to 999 bending operations, and characteristic (A) when the organic EL layer peeled off after 1,000 bending operations or more. The test was performed 10 times (n=10), and the result with the smallest number of bending operations until peeling occurred was adopted.

[0191] (5) Crack resistance test <Crack resistance evaluation> The photosensitive resin composition obtained in each of the Examples and Comparative Examples was applied by spin coating onto a polyimide film substrate so that the film thickness after heat treatment (curing) was 2.0 μm, and the film was prebaked at 120° C. for 120 seconds to prepare a prebaked film. Thereafter, the film was developed with a 2.38 mass% TMAH aqueous solution without UV exposure so that the film loss in the unexposed area was about 0.5 μm. Next, the film was cured at 250° C. for 60 minutes under a nitrogen atmosphere using a high-temperature clean oven INH-9CD-S manufactured by Koyo Thermo Systems Co., Ltd. to prepare a cured film.

[0192] Next, the polyimide film substrate having the cured film was cut into 10 pieces having a size of 50 mm length x 10 mm width. Next, the polyimide film substrate was folded on a vertical line of 25 mm with a radius of curvature of 0.1 to 1.0 mm with the surface of the cured film facing outward, and held for 30 seconds. After 30 seconds, the folded polyimide film substrate was opened, and the folded part on the vertical line of 25 mm on the cured film surface was observed using an FPD inspection microscope (MX-61L; manufactured by Olympus Corporation) to evaluate the appearance change of the cured film surface. The bending test was performed with a radius of curvature in the range of 0.1 to 1.0 mm, and the minimum radius of curvature at which the cured film did not peel off from the polyimide film substrate or the appearance change such as cracks did not occur on the cured film surface was recorded. If the minimum radius of curvature was less than 0.2 mm, it was rated as "A", if it was 0.2 mm or more but less than 0.4 mm, it was rated as "B", if it was 0.4 mm or more but less than 0.6 mm, it was rated as "C", and if it was 0.6 mm or more, it was rated as "D".

[0193] (6) Compounds used in the Examples and Comparative Examples <Resin> Synthesis Example 1: Synthesis of acid dianhydride raw material Under a dry nitrogen stream, 18.3 g (0.05 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter referred to as BAHF) and 17.4 g (0.3 mol) of propylene oxide were dissolved in 100 g of γ-butyrolactone (hereinafter referred to as GBL) and cooled to -15°C. 22.1 g (0.11 mol) of trimellitic anhydride chloride dissolved in 50 g of GBL was added dropwise so that the temperature of the reaction solution did not exceed 0°C. After the dropwise addition, the reaction was carried out at 0°C for 4 hours. The solution was concentrated using a rotary evaporator and poured into 1 L of toluene to obtain the acid dianhydride represented by the following formula.

[0194] [ka]

[0195] Synthesis Example 2: Synthesis of diamine A 18.3 g (0.05 mol) of BAHF was dissolved in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide, and cooled to -15°C. A solution of 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride dissolved in 100 mL of acetone was added dropwise to the solution. After the addition was completed, the mixture was reacted at -15°C for 4 hours, and then the temperature was returned to room temperature. The precipitated white solid was filtered and dried in vacuum at 50°C.

[0196] 30 g of the solid was placed in a 300 mL stainless steel autoclave and dispersed in 250 mL of methyl cellosolve, and 2 g of 5% palladium-carbon was added. Hydrogen was introduced into the autoclave using a balloon, and the reduction reaction was carried out at room temperature. After about 2 hours, the reaction was terminated when it was confirmed that the balloon was no longer deflating. After the reaction was completed, the palladium compound catalyst was removed by filtration, and the mixture was concentrated using a rotary evaporator to obtain diamine A represented by the following formula.

[0197] [ka]

[0198] Synthesis Example 3: Synthesis of diamine B In a 500mL four-neck flask equipped with a stirrer, a thermocouple, and a dropping funnel, 26.70g (0.086 mol) of BisP-HTG (4,4'-(3,3,5-trimethylcyclohexylidene)bisphenol; Honshu Chemical Industry Co., Ltd.) and 100mL of glacial acetic acid were charged and stirred, and the internal temperature was raised to 50°C in a water bath. 2mL (0.026 mol) of concentrated nitric acid was added dropwise over 1 hour, and then the internal temperature was lowered to 13°C by ice cooling, and 13.3mL (0.149 mol) of concentrated nitric acid was added dropwise over 1 hour. Stirring was continued for 3 hours, and the precipitated yellow crystals were filtered, washed with 40mL of glacial acetic acid and 80mL of deionized water, and dried under reduced pressure to obtain a dinitro form.

[0199] Next, 54.06g (0.135mol) of the dinitro derivative, 180mL (3.71mol) of hydrazine monohydrate, and 900mL of ethanol were added to a 2L four-neck flask equipped with a stirrer, thermocouple, Dimroth condenser, and dropping funnel, and stirred under ice cooling. 0.9g of 5% palladium-carbon (FUJIFILM Wako Pure Chemical Industries, Ltd.) suspended in 30mL of ethanol was added dropwise over 1 hour. The solution was then refluxed for 2 hours, and the palladium-carbon was removed by filtration while washing with 300mL of ethanol. All the solvent was removed by heating under reduced pressure, and the residue was washed with 75mL of ice-cold ethanol, filtered, and then washed with 75mL of deionized water and 150mL of diethyl ether in that order, and dried under reduced pressure to obtain diamine B represented by the following formula.

[0200] [ka]

[0201] Synthesis Example 4 Synthesis of diamine C 17.0 g (0.05 mol) of the diamine B was dissolved in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide (manufactured by Tokyo Chemical Industry Co., Ltd.), and cooled to -15°C. A solution of 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 100 mL of acetone was added dropwise thereto. After completion of the dropwise addition, the mixture was stirred at -15°C for 4 hours, and then returned to room temperature. The precipitated white solid was filtered and dried in vacuum at 50°C.

[0202] 30 g of the obtained solid was placed in a 300 mL stainless steel autoclave and dispersed in 250 mL of methyl cellosolve, and 2.0 g of 5% palladium-carbon (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added. Hydrogen was introduced into the mixture using a balloon, and the reduction reaction was carried out at room temperature. After about 2 hours, the reaction was terminated when it was confirmed that the balloon was no longer deflating. After the reaction was completed, the mixture was filtered to remove the palladium compound as a catalyst, and the mixture was concentrated using a rotary evaporator to obtain diamine C represented by the following formula.

[0203] [ka]

[0204] Synthesis Example 5 Synthesis of diamine D A dinitro compound was synthesized using 25.66 g (0.086 mol) of BisP-IOTD (4,4'-(2-ethylhexylidene)diphenol; manufactured by Honshu Chemical Industry Co., Ltd.) instead of BisP-HTG (manufactured by Honshu Chemical Industry Co., Ltd.), and diamine D represented by the following formula was obtained in the same manner as in Synthesis Example 3, except that 52.44 g (0.135 mol) of the dinitro compound was used.

[0205] [ka]

[0206] Synthesis Example 6 Synthesis of diamine E Diamine E represented by the following formula was obtained in the same manner as in Synthesis Example 4, except that diamine D (16.4 g, 0.05 mol) was used instead of diamine B.

[0207] [ka]

[0208] Synthesis Example 7 Synthesis of polyimide precursor resin (PA1) Under a dry nitrogen stream, 62.0 g (0.20 mol) of 3,3',4,4'-diphenylethertetracarboxylic dianhydride (hereinafter referred to as ODPA) was dissolved in 500 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP). 96.7 g (0.16 mol) of diamine A obtained in Synthesis Example 2 was added together with 100 g of NMP, and the mixture was reacted at 20°C for 1 hour, and then at 50°C for 2 hours. Next, 8.7 g (0.08 mol) of 3-aminophenol was added as a terminal blocking agent together with 50 g of NMP, and the mixture was reacted at 50°C for 2 hours. Then, a solution obtained by diluting 47.7 g (0.40 mol) of N,N-dimethylformamide dimethylacetal with 100 g of NMP was dropped over 10 minutes. After dropping, the mixture was stirred at 50°C for 3 hours. After the stirring was completed, the solution was cooled to room temperature, and then the solution was poured into 5 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80° C. for 24 hours to obtain the desired polyimide precursor (PA1).

[0209] Synthesis Example 8 Synthesis of polyimide precursor resin (PA2) Under a dry nitrogen stream, 31.2 g (0.06 mol) of 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride and 43.4 g (0.14 mol) of ODPA were dissolved in 500 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP). 96.7 g (0.16 mol) of diamine A obtained in Synthesis Example 2 was added together with 100 g of NMP, and the mixture was reacted at 20°C for 1 hour, and then at 50°C for 2 hours. Next, 8.7 g (0.08 mol) of 3-aminophenol was added as an end-capping material together with 50 g of NMP, and the mixture was reacted at 50°C for 2 hours. Then, a solution of 47.7 g (0.40 mol) of N,N-dimethylformamide dimethylacetal diluted with 100 g of NMP was added dropwise over 10 minutes. After the dropwise addition, the mixture was stirred at 50°C for 3 hours. After stirring, the solution was cooled to room temperature and then poured into 5 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 24 hours to obtain the desired polyimide precursor (PA2).

[0210] Synthesis Example 9 Synthesis of polyimide precursor resin (PA3) Under a dry nitrogen stream, 142.8 g (0.20 mol) of the acid dianhydride obtained in Synthesis Example 1 was dissolved in 500 g of NMP. 96.7 g (0.16 mol) of diamine A obtained in Synthesis Example 2 was added together with 100 g of NMP, and the mixture was reacted at 20°C for 1 hour, and then at 50°C for 2 hours. Next, 8.7 g (0.08 mol) of 3-aminophenol was added as a terminal blocking agent together with 50 g of NMP, and the mixture was reacted at 50°C for 2 hours. Then, a solution obtained by diluting 47.7 g (0.40 mol) of N,N-dimethylformamide dimethylacetal with 100 g of NMP was dropped over 10 minutes. After dropping, the mixture was stirred at 50°C for 3 hours. After the stirring was completed, the solution was cooled to room temperature, and then the solution was poured into 5 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 24 hours to obtain the desired polyimide precursor (PA3).

[0211] Synthesis Example 10: Synthesis of polyimide resin (PA4) Under a dry nitrogen stream, 124.53g (0.34 mol) of BAHF, 4.97g (0.02 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane, and 8.73g (0.08 mol) of 4-aminophenol as a terminal blocking agent were dissolved in 120g of NMP. 124.09g (0.4 mol) of ODPA was added together with 40g of NMP, and the mixture was reacted at 20°C for 1 hour, and then at 50°C for 4 hours. Then, 40g of xylene was added, and the mixture was stirred at 150°C for 5 hours while azeotropically distilling water with xylene. After the stirring was completed, the solution was cooled to room temperature, and then the solution was poured into 10L of water to obtain a precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 20 hours to obtain a powder of polyimide resin (PA4).

[0212] Synthesis Example 11 Synthesis of polyimide precursor resin (PA5) Under a dry nitrogen stream, 62.0 g (0.20 mol) of ODPA was dissolved in 500 g of NMP. 92.6 g (0.16 mol) of diamine C obtained in Synthesis Example 2 was added together with 100 g of NMP, and the mixture was reacted at 20° C. for 1 hour, and then at 50° C. for 2 hours. Next, 8.7 g (0.08 mol) of 3-aminophenol was added as a terminal blocking agent together with 50 g of NMP, and the mixture was reacted at 50° C. for 2 hours. Then, a solution of 47.7 g (0.40 mol) of N,N-dimethylformamide dimethylacetal diluted with 100 g of NMP was dropped over 10 minutes. After dropping, the mixture was stirred at 50° C. for 3 hours. After the stirring was completed, the solution was cooled to room temperature, and then the solution was poured into 5 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80° C. for 24 hours to obtain the desired polyimide precursor (PA5).

[0213] Synthesis Example 12: Synthesis of polyimide precursor resin (PA6) Under a dry nitrogen stream, 2.0 g (0.20 mol) of ODPA6 was dissolved in 500 g of NMP. 90.7 g (0.16 mol) of diamine E obtained in Synthesis Example 2 was added together with 100 g of NMP, and the mixture was reacted at 20°C for 1 hour, and then at 50°C for 2 hours. Next, 8.7 g (0.08 mol) of 3-aminophenol was added as a terminal blocking agent together with 50 g of NMP, and the mixture was reacted at 50°C for 2 hours. Then, a solution of 47.7 g (0.40 mol) of N,N-dimethylformamide dimethylacetal diluted with 100 g of NMP was dropped over 10 minutes. After dropping, the mixture was stirred at 50°C for 3 hours. After the stirring was completed, the solution was cooled to room temperature, and then the solution was poured into 5 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 24 hours to obtain the desired polyimide precursor (PA6).

[0214] Synthesis Example 13 Synthesis of polybenzoxazole precursor resin (PB1) Under a dry nitrogen stream, 0.18 mol of a mixture of dicarboxylic acid derivatives obtained by reacting 46.5 g (0.18 mol) of diphenyl ether-4,4'-dicarboxylic acid with 48.6 g (0.36 mol) of 1-hydroxy-1,2,3-benzotriazole and 73.3 g (0.20 mol) of BAHF were dissolved in 570 g of NMP, and then reacted at 75 ° C for 12 hours. Next, 6.6 g (0.04 mol) of 5-norbornene-2,3-dicarboxylic anhydride dissolved in 70 g of NMP was added, and the mixture was stirred for another 12 hours to terminate the reaction. After filtering the reaction mixture, the reaction mixture was poured into a solution of water / methanol = 3 / 1 (volume ratio) to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80 ° C for 24 hours to obtain the desired polybenzoxazole precursor (PB1).

[0215] Synthesis Example 14 Synthesis of polybenzoxazole precursor resin (PB2) Under a dry nitrogen stream, 0.18 mol of a mixture of dicarboxylic acid derivatives obtained by reacting 46.5 g (0.18 mol) of diphenyl ether-4,4'-dicarboxylic acid with 48.6 g (0.36 mol) of 1-hydroxy-1,2,3-benzotriazole and 68.1 g (0.20 mol) of diamine B were dissolved in 570 g of NMP and then reacted at 75 ° C for 12 hours. Next, 6.6 g (0.04 mol) of 5-norbornene-2,3-dicarboxylic anhydride dissolved in 70 g of NMP was added, and the mixture was stirred for another 12 hours to terminate the reaction. After filtering the reaction mixture, the reaction mixture was poured into a solution of water / methanol = 3 / 1 (volume ratio) to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80 ° C for 24 hours to obtain the desired polybenzoxazole precursor (PB2).

[0216] Synthesis Example 15 Synthesis of polyhydroxystyrene (PC1) 2400g of tetrahydrofuran was mixed with 2.56g (0.04mol) of sec-butyllithium as an initiator, and 105.75g (0.6mol) of pt-butoxystyrene was added to the mixture. After polymerization with stirring for 3 hours, 12.82g (0.4mol) of methanol was added to terminate the polymerization. Next, the reaction mixture was poured into 3L of methanol to purify the polymer, and the precipitated polymer was dried. The obtained polymer was dissolved in 1.6L of acetone, 2g of concentrated hydrochloric acid was added at 60°C, and the mixture was stirred for 7 hours, and pt-butoxystyrene was deprotected and converted to hydroxystyrene. After the reaction was completed, the solution was poured into water to precipitate the polymer, and the obtained precipitate was washed three times with water and then dried in a vacuum dryer at 50°C for 24 hours to obtain the desired polyhydroxystyrene (PC1).

[0217] <Quinone diazide compounds> Synthesis Example 16: Synthesis of quinone diazide compound (Q1) 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 diazide sulfonyl chloride were dissolved in 450 g of 1,4-dioxane and brought to room temperature. 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature in the system did not exceed 35°C. After the dropwise addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into water. The precipitate was then collected by filtration. The precipitate was dried in a vacuum dryer to obtain a quinone diazide compound (Q1) represented by the following formula.

[0218] [ka]

[0219] <Thermal acid generator> T1: 1,3-propanediol di-p-toluenesulfonate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) <Thermal cross-linking material> HMOM-TPHAP (compound shown in the chemical formula below, manufactured by Honshu Chemical Industry Co., Ltd.)

[0220] [ka]

[0221] <Organic solvent> ·PGME: Propylene glycol monomethyl ether · GBL: gamma-butyrolactone.

[0222] Example 1 Under yellow light, 5.4 g of PA1 obtained in Synthesis Example 3, 4.6 g of PB1 obtained in Synthesis Example 13, 1.7 g of PC1 obtained in Synthesis Example 15, 3.4 g of Q1 obtained in Synthesis Example 16 as a quinone diazide compound, 2.0 g of HMOM-TPHAP as a thermal crosslinking agent, and 0.3 g of T1 as a thermal acid generator were weighed, and these were dissolved in 40.0 g of PGME and 10.0 g of GBL. Then, the obtained solution was filtered through a filter with a pore size of 1 μm to obtain a photosensitive resin composition A. Using the obtained photosensitive resin composition, the above-mentioned evaluations (1) to (5) were performed.

[0223] Examples 2 to 20, Comparative Examples 1 to 5 Photosensitive resin compositions B to T and photosensitive resin compositions a to d were obtained in the same manner as in Example 1, with the types and amounts of compounds being as shown in Tables 1 and 2. The obtained photosensitive resin compositions were used to carry out the above-mentioned evaluations (1) to (5).

[0224] Regarding the photosensitive resin composition A used in Example 1, the method for calculating the molar amount of the imide structure contained in 1 g of all the components excluding the solvent constituting the photosensitive resin composition will be described below. Polyimide (PA1): 5.4g *Amount of imide precursor structure in polyimide PA1: (molar amount of acid dianhydride: 0.20 mol x 2) / (weight of polyimide precursor component: 167.4 g) = 2.4 mmol / g Polybenzoxazole (PB1): 4.6g *Amount of imide precursor structure: (molar amount of acid anhydride: 0.04 mol) / (weight of polybenzoxazole precursor component: 119.5 g)=0.3 mmol / g Phenolic hydroxyl group-containing resin (PC1): 1.7g Total amount of other ingredients excluding solvents: 5.7g The molar amount of the imide structure and the molar amount of the benzoxazole structure contained in 1 g of all the components excluding the solvent constituting the photosensitive resin composition A, calculated using the above values, are as follows: *Molar amount of imide structure: 0.8 mmol / g.

[0225] Tables 1 and 2 show the compositions and evaluation results of the examples and comparative examples, and the molar amount of the imide structure in each photosensitive resin composition.

[0226] [Table 1]

[0227] [Table 2]

[0228] An organic EL display device having a substrate on which a first electrode and a pixel division layer are disposed, an organic EL layer, and a second electrode, the organic EL display device being detected by time-of-flight secondary ion mass spectrometry in a range of 20 nm to 100 nm from the surface of the pixel division layer toward the substrate. 75 C 4 H 12 N + Ion intensity average (I TMA-1 ) is 10.2 × 10 -4 Below 1.0×10 -4 Examples 1 to 20, which satisfied the above conditions, showed extremely good results in terms of long-term reliability or bending reliability, compared with Comparative Examples 1 to 5, which did not satisfy the above conditions. [Explanation of symbols]

[0229] 1: Base material 2: TFT 3: TFT insulating layer 4: Wiring 5: Flattening layer 6: Contact hole 7:First electrode 8: Pixel division layer 9: Organic EL layer 10:Second electrode 11: Alkali-free glass substrate 12:First electrode 13: Auxiliary electrode 14: Pixel division layer 15: Organic EL layer 16:Second electrode 17: Cylinder 18: Organic EL display device

Claims

1. An organic EL display device having a substrate on which a first electrode and a pixel division layer are disposed, an organic EL layer, and a second electrode, the organic EL display device being detected by time-of-flight secondary ion mass spectrometry in a range of 20 nm to 100 nm from the surface of the pixel division layer toward the substrate. ７５ C ４ H １２ N ＋ Ion intensity average value (I ＴＭＡ－１ ) is 10.2 x 10 －４ Below is 1.0 x 10 －４ The organic EL display device is as described above.

2. In the organic EL display device, a detection is performed by a time-of-flight secondary ion mass spectrometry method in a range of 101 nm or more and 300 nm or less from the surface of the pixel division layer toward the substrate. ７５ C ４ H １２ N ＋ Ion intensity average value (I ＴＭＡ－２ ) is 5.0 x 10 －４ The organic electroluminescence display device according to claim 1 , wherein:

3. In the organic EL display device, the detection is performed by time-of-flight secondary ion mass spectrometry in a range of 20 nm to 300 nm from the surface of the pixel division layer toward the substrate. ３１ CF ＋ Ion intensity average value (I ＣＦ ) is 0.5 x 10 －４ 3. The organic EL display device according to claim 1, wherein:

4. 3. The organic electroluminescence display device according to claim 1, wherein the pixel dividing layer contains polyimide and / or polybenzoxazole, and the polyimide and / or polybenzoxazole has a structure represented by formula (1). 【Chemistry 1】 (In formula (1), X １ is a non-cyclic divalent hydrocarbon group having 4 to 10 carbon atoms; R １ each independently represents a hydrocarbon group having 1 to 4 carbon atoms or a hydroxyl group, and each a independently represents an integer of 0 to 4.

5. X in the formula (1) １ The organic electroluminescence display device according to claim 4 , wherein the compound represented by formula (2) is a compound represented by formula (2): 【Chemistry 2】 (In formula (2), R ２ and R ３ are each independently a non-cyclic hydrocarbon group having 1 to 9 carbon atoms or a hydrogen atom, and * indicates a bonding point to the aromatic ring. ２ and R ３ The total number of carbon atoms is 3 to 9.)

6. The pixel division layer has a wavelength of 1365 cm in an infrared spectrum measured by a Fourier transform infrared spectrophotometer (FT-IR). －１ Over 1385cm －１ 3. The organic electroluminescence display device according to claim 1, wherein the index A, which indicates the amount of imide structures present in the pixel dividing layer, is 0.10 or more and 1.10 or less, and has a maximum in the following range: Index A = (1365cm －１ Over 1385cm －１ Maximum value below 1590 cm －１ 1610cm or more －１ Maximum value below (However, the maximum value used in the above index A is the intensity value at the absorption maximum measured by FT-IR.)

7. The pixel division layer has a wavelength of 1040 cm in an infrared spectrum measured by FT-IR. －１ 1060cm or more －１ 3. The organic electroluminescence display device according to claim 1, wherein the pixel dividing layer has a maximum in the following range, and an index B indicating an amount of benzoxazole structures relative to an amount of imide structures contained in the pixel dividing layer is 0.20 or more and 2.50 or less. Index B = (1040cm －１ 1060cm or more －１ Maximum value below 1365 cm －１ Over 1385cm －１ Maximum value below (However, the maximum value used in the above index B is the intensity value at the absorption maximum measured by FT-IR.)

8. The organic electroluminescence display device according to claim 1 , wherein the pixel dividing layer further contains a compound derived from a thermal acid generator.

9. 3. The organic electroluminescence display device according to claim 1, wherein the pixel dividing layer further contains a compound derived from a phenolic hydroxyl group-containing resin.

10. 10. The organic electroluminescence display device according to claim 9, wherein the phenolic hydroxyl group-containing resin is polyhydroxystyrene or a polyhydroxystyrene / polystyrene copolymer.

Images