Organic EL display device and photosensitive resin composition

Abstract

An organic EL display device which comprises, on a substrate, a planarization layer, a first electrode, a pixel division layer, a light emitting pixel and a second electrode, wherein: the planarization layer and / or the pixel division layer contains zirconium nitride particles; and the crystallite size of the zirconium nitride particles as calculated from the half width of the peak associated with the (111) plane in the X-ray diffraction spectrum as obtained using a CuKα ray as the X-ray source is from 5 nm to 20 nm. The present invention provides: an organic EL display device which has excellent visibility, while being suppressed in display defects; and a photosensitive resin composition which is applicable to an insulating layer of the organic EL display device, while exhibiting excellent storage stability. The present invention enables the achievement of a cured film that has high sensitivity and high visible light blocking performance, while being free from opening residue.

Description

[Technical Field]

[0001] The present invention relates to an organic electroluminescence display device and a photosensitive resin composition. [Background technology]

[0002] BACKGROUND ART In recent years, many products using organic electroluminescence (hereinafter, "EL") display devices have been developed for use in thin display devices such as smartphones, tablet PCs, and televisions.

[0003] Organic EL display devices are self-luminous display devices that emit light using energy generated by the recombination of electrons injected from the cathode and holes injected from the anode in the light-emitting layer. Therefore, the presence of substances that inhibit the movement of electrons or holes, or substances that form energy levels that inhibit the recombination of electrons and holes, in the light-emitting layer can reduce the luminous efficiency of the light-emitting device or deactivate the light-emitting material, thereby shortening the lifespan of the light-emitting device. Degassing and the outflow of ionic components from a pixel dividing layer formed adjacent to the light-emitting layer can contribute to the shortening of the lifespan of an organic EL display device. For this reason, a technology has been disclosed (see, for example, Patent Document 1) that uses a positive-type photosensitive polyimide resin composition with excellent heat resistance and reliability as a resin composition for forming the pixel dividing layer.

[0004] In recent years, attempts have been made to impart light-shielding properties to pixel division layers to reduce reflection of external light such as sunlight and improve the visibility and contrast of organic EL display devices. Specific examples of such attempts include an organic EL display device having a pixel division layer using a positive photosensitive resin composition containing carbon black (see, for example, Patent Document 2) and a positive photosensitive resin composition using a zirconium nitride compound (see, for example, Patent Document 3). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2002-91343 [Patent Document 2] Japanese Patent Application Laid-Open No. 2013-533508 [Patent Document 3] International Publication No. 2019-059359 Summary of the Invention [Problem to be solved by the invention]

[0006] However, in an organic EL display device including a planarizing layer or a pixel dividing layer that includes a cured film of a resin composition as disclosed in Patent Document 3, there are problems such as short-circuiting between the first electrode and the second electrode caused by coarse particles in the planarizing layer or the pixel dividing layer, resulting in some pixels not lighting up, and localized non-light-emitting areas resulting from development residues of pigment aggregates.

[0007] An object of the present invention is to solve the above-mentioned problems and to provide an organic EL display device that has no unlit pixels and has excellent visibility. [Means for solving the problem]

[0008] The present invention provides an organic EL display device having a planarizing layer, a first electrode, a pixel dividing layer, light-emitting pixels, and a second electrode on a substrate, wherein the planarizing layer and / or the pixel dividing layer contains zirconium nitride particles (A), and the crystallite size of the zirconium nitride particles (A) is 5 nm or more and 20 nm or less, as determined from the half-width of the peak derived from the (111) plane in an X-ray diffraction spectrum using CuKα rays as an X-ray source.

[0009] The present invention also provides a photosensitive resin composition comprising zirconium nitride particles (A), an alkali-soluble resin (B) containing a repeating structural unit represented by the following general formula (1) and / or a repeating structural unit represented by the following general formula (2), an organic solvent (C), and a photoacid generator (D), wherein the acid equivalent of the alkali-soluble resin (B) is 200 g / mol or more and 500 g / mol or less:

[0010] [ka]

[0011] [ka]

[0012] In general formula (1), R 1 is a tetravalent to decavalent organic group having 5 to 40 carbon atoms, R 2 represents a divalent to octavalent organic group having 5 to 40 carbon atoms; R 3 and R 4 each independently represents a hydroxyl group, a carboxyl group, a sulfonic acid group, or a thiol group; p and q represent integers of 0 to 6, and p+q>0; In general formula (2), R 5 is a divalent to octavalent organic group having 5 to 40 carbon atoms, R 6 represents a divalent to octavalent organic group having 5 to 40 carbon atoms; R 7 and R 8 are each independently a hydroxyl group, a sulfonic acid group, a thiol group, or a COOR 9 Represents;R 9 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms; r and s represent integers of 0 to 6, and r+s>0. [Effects of the Invention]

[0013] According to the present invention, it is possible to obtain an organic EL display device that has no unlit pixels and has excellent visibility. [Brief explanation of the drawings]

[0014] [Figure 1] FIG. 1 is a cross-sectional view of a TFT substrate having a planarization layer and a pixel dividing layer. [Figure 2] FIG. 2 is a process diagram showing the manufacturing process of the organic EL display device of the present invention. [Figure 3] FIG. 3 is a schematic diagram showing the steps for producing an organic EL display device according to the embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0015] An embodiment of the present invention will now be described in detail.

[0016] The organic EL display device of the present invention has at least a substrate, a planarizing layer, a first electrode, a pixel dividing layer, light-emitting pixels, and a second electrode. The organic EL display device of the present invention is preferably an active matrix organic EL display device having a plurality of light-emitting pixels arranged in a matrix. In an active matrix display device, a substrate (hereinafter referred to as a "TFT substrate") having thin film transistors (hereinafter referred to as "TFT") formed thereon is preferably used. A planarizing layer is provided on the TFT substrate so as to cover the light-emitting pixels and the lower portions of areas other than the light-emitting pixels. Furthermore, a first electrode is provided on the planarizing layer so as to cover at least the lower portions of the light-emitting pixels. Light-emitting pixels are provided on the first electrode. Furthermore, a second electrode is provided so as to cover at least the upper portions of the light-emitting pixels. The plurality of light-emitting pixels are separated by an insulating pixel dividing layer.

[0017] FIG. 1 shows a cross-sectional view of a TFT substrate with a planarization layer and pixel division layer formed thereon. Bottom-gate or top-gate TFTs 1 are arranged in a matrix on a substrate 6, and a TFT insulating layer 3 is formed covering the TFTs 1. Wiring 2 electrically connected to the TFTs 1 is provided below the TFT insulating layer 3. The TFT insulating layer 3 has contact holes 7 that open to the wiring 2. A planarization layer 4 is provided above these, and an opening is formed in the planarization layer 4 so that it reaches the contact holes 7 on the wiring 2. An ITO 5 (transparent electrode) is formed on the planarization layer 4. The ITO 5 serves as the first electrode of the organic EL display device. The ITO 5 is electrically connected to the wiring 2 through the contact holes 7. A pixel division layer 8 is formed to cover the periphery of the ITO 5. This organic EL display device may be a top-emission type, in which emitted light is emitted from the opposite side of the substrate 6, or a bottom-emission type, in which light is extracted from the substrate 6 side.

[0018] A color display can be obtained by arranging light-emitting pixels having emission peak wavelengths in the red, green, and blue regions, respectively. In a color display, the peak wavelength of light in the red region displayed is usually in the range of 560 to 700 nm, the peak wavelength of light in the green region is 500 to 560 nm, and the peak wavelength of light in the blue region is 420 to 500 nm.

[0019] <Substrate> The substrate can be appropriately selected from metal, glass, resin film, etc., which are suitable for supporting the display device and transporting it in subsequent processes. When light transmission is particularly required, glass or resin film is used.

[0020] Soda-lime glass or alkali-free glass can be used as the glass substrate. The thickness of the substrate needs to be sufficient to maintain mechanical strength. As for the glass material, alkali-free glass is preferable because it is better to minimize ion elution from the glass, but soda-lime glass coated with a barrier coating such as SiO2 is also commercially available and can be used.

[0021] Resin films with excellent light transmission properties preferably contain a resin material selected from polybenzoxazole, polyamideimide, polyimide, polyamide, and poly(p-xylylene). These resin materials may be used alone or in combination. For example, when the resin film is made of polyimide resin, it can be formed by applying a solution containing polyamic acid (including partially imidized polyamic acid), which is a polyimide precursor, or a soluble polyimide to a support substrate and baking it. Furthermore, since organic EL elements are known to be vulnerable to oxygen and moisture, a gas barrier layer may be provided on the substrate. In particular, when a resin film is used as a substrate, a highly reliable display device can be obtained by laminating an inorganic thin film thereon.

[0022] <Planarization layer> Examples of materials for the planarization layer include acrylic resins, epoxy resins, polyamide resins, siloxane resins, polyimide resins, polybenzoxazole resins, and precursors of these resins. From the viewpoint of the reliability of organic EL display devices, the planarization layer preferably contains a polyimide resin having an imide structure. Furthermore, the planarization layer preferably contains a compound having an indene structure. The compound having an indene structure is a compound derived from the reaction product of a naphthoquinone diazide sulfonic acid ester compound. In other words, the planarization layer containing a compound having an indene structure means that the photosensitive resin composition used to form the planarization layer contains a naphthoquinone diazide sulfonic acid ester compound. By patterning a positive-type photosensitive resin composition containing a naphthoquinone diazide sulfonic acid ester compound as a photosensitizer, it is possible to obtain an organic EL display device with less residue in the openings and fewer dark spots.

[0023] When coloring is required for light-shielding or anti-reflection purposes, the planarizing layer preferably contains a colorant. When the planarizing layer contains a colorant, the colorant preferably contains zirconium nitride particles having a crystallite size of 5 nm to 20 nm, as determined from the half-width of the peak derived from the (111) plane in an X-ray diffraction spectrum using CuKα radiation as an X-ray source. The use of zirconium nitride particles as a colorant provides a visible light-shielding effect. Meanwhile, when a planarizing layer is formed by photolithography using a photosensitive resin composition, the zirconium nitride particles have high light transmittance in the ultraviolet region, which is the exposure wavelength, thereby enhancing the sensitivity of the photosensitive resin composition. By setting the crystallite size of the zirconium nitride particles to 20 nm or less, pixel non-illumination due to short circuits originating from coarse particles is suppressed, resulting in an organic EL display device with fewer display defects. Furthermore, by setting the crystallite size of the zirconium nitride particles to 5 nm or more, an organic EL display device with excellent visible light-shielding properties per unit weight, a significant reduction in external light reflection, and excellent visibility can be obtained.

[0024] The thickness of the planarization layer containing zirconium nitride particles having a crystallite size of 5 nm to 20 nm is preferably 1.5 μm to 3.0 μm. By setting the thickness to 1.5 μm or more, the effect of reducing external light reflection can be improved. On the other hand, by setting the thickness to 3.0 μm or less, residue is less likely to be generated in the openings when the photosensitive resin composition is patterned, and an organic EL display device with fewer display defects can be obtained.

[0025] The planarizing layer can be formed by applying a photosensitive resin composition using a wet coating method such as spin coating, slit coating, dip coating, spray coating, or printing, and then curing the applied composition.

[0026] <First electrode> The first electrode is preferably capable of efficiently injecting holes into the light-emitting pixel. It is also preferably transparent or semi-transparent to allow light to escape. Examples of materials constituting the first electrode include conductive metal oxides such as zinc oxide, tin oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); metals such as gold, silver, and chromium; inorganic conductive substances such as copper iodide and copper sulfide; conductive polymers such as polythiophene, polypyrrole, and polyaniline; carbon nanotubes, graphene, and the like. Two or more of these may be used, or a laminate structure of different materials may be used. The form of the first electrode is not particularly limited, and may include, for example, a fine structure such as a metal mesh or silver nanowires. Among these, ITO glass and NESA glass are preferred.

[0027] The first electrode preferably has low resistance from the viewpoint of power consumption of the organic EL display device. For example, in the case of an ITO substrate, an ITO substrate with an electrical resistance of 300 Ω / □ or less functions as an element electrode. However, since substrates with a resistance of about 10 Ω / □ are now available, it is more preferable to use a substrate with a low resistance of 20 Ω / □ or less. The thickness of the first electrode can be selected arbitrarily according to the electrical resistance, and is generally about 45 to 300 nm.

[0028] <Second electrode> The second electrode is preferably capable of efficiently injecting electrons into the light-emitting pixel. Examples of materials constituting the second electrode include metals such as platinum, gold, silver, copper, iron, tin, aluminum, and indium; and alloys of these metals with low-work-function metals such as lithium, sodium, potassium, calcium, and magnesium. Two or more of these may be used, or a laminate structure of different materials may be used. Among these, aluminum, silver, or magnesium is preferred as the main component in terms of electrical resistance, ease of film formation, film stability, and light-emitting efficiency. The inclusion of magnesium and silver is more preferred, as this facilitates electron injection into the light-emitting layer and further reduces the driving voltage.

[0029] Examples of methods for forming the first electrode and the second electrode include resistance heating, electron beam, sputtering, ion plating, and coating.

[0030] Of the first electrode and the second electrode, the electrode used as the cathode preferably has a protective layer thereon. Examples of materials constituting the protective layer include inorganic substances such as silica, titania, and silicon nitride; and organic polymer compounds such as polyvinyl alcohol, polyvinyl chloride, and hydrocarbon polymer compounds. In the case of a top-emission structure in which light is extracted from the cathode side, the material constituting the protective layer is preferably optically transparent in the visible light region.

[0031] <Light-emitting pixel> The light-emitting pixels have the function of emitting light to display an image on the organic EL display device. The light-emitting pixels have at least a light-emitting layer described below. If necessary, the light-emitting layer may further include a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, etc. The organic EL display device of the present invention preferably has a plurality of light-emitting pixels, which are separated from each other by an insulating pixel dividing layer.

[0032] <Light-emitting layer> The light-emitting layer is a layer in which the light-emitting material is excited by the recombination energy generated by collisions between holes and electrons, resulting in light emission. The light-emitting layer may be a single layer or a laminate of multiple layers. The light-emitting layer is formed from a light-emitting material, i.e., a host material or a dopant material. The light-emitting layer may be composed of only one of a host material and a dopant material, or a combination of a host material and a dopant material. When the light-emitting layer is composed of multiple layers, each light-emitting layer may be composed of only one of a host material and a dopant material, or a combination of a host material and a dopant material. From the viewpoint of efficiently utilizing electrical energy and obtaining light emission with high color purity, the light-emitting layer is preferably composed of a combination of a host material and a dopant material. The dopant material may be contained entirely or partially in the host material. From the viewpoint of suppressing concentration quenching, the content of the dopant material in the light-emitting layer is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, per 100 parts by weight of the host material. The light-emitting layer can be formed by a method of co-evaporating a host material and a dopant material, or a method of mixing a host material and a dopant material in advance and then evaporating the mixture.

[0033] Examples of host materials constituting the light-emitting material include compounds having a condensed aryl ring, such as naphthalene, anthracene, phenanthrene, pyrene, chrysene, naphthacene, triphenylene, perylene, fluoranthene, fluorene, and indene. Two or more of these compounds may be used to form the light-emitting material.

[0034] Suitable hosts used when the light-emitting layer emits triplet light (phosphorescence) include metal chelated oxide compounds, dibenzofuran derivatives, dibenzothiophene derivatives, carbazole derivatives, indolocarbazole derivatives, triazine derivatives, triphenylene derivatives, etc. Among these, compounds having an anthracene skeleton or a pyrene skeleton are more preferred because they are likely to provide highly efficient light emission.

[0035] Examples of dopant materials that constitute the light-emitting material include fused ring derivatives such as anthracene and pyrene; metal complex compounds such as tris(8-quinolinolato)aluminum; bisstyryl derivatives such as bisstyrylanthracene derivatives and distyrylbenzene derivatives; tetraphenylbutadiene derivatives; dibenzofuran derivatives; carbazole derivatives; indolocarbazole derivatives; and polyphenylenevinylene derivatives.

[0036] The dopant material used when the light-emitting layer exhibits triplet emission (phosphorescence) is preferably 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). 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 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, and tetraethylporphyrin platinum complex. Two or more of these may be used to form the metal complex compound.

[0037] <Pixel division layer> Examples of materials for the pixel division layer include acrylic resins, epoxy resins, polyamide resins, siloxane resins, polyimide resins, polybenzoxazole resins, and precursors of these resins. From the viewpoint of the reliability of the organic EL display device, the pixel division layer preferably contains a polyimide resin having an imide structure. Furthermore, the pixel division layer preferably contains a compound having an indene structure. As mentioned above, the compound having an indene structure is a compound derived from the reaction product of a naphthoquinone diazide sulfonic acid ester compound. By patterning a positive-type photosensitive resin composition containing a naphthoquinone diazide sulfonic acid ester compound as a photosensitizer, it is possible to obtain an organic EL display device with fewer dark spots and less residue in the openings.

[0038] When coloring is required for light-blocking or anti-reflection purposes, the pixel division layer preferably contains a colorant. When the pixel division layer contains a colorant, the colorant preferably contains zirconium nitride particles having a crystallite size of 5 nm to 20 nm, as determined from the half-width of the peak derived from the (111) plane in an X-ray diffraction spectrum using CuKα radiation as an X-ray source. The use of zirconium nitride particles as a colorant provides a visible light-blocking effect. Meanwhile, when forming pixel division layers by photolithography using a photosensitive resin composition, the zirconium nitride particles have high light transmittance in the ultraviolet region, which is the exposure wavelength, thereby enhancing the sensitivity of the photosensitive resin composition. By setting the zirconium nitride crystallite size to 20 nm or less, pixel non-illumination due to short circuits originating from coarse particles is suppressed, resulting in an organic EL display device with fewer display defects. Furthermore, by setting the zirconium nitride particles' crystallite size to 5 nm or more, an organic EL display device with excellent visible light blocking per unit weight, a significant reduction in external light reflection, and excellent visibility can be obtained.

[0039] The pixel division layer containing zirconium nitride particles having a crystallite size of 5 nm to 20 nm preferably has a thickness of 1.5 μm to 3.0 μm. By setting the thickness to 1.5 μm or more, the effect of reducing external light reflection can be improved. On the other hand, by setting the thickness to 3.0 μm or less, residue is less likely to be generated in the openings when the photosensitive resin composition is patterned, and an organic EL display device with fewer display defects can be obtained.

[0040] The pixel dividing layer can be formed by applying a photosensitive resin composition using a wet coating method such as spin coating, slit coating, dip coating, spray coating, or printing, and then curing the applied composition.

[0041] Either the planarizing layer or the pixel dividing layer may contain zirconium nitride particles, or both may contain zirconium nitride particles. By including zirconium nitride particles in the planarizing layer and / or the pixel dividing layer, it is possible to prevent the generation of colorant-derived residues during the formation of the planarizing layer and / or the pixel dividing layer, reduce external light reflection, and obtain an organic EL display device with excellent visibility.

[0042] The OD values ​​of the planarizing layer and pixel dividing layer are preferably smaller than the OD value of the black matrix of the color filter described below. By making the OD of the black matrix higher than the OD of the planarizing layer and pixel dividing layer, it is possible to more efficiently suppress external light reflection and obtain an organic EL display device with high visibility.

[0043] It is more preferable that the difference between the OD value of the black matrix and the OD value of the layer containing the zirconium nitride particles, out of the planarizing layer and the pixel dividing layer, is 2.0 or more and 3.5 or less.

[0044] By setting the difference between the OD value of the black matrix and the OD value of the planarizing layer and / or pixel dividing layer to 2.0 or more, colorant residue is less likely to be generated during the formation of the planarizing layer and / or pixel dividing layer, and dark spots, which are localized non-luminescent areas within a pixel, can be suppressed. Furthermore, by setting the difference between the OD values ​​of the planarizing layer or pixel dividing layer and the black matrix to 3.5 or less, external light reflection can be sufficiently suppressed, resulting in an organic EL display device with excellent visibility.

[0045] <Manufacturing method for organic EL display device> An example of the method for producing an organic EL display device of the present invention will be described with reference to Fig. 2. In Fig. 2, a cured film of a positive photosensitive resin composition is used as a light-shielding pixel dividing layer. Note that (1) to (7) in Fig. 2 correspond to the following processes (1) to (7), respectively.

[0046] (1) A thin film transistor (hereinafter, "TFT") 102 is formed on a glass substrate 101. A photosensitive material for a planarization layer is formed on the entire surface of the TFT 102, patterned by photolithography, and then thermally cured to form a planarization layer 103.

[0047] (2) A film of an alloy of magnesium and silver is formed by sputtering on the entire surface of the planarizing layer 103, and is patterned by etching using a photoresist to form the first electrode 104, which is a reflective electrode.

[0048] (3) A positive photosensitive resin composition for a pixel dividing layer is applied to the entire surface of the first electrode 104 and prebaked to form a prebaked film 105a.

[0049] (4) The pre-baked film 105a is irradiated with actinic rays 107 through a mask 106 having a desired pattern.

[0050] (5) The pre-baked film 105a is developed and patterned, and then bleaching exposure and middle baking are performed as necessary, followed by thermal curing to form a pixel dividing layer 105b having a desired pattern.

[0051] (6) An EL material is deposited between the pixel dividing layers 105b by vapor deposition through a mask to form the light-emitting pixels 108. ITO is deposited by sputtering over the entire surface of the light-emitting pixels 108, and then patterned by etching using photoresist to form the second electrode 109, which is a transparent electrode.

[0052] (7) A photosensitive material for a planarization layer is formed on the entire surface of the second electrode 109, patterned by photolithography, and then thermally cured to form a planarization cured film 110. A cover glass or color filter 111 is then bonded thereon to obtain an organic EL display device.

[0053] The first electrode or the second electrode can be patterned by, for example, etching. The following describes a method for patterning the first electrode by etching.

[0054] After forming a first electrode on a substrate, a photoresist is applied to the first electrode and pre-baked. The photoresist is then exposed and developed through a mask having a desired pattern, forming a photoresist pattern on the first electrode by photolithography. After development, the resulting pattern is preferably heat-treated. Heat-treatment thermally hardens the photoresist, improving its chemical resistance and dry etching resistance, making the photoresist pattern suitable for use as an etching mask. Examples of heat-treatment devices include ovens, hot plates, infrared devices, flash annealing devices, and laser annealing devices. The heat-treatment temperature is preferably 70 to 200°C, and the heat-treatment time is preferably 30 seconds to several hours.

[0055] Next, the first electrode is patterned by etching using the photoresist pattern as an etching mask. Examples of etching methods include wet etching using an etching solution and dry etching using an etching gas. Examples of etching solutions include acidic or alkaline etching solutions and organic solvents. Two or more of these etching solutions may be used.

[0056] After etching, the photoresist remaining on the first electrode is removed to obtain the pattern of the first electrode.

[0057] The light-emitting pixels can be formed by, for example, a mask vapor deposition method or an inkjet method. A typical mask vapor deposition method is a method in which a vapor deposition mask having openings with a desired pattern is placed on the vapor deposition source side of a substrate and vapor deposition is performed.

[0058] <Color filter> The organic EL display device may further include a color filter having a black matrix in order to enhance the effect of reducing external light reflection.

[0059] The black matrix preferably contains a resin such as an epoxy resin, an acrylic resin, a urethane resin, a polyester resin, a polyimide resin, a polyolefin resin, or a siloxane resin.

[0060] The black matrix contains a colorant. Examples of colorants include black organic pigments, mixed-color organic pigments, and inorganic pigments. Examples of black organic pigments include carbon black, perylene black, aniline black, and benzofuranone-based pigments. Examples of mixed-color organic pigments include pseudo-black pigments obtained by mixing two or more pigments, such as red, blue, green, purple, yellow, magenta, and / or cyan. Examples of black inorganic pigments include graphite; fine particles of metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver; metal oxides; metal composite oxides; metal sulfides; metal nitrides; metal oxynitrides; and metal carbides. Among these, carbon black, titanium nitride, titanium carbide, and composite particles of these with metals such as silver, which have high light-shielding properties, are preferred.

[0061] The OD value of the black matrix is ​​preferably 1.5 or more, more preferably 2.5 or more, and even more preferably 4.5 or more.

[0062] A common method for forming a black matrix is ​​photolithography using a photosensitive resin composition containing a colorant or a non-photosensitive resin composition. When a non-photosensitive resin composition containing a colorant is used, a photoresist film is formed on a coating of the composition, and then the composition is exposed to light and developed for patterning, thereby obtaining a black matrix with the desired pattern. The resulting black matrix is ​​then heat-treated in a hot air oven or on a hot plate at 180 to 300°C for 5 to 60 minutes.

[0063] The color filter may have colored pixels in the openings of the black matrix.

[0064] Examples of colorants contained in the resin composition for forming the colored pixels include organic pigments, inorganic pigments, and dyes. Organic pigments and dyes are preferred to enhance the transparency of the colored pixels. Examples of red pigments include Pigment Red (hereinafter referred to as "PR") 9, PR48, PR97, PR122, PR123, PR144, PR149, PR166, PR168, PR177, PR179, PR180, PR192, PR209, PR215, PR216, PR217, PR220, PR223, PR224, PR226, PR227, PR228, PR240, PR254, and diketopyrrolopyrrole pigments having a bromine group. Examples of orange pigments include Pigment Orange (hereinafter referred to as "PO") 13, PO31, PO36, PO38, PO40, PO42, PO43, PO51, PO55, PO59, PO61, PO64, PO65, and PO71. Examples of green pigments include Pigment Green (hereinafter referred to as "PG") 7, PG10, PG36, and PG58. Examples of yellow pigments include Pigment Yellow (hereinafter referred to as "PY") PY12, PY13, PY17, PY20, PY24, PY83, PY86, PY93, PY95, PY109, PY110, PY117, PY125, PY129, PY137, PY138, PY139, PY147, PY148, PY150, PY153, PY154, PY166, PY168, and PY85. Examples of blue pigments include Pigment Blue (hereinafter referred to as "PB") 15:3, PB15:4, PB15:6, PB21, PB22, PB60, and PB64. Examples of purple pigments include Pigment Violet (hereinafter referred to as "PV") 19, PV23, PV29, PV30, PV37, PV40, and PV50 (all numbers are Color Index Nos.).

[0065] The colored pixels are generally formed by photolithography, similar to the method for forming the black matrix.

[0066] Examples of the process for bonding the color filter substrate and the organic EL element substrate include a method in which the color filter substrate and the organic EL element substrate are placed opposite each other in a vacuum, a reduced pressure atmosphere, a nitrogen atmosphere, or the like, and a sealant is applied thereto, and the sealant is cured by light, heat, or the like.

[0067] <Photosensitive resin composition> Next, we will explain the photosensitive resin composition that serves as the raw material for the cured film that constitutes the planarization layer and / or pixel division layer containing zirconium nitride particles (A). The photosensitive resin composition contains zirconium nitride particles (A), an alkali-soluble resin (B) containing a repeating structural unit represented by general formula (1) and / or a repeating structural unit represented by general formula (2), an organic solvent (C), and a photoacid generator (D), and the acid equivalent of the alkali-soluble resin (B) is 200 g / mol or more and 500 g / mol or less.

[0068] [ka]

[0069] [ka]

[0070] In general formula (1), R 1 is a tetravalent to decavalent organic group having 5 to 40 carbon atoms, R 2 represents a divalent to octavalent organic group having 5 to 40 carbon atoms; R 3 and R 4 each independently represents a hydroxyl group, a carboxyl group, a sulfonic acid group, or a thiol group; p and q represent integers of 0 to 6, and p+q>0; In general formula (2), R 5 is a divalent to octavalent organic group having 5 to 40 carbon atoms, R 6 represents a divalent to octavalent organic group having 5 to 40 carbon atoms; R 7 and R 8 are each independently a hydroxyl group, a sulfonic acid group, a thiol group, or a COOR 9 Represents;R9 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms; r and s represent integers of 0 to 6, and r+s>0.

[0071] Zirconium nitride particles (A) (hereinafter sometimes referred to as component (A)) preferably have a low content of zirconium oxide and zirconium oxynitride, which are by-products of zirconium nitride. The content of zirconium oxide and zirconium oxynitride in component (A) is preferably such that the ratio of the X-ray diffraction peak intensity of zirconium oxide and zirconium oxynitride to the X-ray diffraction peak intensity of zirconium nitride is 1.0 or less, more preferably 0.5 or less, and even more preferably so small that no X-ray diffraction peaks of zirconium oxide and zirconium oxynitride are observed.

[0072] Component (A) more preferably contains particles of a composite nitride of zirconium atoms and metal atoms other than zirconium. By combining zirconium nitride with metal atoms other than zirconium, it is possible to suppress oxidation of zirconium nitride, improving the visible light blocking properties and improving the stability as an inorganic pigment.

[0073] Here, the metal atom refers to an atom selected from the elements in groups 1 to 12 of the periodic table excluding hydrogen atoms, as well as zinc, cadmium, mercury, copernicium, aluminum, gallium, indium, thallium, tin, lead, bismuth, and polonium.

[0074] The metal atom other than zirconium is not particularly limited, and preferred examples include at least one selected from titanium, aluminum, copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantalum, calcium, bismuth, antimony, lead, and alloys thereof. More preferred metal atoms include titanium and aluminum.

[0075] The content of metal atoms other than zirconium in component (A) is preferably 2% by mass or more and 20% by mass or less, and more preferably 3% by mass or more and 15% by mass or less, based on the total mass of component (A). By making the content of metal atoms other than zirconium 2% by mass or more, it is possible to further improve the visible light blocking properties. On the other hand, by making the content 20% by mass or less, it is possible to further improve the sensitivity.

[0076] The zirconium atom content and metal atom content in component (A) can be analyzed by ICP atomic emission spectroscopy, the nitrogen atom content can be analyzed by inert gas fusion-thermal conductivity analysis, and the oxygen atom content can be analyzed by inert gas fusion-infrared absorption analysis.

[0077] The specific surface area of ​​component (A) is 5m 2 / g or more 100m 2 / g or less. 2 By making the specific surface area 100 m / g or more, the pigment can be easily dispersed finely, and the dispersion stability in the photosensitive resin composition and the flatness and adhesion of the photosensitive resin film can be improved. 2 By adjusting the specific surface area to 60 m / g or less, re-aggregation of the pigment can be suppressed, and the dispersion stability in the photosensitive resin composition and the light-shielding properties of the photosensitive resin film can be further improved. 2 / g or less is more preferable. The specific surface area of ​​component (A) can be determined by the BET multipoint method using a nitrogen gas adsorption method using a gas adsorption specific surface area analyzer. One method for adjusting the specific surface area within the above range is to adjust the crystal growth conditions during particle synthesis by a gas phase reaction. For example, in the thermal plasma method, the specific surface area can be easily adjusted to the above range by adjusting the cooling time and cooling rate after vaporizing the particles.

[0078] Gas-phase reaction methods such as electric furnaces and thermal plasma processes are generally used to produce component (A). Of these, thermal plasma processes are preferred because they result in less impurity contamination, more uniform particle diameters, and higher productivity. Methods for generating thermal plasma include, for example, direct current arc discharge, multilayer arc discharge, radio frequency (RF) plasma, and hybrid plasma. Of these, radio frequency plasma is preferred because it results in less impurity contamination from the electrodes. Specifically, for example, in the case of producing zirconium nitride particles, examples include a method in which zirconium is vaporized and atomized in a nitrogen atmosphere by a thermal plasma method to synthesize zirconium nitride particles (e.g., Surface Science, Vol. 5 (1984), No. 4), a method in which zirconium chloride is reacted with ammonia in a gas phase by an electric furnace to synthesize zirconium nitride particles (e.g., Surface Science, Vol. 8 (1987), No. 5), and a method in which a mixture of zirconium dioxide, magnesium oxide, and metallic magnesium is fired at a high temperature in a nitrogen atmosphere to obtain low-order zirconium oxide-zirconium nitride composite particles (e.g., JP 2009-91205 A).

[0079] The photosensitive resin composition of the present invention may contain other coloring materials as needed.

[0080] Examples of organic black pigments include carbon black, perylene black, aniline black, and benzofuranone pigments (described in JP-A No. 2012-515233).

[0081] Blue pigments include, for example, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6 or 60.

[0082] Green pigments include, for example, CI Pigment Green 7, 36, or 58.

[0083] Yellow pigments include, for example, CI Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 18, or 185.

[0084] Examples of purple pigments include CI Pigment Violet 19 and 23.

[0085] Red pigments include, for example, CI Pigment Red 48:1122, 168, 177, 202, 206, 207, 209, 224, 242, or 254.

[0086] Orange pigments include, for example, CI Pigment Orange 38 or 71.

[0087] By combining these pigments, a photosensitive resin composition having desired optical properties can be obtained.

[0088] The photosensitive resin composition of the present invention contains an alkali-soluble resin (B) (hereinafter, sometimes referred to as component (B)) containing a repeating structural unit represented by general formula (1) and / or a repeating structural unit represented by general formula (2).

[0089] The alkali-soluble resin in the present invention refers to a resin containing any alkali-soluble group selected from a hydroxyl group, a carboxyl group, a sulfonic acid group, and a thiol group.

[0090] [ka]

[0091] [ka]

[0092] In general formula (1), R 1 is a tetravalent to decavalent organic group having 5 to 40 carbon atoms, R 2 R represents a divalent to octavalent organic group having 5 to 40 carbon atoms. 3 and R 4 each independently represents a hydroxyl group, a carboxyl group, a sulfonic acid group, or a thiol group, and p and q represent integers of 0 to 6, with p+q>0.

[0093] In general formula (2), R 5 is a divalent to octavalent organic group having 5 to 40 carbon atoms, R 6 R represents a divalent to octavalent organic group having 5 to 40 carbon atoms. 7 and R 8 are each independently a hydroxyl group, a sulfonic acid group, a thiol group, or a COOR 9 represents R 9 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, r and s represent integers of 0 to 6, and r+s>0.

[0094] The component (B) preferably has a total of 5 to 100,000 repeating structural units selected from general formula (1) and general formula (2) per molecule. The component (B) may also have other structural units in addition to the structural units represented by general formula (1) and / or general formula (2). In this case, the component (B) preferably has structural units selected from general formula (1) and general formula (2) in an amount of 50 mol % or more of the total number of structural units.

[0095] In the above general formula (1), R 1 -(R 3 ) p represents the residue of an acid dianhydride. 1 is a tetravalent to decavalent organic group having 5 to 40 carbon atoms, and among these, an organic group containing an aromatic ring or a cyclic aliphatic group is preferred.

[0096] Specific examples of the acid dianhydride 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, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3 Examples of the dianhydride include aromatic tetracarboxylic acid dianhydrides such as 9,9-bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorene dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 2,3,5,6-pyridinetetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, and acid dianhydrides having the structures shown below; and aliphatic tetracarboxylic acid dianhydrides such as butanetetracarboxylic acid dianhydride and 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride. Two or more of these may be used.

[0097] [ka]

[0098] R 10 represents an oxygen atom, C(CF3)2, or C(CH3)2. 11 and R 12 represents a hydrogen atom or a hydroxyl group.

[0099] In the above general formula (2), R 5-(R 7 ) r represents a carboxylic acid residue. 5 is a divalent to octavalent organic group having 5 to 40 carbon atoms, and among these, an organic group containing an aromatic ring or a cyclic aliphatic group is preferred.

[0100] Examples of acids include dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, and triphenyl dicarboxylic acid; tricarboxylic acids such as trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, and biphenyl tricarboxylic acid; and tetracarboxylic acids such as 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, and 2,2-bis(3,4-dicarboxyphenyl) Examples of suitable tetracarboxylic acids include 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, and aromatic tetracarboxylic acids having the structures shown below, as well as aliphatic tetracarboxylic acids such as butanetetracarboxylic acid and 1,2,3,4-cyclopentanetetracarboxylic acid. Two or more of these may be used.

[0101] [ka]

[0102] R 10represents an oxygen atom, C(CF3)2, or C(CH3)2. 11 and R 12 represents a hydrogen atom or a hydroxyl group.

[0103] Among these, in the residues of tricarboxylic acids and tetracarboxylic acids, one or two carboxy groups are R 7 In addition, the hydrogen atoms of the dicarboxylic acids, tricarboxylic acids, and tetracarboxylic acids exemplified above can be substituted with R 7 More preferred are those substituted with 1 to 4 groups, preferably hydroxyl groups. These acids can be used as they are or as acid anhydrides or activated esters.

[0104] R in the above general formula (1) 2 -(R 4 ) q and R in the above general formula (2) 6 -(R 8 ) s represents a diamine residue. 2 and R 6 is a divalent to octavalent organic group having 5 to 40 carbon atoms, and among these, an organic group containing an aromatic ring or a cyclic aliphatic group is preferred.

[0105] Specific examples of diamines 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, 2,2'-diethyl-4,4'-diaminobiphenyl, and the like. Examples of suitable aromatic compounds include fluorene, 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 have been 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.

[0106] [ka]

[0107] R 10 represents an oxygen atom, C(CF3)2, or C(CH3)2. 11 ~R 14 each independently represents a hydrogen atom or a hydroxyl group.

[0108] These diamines can be used as they are or as the corresponding diisocyanate compounds or trimethylsilylated diamines.

[0109] Furthermore, by capping the terminals of these resins with monoamines, acid anhydrides, acid chlorides, or monocarboxylic acids having acidic groups, resins having acidic groups at the terminals of the main chain can be obtained.

[0110] Preferred examples of such monoamines include 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminophenol, 3-aminophenol, 4-aminophenol, etc. Two or more of these may be used.

[0111] Preferred examples of such acid anhydrides, acid chlorides, and monocarboxylic acids include acid anhydrides such as phthalic anhydride, maleic anhydride, and Nadic anhydride; monocarboxylic acids such as 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, and 4-carboxythiophenol, and monoacid chloride compounds in which the carboxy group of these monocarboxylic acids is converted to an acid chloride; and monoacid chloride compounds in which only one carboxy group of dicarboxylic acids such as terephthalic acid, phthalic acid, maleic acid, and cyclohexanedicarboxylic acid is converted to an acid chloride. Two or more of these may be used.

[0112] The content of the end-capping agent such as the monoamine, acid anhydride, acid chloride, or monocarboxylic acid is preferably 2 to 25 mol % relative to 100 mol % of the total of the acid and amine components constituting the resin.

[0113] The acid equivalent of component (B) is 200 g / mol or more and 500 g / mol or less.

[0114] If the acid equivalent of component (B) is less than 200 g / mol, for example, when obtaining a cured film of the positive photosensitive resin composition, the alkali solubility of the unexposed areas will be high, the difference in dissolution rate between the unexposed areas will be small, and the desired pattern will not be formed. By setting the acid equivalent to 200 g / mol or more, more preferably 300 g / mol or more, the solubility of the unexposed areas can be suppressed, making it possible to form a pattern with less residue in openings due to adhesion of eluted material from the unexposed areas.

[0115] By setting the acid equivalent to 500 g / mol or less, a photosensitive resin composition having sufficient acidic groups to promote dispersion stabilization of component (A) and excellent storage stability can be obtained without using a polymer dispersant. To ensure sufficient dispersion stability of component (A), it is more preferable that the acid equivalent be 450 g / mol or less. The acid equivalent here refers to the mass of resin per mole of acidic groups, and is expressed in units of g / mol. The number of acidic groups in the resin can be determined from the acid equivalent value, and the acid equivalent value can also be calculated from the acid value.

[0116] Examples of acidic groups contained in component (B) include carboxy groups, hydroxyl groups, sulfonic acid groups, and thiol groups. When the photosensitive resin composition of the present invention is patterned onto a metal substrate, the acidic group contained in component (B) is preferably an acidic group with low polarity, specifically a carboxy group or a hydroxyl group, from the viewpoint of suppressing residue on the metal substrate. Furthermore, from the viewpoint of further stabilizing the pigment dispersion due to high acidity, it is even more preferable that component (B) contain a carboxy group.

[0117] Component (B) of the present invention is synthesized by a known method. When component (B) is a polyamic acid or a polyamic acid ester, examples of the production method include reacting a tetracarboxylic dianhydride with a diamine compound at low temperature, obtaining a diester from a tetracarboxylic dianhydride with an alcohol and then reacting it with an amine in the presence of a condensing agent, or 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.

[0118] In the case of polyhydroxyamide (B), it can be produced by a condensation reaction between a bisaminophenol compound and a dicarboxylic acid. Specifically, this can be achieved by reacting a dehydration condensing agent such as dicyclohexylcarbodiimide (DCC) with an acid and then adding the bisaminophenol compound, or by adding a dicarboxylic acid dichloride solution dropwise to a solution of a bisaminophenol compound to which a tertiary amine such as pyridine has been added.

[0119] The polyimide (B) can be obtained by dehydrating and ring-closing the polyamic acid or polyamic acid ester obtained by the above-mentioned method through heating or chemical treatment with an acid or base.

[0120] The photosensitive resin composition of the present invention contains an organic solvent (C) (hereinafter, sometimes referred to as component (C)). Examples of component (C) include ethers, acetates, esters, cyclic esters, ketones, aromatic hydrocarbons, amides, and alcohols.

[0121] Examples of ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether (hereinafter referred to as "PGME"), propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, and tetrahydrofuran.

[0122] Examples of acetates include butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 3-methoxy-3-methyl-1-butyl acetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanediol diacetate.

[0123] Examples of esters include alkyl lactate esters such as methyl 2-hydroxypropionate (hereinafter referred to as methyl lactate) and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, n-butyl propionate, and ethyl butyrate.

[0124] Examples of cyclic esters include β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, and ε-caprolactone.

[0125] Examples of ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone.

[0126] Examples of aromatic hydrocarbons include toluene, xylene, etc. Examples of amides include N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, etc.

[0127] Examples of alcohols include butyl alcohol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, diacetone alcohol, etc. Two or more of these may be contained.

[0128] Among these, it is preferred that the organic solvent (C) contains a cyclic ester solvent (C-1) (hereinafter sometimes referred to as component (C-1)) having a boiling point of 150°C or higher under atmospheric pressure and an organic solvent (C-2) (hereinafter sometimes referred to as component (C-2)) having a boiling point of less than 150°C under atmospheric pressure, and that the content of component (C-1) in 100% by mass of component (C) is 10% by mass or more and 40% by mass or less.

[0129] By including the (C-1) component and the (C-2) component and by ensuring that the content of the (C-1) component in 100% by mass of the (C) component is 10% by mass or more and 40% by mass or less, the dispersion stability of the (A) component in the (B) component can be improved.

[0130] Specific examples of the component (C-1) include γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, and ε-caprolactone. From the viewpoint of the solubility of the component (B), it is preferable that the component (C-1) contains γ-butyrolactone, and it is more preferable that the component (C-1) consists solely of γ-butyrolactone.

[0131] Furthermore, the inclusion of component (C-2) allows for favorable volatility and drying properties during application using a die coating device. Examples of component (C-2) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propyl acetate, butyl acetate, isobutyl acetate, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclopentanone, butyl alcohol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, methyl lactate, toluene, and xylene. Among these, from the viewpoints of improving the solubility of the alkali-soluble resin, reducing the amount of solvent remaining upon drying when the photosensitive resin composition is formed, minimizing film loss during development in unexposed areas, and suppressing residues in openings due to adhesion of eluates from the unexposed areas, it is more preferable for component (C-2) to include propylene glycol monomethyl ether and / or methyl lactate, and even more preferably to consist solely of propylene glycol monomethyl ether and / or methyl lactate.

[0132] The photosensitive resin composition of the present invention may contain any organic solvent in addition to the components (C-1) and (C-2).

[0133] (C-1) The mass of the component is W c1 The mass of the (C-2) component is W c2 When the mass ratio of component (C-1) to component (C-2) in component (C) is W c2 / W c1 From the viewpoint of enhancing the dispersion stability of the component (A), W is preferably 9.0 or less. c2 / W c1 By making the ratio 1.5 or more, favorable volatility and drying properties can be achieved during application, and when a positive-type photosensitive resin composition is formed, for example, the loss of the developed film in the unexposed areas is small, making it easy to obtain a cured film with excellent patterning properties.

[0134] The photosensitive resin composition of the present invention contains a photoacid generator (D). The photoacid generator generates an acid at the irradiated portion, which increases the solubility of the irradiated portion in an alkaline aqueous solution, thereby making it possible to obtain a positive-type photosensitive resin composition in which the irradiated portion dissolves.

[0135] Examples of the photoacid generator (D) include quinone diazide compounds, sulfonium salts, phosphonium salts, diazonium salts, iodonium salts, etc. Among the photoacid generators (D), quinone diazide compounds are particularly preferred because they allow for the formation of high-resolution patterns with high sensitivity without the need for heat treatment after exposure.

[0136] The quinone diazide compound is preferably a compound having a phenolic hydroxyl group and a naphthoquinone diazide sulfonic acid bonded to the compound via an ester bond. Examples of the compound 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 (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, and 4P. Preferred examples include compounds such as bisphenol C, BIR-BIPC-F, TEP-BIP-A (trade names, manufactured by Asahi Organic Materials Co., Ltd.), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, bisphenol A, bisphenol E, methylene bisphenol, and BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) to which 4-naphthoquinone diazide sulfonic acid or 5-naphthoquinone diazide sulfonic acid has been introduced via an ester bond, but other compounds can also be used.

[0137] 4-Naphthoquinone diazide sulfonyl ester compounds have absorption in the i-line region of mercury lamps, making them suitable for i-line exposure. 5-Naphthoquinone diazide sulfonyl ester compounds have absorption extending into the g-line region of mercury lamps, making them suitable for g-line exposure.

[0138] Therefore, it is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazide sulfonyl ester compound depending on the wavelength of exposure. Furthermore, the photoacid generator (D) may contain a naphthoquinone diazide sulfonyl ester compound having both a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule, or may contain a mixture of a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound.

[0139] The naphthoquinone diazide compounds can be synthesized by esterification of a compound having a phenolic hydroxyl group with a quinone diazide sulfonic acid compound by a known method. The use of these naphthoquinone diazide compounds improves resolution, sensitivity, and film retention.

[0140] The content of the photoacid generator (D) is preferably 0.1 parts by mass or more and 30 parts by mass or less per 100 parts by mass of the component (B). By setting the content of the photoacid generator (D) to 0.1 parts by mass or more, pattern formation of the photosensitive resin composition becomes easier. By setting the content of the photoacid generator (D) to 30 parts by mass or less, the amount of outgassing derived from the photoacid generator can be suppressed.

[0141] The photosensitive resin composition of the present invention may further contain a thermal crosslinking agent. The thermal crosslinking agent refers to a compound having at least two thermally reactive functional groups in the molecule, such as an alkoxymethyl group, a methylol group, an epoxy group, or an oxetanyl group. The thermal crosslinking agent crosslinks the alkali-soluble resin (B) or other additive components, thereby improving the heat resistance, chemical resistance, and hardness of the film after thermal curing.

[0142] Preferred examples of compounds having at least two alkoxymethyl groups or methylol groups include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, and HMOM-TPHAP (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), and NIKALAC (registered trademark) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, and NIKALAC MX-750LM (all trade names, manufactured by Sanwa Chemical Co., Ltd.).

[0143] Preferred examples of the compound having at least two epoxy groups include Denacol EX-212L, Denacol EX-214L, Denacol EX-216L, and Denacol EX-850L (all manufactured by Nagase ChemteX Corporation), GAN and GOT (all manufactured by Nippon Kayaku Co., Ltd.), Epikote 828, Epikote 1002, Epikote 1750, Epikote 1007, YX8100-BH30, E1256, E4250, and E 4275 (all manufactured by Japan Epoxy Resins Co., Ltd.), Epiclon EXA-9583, HP4032 (all manufactured by Dainippon Ink and Chemicals, Inc.), VG3101 (manufactured by Mitsui Chemicals, Inc.), Tepic S, Tepic G, Tepic P (all manufactured by Nissan Chemical Industries, Ltd.), NC6000 (manufactured by Nippon Kayaku Co., Ltd.), Epotohto YH-434L (manufactured by Tohto Kasei Co., Ltd.), EPPN502H, NC3000 (manufactured by Nippon Kayaku Co., Ltd.), and the like.

[0144] Preferred examples of the compound having at least two oxetanyl groups include Ethanacol EHO, Ethanacol OXBP, Ethanacol OXTP, Ethanacol OXMA (all manufactured by Ube Industries, Ltd.), oxetanized phenol novolak, and the like.

[0145] Two or more types of thermal crosslinking agents may be used in combination.

[0146] The content of the thermal crosslinking agent is preferably 0.1 to 30 parts by mass per 100 parts by mass of component (B). If the content of the thermal crosslinking agent is 0.1 to 30 parts by mass, the chemical resistance and hardness of the film after baking or curing can be improved, and the storage stability of the photosensitive resin composition will also be excellent.

[0147] The photosensitive resin composition used in the present invention may further 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 chelating agents; aluminum chelating agents; and compounds obtained by reacting an aromatic amine compound with an alkoxy group-containing silicon compound. Two or more of these may be contained. The inclusion of these adhesion improvers can improve adhesion to underlying substrates such as silicon wafers, ITO, SiO2, and silicon nitride during development of the photosensitive resin film. Furthermore, it can improve resistance to oxygen plasma and UV ozone treatments used for cleaning. The content of the adhesion improver is preferably 0.1 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the component (B).

[0148] The photosensitive resin composition used in the present invention may further contain a surfactant, if necessary, to improve wettability with the substrate or to improve the thickness uniformity of the photosensitive resin film. Commercially available surfactants can be used. Specific examples of silicone surfactants include the SH series, SD series, and ST series from Dow Corning Toray Silicones, the BYK series from BYK Japan, the KP series from Shin-Etsu Silicones, the Disform series from NOF Corporation, and the TSF series from Toshiba Silicones. Fluorine-based surfactants include the Megafac® series from Dainippon Ink Mfg. Co., Ltd., the Fluorad series from Sumitomo 3M, the Surflon® series and Asahi Guard® series from Asahi Glass Co., Ltd., the EF series from Shin-Akita Chemical Co., Ltd., and the Polyfox series from Omnova Solutions. Examples of surfactants made from acrylic and / or methacrylic polymers include, but are not limited to, the Polyflow series from Kyoeisha Chemical Co., Ltd. and the Disparlon® series from Kusumoto Chemicals.

[0149] The content of the surfactant is preferably 0.001 part by mass or more and 1 part by mass or less per 100 parts by mass of the component (B).

[0150] The photosensitive resin composition used in the present invention may further contain a compound having a phenolic hydroxyl group, if necessary, for the purpose of supplementing the alkaline developability of the photosensitive resin composition. Examples of the compound having a phenolic hydroxyl group include Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP-Z, BisOCR-CP, BisP-MZ, BisP-EZ, Bis26X-CP, BisP-PZ, BisP-IPZ, BisCRIPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP-4HBPA (tetrakis-P-DO-BPA), TrisPHAP, TrisP-PA, TrisP-PHBA, TrisP-SA, TrisOCR-PA (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP- Examples of such compounds include PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, and TEP-BIP-A (trade names, manufactured by Asahi Organic Chemicals Co., Ltd.), 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,4-dihydroxyquinoline, 2,6-dihydroxyquinoline, 2,3-dihydroxyquinoxaline, anthracene-1,2,10-triol, anthracene-1,8,9-triol, and 8-quinolinol. By including such a compound having a phenolic hydroxyl group, the resulting photosensitive resin composition is hardly soluble in an alkaline developer before exposure, but is easily soluble in an alkaline developer after exposure, so that film loss due to development is small and development can be easily performed in a short time, which tends to improve sensitivity.

[0151] The content of such a compound having a phenolic hydroxyl group is preferably from 1 to 40 parts by mass per 100 parts by mass of the component (B).

[0152] Examples of methods for producing the photosensitive resin composition include a method in which component (A) is directly dispersed in a solution containing components (B), (C), and a photoacid generator (D) using a disperser, and a method in which component (A) is dispersed in component (C) using a disperser to prepare a colored dispersion, and then the colored dispersion is mixed with component (B) and a photoacid generator (D).

[0153] Examples of dispersing machines include ball mills, sand grinders, three-roll mills, and high-speed impact mills. Among these, bead mills are preferred from the viewpoints of improving dispersion efficiency and achieving fine dispersion. Examples of bead mills include co-ball mills, basket mills, pin mills, and dyno mills. Examples of beads for bead mills include titania beads, zirconia beads, and zircon beads. The bead diameter of the bead mill is preferably 0.03 to 1.0 mm. When the primary particle diameter of component (A) and the particle diameter of the secondary particles formed by aggregation of the primary particles are small, fine dispersion beads of 0.03 to 0.10 mm are preferred.

[0154] In this case, a bead mill equipped with a centrifugal separator capable of separating the fine beads from the dispersion liquid is preferred. On the other hand, when dispersing component (A) containing coarse particles of the submicron order, beads with a diameter of 0.10 mm or more are preferred because they provide sufficient crushing power. The bead diameter can be calculated by measuring the equivalent circle diameter of 100 beads randomly selected by microscopic observation and calculating the number average value.

[0155] A cured film can be obtained by curing the photosensitive resin composition of the present invention. Specifically, the photosensitive resin composition is preferably cured by a heat curing method, which will be described later.

[0156] The method for forming a cured film by curing the photosensitive resin composition of the present invention will be described in detail below.

[0157] The method for producing a cured film includes the steps of applying a photosensitive resin composition to form a photosensitive resin film, drying the photosensitive resin film, exposing the dried photosensitive resin film to light, developing the exposed photosensitive resin film, and heat-curing the photosensitive resin film.

[0158] Each step will be described in detail below. In the present invention, of the film formed on the substrate, the film after coating the photosensitive resin composition on the substrate and before heat curing is referred to as the photosensitive resin film, and the film after heat curing is referred to as the cured film.

[0159] First, the process of forming a photosensitive resin film by applying a photosensitive resin composition will be described. In this process, the photosensitive resin composition of the present invention is applied to a substrate using a method such as spin coating, slit coating, dip coating, spray coating, or printing to obtain a photosensitive resin film. Among these, slit coating is preferably used. The coating speed in slit coating is generally in the range of 10 mm / sec to 400 mm / sec. The thickness of the photosensitive resin film varies depending on the solids concentration and viscosity of the photosensitive resin composition, but it is usually applied so that the film thickness after drying is preferably 0.1 to 10 μm, more preferably 0.3 to 3 μm.

[0160] Examples of the substrate include glass, quartz, silicon, ceramic, plastic, and those having electrodes of ITO, Cu, Ag, etc. partially formed thereon.

[0161] Prior to coating, the substrate to which the photosensitive resin composition is to be applied may be pretreated with the aforementioned adhesion promoter. For example, the substrate surface may be treated with a solution prepared by dissolving 0.5 to 20% by mass of the adhesion promoter in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, PGME, ethyl lactate, or diethyl adipate. Examples of methods for treating the substrate surface include spin coating, slit die coating, bar coating, dip coating, spray coating, and steam treatment.

[0162] Next, the step of drying the photosensitive resin film will be described. In this step, the photosensitive resin film obtained by applying the photosensitive resin composition is dried. The drying in this step refers to vacuum drying or heat drying. Both vacuum drying and heat drying may be performed, or only one of them may be performed.

[0163] This section describes heat drying. This process is also called pre-baking. Heating can be done using a hot plate, oven, infrared rays, etc. The heating temperature varies depending on the type and purpose of the photosensitive resin film, but it is preferable to heat the film at a temperature between 50°C and 180°C for one minute to several hours.

[0164] Next, the step of exposing the photosensitive resin film will be described. In this step, to form a pattern from the obtained photosensitive resin film, the photosensitive resin film is exposed to actinic radiation through a mask having a desired pattern. Actinic radiation used for exposure includes 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), or g-rays (436 nm) from a mercury lamp. If the photosensitive resin film has positive photosensitivity, the exposed areas will dissolve in a developer.

[0165] Next, we will discuss the process of developing the exposed photosensitive resin film. In this process, after exposure, in the case of a positive-tone film, the exposed areas are removed using a developer to form the desired pattern. Preferred developers are aqueous solutions of alkaline compounds such as tetramethylammonium hydroxide (TMAH), diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine. In some cases, these alkaline aqueous solutions may contain polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, and dimethylacrylamide; alcohols such as methanol, ethanol, and isopropanol; esters such as ethyl lactate and propylene glycol monomethyl ether acetate; and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone, either singly or in combination. Possible development methods include spray, paddle, immersion, and ultrasonic.

[0166] Next, the pattern formed by development is preferably rinsed with distilled water. Here, too, 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.

[0167] Next, the step of heat-curing the photosensitive resin film will be described. In this step, components with low heat resistance can be removed by heat curing, thereby improving the heat resistance and chemical resistance of the resulting cured film. In particular, when the photosensitive resin composition of the present invention contains an alkali-soluble resin selected from polyimide precursors and polybenzoxazole precursors, or an alkali-soluble resin that is a copolymer of these with polyimide, heat curing can form an imide ring or oxazole ring, thereby improving the heat resistance and chemical resistance. Furthermore, when the photosensitive resin composition of the present invention contains a compound having at least two alkoxymethyl groups, methylol groups, epoxy groups, or oxanyl groups, a thermal crosslinking reaction can be promoted in the heat curing step, thereby improving the heat resistance and chemical resistance of the resulting cured film.

[0168] The heating temperature is preferably 150 to 300° C., and the heating time is preferably 0.25 to 5 hours. The heating temperature may be changed continuously or stepwise.

[0169] The organic EL display device of the present invention has at least a substrate, a first electrode, a second electrode, light-emitting pixels, a planarizing layer, and a pixel dividing layer. The organic EL display device of the present invention is preferably an active matrix organic EL display device having a plurality of light-emitting pixels arranged in a matrix. In an active matrix display device, a planarizing layer is provided on a TFT substrate in which TFTs are formed on a substrate such as glass. Furthermore, a first electrode is provided on the planarizing layer so as to cover at least the lower portions of the light-emitting pixels. Light-emitting pixels are provided above the first electrode. Furthermore, a second electrode is provided so as to cover at least the upper portions of the light-emitting pixels. The plurality of light-emitting pixels are divided by an insulating pixel dividing layer. A cured film obtained from the photosensitive resin composition of the present invention can be suitably used for the planarizing layer and the pixel dividing layer.

[0170] Furthermore, since the photosensitive resin composition of the present invention can form high-definition patterns that do not leave residues in the openings, it can also be used for colored partition walls for solid-state imaging devices, micro LEDs, and mini LED display devices, and black matrices and black column spacers used in color filters for liquid crystal display devices. [Example]

[0171] EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.

[0172] <Evaluation method> [Crystallite size of zirconium nitride particles] Zirconium nitride compound particles Zr-1 to Zr-3 were packed into an aluminum standard sample holder, and X-ray diffraction spectra were measured by wide-angle X-ray diffraction using CuKα radiation as the X-ray source in an RU-200R spectrometer manufactured by Rigaku Co., Ltd. The measurement conditions were: output: 50 kV / 200 mA, slit system: 1°-1°-0.15 mm-0.45 mm, measurement step (2θ): 0.02°, and scan speed: 2° / min.

[0173] The diffraction angle and half-width of the peak originating from the ZrN (111) plane observed around the diffraction angle 2θ = 33.8° were measured, and the crystallite size constituting the particles was calculated using the Scherrer equation expressed as equation (1).

[0174]

number

[0175] [Crystalline size of zirconium nitride particles in colored dispersion] The color pigment dispersion obtained in each production example was applied by spin coating to an alkali-free glass substrate OA-10G (manufactured by Nippon Electric Glass Co., Ltd.) using a spin coater (MS-A100; manufactured by Mikasa Co., Ltd.), and then prebaked at 100°C for 120 seconds using a hot plate (SCW-636; manufactured by Dainippon Screen Mfg. Co., Ltd.) to produce a prebaked film with a thickness of 3.0 μm.

[0176] The X-ray diffraction spectrum of the obtained prebaked film was measured by wide-angle X-ray diffraction using CuKα1 radiation as an X-ray source using an RU-200R manufactured by Rigaku Co., Ltd. The measurement conditions were as follows: output: 50 kV / 200 mA, slit system: 1°-1°-0.15 mm-0.45 mm, measurement step (2θ): 0.02°, and scan rate: 0.4° / min.

[0177] The diffraction angle and half-width of the peak derived from the ZrN (111) plane observed around a diffraction angle 2θ = 33.8° were measured, and the crystallite size constituting the zirconium nitride particles in the resin film was calculated using the Scherrer equation described above.

[0178] [Zirconium nitride particle crystallite size in cured film] For the cured films obtained in each example and comparative example, X-ray diffraction spectra were measured by wide-angle X-ray diffraction using CuKα1 radiation as an X-ray source using an RU-200R manufactured by Rigaku Co., Ltd. The measurement conditions were: output 50 kV / 200 mA, slit system 1°-1°-0.15 mm-0.45 mm, measurement step (2θ) 0.02°, and scan speed 2° / min.

[0179] The diffraction angle and half-width of the peak originating from the ZrN (111) plane observed around the diffraction angle 2θ = 33.8° were measured, and the crystallite size constituting the particles was calculated using the Scherrer equation expressed as equation (1).

[0180] [Dispersion stability] The initial viscosity of the photosensitive resin compositions obtained in the examples and comparative examples and the viscosity after standing at 23°C for 7 days were measured using an E-type viscometer RE105L (manufactured by Toki Sangyo Co., Ltd.) with the measurement sample temperature set to 25°C. A smaller rate of change in viscosity after 7 days relative to the initial viscosity was determined to indicate superior pigment dispersion stability. evaluation A: Viscosity change rate less than ±5% B: Viscosity change rate: ±5% or more, less than ±10% C: Viscosity change rate: ±10% or more, less than ±20% D: Viscosity change rate: ±20% or more, less than ±50% E: Viscosity change rate of ±50% or more.

[0181] [sensitivity] The presence or absence of residues in the openings of the cured films obtained in each of the Examples and Comparative Examples was observed under an optical microscope. The minimum exposure amount at which the opening width became the same line width (50 μm) as the mask design was taken as the sensitivity. evaluation A: 100mJ / cm 2 less than B: 100mJ / cm 2 More than 200mJ / cm 2 less than C: 200mJ / cm 2 More than 500mJ / cm 2 less than D: 500mJ / cm 2 That's all.

[0182] [Light blocking property] The intensities of incident light and transmitted light of the cured films obtained in each of the Examples and Comparative Examples were measured using an X-rite 361T (visual) densitometer, and the OD values ​​of the cured films were calculated using the following formula (3). OD value = log 10 (I0 / I) Equation (3) I0: Incident light intensity I: transmitted light intensity Furthermore, the thickness of the cured film was measured using a contact-type film thickness meter DEKTAK150 (manufactured by ULVAC, Inc.), and the light-blocking ability per 1 μm of each cured film was evaluated by calculating the OD value / film thickness.

[0183] [Amount of developed film loss in unexposed areas] The thickness of the photosensitive resin film obtained in each example and comparative example was measured and recorded as the post-drying film thickness. Furthermore, the photosensitive resin film was developed for 60 seconds with an alkaline developer of 2.38% by mass TMAH aqueous solution, after which the film thickness was measured and recorded as the post-development film thickness. The amount of film loss in the unexposed area after development is expressed as (post-drying film thickness) - (post-development film thickness). It was determined that a smaller amount of film loss in the unexposed area after development facilitates pattern formation with a desired film thickness, suppresses residue in openings, and provides excellent processability.

[0184] [Opening residue] The openings of the patterned substrates obtained in each of the Examples and Comparative Examples were observed with an optical microscope to evaluate whether or not there was any residue in the openings. evaluation A: No residue within a 50 μm square B: Less than 10 residues per 50 μm square C: 10 or more but less than 20 residues per 50 μm square D: More than 20 residues per 50 μm square.

[0185] [Visibility of OLED display devices] The organic EL display devices fabricated in each example and comparative example were subjected to a current of 10 mA / cm 2 The brightness (Y') when external light was irradiated onto the pixel division layer and the brightness (Y0) when external light was not irradiated were measured. The contrast was calculated using the following formula as an index of reduction in external light reflection. Contrast = Y0 / Y'. The higher the contrast, the better the visibility, and the visibility was evaluated according to the following criteria. evaluation A: Contrast is 0.95 to 1.00 B: Contrast is 0.90 to 0.94 C: Contrast is 0.80 to 0.89 D: Contrast is 0.70 to 0.79 E: Contrast is 0.50 to 0.69 F: Contrast is 0.01 to 0.49.

[0186] [Organic EL display device non-lighting device] A total of 20 organic EL display devices were created using the methods of each example and comparative example, and display tests were conducted to observe the number of unlit devices. The fewer the number of unlit devices, the better the performance, and the devices were evaluated according to the following criteria. evaluation A: All devices are lit B: 1 to 4 non-lighting devices C: 5 to 10 non-lighting devices D: 10 or more unlit devices.

[0187] [Dark spots on organic EL displays] The organic EL display devices produced in each Example and Comparative Example were prepared, and 10 light-emitting pixel areas located in the center of the device were observed by magnifying them 50 times on a monitor, and the number of local non-light-emitting areas with a major axis of 0.1 μm or more in each opening was counted. The lower the average number of local non-light-emitting areas observed per opening, the better the result, and the results were evaluated based on the following criteria.

[0188] evaluation A: No dark spots are visible B: Fewer than 5 dark spots are observed C: 5 or more but less than 10 dark spots are observed D: 10 or more but less than 15 dark spots are observed E: 15 or more dark spots are observed.

[0189] [Long-term reliability of organic EL displays] The organic EL display devices manufactured in each of the examples and comparative examples were placed on a hot plate heated to 80°C with the light-emitting surface facing up, and the light was irradiated with a wavelength of 365 nm and an illuminance of 0.6 kmW / cm. 2 The organic EL display devices were irradiated with UV light of 0.625 mA. Immediately after irradiation (0 hours) and after 1000 hours had elapsed, the organic EL display devices were driven with a direct current of 0.625 mA to emit light, and the area ratio of the light-emitting portion to the area of ​​the light-emitting pixel (pixel light-emitting area ratio) was measured. If the pixel light-emitting area ratio after 1000 hours using this evaluation method was 80% or higher, it could be said that the device had excellent long-term reliability, and if it was 90% or higher, that was even better. evaluation A: Pixel luminous area ratio 95% or more B: Pixel light-emitting area ratio 90% or more, less than 95% C: Pixel light-emitting area ratio 80% or more, less than 90% D: Pixel light-emitting area ratio 70% or more, less than 80% E: Pixel light-emitting area ratio less than 70%.

[0190] <Production example> (Synthesis Example 1: Synthesis of hydroxyl group-containing diamine compound (HA)) 18.3 g (0.05 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter referred to as 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 complete, 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 vacuo at 50°C.

[0191] 30 g of the resulting white solid was placed in a 300 mL stainless steel autoclave and dispersed in 250 mL of methyl cellosolve, followed by the addition of 2 g of 5% palladium-carbon. Hydrogen was then introduced using a balloon, and the reduction reaction was carried out at room temperature. After approximately 2 hours, the reaction was terminated by confirming that the balloon no longer deflated. After the reaction was complete, the palladium catalyst was removed by filtration, and the mixture was concentrated using a rotary evaporator to obtain a hydroxyl group-containing diamine compound (hereinafter referred to as HA) represented by the following formula:

[0192] [ka]

[0193] (Synthesis Example 2: Alkali-soluble Resin P-1) Under a dry nitrogen stream, 21.2 g (0.035 mol) of HA obtained in Synthesis Example 1, 7.0 g (0.035 mol) of 4,4'-diaminodiphenyl ether (DAE), and 1.2 g (0.005 mol) of bis(3-aminopropyl)tetramethyldisiloxane (SiDA) were dissolved in 400 g of N-methyl-2-pyrrolidone (NMP). 31.0 g (0.10 mol) of 4,4'-oxydiphthalic dianhydride (ODPA) was added along with 50 g of NMP and stirred at 40°C for 1 hour. 5.5 g (0.050 mol) of 3-aminophenol (MAP) was then added and stirred at 40°C for 1 hour. After stirring, the solution was cooled to room temperature and then poured into 3 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 50°C for 72 hours to obtain an alkali-soluble resin (P-1) consisting of a polyimide precursor. The alkali-soluble resin (P-1) is a compound represented by the general formula (1) where p = 0, q = 2, and R 4 is a structural unit represented by a hydroxyl group, and in general formula (2), r=2, s=2, and R 7 is a carboxy group, R 8 The compound had a structural unit represented by a hydroxyl group and an acid equivalent of 220 g / mol.

[0194] (Synthesis Example 3: Alkali-soluble resin P-2) Under a dry nitrogen stream, 21.2 g (0.035 mol) of HA obtained in Synthesis Example 1, 7.0 g (0.035 mol) of DAE, and 1.2 g (0.005 mol) of SiDA were dissolved in 400 g of NMP. 31.0 g (0.10 mol) of ODPA was added to the solution along with 50 g of NMP, and the mixture was stirred at 40°C for 1 hour. 5.5 g (0.050 mol) of MAP was then added and the mixture was stirred at 40°C for 1 hour. A solution of 8.3 g (0.07 mol) of N,N-dimethylformamide dimethyl acetal (hereinafter referred to as DFA) dissolved in 10 g of NMP was then added dropwise over 10 minutes. After the addition was complete, the mixture was stirred at 40°C for 3 hours. After stirring, the solution was cooled to room temperature and then poured into 3 L of water, yielding a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 50°C for 72 hours to obtain an alkali-soluble resin (P-2) consisting of a polyimide precursor. The alkali-soluble resin (P-2) is a compound represented by the general formula (1), where p = 0, q = 1 or 2, and R 4 is a structural unit represented by a hydroxyl group, and in general formula (2), r=1 or 2, s=1 or 2, and R 7 is a carboxy group, R 8 The compound had a structural unit represented by a hydroxyl group and an acid equivalent of 275 g / mol.

[0195] (Synthesis Example 4: Alkali-soluble resin P-3) An alkali-soluble resin (P-3) consisting of a polyimide precursor was obtained by adding 13.1 g (0.11 mol) of DFA in the same manner as in Synthesis Example 3. The alkali-soluble resin (P-3) is a polyimide precursor represented by the general formula (1), where p = 0, q = 1 or 2, and R 4 is a structural unit represented by a hydroxyl group, and in general formula (2), r=1 or 2, s=1 or 2, and R 7 is a carboxy group, R 8 The compound had a structural unit represented by a hydroxyl group and an acid equivalent of 329 g / mol.

[0196] (Synthesis Example 5: Alkali-soluble resin P-4) An alkali-soluble resin (P-4) consisting of a polyimide precursor was obtained by adding 16.7 g (0.14 mol) of DFA in the same manner as in Synthesis Example 3. The alkali-soluble resin (P-4) is a polyimide precursor represented by the general formula (1), where p = 0, q = 1 or 2, and R 4 is a structural unit represented by a hydroxyl group, and in general formula (2), r=1 or 2, s=1 or 2, and R 7 is a carboxy group, R 8 The compound had a structural unit represented by a hydroxyl group and an acid equivalent of 366 g / mol.

[0197] (Synthesis Example 6: Alkali-soluble resin P-5) An alkali-soluble resin (P-5) consisting of a polyimide precursor was obtained by adding 19.1 g (0.16 mol) of DFA in the same manner as in Synthesis Example 3. The alkali-soluble resin (P-5) is a polyimide precursor represented by the general formula (1), where p = 0, q = 1 or 2, and R 4 is a structural unit represented by a hydroxyl group, and in general formula (2), r=1 or 2, s=1 or 2, and R 7 is a carboxy group, R 8 The compound had a structural unit represented by a hydroxyl group and an acid equivalent of 411 g / mol.

[0198] (Synthesis Example 7: Alkali-soluble resin P-6) An alkali-soluble resin (P-6) consisting of a polyimide precursor was obtained by adding 22.6 g (0.19 mol) of DFA in the same manner as in Synthesis Example 3. The alkali-soluble resin (P-6) is a polyimide precursor represented by the general formula (1), where p = 0, q = 1 or 2, and R 4 is a structural unit represented by a hydroxyl group, and in general formula (2), r=1 or 2, s=1 or 2, and R 7 is a carboxy group, R 8 The compound had a structural unit represented by a hydroxyl group and an acid equivalent of 471 g / mol.

[0199] (Synthesis Example 8: Alkali-soluble resin P-7) Under a dry nitrogen stream, 29.3 g (0.08 mol) of BAHF and 1.2 g (0.05 mol) of SiDA were dissolved in 400 g of NMP. 31.0 g (0.10 mol) of ODPA was added to the solution along with 50 g of NMP and stirred at 40°C for 1 hour. 3.3 g (0.03 mol) of MAP was then added and stirred at 40°C for 1 hour, followed by stirring at 150°C for 5 hours. After stirring, the solution was cooled to room temperature and poured into 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 50°C for 72 hours to obtain alkali-soluble resin (P-7) consisting of a polyimide resin with no carboxyl groups derived from polyamic acid and in which imidization was 100% complete. The alkali-soluble resin (P-7) was a polyimide resin with general formula (1) where p = 0, q = 2, and R 4 It had a structural unit represented by a hydroxyl group and had an acid equivalent of 341 g / mol.

[0200] (Synthesis Example 9: Alkali-soluble resin P-8) Under a dry nitrogen stream, 0.08 mol of a mixture of dicarboxylic acid derivatives obtained by reacting 35.3 g (0.09 mol) of 2,2-bis(2-carboxyphenyl)hexafluoropropane with 21.6 g (0.16 mol) of 1-hydroxy-1,2,3-benzotriazole and 36.7 g (0.10 mol) of BAHF were dissolved in 285 g of NMP and reacted at 75 °C for 12 hours. Next, 5.5 g (0.02 mol) of 3-carboxyphenol dissolved in 35 g of NMP was added and stirred for an additional 12 hours to complete the reaction. After cooling to room temperature, the solution was poured into 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum oven at 50 °C for 72 hours to obtain an alkali-soluble resin (P-8) consisting of a polybenzoxazole precursor with an acid equivalent weight of 339 g / mol.

[0201] (Synthesis Example 10: Alkali-soluble resin P-9) The monomers added in the same manner as in P-1 were 25.6 g (0.07 mol) of BAHF, 1.2 g (0.005 mol) of SiDA, 31.0 g (0.10 mol) of ODPA, and 5.5 g (0.050 mol) of MAP, to obtain an alkali-soluble resin (P-9) consisting of a polyimide precursor. The alkali-soluble resin (P-9) is represented by the general formula (1) where p = 0, q = 2, and R 4 is a structural unit represented by a hydroxyl group, and in general formula (2), r=2, s=2, and R 7 is a carboxy group, R 8 The compound had a structural unit represented by a hydroxyl group and an acid equivalent of 170 g / mol.

[0202] (Synthesis Example 11: Alkali-soluble resin P-10) Alkali-soluble resin (P-10) was obtained by the method described in Synthesis Example 2 of WO2019 / 059359. The alkali-soluble resin (P-10) is a resin represented by the general formula (1) in which p = 0, q = 1 or 2, and R 4 is a structural unit represented by a hydroxyl group, and in general formula (2), r=1 or 2, s=1 or 2, and R 7 is a carboxy group, R 8 The compound had a structural unit represented by a hydroxyl group and an acid equivalent of 550 g / mol.

[0203] (Synthesis Example 11) Using the method described in Example 1 of Japanese Patent No. 3120476, a methyl methacrylate / methacrylic acid / styrene copolymer (weight ratio 30 / 40 / 30) was synthesized, and then 40 parts by weight of GMA was added. The copolymer was then reprecipitated in purified water, filtered, and dried to obtain an acrylic copolymer (P-11) with a weight-average molecular weight (Mw) of 10,000 and an acid value of 110 (mgKOH / g).

[0204] (Synthesis Example 12: Quinone diazide compound (D-1)) Under a dry nitrogen stream, 21.22 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 36.27 g (0.135 mol) of 5-naphthoquinone diazide sulfonyl chloride were dissolved in 450 g of 1,4-dioxane and the solution was allowed to cool to room temperature. To this solution, 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise, ensuring that the temperature in the system did not exceed 35°C. After the 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. This precipitate was dried in a vacuum dryer to obtain the quinone diazide compound (D-1) represented by the following formula:

[0205] [ka]

[0206] (Production Example 1: Production of Color Pigment Dispersion (DB-1)) 200 g of zirconium nitride particles (ZrN-1) (Nisshin Engineering, Inc.) with a crystallite size of 30 nm in powder form, produced by thermal plasma processing, 50 g of alkali-soluble resin (P-1), and 1,000 g of γ-butyrolactone were charged into a tank and stirred for 20 minutes using a homomixer to obtain a preliminary dispersion. The resulting preliminary dispersion was fed into an Ultra Apex Mill (Hiroshima Metal & Machinery Co., Ltd.) equipped with a centrifugal separator filled with 75% by volume of 0.05 mm diameter zirconia beads and dispersed at a rotation speed of 10 m / s for 3 hours to obtain a color pigment dispersion (DB-1) with a solids concentration of 20% by mass, a colorant / resin (mass ratio) of 80 / 20, and zirconium nitride particle crystallite size of 15 nm.

[0207] (Production Examples 2 to 10: Production of Color Pigment Dispersions (DB-2 to DB-10)) Color pigment dispersions (DB-2) to (DB-10) were obtained in the same manner as in DB-1, except that the alkali-soluble resins added were (P-2) to (P-10), respectively.

[0208] (Production Example 11: Production of Color Pigment Dispersion (DB-11)) A color pigment dispersion (DB-11) was obtained in the same manner as in DB-1, except that the pigment used was composite particles ZrN-Al (manufactured by Nisshin Engineering Inc., Al content = 4 wt%) composed of zirconium nitride and aluminum, produced by the method described in Production Example 3 of WO2019 / 059359 specification, and the alkali-soluble resin was (P-4).

[0209] (Production Example 12: Production of Color Pigment Dispersion (DB-12)) A color pigment dispersion (DB-12) was obtained in the same manner as in DB-1, except that the organic solvent used was γ-valerolactone and the alkali-soluble resin was (P-4).

[0210] (Production Example 13: Production of Color Pigment Dispersion (DB-13)) A color pigment dispersion (DB-13) was obtained in the same manner as in DB-1, except that 1000 g of PGME was used as the organic solvent and (P-4) was used as the alkali-soluble resin.

[0211] (Production Example 14: Production of Color Pigment Dispersion (DB-14)) A color pigment dispersion (DB-12) was obtained in the same manner as in DB-1, except that the organic solvents added were 500 g of γ-butyrolactone and 500 g of PGME, and the alkali-soluble resin was (P-4).

[0212] (Production Example 15: Production of Color Pigment Dispersion (DB-15)) A color pigment dispersion (DB-15) was obtained in which the zirconium nitride particles had a crystallite size of 4 nm, using the same method as in DB-1, except that the zirconium nitride particles used were zirconium nitride particles (ZrN-2) (manufactured by Nisshin Engineering Inc.) produced by a thermal plasma method and having a powder crystallite size of 15 nm, and the alkali-soluble resin was (P-4).

[0213] (Production Example 16: Production of Color Pigment Dispersion (DB-16)) Using the same method as DB-1, the zirconium nitride particles (ZrN-2) and alkali-soluble resin (P-4) were added, and the dispersion time was set to 2 hours to obtain a color pigment dispersion (DB-16) with a zirconium nitride particle crystallite size of 8 nm.

[0214] (Production Example 17: Production of Color Pigment Dispersion (DB-17)) A color pigment dispersion (DB-17) with a crystallite size of 20 nm for zirconium nitride particles was obtained by using the same method as DB-1, but using alkali-soluble resin (P-4) for a dispersion time of 2 hours.

[0215] (Production Example 18: Production of Color Pigment Dispersion (DB-18)) A color pigment dispersion (DB-16) with a crystallite size of 25 nm for zirconium nitride particles was obtained by using the same method as DB-1, but using alkali-soluble resin (P-4) for a dispersion time of 1 hour.

[0216] (Production Example 19: Production of Colored Dispersion (DB-19)) A color pigment dispersion (DB-19) was obtained in the same manner as in DB-1, using 200 g of zirconium nitride particles, 25 g of alkali-soluble resin (P-10), 25 g of "BYK" (registered trademark) 2200 (manufactured by BYK-Chemie), and 1,000 g of γ-butyrolactone.

[0217] (Production Example 20: Production of Colored Dispersion (DB-20)) Using the same method as for DB-1, 200 g of zirconium nitride particles (ZrN-1), 25 g of alkali-soluble resin (P-11), 25 g of "BYK" (registered trademark) 2200 (manufactured by BYK-Chemie), and 1000 g of propylene glycol monomethyl ether acetate (hereinafter, PGMEA) were used to obtain a color pigment dispersion (DB-20) in which the crystallite size of the zirconium nitride particles was 15 nm.

[0218] (Production Example 21: Production of Colored Dispersion (DB-21)) A color pigment dispersion (DB-21) containing zirconium nitride particles with a crystallite size of 4 nm was obtained in the same manner as in DB-20, except that the zirconium nitride particles used were (ZrN-2).

[0219] (Production Example 22: Production of Colored Dispersion (DB-22)) A color pigment dispersion (DB-22) with a crystallite size of 8 nm for the zirconium nitride particles was obtained in the same manner as in DB-20, except that the zirconium nitride particles (ZrN-2) were added and the dispersion time was set to 2 hours.

[0220] (Production Example 23: Production of Colored Dispersion (DB-23)) A color pigment dispersion (DB-23) containing zirconium nitride particles with a crystallite size of 20 nm was obtained by dispersing for 2 hours in the same manner as in DB-20.

[0221] (Production Example 24: Production of Colored Dispersion (DB-24)) A color pigment dispersion (DB-24) containing zirconium nitride particles with a crystallite size of 25 nm was obtained by dispersing for 1 hour in the same manner as in DB-20.

[0222] [Table 1]

[0223] Example 1 To 93.8 g of the color pigment dispersion (DB-1), 50.5 g of an alkali-soluble resin (P-1), 17.0 g of a quinone diazide compound (D-1) as a photoacid generator, 13.6 g of the phenol compound bisphenol-AF (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.2 g of a silicone surfactant "BYK" (registered trademark) 333 (manufactured by BYK-Chemie), 105.0 g of γ-butyrolactone, and 720.0 g of PGME were added to obtain a positive photosensitive resin composition (PB-1) with a total solids concentration of 10 mass% and a pigment / resin (mass ratio) of 15 / 85.

[0224] The obtained positive photosensitive resin composition (PB-1) was evaluated for the dispersion stability described above.

[0225] Next, the obtained positive photosensitive resin composition (PB-1) was applied to an ITO substrate using a spinner (MS-A150) manufactured by Mikasa Co., Ltd. so that the OD value of the obtained photosensitive resin film was 1, and the coating was dried by heating on a hot plate at 100°C for 2 minutes to obtain a photosensitive resin film. The obtained photosensitive resin film was irradiated with ultraviolet light at 500 mJ / cm using a mask aligner (PEM-6M) manufactured by Union Optical Co., Ltd. through a positive mask (stripe design line width 50 μm) manufactured by HOYA Corporation. 2 with a maximum exposure of 10 mJ / cm 2 The exposure dose was reduced for each exposure, and the substrate was developed for 60 seconds with an alkaline developer of 2.38% by mass TMAH aqueous solution to obtain a patterned substrate with a photosensitive resin film formed in the specified pattern. The sensitivity was evaluated using the patterned substrates with each exposure dose.

[0226] Next, a photosensitive resin film was prepared so that the OD value was 1, in the same manner as in the above sensitivity evaluation, and the amount of film loss due to development in the unexposed area was evaluated.

[0227] The resulting patterned substrate was then baked in a hot air oven at 230°C for 60 minutes to obtain a cured film (BK-1). Using the patterned substrates with each exposure dose, evaluations were made of [light-blocking properties] and [opening residue].

[0228] In order to evaluate the storage stability of the positive photosensitive resin composition, the positive photosensitive resin composition was allowed to stand at 23°C for 7 days, and then a patterned substrate was prepared in the same manner as above, and the sensitivity was evaluated.

[0229] Examples 2 to 8 In the same manner as in Example 1, DB-2 to DB-8 were used as the color pigment dispersions and P-2 to P-8 were used as the alkali-soluble resins to obtain positive-type photosensitive resin compositions (PB-2) to (PB-8) and their cured films (BK-2) to (BK-8). Evaluations were carried out in the same manner as in Example 1.

[0230] Example 9 A positive photosensitive resin composition (PB-9) and its cured film (BK-9) were obtained by changing the type of color pigment dispersion to DB-11 and the alkali-soluble resin to P-4 in the same manner as in Example 1. Evaluations were carried out in the same manner as in Example 1.

[0231] Example 10 In the same manner as in Example 1, the type of color pigment dispersion added was changed to DB-12, the alkali-soluble resin was changed to P-4, and γ-valerolactone was used as the organic solvent instead of γ-butyrolactone, thereby obtaining a positive photosensitive resin composition (PB-10) and its cured film (BK-10). Evaluations were carried out in the same manner as in Example 1.

[0232] Example 11 In the same manner as in Example 1, the type of color pigment dispersion used was DB-14, the alkali-soluble resin was P-4, and the type of organic solvent was changed from PGME to methyl lactate, thereby obtaining a positive photosensitive resin composition (PB-11) and its cured film (BK-11). Evaluations were carried out in the same manner as in Example 1.

[0233] Example 12 A positive photosensitive resin composition (PB-12) and its cured film (BK-12) were obtained in the same manner as in Example 1, except that the type of color pigment dispersion used was DB-14, the alkali-soluble resin was P-4, and the type of organic solvent was ethyl lactate instead of PGME. Evaluations were performed in the same manner as in Example 1.

[0234] Example 13 In the same manner as in Example 1, a positive photosensitive resin composition (PB-13) and its cured film (BK-13) were obtained by changing the type of color pigment dispersion to DB-13, the alkali-soluble resin to P-4, and the organic solvent to PGME. Evaluations were carried out in the same manner as in Example 1.

[0235] Example 14 In the same manner as in Example 1, a positive photosensitive resin composition (PB-14) and its cured film (BK-14) were obtained by changing the type of color pigment dispersion to DB-14, the alkali-soluble resin to P-4, and the organic solvents to 7.50 g of γ-butyrolactone and 817.5 g of PGME. Evaluations were performed in the same manner as in Example 1.

[0236] Example 15 In the same manner as in Example 1, a positive photosensitive resin composition (PB-15) and its cured film (BK-15) were obtained by changing the type of color pigment dispersion to DB-4, the alkali-soluble resin to P-4, and the organic solvent to 15.0 g of γ-butyrolactone and 810.0 g of PGME. Evaluations were performed in the same manner as in Example 1.

[0237] Example 16 In the same manner as in Example 1, a positive photosensitive resin composition (PB-16) and its cured film (BK-16) were obtained by changing the type of color pigment dispersion to DB-4, the alkali-soluble resin to P-4, and the organic solvents to 285.0 g of γ-butyrolactone and 540.0 g of PGME. Evaluations were performed in the same manner as in Example 1.

[0238] Example 17 In the same manner as in Example 1, a positive photosensitive resin composition (PB-17) and its cured film (BK-17) were obtained by changing the type of color pigment dispersion to DB-4, the alkali-soluble resin to P-4, and the organic solvents to 375.0 g of γ-butyrolactone and 450.0 g of PGME. Evaluations were performed in the same manner as in Example 1.

[0239] (Examples 18 to 21) Positive photosensitive resin compositions (PB-18) to (PB-21) and their cured films (BK-18) to (BK-21) were obtained by using DB-15 to DB-18 as the color pigment dispersions in the same manner as in Example 1. Evaluations were carried out in the same manner as in Example 1.

[0240] (Comparative Example 1) In the same manner as in Example 1, the type of color pigment dispersion added was changed to DB-9, and P-9 was used instead of the alkali-soluble resin P-1, to obtain a positive photosensitive resin composition (PB-22) and its cured film (BK-22). Evaluations were carried out in the same manner as in Example 1.

[0241] (Comparative Example 2) A positive photosensitive resin composition (PB-23) and its cured film (BK-23) were obtained by changing the type of color pigment dispersion to DB-10 and the alkali solubility to P-10 in the same manner as in Example 1. Evaluations were carried out in the same manner as in Example 1.

[0242] (Comparative Example 3) A positive photosensitive resin composition (PB-24) and its cured film (BK-24) were obtained in the same manner as in Example 1, except that the type of color pigment dispersion used was DB-19 and the alkali-soluble resin was P-10. Evaluations were carried out in the same manner as in Example 1. The results are shown in Table 3.

[0243] [Table 2]

[0244] [Table 3]

[0245] The photosensitive resin compositions of the Examples have excellent storage stability, with small changes in viscosity and sensitivity after 7 days at room temperature. Furthermore, the amount of film loss in the unexposed areas is small, allowing the formation of patterns with little residue in the openings due to the adhesion of eluates from the unexposed areas. On the other hand, the photosensitive resin compositions of the Comparative Examples have poor storage stability, and tend to increase in viscosity and decrease in sensitivity. Furthermore, in Comparative Example 2, the film loss in the unexposed areas after development was large, resulting in the failure to obtain a pattern with little residue in the openings.

[0246] Next, a method for producing an organic EL display device using the photosensitive resin composition of the present invention and the evaluation results will be described.

[0247] (Production Example 25: Preparation of negative photosensitive resin composition NB-1) To 93.8 g of the color pigment dispersion (DB-20), 127.3 g of a 35 wt % solution of the alkali-soluble resin (P-11) in PGMEA, 31.0 g of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) as a polyfunctional monomer, 5.4 g of "ADEKA ARCLES" (registered trademark) NCI-831 (manufactured by ADEKA Corporation) as a photopolymerization initiator, and 3.0 g of a 10 wt % solution of the silicone surfactant "BYK" (registered trademark) 333 (manufactured by BYK-Chemie) in PGMEA were added in 739.5 g of PGMEA to obtain a negative photosensitive black resin composition NB-1 with a total solids concentration of 10 wt % and a (A) zirconia compound particle / (B) alkali-soluble resin (weight ratio) of 15 / 85.

[0248] (Production Example 26: Preparation of negative photosensitive resin composition NB-2) To 143.8 g of the color pigment dispersion (DB-20), 110.1 g of a 35 wt % solution of the alkali-soluble resin (P-11) in PGMEA, 27.6 g of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) as a polyfunctional monomer, 4.8 g of "ADEKA ARCLES" (registered trademark) NCI-831 (manufactured by ADEKA Corporation) as a photopolymerization initiator, and 3.0 g of a 10 wt % solution of the silicone surfactant "BYK" (registered trademark) 333 (manufactured by BYK-Chemie) in PGMEA were added in 710.8 g of PGMEA to obtain a negative photosensitive black resin composition NB-2 with a total solids concentration of 10 wt % and a (A) zirconia compound particle / (B) alkali-soluble resin (weight ratio) of 23 / 77.

[0249] (Production Example 27: Preparation of negative photosensitive resin composition NB-3) To 125.0 g of the color pigment dispersion (DB-20), 116.5 g of a 35 wt % solution of the alkali-soluble resin (P-11) in PGMEA, 28.9 g of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) as a polyfunctional monomer, 5.1 g of "ADEKA ARCLES" (registered trademark) NCI-831 (manufactured by ADEKA Corporation) as a photopolymerization initiator, and 3.0 g of a 10 wt % solution of the silicone surfactant "BYK" (registered trademark) 333 (manufactured by BYK-Chemie) in PGMEA (721.6 g) were added to obtain a negative photosensitive black resin composition NB-3 with a total solids concentration of 10 wt % and a (A) zirconia compound particle / (B) alkali-soluble resin (weight ratio) of 20 / 80.

[0250] (Production Example 28: Preparation of negative photosensitive resin composition NB-4) To 62.5 g of the color pigment dispersion (DB-20), 138.1 g of a 35 wt % solution of the alkali-soluble resin (P-11) in PGMEA, 33.1 g of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) as a polyfunctional monomer, 5.8 g of "ADEKA ARCLES" (registered trademark) NCI-831 (manufactured by ADEKA Corporation) as a photopolymerization initiator, and 3.0 g of a 10 wt % solution of the silicone surfactant "BYK" (registered trademark) 333 (manufactured by BYK-Chemie) in PGMEA were added in 757.5 g of PGMEA to obtain a negative photosensitive black resin composition NB-4 with a total solids concentration of 10 wt % and a weight ratio of (A) zirconia compound particles / (B) alkali-soluble resin = 10 / 90.

[0251] (Production Example 29: Preparation of negative photosensitive resin composition NB-5) To 43.8 g of the color pigment dispersion (DB-20), 144.6 g of a 35 wt % solution of the alkali-soluble resin (P-11) in PGMEA, 34.3 g of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) as a polyfunctional monomer, 6.0 g of "ADEKA ARCLES" (registered trademark) NCI-831 (manufactured by ADEKA Corporation) as a photopolymerization initiator, and 3.0 g of a 10 wt % solution of the silicone surfactant "BYK" (registered trademark) 333 (manufactured by BYK-Chemie) in PGMEA were added in 768.3 g of PGMEA to obtain a negative photosensitive black resin composition NB-5 with a total solids concentration of 10 wt % and a weight ratio of (A) zirconia compound particles / (B) alkali-soluble resin = 10 / 90.

[0252] (Production Examples 30 to 33: Preparation of Negative Photosensitive Resin Compositions NB-6 to NB-9) Negative photosensitive black resin compositions NB-6 to NB-9 having a total solids concentration of 10% by weight and a weight ratio of (A) zirconia compound particles / (B) alkali-soluble resin of 15 / 85 were obtained by using color pigment dispersions DB-21 to DB-24 in the same manner as in Production Example 25.

[0253] Example 22 The fabrication procedure for the organic EL display device will be described with reference to Figures 3A to 3D. First, a positive photosensitive resin composition PC-1 (photosensitive resin composition R-4 described in paragraph

[0310] of JP 2020-004717 A) was applied to the entire surface of a 38 mm x 46 mm alkali-free glass substrate 201 by spin coating using a spin coater (MS-A100; manufactured by Mikasa Co., Ltd.), and then prebaked at 100 ° C. for 120 seconds using a hot plate (SCW-636; manufactured by Dainippon Screen Mfg. Co., Ltd.) to produce a prebaked film with a thickness of 3.0 μm.

[0254] The prebaked film was exposed to i-, h-, and g-rays from an ultra-high pressure mercury lamp through a photomask with a predetermined pattern using a double-sided alignment single-sided exposure system (Mask Aligner PEM-6M; manufactured by Union Optical Co., Ltd.). The film was then developed for 60 seconds with a 2.38% by weight TMAH aqueous solution using a compact photolithography developing system (AC3000; manufactured by Takizawa Sangyo Co., Ltd.), followed by rinsing with water for 30 seconds. The substrate was then thermally cured at 230°C using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.) to produce a planarization layer 202 with a thickness of approximately 2.0 μm.

[0255] Next, a 100 nm thick ITO transparent conductive film was formed by sputtering and etched to form a transparent electrode as the first electrode 203. An auxiliary electrode 204 for connecting the second electrode was also formed at the same time (FIG. 3A). The resulting substrate was ultrasonically cleaned with Semicoclean 56 (trade name, manufactured by Furuuchi Chemical Co., Ltd.) for 10 minutes and then washed with ultrapure water. Next, the positive photosensitive resin composition PB-1 was applied to the entire surface of the substrate by spin coating at an arbitrary rotation speed using a spin coater (MS-A100; manufactured by Mikasa Co., Ltd.), and then prebaked at 100°C for 120 seconds using a hot plate (SCW-636; manufactured by Dainippon Screen Mfg. Co., Ltd.) to produce a prebaked film with a thickness of approximately 3.0 μm.

[0256] The prebaked film was patterned using a double-sided alignment single-sided exposure system (Mask Aligner PEM-6M; manufactured by Union Optical Co., Ltd.) by i-line, h-line, and g-line irradiation from an ultra-high pressure mercury lamp through a photomask with a predetermined pattern. It was then developed for 60 seconds in a 2.38% by weight TMAH aqueous solution using a compact photolithography developer (AC3000; manufactured by Takizawa Sangyo Co., Ltd.) and rinsed with water for 30 seconds. In this way, pixel division layers 205 were formed in the effective substrate area, with 50 μm wide and 260 μm long openings arranged at a widthwise pitch of 155 μm and a lengthwise pitch of 465 μm, each with the first electrode exposed (Figure 3B). These openings will ultimately become the light-emitting pixels of the organic EL display device. The effective substrate area (display area) was 16 mm square, and the pixel division layers 205 were arranged to achieve an aperture ratio of 18%. The pixel dividing layer 205 was formed to a thickness of about 2.0 μm.

[0257] After nitrogen plasma treatment was performed on the obtained substrate, light-emitting pixels 206 including a light-emitting layer were formed by vacuum deposition (FIG. 3C). Note that the degree of vacuum during deposition was 1×10 -3 The pressure was below 1 Pa, and the substrate was rotated relative 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, a 40 nm thick emissive layer was evaporated using compound (GH-1) as a host material and compound (GD-1) as a dopant material, with a doping concentration of 10%. Next, compound (ET-1) and compound (LiQ) were stacked as electron transport materials in a volume ratio of 1:1 to a thickness of 40 nm, resulting in emissive pixel 206. The structures of each compound used in the emissive pixel are shown below.

[0258] [ka]

[0259] Next, a 2-nm thick compound (LiQ) was vapor-deposited on the light-emitting pixel 206, followed by 100-nm thick deposition of Mg and Ag at a volume ratio of 10:1 to form the second electrode 207 (Figure 3D). Finally, a color filter substrate (CF-1) with a black matrix having an OD value of 4.5 was prepared using the method described in the literature (JP 2019-148619 A; Example 1). The substrate was sealed by adhering it to the second electrode 207 using an epoxy resin adhesive, completing a top-emission organic EL display device with a square shape measuring 5 mm on a side. The color filter substrate was fabricated with 50 μm wide, 260 μm long openings arranged at a pitch of 155 μm in the width direction and 465 μm in the length direction, and colored pixels were arranged in the openings. Four such organic EL display devices were fabricated on one substrate. The film thickness referred to here is the display value on a quartz crystal oscillator film thickness monitor.

[0260] Example 23 An organic EL display device was fabricated in the same manner as in Example 22, by forming a planarizing layer using PB-1 and a pixel dividing layer using PC-1.

[0261] (Examples 24 to 39) In the same manner as in Example 22, pixel dividing layers were formed using PB-2 to PB-17, respectively, to fabricate organic EL display devices.

[0262] Examples 40 to 44 In the same manner as in Example 22, pixel dividing layers were formed using NB-1 to NB-5, respectively, using a negative photomask for forming pixel dividing layers, thereby producing an organic EL display device.

[0263] (Examples 45 to 46) Using the same method as in Example 23, an organic EL display device was fabricated by using a color filter substrate (CF-2) having a black matrix with an OD value of 2.5 instead of CF-1, and a color filter substrate (CF-3) having a black matrix with an OD value of 1.5.

[0264] (Examples 47 to 51) An organic EL display device was fabricated in the same manner as in Example 22, with the film thickness of NB-1 used for the pixel dividing layer set as shown in Table 4, and an alkali-free glass substrate was used instead of a color filter, and the device was sealed by bonding it with an epoxy resin adhesive.

[0265] (Examples 52 to 53) In the same manner as in Example 22, the photosensitive resin compositions used for the pixel dividing layer were changed to NB-7 and NB-8, respectively, and an alkali-free glass substrate was used instead of a color filter. The substrate was sealed by bonding it with an epoxy resin adhesive to prepare an organic EL display device.

[0266] (Comparative Examples 4 to 5) In the same manner as in Example 22, the photosensitive resin compositions used for the pixel dividing layer were changed to NB-6 and NB-9, respectively, and an alkali-free glass substrate was used instead of a color filter. The substrate was sealed by bonding it with an epoxy resin adhesive to prepare an organic EL display device.

[0267] (Comparative Example 6) An organic EL display device was fabricated in the same manner as in Example 22, except that the photosensitive resin composition used for the pixel dividing layer was PC-1.

[0268] [Table 4]

[0269] [Table 5]

[0270] The organic EL display devices of the Examples showed a small difference in brightness between when external light was irradiated and when it was not, excellent visibility, a low frequency of non-lighting devices and dark spots, and excellent long-term light emission reliability. On the other hand, the organic EL display devices described in the Comparative Examples showed a small effect of reducing external light reflection, poor visibility and long-term reliability, or were prone to wiring short circuits due to the large crystallite size of the zirconium nitride particles used as a color pigment, resulting in a high frequency of non-lighting devices and dark spots. [Explanation of symbols]

[0271] 1 TFT 2 Wiring 3 TFT insulating layer 4 Planarization layer 5 ITO 6 PCB 7 Contact Hole 8 pixel division layer 101 Glass substrate 102 TFT 103 Planarization layer 104 First electrode 105a Pre-baked film 105b Pixel division layer 106 Mask 107 Actinic radiation 108 luminous pixels 109 Second electrode 110 Cured film for planarization 111 Color filter or cover glass 201 Glass substrate 202 Planarization layer 203 First electrode 204 Auxiliary electrode 205 Pixel Division Layer 206 luminescent pixels 207 Second electrode

Claims

1. A positive photosensitive resin composition comprising zirconium nitride particles (A), an alkali-soluble resin (B) containing a repeating structural unit represented by the following general formula (1) and / or a repeating structural unit represented by the following general formula (2), an organic solvent (C), and a photoacid generator (D), wherein the acid equivalent of the alkali-soluble resin (B) is 200 g / mol or more and 500 g / mol or less: 【Chemistry 1】 【Chemistry 2】 In general formula (1), R １ represents a tetravalent to decavalent organic group having 5 to 40 carbon atoms, R ２ represents a divalent to octavalent organic group having 5 to 40 carbon atoms; R ３ and R ４ each independently represents a hydroxyl group, a carboxyl group, a sulfonic acid group, or a thiol group; p and q represent integers of 0 to 6, and p+q>0; In general formula (2), R ５ represents a divalent to octavalent organic group having 5 to 40 carbon atoms, R ６ represents a divalent to octavalent organic group having 5 to 40 carbon atoms; R ７ and R ８ are each independently a hydroxyl group, a sulfonic acid group, a thiol group, or COOR ９ represents; R ９ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms; r and s represent integers of 0 to 6, and r+s>0.

2. 2. The photosensitive resin composition according to claim 1, wherein the crystallite size of the zirconium nitride particles (A) in the cured film is 5 nm or more and 20 nm or less, as determined from the half-width of the peak derived from a (111) plane in an X-ray diffraction spectrum of the zirconium nitride particles (A) in the photosensitive resin composition using CuKα radiation as an X-ray source.

3. 3. The photosensitive resin composition according to claim 1, wherein the zirconium nitride particles (A) comprise particles of a composite nitride of zirconium atoms and atoms of a metal other than zirconium.

4. 4. The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (B) contains a carboxy group.

5. The photosensitive resin composition according to any one of claims 1 to 4, wherein the organic solvent (C) comprises a cyclic ester solvent (C-1) having a boiling point of 150°C or higher at atmospheric pressure and an organic solvent (C-2) having a boiling point of less than 150°C at atmospheric pressure, and the content of the cyclic ester solvent (C-1) having a boiling point of 150°C or higher at atmospheric pressure is 10% by mass or more and 40% by mass or less in 100% by mass of the organic solvent (C).

6. 6. The photosensitive resin composition according to claim 5, wherein the cyclic ester solvent (C-1) having a boiling point of 150° C. or higher under atmospheric pressure contains at least γ-butyrolactone.

7. 7. The photosensitive resin composition according to claim 5, wherein the organic solvent (C-2) contains at least propylene glycol monomethyl ether and / or methyl lactate.

8. The mass W of the cyclic ester solvent (C-1) having a boiling point of 150° C. or higher under atmospheric pressure in the organic solvent (C) ｃ１ and the mass W of the organic solvent (C-2) Ｃ２ Mass ratio W ｃ２ / W ｃ１ 8. The photosensitive resin composition according to claim 5, wherein the σ is 1.5 to 9.

0.

9. An organic EL display device having at least a substrate, a first electrode, a second electrode, a light-emitting pixel, a planarizing layer, and a pixel dividing layer, An organic EL display device, wherein the planarizing layer and / or the pixel dividing layer is a cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 8.

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