Photosensitive resin composition, cured product, organic electroluminescent display device, semiconductor device, and method for producing cured product

Abstract

The present invention aims to provide a photosensitive resin composition, a cured product, an organic electroluminescent display device, a semiconductor device, and a method for producing the cured product, all having excellent visible light transmittance after thermal curing. To achieve the above-mentioned purpose, the photosensitive resin composition of the present invention has the following structure. Specifically, the photosensitive resin composition comprises: (A) an alkali-soluble resin, (B) a photoacid generator, and (C) a compound having a phenolic hydroxyl group and an octanol / water partition coefficient (LogP) of 4.6 to 20.0 (hereinafter referred to as component (C)). The photosensitive resin composition has a transmittance at 400 nm at a thickness of 1.5 μm after thermal curing of 80% to 99%, and a yellowness index of 0.1 to 7.0.

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition, a cured product, a display device, a semiconductor device, and a method for manufacturing the cured product. Background Art

[0002] Many products using organic electroluminescence (hereinafter referred to as organic EL) display devices have been developed as display devices having thin displays, such as smartphones, tablet personal computers (PCs), and televisions.

[0003] Typically, an organic EL display device comprises a driving circuit, a planarization layer, a first electrode, a pixel segmentation layer, a light-emitting layer, and a second electrode on a substrate. Light is emitted by applying a voltage between the first and second electrodes facing each other. Among these, photosensitive resin compositions that can be patterned by ultraviolet irradiation are commonly used as materials for the planarization layer and the pixel segmentation layer.

[0004] Examples of positive photosensitive resin compositions proposed so far include: positive photosensitive resin compositions comprising naphthoquinonediazidesulfonic acid esters having a photosensitive component mixed with an alkali-soluble resin; positive photosensitive resin compositions using a polyimide precursor as a resin (e.g., see Patent Document 1); and positive photosensitive resin compositions using a polybenzoxazole precursor (e.g., see Patent Document 2).

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Laid-Open No. 2002-91343

[0008] Patent Document 2: Japanese Patent Application Laid-Open No. 2002-116715 Summary of the Invention

[0009] Problems to be solved by the invention

[0010] The requirements for the characteristics of organic EL display devices are becoming increasingly higher year by year. For materials used in planarization layers and pixel segmentation layers, transmittance in the visible light range is also required from the perspective of diversifying designs and shapes, such as placing cameras directly below the displays of transmissive organic EL displays or mobile terminals, or further functionalization.

[0011] However, the materials proposed in the aforementioned patent documents do not have sufficient visible light transmittance after thermal curing.

[0012] Technical means to solve the problem

[0013] The photosensitive resin composition of the present invention has the following structure.

[0014] A photosensitive resin composition comprising:

[0015] (A) alkali-soluble resin,

[0016] (B) Photoacid generating materials, and

[0017] (C) a compound having a phenolic hydroxyl group and having an octanol / water partition coefficient (LogP) of 4.6 to 20.0 (hereinafter referred to as component (C)), and

[0018] The photosensitive resin composition has a transmittance at 400 nm of 80% to 99% inclusive at a thickness of 1.5 μm after thermal curing, and a yellowness index of 0.1 to 7.0 inclusive.

[0019] The first embodiment of the cured product of the present invention is a cured product obtained by curing the photosensitive resin composition of the present invention.

[0020] The method for producing a cured product of the present invention comprises the steps of applying the photosensitive resin composition of the present invention on a substrate to form a resin film; drying the resin film; exposing the dried resin film to light; developing the exposed resin film; and heating the developed resin film to obtain a cured product.

[0021] A second embodiment of the cured product of the present invention is a cured product having a transmittance at 400 nm of 80% or more and 99% or less at a thickness of 1.5 μm, a yellowness index of 0.1 or more and 7 or less, and containing a compound having an imide ring structure, a compound having an indene structure, a compound having a structure represented by formula (2), and a compound having a structure represented by formula (1).

[0022] [Chemistry 1]

[0023]

[0024] In formula (2), R 2 、R 3 , and R 4 Each is independently a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms which may contain a heteroatom.

[0025] [Chemistry 2]

[0026]

[0027] R 1 Each independently represents a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom.

[0028] The organic EL display device of the present invention is an organic EL display device including the cured product of the present invention.

[0029] The semiconductor device of the present invention is a semiconductor device including the cured product of the present invention.

[0030] Effects of the Invention

[0031] The photosensitive resin composition of the present invention is excellent in visible light transmittance after thermal curing. DETAILED DESCRIPTION

[0032] Embodiments of the present invention will be described in detail.

[0033] The photosensitive resin composition of the present invention comprises:

[0034] (A) alkali-soluble resin,

[0035] (B) Photoacid generating materials, and

[0036] (C) a compound having a phenolic hydroxyl group and having an octanol / water partition coefficient (LogP) of 4.6 to 20.0, and

[0037] The photosensitive resin composition has a transmittance of 80% to 99% at 400 nm at a thickness of 1.5 μm after thermal curing and a yellowness index of 0.1 to 7.0. The photosensitive resin composition can improve visible light transmittance after thermal curing.

[0038] The photosensitive resin composition of the present invention is preferably used in a planarization layer and / or a pixel segmentation layer of an organic EL display device. By using the photosensitive resin composition in these layers, the visible light transmittance of the organic EL display device can be easily improved.

[0039] The photosensitive resin composition of the present invention is more preferably used in mobile devices that include a camera and / or sensor directly below the active area of ​​an organic EL display device. Using the photosensitive resin composition in each of the aforementioned layers easily improves the visible light transmittance of the organic EL display device, making it easier to use in mobile devices that include a camera and / or sensor directly below the active area of ​​the organic EL display device. This makes it easier to accommodate various designs and shapes, such as for transmissive organic EL displays.

[0040] The photosensitive resin composition of the present invention contains (A) an alkali-soluble resin. In the present invention, alkali-soluble means that a solution of the resin dissolved in γ-butyrolactone is applied to a silicon wafer and prebaked at 120°C for 4 minutes to form a prebaked film having a thickness of 10 μm ± 0.5 μm. After the prebaked film is immersed in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 23±1°C for one minute, the dissolution rate, as determined by the reduction in film thickness during rinsing with pure water, is 50 nm / min or greater.

[0041] As (A) alkali-soluble resin, polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyaminoamide, acrylic resin, cardo resin, phenolic resin, cyclic olefin polymer, polysiloxane, etc. can be cited, but are not limited thereto. (A) alkali-soluble resin may also contain two or more of the resins described above. Among these alkali-soluble resins, resins with excellent heat resistance and low outgassing at high temperatures are preferred. Specifically, it is preferred to be selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, copolymers thereof, and polysiloxane. In addition, in terms of excellent film properties such as bending resistance, in the photosensitive resin composition of the present invention, (A) alkali-soluble resin is further preferably selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, and copolymers thereof. Furthermore, from the viewpoint of visible light transmittance, exposure sensitivity, or chemical resistance, one or more alkali-soluble resins selected from the group consisting of polyimide precursors, polybenzoxazole precursors, and copolymers thereof are particularly preferred.

[0042] (A) The alkali-soluble resin preferably has an acidic group in the resin's structural unit and / or at its main chain end. The presence of an acidic group facilitates alkali solubility. Examples of the acidic group include a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group. Among these, carboxyl groups and phenolic hydroxyl groups are preferred in terms of not containing a sulfur atom.

[0043] The alkali-soluble resin (A) preferably contains fluorine atoms. Fluorine atoms impart hydrophobicity to the interface between the film and the substrate during development using an alkaline aqueous solution, thereby inhibiting the penetration of the alkaline aqueous solution into the interface. From the perspective of preventing the penetration of the alkaline aqueous solution into the interface, the fluorine atom content in the alkali-soluble resin is preferably 5% by mass or more based on 100% by mass of the alkali-soluble resin (A), and is preferably 20% by mass or less in terms of solubility in an alkaline aqueous solution.

[0044] (A) The alkali-soluble resin can be synthesized by a known method.

[0045] In the case of a polyimide precursor, examples of the production method include synthesis by the following methods: a method in which tetracarboxylic dianhydride and a diamine compound are reacted at low temperature; a method in which tetracarboxylic dianhydride and a diamine compound are reacted at low temperature, and then the amic acid structure is partially esterified using N,N-dimethylformamide dimethyl acetate or the like; a method in which a diester is obtained by reacting tetracarboxylic dianhydride with an alcohol, and then the diester is reacted with an amine in the presence of a condensing agent; a method in which a diester is obtained by reacting tetracarboxylic dianhydride with an alcohol, and then the residual dicarboxylic acid is chlorinated and reacted with an amine, etc.

[0046] In the case of polyimide, for example, the polyimide precursor obtained by the above method can be obtained by heating it in a solvent or by chemically treating it with an acid, an alkali, or the like to cause dehydration and ring closure.

[0047] In the case of a polybenzoxazole precursor, as a manufacturing method, for example, a bisaminophenol compound can be obtained by condensing a dicarboxylic acid. For example, a method in which a dehydration condensation agent is reacted with an acid and a bisaminophenol compound is added thereto; or a solution of a dicarboxylic acid dichloride is added dropwise to a solution of a bisaminophenol compound to which a tertiary amine is added. Examples of the dehydration condensation agent include dicyclohexylcarbodiimide (DCC). In addition, examples of the tertiary amine include pyridine.

[0048] In the case of polybenzoxazole, for example, the polybenzoxazole precursor obtained by the above method can be heated in a solvent or subjected to chemical treatment with an acid, an alkali, or the like to undergo dehydration ring closure.

[0049] Examples of the acid dianhydride used for the polyamide, polyamide precursor, and copolymer thereof 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)ethane dianhydride, and bis(3,4-dicarboxyphenyl)ethane dianhydride. Aromatic tetracarboxylic dianhydrides such as bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorene dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride; or aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic dianhydride and 1,2,3,4-cyclopentanetetracarboxylic dianhydride. Two or more of these may be used.

[0050] Examples of the acid component used in polybenzoxazole, polybenzoxazole precursors, and copolymers thereof include dicarboxylic acids, tricarboxylic acids, and tetracarboxylic acids. Examples of dicarboxylic acids include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, and triphenyl dicarboxylic acid. Examples of tricarboxylic acids include trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, and biphenyl tricarboxylic acid. Examples of tetracarboxylic acids include aromatic tetracarboxylic acids and aliphatic tetracarboxylic acids. Examples of aromatic tetracarboxylic acids include pyromellitic acid, 3,3′,4,4′-biphenyltetracarboxylic acid, 2,3,3′,4′-biphenyltetracarboxylic acid, 2,2′,3,3′-biphenyltetracarboxylic acid, 3,3′,4,4′-benzophenonetetracarboxylic acid, 2,2′,3,3′-benzophenonetetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane, ) 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, etc. Examples of aliphatic tetracarboxylic acids include butanetetracarboxylic acid and 1,2,3,4-cyclopentanetetracarboxylic acid. Two or more of these may be used.

[0051] 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′-diamino Biphenyl, 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′-bis(trifluoromethyl)-4,4′-diaminobiphenyl, 9,9-bis(4-aminophenyl)fluorene, or compounds in which at least some of the hydrogen atoms of these aromatic rings are substituted with alkyl groups or halogen atoms, or aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, and diamines having the following structures. Two or more of these may be used.

[0052] [Chemistry 3]

[0053]

[0054] R 5 and R 8 represents an oxygen atom, C(CF3)2 or C(CH3)2. 6 、R 7 , and R 9 ~R 16 Each independently represents a hydrogen atom or a hydroxyl group.

[0055] These diamines can be used as diamines or as corresponding diisocyanate compounds or trimethylsilylated diamines.

[0056] In addition, by capping the ends of these resins with a capping agent, a resin having an acidic group at the end of the main chain can be obtained. Examples of the capping agent include monoamines, acid anhydrides, acid chlorides, and monocarboxylic acids having an acidic group.

[0057] The content of the terminal blocking agent is preferably 2 to 25 parts by mole relative to 100 parts by mole of the total of the acid and amine components constituting the resin.

[0058] As the acrylic resin, a resin obtained by radical polymerization of (meth)acrylic acid or (meth)acrylate is preferred. Examples of the (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, cyclopropyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cyclohexenyl (meth)acrylate, 4-methoxycyclohexyl (meth)acrylate, 2-cyclopropyloxycarbonylethyl (meth)acrylate, 2-cyclopentyloxycarbonylethyl (meth)acrylate, 2-cyclohexyloxycarbonylethyl (meth)acrylate, 2-cyclohexenyloxycarbonylethyl (meth)acrylate, 2-(4-methoxycyclohexyl)oxycarbonylethyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, tetracyclodecanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, adamantyl (meth)acrylate, adamantyl methyl (meth)acrylate, and 1-methyladamantyl (meth)acrylate. Aromatic vinyl compounds such as styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, α-methylstyrene, etc. may also be copolymerized with the (meth)acrylic acid or (meth)acrylate.

[0059] Furthermore, an ethylenically unsaturated double bond group can be introduced by subjecting an epoxy compound having an ethylenically unsaturated double bond group to an addition reaction with (meth)acrylic acid.

[0060] Examples of cardo resins include resins having a cardo structure, that is, a skeleton structure in which two ring structures are bonded to a quaternary carbon atom constituting a ring structure. The cardo structure generally comprises a benzene ring bonded to a fluorene ring.

[0061] Specific examples of the skeleton structure in which two cyclic structures are bonded to the quaternary carbon atom constituting the cyclic structure include a fluorene skeleton, a bisphenol fluorene skeleton, a bisaminophenyl fluorene skeleton, a fluorene skeleton having an epoxy group, and a fluorene skeleton having an acrylic group.

[0062] Cardo resin is formed by polymerization of a skeleton having the cardo structure through reactions between functional groups bonded thereto. Cardo resin has a structure (cardo structure) in which a main chain and bulky side chains are connected by a single element, and has a cyclic structure in a direction approximately perpendicular to the main chain.

[0063] Specific examples of monomers having a cardo structure include: bis(glycidyloxyphenyl)fluorene-type epoxy resins, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene and other bisphenols containing a cardo structure, or 9,9-bis(cyanomethyl)fluorene and other 9,9-bis(cyanoalkyl)fluorenes, 9,9-bis(3-aminopropyl)fluorene and other 9,9-bis(aminoalkyl)fluorenes, etc.

[0064] Cardo resin is a polymer obtained by polymerizing monomers having a cardo structure, but may also be a copolymer with other copolymerizable monomers.

[0065] Examples of the phenol resin include novolac phenol resins and resol phenol resins. The phenol resin is obtained by polycondensing, for example, a plurality of phenols alone or a mixture thereof with an aldehyde such as formalin.

[0066] Examples of the phenols include phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2,4,5-trimethylphenol, methylenebis(meth)ol Phenol, methylenebis(p-cresol), resorcinol, o-catechol, 2-methylresorcinol, 4-methylresorcinol, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichlorophenol, m-methoxyphenol, p-methoxyphenol, p-butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3-diethylphenol, 2,5-diethylphenol, p-isopropylphenol, α-naphthol, β-naphthol, etc. These phenols can be used alone or as a mixture of a plurality of them.

[0067] In addition, examples of aldehydes include, in addition to formalin, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde, etc. These aldehydes may be used alone or as a mixture of two or more.

[0068] The weight average molecular weight of the phenol resin is preferably 2,000 to 50,000, more preferably 3,000 to 30,000. A weight average molecular weight of 50,000 or less facilitates improved developability and sensitivity. A weight average molecular weight of 2,000 or greater facilitates improved pattern shape, resolution, developability, and heat resistance. The weight average molecular weight of the phenol resin is measured using gel permeation chromatography and calculated in terms of polystyrene.

[0069] Examples of the polysiloxane include polysiloxanes obtained by hydrolyzing and dehydrating at least one selected from tetrafunctional organosilanes, trifunctional organosilanes, difunctional organosilanes, and monofunctional organosilanes.

[0070] Specific examples of tetrafunctional organosilanes include tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, and tetraphenoxysilane. Specific examples of trifunctional organosilanes include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, 1-(p-hydroxyphenyl)ethyltrimethoxysilane, 2-(p-hydroxyphenyl)ethyltrimethoxysilane, 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyltrimethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, 3,3,3- Trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, [(3-ethyl-3-oxetanyl)methoxy]propyltrimethoxysilane, [(3-ethyl-3-oxetanyl)methoxy]propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic acid, 1-naphthyltrimethoxysilane, 1-naphthyltriethoxysilane, 1-naphthyltri-n-propoxysilane, 2-naphthyltrimethoxysilane, and the like. Specific examples of difunctional organosilanes include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, di-n-butyldimethoxysilane, diphenyldimethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, di(1-naphthyl)dimethoxysilane, and di(1-naphthyl)diethoxysilane. Specific examples of monofunctional organosilanes include trimethylmethoxysilane, tri-n-butylethoxysilane, (3-glycidoxypropyl)dimethylmethoxysilane, and (3-glycidoxypropyl)dimethylethoxysilane. Two or more of these organosilanes may be used. Alternatively, silicate compounds such as methyl silicate 51 manufactured by Fuso Chemical Co., Ltd. and M silicate 51 manufactured by Tama Chemical Co., Ltd. may be copolymerized.

[0071] The weight average molecular weight (Mw) of the polysiloxane is not particularly limited, but is preferably 1,000 or greater in terms of polystyrene as measured by gel permeation chromatography (GPC). A weight average molecular weight of 1,000 or greater tends to improve film coating properties. On the other hand, from the perspective of solubility in a developer, the Mw of the polysiloxane is preferably 100,000 or less, and more preferably 50,000 or less.

[0072] Polysiloxane can be synthesized by hydrolyzing and partially condensing monomers such as organosilane. Here, the so-called partial condensation means that not all Si-OH groups in the hydrolyzate are condensed, but a portion of Si-OH groups remain in the resulting polysiloxane. Conventional methods can be used for hydrolysis and partial condensation. For example, there can be mentioned a method of adding a solvent, water, and a catalyst as needed to an organosilane mixture, and heating and stirring at 50°C to 150°C for about 0.5 hours to 100 hours. During stirring, hydrolysis by-products (alcohols such as methanol) or condensation by-products (water) can be removed by distillation as needed.

[0073] The catalyst is not particularly limited, and acid catalysts and base catalysts can be preferably used. Specific examples of the acid catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acids or their anhydrides, and ion exchange resins. Specific examples of the base catalyst include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, sodium hydroxide, potassium hydroxide, alkoxysilanes having an amino group, and ion exchange resins.

[0074] In the total amount 100% by mass of the photosensitive resin composition other than the organic solvent, the total content of (A) to (C) components is preferably 50% by mass or more, and from the perspective of visible light transmittance or exposure sensitivity, more preferably 80% by mass or more, and further preferably 90% by mass or more, particularly preferably 95% by mass or more. The upper limit of the total content is not particularly limited and is 100% by mass. In addition to including (A) to (C) components, when also including (D) components, the total content of (A) to (D) components is preferably 50% by mass or more, and from the perspective of visible light transmittance or exposure sensitivity, more preferably 80% by mass or more, and further preferably 90% by mass or more, particularly preferably 95% by mass or more. The upper limit of the total content is not particularly limited and is 100% by mass.

[0075] The photosensitive resin composition of the present invention contains (B) a photoacid generator. In the present invention, (B) a photoacid generator is sometimes referred to as simply (B) component. In the present invention, (B) a photoacid generator generates acid by irradiation with light and has the function of increasing the solubility of the light-irradiated portion in an alkaline aqueous solution. Examples of (B) a photoacid generator include naphthoquinone diazide sulfonic acid esters, diaryliodonium salts, triarylsulfonium salts, oxime sulfonic acid ester compounds, and naphthalimide compounds. In order to obtain a positive-type photosensitive resin precursor composition that is efficiently sensitive to i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) of a mercury lamp, which are general ultraviolet rays, the (B) photoacid generator preferably contains naphthoquinone diazide sulfonic acid esters.

[0076] In the photosensitive resin composition of the present invention, the photoacid generator (B) more preferably contains one or more selected from the group consisting of naphthoquinonediazidesulfonic acid esters, diaryliodonium salts, triarylsulfonium salts, oximesulfonate compounds, and naphthalimide compounds. By having such a structure as the photoacid generator (B), the dissolution rate of the unexposed portion during development with an alkaline aqueous solution is reduced, and the solubility difference between the exposed and unexposed portions is increased, thereby easily obtaining a positive-type photosensitive resin precursor composition that is highly sensitive. Furthermore, by containing at least one of the triarylsulfonium salts, oximesulfonate compounds, and naphthalimide compounds, the unexposed portion undergoes thermal decomposition during thermal curing to generate acid. This allows the crosslinking reaction of the crosslinking agent to proceed sufficiently even during low-temperature curing at 250°C or below, significantly improving the chemical resistance of the cured film. Furthermore, when component (A) contains one or more alkali-soluble resins selected from the group consisting of polyimide precursors, polybenzoxazole precursors, and copolymers thereof, the cyclization of these imide and oxazole rings is promoted, allowing the cyclization reaction to proceed sufficiently even during low-temperature curing, thereby improving the chemical resistance of the cured film. Among these photoacid generators, oxime sulfonate compounds are preferred because they readily and efficiently undergo thermal decomposition at low temperatures of 250°C or less.

[0077] In the photosensitive resin composition of the present invention, as described above, the photoacid generator (B) preferably contains naphthoquinonediazidesulfonic acid ester. The naphthoquinonediazidesulfonic acid ester is preferably a compound in which naphthoquinonediazidesulfonic acid is ester-bonded to a compound having a phenolic hydroxyl group.

[0078] Examples of the compound having a phenolic hydroxyl group 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, methylene tris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dihydroxymethyl-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, and TriML-3 5XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (trade names, manufactured by Asahi Organic Materials Industry Co., Ltd.), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), etc., but are not limited to these.

[0079] The naphthoquinonediazidesulfonic acid ester can be synthesized, for example, by an esterification reaction between a compound having a phenolic hydroxyl group and a quinonediazidesulfonic acid compound. Examples of quinonediazidesulfonic acid compounds include, but are not limited to, naphthoquinonediazide-4-sulfonic acid and naphthoquinonediazide-5-sulfonic acid. A photosensitive resin composition containing the naphthoquinonediazidesulfonic acid ester obtained by the esterification reaction between the compound having a phenolic hydroxyl group and the quinonediazidesulfonic acid compound further improves resolution, sensitivity, and residual film rate.

[0080] Naphthoquinonediazide-4-sulfonate compounds absorb in the i-ray region of a mercury lamp and are suitable for i-ray exposure. Furthermore, naphthoquinonediazide-5-sulfonate compounds absorb up to the g-ray region of a mercury lamp and are suitable for g-ray exposure. The photosensitive resin composition of the present invention may contain either a naphthoquinonediazide-4-sulfonate compound or a naphthoquinonediazide-5-sulfonate compound. Furthermore, naphthoquinonediazide-5-sulfonate compounds having both a naphthoquinonediazide-4-sulfonyl group and a naphthoquinonediazide-5-sulfonyl group in the same molecule may also be contained. Furthermore, both a naphthoquinonediazide-4-sulfonate compound and a naphthoquinonediazide-5-sulfonate compound may also be contained.

[0081] Specific examples of diaryliodonium salts, triarylsulfonium salts, oxime sulfonate compounds, and naphthalimide compounds are shown below, but the invention is not limited thereto.

[0082] Examples of diaryliodonium salts include SP-130 and SP-140 (trade names, manufactured by ADEKA Co., Ltd.). Examples of triarylsulfonium salts include WPAG-567 (trade name, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), SP-056 (trade name, manufactured by ADEKA Co., Ltd.), and SI-200, SI-210, and SI-220 (trade names, manufactured by Sanshin Chemical Industry Co., Ltd.). Examples of the oxime sulfonate compounds include PAG121 and PAG103 (trade names, manufactured by BASF Japan Co., Ltd.), PA-480, PA-411, and PA-528 (trade names, manufactured by Heraeus Co., Ltd.), PAI-01, PAI-101, PAI-106, PAI-1001, PAI-1002, PAI-1003, and PAI-1004 (Midori Kagaku). Examples of the naphthalene imide compound include SP-082, SP-601, SP-606, SP-607, and SP-612 (trade names, manufactured by ADEKA Co., Ltd.), NIT, MIN, ILP-110, ILP-110N, ILP-118, ILP-113, PA-223, and PA-298 (trade names, manufactured by Heraeus Co., Ltd.), and NAI-105, NAI-106, and NAI-109 (trade names, manufactured by Midori Kagaku Co., Ltd.).

[0083] The content of the (B) component relative to the total amount of 100 parts by mass of the (A) alkali-soluble resin is preferably 3 parts by mass or more and 50 parts by mass or less. When it is 3 parts by mass or more, the exposure sensitivity is improved, and when it is 50 parts by mass or less, the visible light transmittance is further improved. The content of the (B) component is more preferably 5 parts by mass or more and 40 parts by mass or less, and further preferably 7 parts by mass or more and 40 parts by mass or less, and particularly preferably 10 parts by mass or more and 35 parts by mass or less. In addition, when the (B) component contains any one of a triarylsulfonium salt, an oxime sulfonate compound, or a naphthalimide compound, the total content of these salts or compounds relative to the total amount of 100 parts by mass of the (A) alkali-soluble resin is preferably 0.01 parts by mass or more, and more preferably 0.1 parts by mass or more. By containing 0.01 parts by mass or more, the cross-linking reaction and the cyclization of the unclosed ring structure of the resin are promoted, and thus the mechanical properties and chemical resistance of the cured film can be further improved. Furthermore, from the viewpoint of visible light transmittance, the total content of these salts or compounds is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less.

[0084] The photosensitive resin composition of the present invention contains (C) a compound having a phenolic hydroxyl group and having a LogP of 4.6 to 20.0 (hereinafter sometimes referred to as component (C)). By including component (C), the resulting photosensitive resin composition is substantially insoluble in an alkaline developer before exposure, but readily dissolves in an alkaline developer after exposure. This minimizes film thinning due to development and facilitates development in a short time. Consequently, sensitivity is readily improved.

[0085] In the photosensitive resin composition of the present invention, the molecular weight of the component (C) is preferably in the range of 90 to 2000. More preferably, it is 200 to 1500, and more preferably 300 to 1200.

[0086] Meanwhile, the present inventors have discovered that the polarity of component (C) affects the visible light transmittance of a cured film of a photosensitive resin composition. In the present invention, the higher the polarity of component (C) in the photosensitive resin composition, the lower the visible light transmittance of the resulting cured product. By reducing the polarity of component (C), the visible light transmittance of the cured product can be improved.

[0087] The octanol / water partition coefficient (LogP) (also called LogPow) as an indicator of the polarity of component (C) is explained. LogP is a physical property value related to the affinity of the target substance for water, and the higher the value, the lower the polarity. LogP is based on the case where the target substance is in equilibrium in a two-phase system of water and octanol (1-octanol), and is expressed by the common logarithm of the concentration ratio of each phase of the target substance. LogP is calculated by the following relationship: LogP = Log 10Co / Cw (Co represents the concentration of the target substance in the octanol phase, and Cw represents the concentration of the target substance in the aqueous phase) is calculated. LogP can be determined from the compound structure using the calculation function of commercially available software such as "ChemDraw" (PerkinElmer Informatics, Inc.). In the Examples and Comparative Examples described below, values ​​calculated using the "Chemical Properties Window" included in "ChemDraw ver. 19.1.0.8" (PerkinElmer Informatics, Inc.) are used.

[0088] In the photosensitive resin composition of the present invention, the LogP value of component (C) is 4.6 to 20.0. When the LogP value of component (C) is less than 4.6, the visible light transmittance of the cured product tends to decrease. On the other hand, when the LogP value exceeds 20.0, the solubility in the solvent decreases or the exposure sensitivity decreases. From the viewpoint of improving visible light transmittance, the LogP of component (C) is preferably 5.5 or more, more preferably 6.0 or more, further preferably 7.0 or more, and particularly preferably 8.0 or more. From the viewpoint of achieving a balance between solubility and exposure sensitivity, the upper limit of LogP is preferably 15.0 or less, more preferably 13.0 or less, and particularly preferably 12.0 or less. In addition, from the viewpoint of further reducing the yellowness index, the LogP of component (C) is preferably 8.0 to 15.0.

[0089] The content of component (C) relative to 100 parts by mass of the total amount of the alkali-soluble resin (A) is preferably 5 parts by mass or more and 40 parts by mass or less. A decrease in the content may reduce sensitivity, while an increase in the content may reduce visible light transmittance after thermal curing. Therefore, the content is more preferably 10 parts by mass or more and 35 parts by mass or less. From the perspective of balancing sensitivity and visible light transmittance after thermal curing, the content is more preferably 15 parts by mass or more and 30 parts by mass or less.

[0090] Examples of the component (C) having a LogP value within the range of 4.6 to 20.0 are shown below, but the component is not limited to these examples as long as it has a phenolic hydroxyl group and has a LogP value within the range of 4.6 to 20.0.

[0091] [Chemistry 4]

[0092]

[0093] As the number of phenolic hydroxyl groups in component (C) increases, the LogP value tends to decrease, while as the number of substituents or aromatic rings increases, the LogP value tends to increase. A cyclohexane ring structure in component (C) is particularly effective in increasing the LogP value. Furthermore, component (C) is preferred because its solubility in solvents is less likely to decrease and coloration during thermal curing is minimized. From the perspective of efficiently increasing the LogP value and reducing coloration during thermal curing, component (C) is more preferably a compound containing two or more cyclohexane ring structures within the molecule.

[0094] On the other hand, a structure having a hydrogen atom at the benzyl position is likely to be colored during thermal curing, particularly during curing in an oxygen atmosphere. Therefore, it is preferred that no hydrogen be contained at the benzyl position.

[0095] From the viewpoint of visible light transmittance, further preferred structures are represented by the following formulas (3) and (4).

[0096] From the viewpoint of increasing the LogP value and improving visible light transmittance, the component (C) in the photosensitive resin composition of the present invention preferably contains one or more selected from the group consisting of compounds represented by formula (3) and compounds represented by formula (4).

[0097] [Chemistry 5]

[0098]

[0099] In formula (3), R 17 are independently methyl or a group represented by formula (5), and at least one R 17 is a group represented by formula (5). In formula (5), c is an integer of 1 to 4. * represents a bonding site.

[0100] In formula (4), R 18 It is a divalent organic group having 1 to 10 carbon atoms. a and b are each independently an integer of 0 to 4, and a + b is 1 or greater. The divalent organic group having 1 to 10 carbon atoms is preferably an alkyl group, an aryl group, or a group having a cyclohexane ring structure. Furthermore, the divalent organic group having 1 to 10 carbon atoms is particularly preferably a group having a cyclohexane ring structure, from the perspectives of easily increasing the LogP value of component (C), less likely to decrease solubility in solvents, and further reducing coloration during thermal curing.

[0101] The compound represented by formula (3) and the compound represented by formula (4) both have a cyclohexane structure, and therefore the LogP value of the component (C) can be easily increased, the solubility in the solvent is less likely to decrease, and coloration during thermal curing is also reduced.

[0102] From the viewpoint of visible light transmittance, particularly preferred compounds are shown below.

[0103] [Chemistry 6]

[0104]

[0105] The compound having a phenolic hydroxyl group may be contained in combination of two or more types.

[0106] It may also contain a component (C) having a LogP value of 4.6 or more, and a compound having a phenolic hydroxyl group whose LogP is less than 4.6. In this case, the LogP average value of the compound having a phenolic hydroxyl group is preferably in the range of 4.6 to 20.0. From the viewpoint of improving visible light transmittance, the lower limit of the LogP average value is preferably 5.5 or more, more preferably 6.0 or more, further preferably 7.0 or more, and particularly preferably 8.0 or more. From the viewpoint of achieving a balance between solubility and exposure sensitivity, the upper limit of the LogP average value is preferably 15.0 or less, more preferably 13.0 or less, and particularly preferably 12.0 or less. Here, the LogP average value refers to the value obtained by summing up the LogP value of each compound having a phenolic hydroxyl group contained in the photosensitive resin composition, calculated for each phenol compound, multiplied by the mass ratio of each phenol compound relative to all phenol compounds.

[0107] The transmittance at 400 nm at a thickness of 1.5 μm after thermal curing of the photosensitive resin composition of the present invention is 80% or more and 99% or less, and the yellowness index is 0.1 or more and 7.0 or less. When the transmittance and the yellowness index are within the above ranges, when the cured product of the photosensitive resin composition is applied to an organic EL display device, the visible light transmittance of the organic EL display device is easily improved, and thus it becomes easy to use in a mobile device including a camera and / or a sensor directly below the active area of ​​the organic EL display device. In addition, it is easy to cope with various designs / models such as transmissive organic EL displays. As methods for making the transmittance within the above range and the yellowness index within the above range, for example, the following methods can be cited: containing a substance with a large LogP as component (C), containing component (D) described later, lowering the maximum heating temperature in the step of heat-treating the resin film described later to obtain the cured product, and the like.

[0108] The photosensitive resin composition of the present invention preferably contains a compound represented by (D) formula (1) (hereinafter sometimes referred to as (D) component).

[0109] [Chemistry 7]

[0110]

[0111] R 1Each independently represents a monovalent organic group having 1 to 20 carbon atoms, which may contain a heteroatom. In terms of visible light transmittance, the monovalent organic group preferably has 1 to 15 carbon atoms, further preferably 1 to 10 carbon atoms, and particularly preferably 1 to 7 carbon atoms. In terms of further improving visible light transmittance, the monovalent organic group having 1 to 20 carbon atoms preferably contains a hydroxyl group or an acrylic group. On the other hand, in terms of improving heat resistance, chemical resistance, and hardness, the monovalent organic group having 1 to 20 carbon atoms preferably contains an epoxy group or an oxetanyl group.

[0112] The inclusion of component (D) can more easily suppress coloration during thermal curing and improve visible light transmittance. In particular, when component (C) having a LogP range of 4.6 to 5.5 is included, the visible light transmittance may be high, making it difficult to reduce the yellowness index. Even in such cases, the inclusion of component (D) increases the visible light transmittance, making it easier to reduce the yellowness index.

[0113] Relative to the total amount of 100 parts by mass of the (A) alkali-soluble resin, the content of the (D) component is preferably 5 parts by mass or more and 70 parts by mass or less. By setting the content of the (D) component to 5 parts by mass or more, it is easier to improve the visible light transmittance after thermal curing. In addition, by setting the content to 70 parts by mass or less, storage stability is easily improved. The content of the (D) component is more preferably 15 parts by mass or more and 65 parts by mass or less, and further preferably 25 parts by mass or more and 60 parts by mass or less.

[0114] (D) Component may contain two or more types in combination. (D) Component is exemplified by the following chemical formula, but is not limited to these.

[0115] [Chemistry 8]

[0116]

[0117] In the photosensitive resin composition of the present invention, it is preferred that the compound represented by formula (1) comprises: (Da) at least two R 1 A compound containing a monovalent epoxy group (hereinafter sometimes referred to as (Da) or (Da) component), and / or at least two R in formula (1) (Db) 1A compound containing a monovalent group of an acrylic acid group and / or a hydroxyl group (hereinafter sometimes referred to as (Db) or (Db) component). When the compound represented by formula (1) contains component (Da), in addition to further improving transparency, a cross-linking reaction can occur during thermal curing, thereby improving the heat resistance, chemical resistance, and hardness of the thermally cured film, thereby reducing the amount of outgassing from the cured product and improving the long-term reliability of the organic EL display device. On the other hand, when the compound represented by formula (1) contains component (Db), in addition to further improving transparency, it can also easily increase exposure sensitivity, thereby maintaining high storage stability of the photosensitive resin composition.

[0118] In order to further improve visible light transmittance and maintain high chemical resistance, exposure sensitivity, and storage stability, it is preferable to contain both the components (Da) and (Db). Furthermore, from the perspective of achieving a balance between visible light transmittance, chemical resistance, exposure sensitivity, and storage stability, the mass ratio (Da) / (Db) is preferably 1 / 9 to 9 / 1, more preferably 1 / 9 to 8 / 2, and particularly preferably 2 / 8 to 7 / 3.

[0119] In the photosensitive resin composition of the present invention, it is preferred that the compound represented by the formula (1) (D) contains at least two R 1 is a compound containing a monovalent epoxy group, and (Db) at least two R 1 The compound is a monovalent compound containing an acrylic acid group and / or a hydroxyl group, and the mass ratio (Da) / (Db) is 1 / 9 to 9 / 1. By simultaneously containing the components (Da) and (Db) and keeping their mass ratio within the above range, not only is visible light transparency significantly improved, but the heat resistance and chemical resistance of the heat-cured film are also improved, and the exposure sensitivity can be easily increased, thereby maintaining high storage stability of the photosensitive resin composition.

[0120] The photosensitive resin composition of the present invention can more easily improve visible light transmittance by containing both the component (C) and the compound represented by the formula (1) (D).

[0121] From the perspective of further improving visible light transmittance, it is preferred that, when the contents (parts by mass) of the component (C) and the compound represented by the formula (1) (D) are represented by Cm and Dm, respectively, relative to 100 parts by mass of the total amount of the alkali-soluble resin (A), the total contents (Cm + Dm) be 20 parts by mass or more and 110 parts by mass or less, and the content ratio (Dm / Cm) be 1 / 9 to 9 / 1. The total contents (Cm + Dm) are more preferably 25 parts by mass or more and 100 parts by mass or less, and particularly preferably 40 parts by mass or more and 90 parts by mass or less. The content ratio (Dm / Cm) is more preferably 3 / 7 to 9 / 1, and particularly preferably 5 / 5 to 8 / 2.

[0122] The photosensitive resin composition of the present invention may contain a thermal crosslinking agent within a range that does not impair the visible light transmittance of its cured product. In the present invention, a thermal crosslinking agent refers to a compound having at least two thermally reactive functional groups in the molecule. Examples of thermally reactive functional groups include alkoxymethyl, hydroxymethyl, epoxy, and oxetane. By including a thermal crosslinking agent, the resin of component (A) or other added components can be crosslinked, thereby improving the heat resistance, chemical resistance, and hardness of the film after thermal curing, thereby reducing the amount of outgassing from the cured product and improving the long-term reliability of the organic EL display device.

[0123] The thermal crosslinking agents may be contained in combination of two or more.

[0124] The content of the thermal crosslinking agent is preferably from 1% to 30% by mass based on 100% by mass of the total amount of the photosensitive resin composition excluding the organic solvent. When the content of the thermal crosslinking agent is from 1% to 30% by mass, the chemical resistance and hardness of the film after firing or curing can be improved, and the amount of outgassing from the cured product can be reduced, thereby improving the long-term reliability of the organic EL display device and providing excellent storage stability of the photosensitive resin composition.

[0125] The photosensitive resin composition of the present invention preferably contains an organic solvent, which can be used as a varnish and improve coating properties.

[0126] Examples of the organic solvent include polar aprotic solvents such as γ-butyrolactone, ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tetrahydrofuran, and dioxane; ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, and diacetone alcohol; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, Esters such as propylene glycol monoethyl ether acetate and ethyl lactate; esters such as ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, methyl acetoacetate, and ethyl acetoacetate; aromatic hydrocarbons such as toluene and xylene; amides such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylpropionamide, and 3-methoxy-N,N-dimethylpropionamide; two or more of these organic solvents may also be included.

[0127] The content of the organic solvent is not particularly limited, but is preferably 100 to 3,000 parts by mass, and more preferably 150 to 2,000 parts by mass, relative to 100 parts by mass of the total amount of the photosensitive resin composition excluding the organic solvent. Furthermore, the proportion of organic solvents having a boiling point of 180°C or higher in the total amount of the organic solvent is preferably 20% by mass or less, and more preferably 10% by mass or less. By setting the proportion of organic solvents having a boiling point of 180°C or higher to 20% by mass or less, the amount of outgassing from the planarizing layer or insulating layer after thermal curing can be suppressed to a low level, thereby improving the long-term reliability of the organic EL device.

[0128] The resin composition of the present invention may contain a close contact improver. Examples of the close contact improver include: silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-phenylyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane; titanium chelating agents; aluminum chelating agents; compounds obtained by reacting aromatic amine compounds with alkoxy-containing silicon compounds, etc. Two or more of these may also be included. By containing these close contact improvers, when the resin film is developed, the close contact with base substrates such as silicon wafers, indium tin oxide (ITO), SiO2, and silicon nitride can be improved. In addition, the resistance to oxygen plasma and UV ozone treatment used in cleaning, etc. can be improved. The content of the adhesion improver is preferably 0.1% by mass to 10% by mass based on 100% by mass of the total amount of the photosensitive resin composition excluding the organic solvent.

[0129] The photosensitive resin composition of the present invention may contain a surfactant as needed. By containing a surfactant, wettability with the substrate can be improved. Commercially available compounds can be used as the surfactant. For example, 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 Disfoam series from NOF Corporation, and the TSF series from Toshiba Silicones. Fluorosurfactants include the “Megafac (registered trademark)” series from Dainippon Ink Industries, the Fluorad series from Sumitomo 3M, the “Surflon (registered trademark)” series and the “Asahi Guard (registered trademark)” series from Asahi Glass, the EF series from Shin-Akita Chemical, and the Polyfox series from Omnova Solutions. Surfactants containing acrylic and / or methacrylic polymers include the Polyflow series from Kyoeisha Chemical and the “Disparlon (registered trademark)” series from Kusumoto Chemical, but are not limited to these.

[0130] The content of the surfactant is preferably 0.001% by mass to 1% by mass based on 100% by mass of the total amount of the photosensitive resin composition excluding the organic solvent.

[0131] The photosensitive resin composition of the present invention may also contain inorganic particles. Specific examples of inorganic particles include, but are not limited to, silicon oxide, titanium oxide, barium titanate, aluminum oxide, and talc. The primary particle size of these inorganic particles is preferably 100 nm or less, more preferably 60 nm or less.

[0132] The content of the inorganic solvent is preferably 5% by mass to 50% by mass based on 100% by mass of the total amount of the photosensitive resin composition excluding the organic solvent.

[0133] The photosensitive resin composition of the present invention may contain a thermal acid generator within a range that does not impair visible light transmittance. In addition to generating an acid upon heating to promote the crosslinking reaction of the thermal crosslinker, the thermal acid generator can also promote the cyclization of unclosed imide or oxazole ring structures when the resin of component (A) has these rings, thereby further improving the mechanical properties of the cured film.

[0134] The thermal decomposition starting temperature of the thermal acid generator used in the present invention is preferably 50°C to 270°C, more preferably 250°C or lower. Furthermore, it is preferred that the thermal acid generator not generate acid during drying (pre-baking: approximately 70°C to 140°C) after coating the photosensitive resin composition of the present invention on a substrate, but generate acid during final heating (curing: approximately 100°C to 400°C) after patterning during subsequent exposure and development, because this can suppress a decrease in sensitivity during development.

[0135] The acid generated by the thermal acid generator used in the present invention is preferably a strong acid, for example, an arylsulfonic acid such as p-toluenesulfonic acid and benzenesulfonic acid, an alkylsulfonic acid such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, and butanesulfonic acid, or a halogenated alkylsulfonic acid such as trifluoromethylsulfonic acid. These can be used as acid-protected compounds such as alkyl esters. Two or more of these can also be included.

[0136] The content of the thermal acid generator used in the present invention is preferably 0.01% by mass or more, and more preferably 0.1% by mass or more, based on 100% by mass of the total amount of the photosensitive resin composition excluding the organic solvent. The inclusion of 0.01% by mass or more promotes cross-linking reactions and cyclization of unclosed ring structures in the resin, thereby further improving the mechanical properties and chemical resistance of the cured film. Furthermore, from the perspective of long-term reliability of organic EL display devices, the content is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 2% by mass or less.

[0137] The method for producing the photosensitive resin composition of the present invention will be described. The photosensitive resin composition of the present invention can be produced, for example, by suspending components (A) to (C), and optionally component (D), as well as other constituent components, in a solvent and stirring until dissolved. As long as a uniform composition is obtained, the order in which the components are added is not particularly limited. From the perspective of solubility and inhibition of the reaction of the components, the dissolution temperature is preferably 5°C or higher and 60°C or lower. The stirring step is preferably carried out under an inert gas environment such as nitrogen.

[0138] The photosensitive resin composition of the present invention is suitable for use as a surface protective film of a semiconductor element, an interlayer insulating film, an insulating film of an organic EL element, a planarizing film of a thin film transistor (TFT) substrate, and the like.

[0139] The first embodiment of the cured product of the present invention is a cured product obtained by curing the photosensitive resin composition of the present invention.

[0140] The first form of the cured product of the present invention preferably has a transmittance of 80% or more and 99% or less at 400 nm at a thickness of 1.5 μm. From the perspective of diversifying designs and shapes, such as placing a camera directly below a transmissive organic EL display or a mobile terminal display, the visible light transmittance is preferably high, more preferably 85% or more, and particularly preferably 90% or more. The upper limit of the transmittance is not particularly limited, but may be, for example, 99%, 98%, or 97%.

[0141] The first form of the cured product of the present invention preferably has a yellowness index of 0.1 or greater and 7.0 or less at a thickness of 1.5 μm. From the perspective of design and styling diversification, such as when a camera is positioned directly below a transmissive organic EL display or a mobile terminal display, a low yellowness index is preferred, more preferably 5.0 or less, and particularly preferably 3.0 or less. The lower limit of the yellowness index is not particularly limited, but may be, for example, 0.1, 0.2, or 0.3.

[0142] The method for producing a cured product of the present invention comprises: applying the photosensitive resin composition of the present invention on a substrate to form a resin film; drying the resin film; exposing the dried resin film to light; developing the exposed resin film; and heating the developed resin film to obtain a cured product.

[0143] First, the process of coating the photosensitive resin composition of the present invention on a substrate to form a resin film will be described. The photosensitive resin composition can be coated on the substrate by, for example, spin coating, slit coating, dip coating, spray coating, printing, etc. to obtain a coating film of the photosensitive resin composition.

[0144] Prior to coating, the substrate to be coated with the photosensitive resin composition may be pre-treated with the adhesion improver described above. For example, the following method can be used: treating the substrate surface with a solution of 0.5% to 20% by mass of the adhesion improver dissolved in a solvent such as isopropyl alcohol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, or diethyl adipate. Examples of substrate surface treatment methods include spin coating, slit die coating, bar coating, dip coating, spray coating, and steam treatment.

[0145] Substrate can suitably select the support of metal, glass, resin film etc. that are suitable for display device or the substrate of subsequent process of conveying.If it is a glass substrate, soda-lime glass or alkali-free glass etc. can be used.The thickness of substrate is as long as being enough to keep the thickness of mechanical strength.Because the dissolved ions from glass are less advisable, the material of glass is preferably alkali-free glass, and the soda-lime glass of the isolation coating of SiO2 etc. can also be used.If it is a resin film, then preferably contain the resin material selected from polyimide, polyamide, polybenzoxazole, polyamide-imide and poly (p-xylene), can contain these resin materials alone, also can combine multiple.For example, in the case of being formed by polyimide resin, also can be by containing the polyamic acid (comprising a part of imidized polyamic acid) as the precursor of polyimide or the solution of soluble polyimide be coated on supporting substrate and be fired to form.

[0146] Next, the step of drying the resin film will be described.

[0147] After coating, drying is performed, and if necessary, reduced pressure drying is performed. Then, heat treatment is performed at 50° C. to 180° C. for 1 minute to several hours using, for example, a hot plate, an oven, or infrared rays to obtain a resin film.

[0148] Next, the step of exposing the dried resin film to light will be described.

[0149] For example, chemical radiation can be applied to the resin film through a mask having a desired pattern. Examples of chemical radiation used for exposure include ultraviolet rays, visible light, electron beams, and X-rays. Among these, i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) using a mercury lamp are preferred.

[0150] Next, the step of developing the exposed resin film will be described.

[0151] After exposure, the exposed portion can be removed using a developer, for example. The developer is preferably an aqueous solution of a compound exhibiting alkalinity, such as tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine. In addition, as appropriate, these alkaline aqueous solutions may contain separately 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; ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone; or an alkaline aqueous solution composed of a combination of several of these may be added. Examples of developing methods include spraying, coating, immersion, and ultrasonic waves.

[0152] Next, the pattern formed by development is preferably rinsed with distilled water.

[0153] For example, rinsing treatment may be performed by adding alcohols such as ethanol and isopropyl alcohol; esters such as ethyl lactate and propylene glycol monomethyl ether acetate, etc. to distilled water.

[0154] The method for manufacturing a cured product of the present invention may also include a step of irradiating the developed resin film with ultraviolet rays. (B) The photoacid generating material is decomposed by ultraviolet irradiation, and the outgas component can be efficiently removed in the heat treatment step described later. When the (B) component is naphthoquinone diazide sulfonic acid ester, it is changed to an indene carboxylic acid compound. In the heat treatment step described later, the indene carboxylic acid compound further promotes the removal of sulfur dioxide derived from the sulfonic acid ester structure to the outside of the film. Therefore, the sulfur concentration in the cured product can be further reduced, and the long-term reliability of the organic EL device can be further improved. Here, the ultraviolet rays are preferably light of any wavelength including i-rays (365nm), h-rays (405nm), and g-rays (436nm) of a mercury lamp. In addition, the irradiation amount of ultraviolet rays is preferably 50mJ / cm 2 ~10000mJ / cm 2 By treating with these wavelengths and / or irradiation doses, it is possible to efficiently convert the indene carboxylic acid compound.

[0155] Next, a description will be given of a step of heat-treating the developed resin film to obtain a cured product.

[0156] Since residual solvents or components with low heat resistance can be removed by heat treatment, heat resistance and chemical resistance can be improved. In particular, when the alkali-soluble resin (A) contained in the photosensitive resin composition of the present invention contains a polyimide precursor, a polybenzoxazole precursor or a copolymer thereof, an imide ring or an oxazole ring can be formed by heat treatment, thereby improving heat resistance and chemical resistance. In addition, when a thermal crosslinking agent is included, a thermal crosslinking reaction can be carried out by heat treatment, thereby improving heat resistance and chemical resistance. The heat treatment can be maintained at the maximum heating temperature after staged heating, or maintained at the maximum heating temperature after continuous heating, or maintained at the maximum heating temperature from the beginning. Here, the maximum heating temperature refers to the temperature range in which the resin film has experienced more than the temperature for more than 1 minute in the temperature range that the resin film has experienced by heating. From the perspective of visible light transmittance of the cured film, the maximum heating temperature is preferably low. On the other hand, from the perspective of improving heat resistance and chemical resistance, the maximum heating temperature is preferably high. Considering the balance of these properties, the maximum heating temperature is preferably 200°C to 350°C, more preferably 220°C to 300°C, and even more preferably 230°C to 280°C. The holding time at the maximum heating temperature is not particularly limited, but is preferably 15 minutes or longer, more preferably 30 minutes or longer, and even more preferably 45 minutes or longer. From the perspective of productivity, the holding time is preferably 180 minutes or shorter, more preferably 150 minutes or shorter, and even more preferably 120 minutes or shorter.

[0157] Next, a method of manufacturing an organic EL display device will be described.

[0158] In the present invention, as a method for manufacturing an organic EL display device, for example, there can be mentioned a method for manufacturing an organic EL display device comprising the steps of sequentially forming a planarizing layer, a first electrode, a pixel partitioning layer, an organic EL layer, and a second electrode on a substrate. In this method, the method for manufacturing a cured product contained in the planarizing layer and / or the pixel partitioning layer is a method for manufacturing a cured product comprising the steps of applying the photosensitive resin composition of the present invention on a substrate to form a resin film, drying the resin film, exposing the dried resin film to light, developing the exposed resin film, and heat-treating the developed resin film to obtain a cured product.

[0159] Next, the second embodiment of the cured product of the present invention will be described.

[0160] The second embodiment of the cured product of the present invention has a transmittance at 400 nm of 80% or more and 99% or less at a thickness of 1.5 μm, a yellowness index of 0.1 or more and 7 or less, and contains a compound having an imide ring structure, a compound having an indene structure, a compound having a structure represented by formula (2), and a compound having a structure represented by formula (1).

[0161] [Chemistry 9]

[0162]

[0163] In formula (2), R 2 、R 3 , and R 4 Each is independently a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms which may contain a heteroatom.

[0164] [Chemistry 10]

[0165]

[0166] R 1 Each independently represents a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom. 1 The preferred embodiment is as described above.

[0167] In formula (2), examples of the monovalent organic group having 1 to 30 carbon atoms which may contain a heteroatom include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group.

[0168] The alkyl group may be linear, branched, or cyclic. The number of carbon atoms in linear and branched alkyl groups is usually 1 to 30, preferably 1 to 20, and more preferably 1 to 10 from the perspective of maintaining high visible light transmittance. The number of carbon atoms in cyclic alkyl groups is usually 3 to 30, preferably 3 to 20, and more preferably 3 to 10 from the perspective of maintaining high visible light transmittance. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, and decyl.

[0169] The alkenyl group may be linear, branched, or cyclic. The number of carbon atoms in linear and branched alkenyl groups is generally 2 to 30, preferably 2 to 20, and more preferably 2 to 10 from the perspective of maintaining high visible light transmittance. The number of carbon atoms in cyclic alkenyl groups is generally 3 to 30, preferably 3 to 20, and more preferably 3 to 10 from the perspective of maintaining high visible light transmittance. Examples of the alkenyl group include ethenyl, propenyl, isopropenyl, butenyl, pentenyl, hexenyl, nonenyl, and decenyl.

[0170] The alkynyl group may be linear, branched, or cyclic. The number of carbon atoms in linear and branched alkynyl groups is generally 2 to 30, preferably 2 to 20, and more preferably 2 to 10 from the perspective of maintaining high visible light transmittance. The number of carbon atoms in cyclic alkynyl groups is generally 3 to 30, preferably 3 to 20, and more preferably 3 to 10 from the perspective of maintaining high visible light transmittance. Examples of the alkynyl group include ethynyl, propynyl, butynyl, pentynyl, and hexynyl.

[0171] The aryl group is an atomic group remaining after removing a hydrogen atom directly bonded to a carbon atom constituting an aromatic ring from an aromatic hydrocarbon, and contains an aryl group having a hydroxyl group or the alkyl group, the alkenyl group, or the alkynyl group as a functional group. The number of carbon atoms in the aryl group is usually 6 to 30, preferably 6 to 20. Examples of the aryl group include phenyl, hydroxyphenyl, alkylphenyl, and alkylhydroxyphenyl. From the perspective of achieving a balance between visible light transmittance and heat resistance, hydroxyphenyl and alkylhydroxyphenyl are preferred. Examples of the alkylphenyl group include methylphenyl, ethylphenyl, dimethylphenyl, propylphenyl, methylethylphenyl, propylphenyl, isopropylphenyl, butylphenyl, isobutylphenyl, tert-butylphenyl, pentylphenyl, hexylphenyl, cyclohexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, and decylphenyl. Examples of the alkylhydroxyphenyl group include methylhydroxyphenyl, ethylhydroxyphenyl, dimethylhydroxyphenyl, propylhydroxyphenyl, methylethylhydroxyphenyl, propylhydroxyphenyl, isopropylhydroxyphenyl, butylhydroxyphenyl, isobutylhydroxyphenyl, tert-butylhydroxyphenyl, pentylhydroxyphenyl, hexylhydroxyphenyl, cyclohexylhydroxyphenyl, heptylhydroxyphenyl, octylhydroxyphenyl, nonylhydroxyphenyl, and decylhydroxyphenyl.

[0172] From the viewpoint of achieving a balance between visible light transmittance and heat resistance, R 2 、R 3 , and R 4 At least one of them is an alkyl group, an alkenyl group, an alkynyl group, or an aryl group. More preferably, it contains both an alkyl group and a hydroxyphenyl group and / or an alkylhydroxyphenyl group.

[0173] When the cured product contains a compound having an imide ring structure, a compound having an indene structure, a compound having a structure represented by formula (2), and a compound having a structure represented by formula (1), it is easy to obtain a cured product having a transmittance of 80% or more and 99% or less at 400 nm at a thickness of 1.5 μm and a yellowness index of 0.1 or more and 7.0 or less at a thickness of 1.5 μm.

[0174] In the second embodiment of the cured product of the present invention, the transmittance at 400 nm at a thickness of 1.5 μm is 80% or more and 99% or less. High visible light transmittance is preferred from the perspective of diversifying designs and shapes, such as when placing a camera directly below a transmissive organic EL display or a mobile terminal display. Specifically, the visible light transmittance of the cured product is preferably 85% or more, more preferably 88% or more, and particularly preferably 90% or more. The upper limit of the transmittance is not particularly limited, but may be, for example, 99%, 98%, or 97%.

[0175] In the second embodiment of the cured product of the present invention, the yellowness index at a thickness of 1.5 μm is 7.0 or less. From the perspective of design and styling diversification, such as when a camera is positioned directly below a transmissive organic EL display or a mobile terminal display, the cured product preferably has a low yellowness index, specifically, preferably 5.0 or less. The yellowness index of the cured product is particularly preferably 3.0 or less. The lower limit of the yellowness index is not particularly limited, but may be, for example, 0.1, 0.2, or 0.3.

[0176] Regarding the second embodiment of the cured product of the present invention, as described above, the cured product contains a compound having an imide ring structure; a compound having an indene structure; a compound having a structure represented by formula (2); and a compound having a structure represented by formula (1), thereby maintaining high visible light transmittance of the cured product.

[0177] The compounds contained in the second embodiment of the cured product of the present invention will be described. The compound having an imide ring structure can be obtained, for example, as a structure derived from the polyimide resin (A) or its residue; the compound having an indene structure can be obtained, for example, as a structure derived from the naphthoquinone diazidesulfonic acid ester contained as the photoacid generator (B) or its residue; the compound having a structure represented by formula (2) can be obtained, for example, as a structure derived from the component (C) or its residue; and the compound having a structure represented by formula (1) can be obtained, for example, as a structure derived from the compound represented by formula (1) (D) or its residue.

[0178] The cured product of the present invention can be used in organic EL display devices, semiconductor devices, multilayer wiring boards, and the like. More preferably, it can be used in insulating layers of organic EL display devices, planarizing layers of substrates with driver circuits for organic EL display devices, interlayer insulating films between redistribution wiring in semiconductor devices, passivation films for semiconductors, protective films for semiconductor devices, interlayer insulating films for multilayer wiring for high-density packaging, wiring protective insulating layers for circuit boards, on-chip microlenses for solid-state imaging devices, and planarizing layers for various displays and solid-state imaging devices.

[0179] The organic EL display device of the present invention includes the cured product of the present invention.

[0180] The organic EL display device of the present invention preferably includes at least a substrate, a first electrode, a second electrode, an organic EL layer, a planarization layer, and a pixel segmentation layer, and the planarization layer and / or the pixel segmentation layer contain the hardened material of the present invention. Taking an active matrix display device as an example, a substrate such as glass or a resin film is provided with a TFT (thin film transistor) and wiring located on the side of the TFT and connected to the TFT, and a planarization layer is provided thereon in a manner covering the concave and convex portions, and a display element is further provided on the planarization layer. The display element and the wiring are connected via contact holes formed in the planarization layer. The hardened material of the present invention is preferably used in the planarization layer and / or the pixel segmentation layer due to its excellent visible light transmittance. In particular, in recent years, the flexibility of organic EL display devices has become mainstream, and the substrate having the driving circuit may also be an organic EL display device including a resin film.

[0181] The organic EL display device of the present invention is preferably used in mobile devices that include a camera and / or sensor directly below the active area of ​​the organic EL display device. The organic EL display device of the present invention includes the cured material of the present invention, thereby improving the visible light transmittance of the organic EL display device, enabling visible light to efficiently pass through the active area of ​​the organic EL display device. This makes it suitable for mobile devices that include a camera and / or sensor directly below the active area. Furthermore, it can easily accommodate various designs and shapes, such as those for transmissive organic EL displays.

[0182] In the organic EL display device of the present invention, the planarization layer and the pixel segmentation layer are preferably composed of a single layer or multiple layers, respectively. At the stacking interface of the hardened materials forming the planarization layer and the pixel segmentation layer, the refractive index difference between the hardened materials forming the stacking interface at a wavelength of 550 nm is 0.3 or less at all stacking interfaces. The refractive index difference is more preferably 0.2 or less, further preferably 0.1 or less, and particularly preferably 0.05 or less. Furthermore, it is most preferred that there is no refractive index difference. With the recent advancement in the design of organic EL display devices, the use of a multilayer structure for the planarization layer and the pixel segmentation layer has become mainstream. In particular, when a multilayer structure is used, by setting the refractive index difference between the hardened materials forming the stacking interface at the stacking interface of the hardened materials forming the planarization layer and the pixel segmentation layer to the range described above, reflection at the interface is less likely to occur, thereby easily improving the visible light transparency of the organic EL display device. In order to reduce the refractive index difference, it can be achieved by making the refractive indices of the hardened materials forming the stacking interface close to each other. For example, there is a method of making the types of resins contained in the cured products forming the lamination interface uniform, and the most preferred method is a method of producing the cured products forming the respective layers using the same photosensitive resin composition.

[0183] The organic EL display device of the present invention may include a cured product of a photosensitive resin composition containing polysiloxane. The cured product of the photosensitive resin composition containing polysiloxane is obtained by curing a photosensitive resin composition containing at least the polysiloxane and the photoacid generator (B) according to, for example, the method described in the method for producing the cured product.

[0184] In a first preferred embodiment of the organic EL display device of the present invention, the planarization layer and the pixel segmentation layer are each composed of a single layer or multiple layers, the planarization layer contains the cured product, and the pixel segmentation layer contains a cured product of a photosensitive resin composition containing polysiloxane. Cured products of photosensitive resin compositions containing polysiloxane generally tend to improve visible light transmittance, so by including a cured product of a photosensitive resin composition containing polysiloxane as the pixel segmentation layer, the visible light transparency of the organic EL display device can be easily improved. In addition, since the planarization layer contains the cured product, the flexibility of the organic EL display device can be easily improved, so by setting the planarization layer to contain the cured product in the first preferred embodiment, the visible light transparency of the organic EL display device can be easily improved, thereby improving the flexibility of the organic EL display device.

[0185] In a second preferred embodiment of the organic EL display device of the present invention, the planarization layer and the pixel segmentation layer are each composed of a single layer or multiple layers, the planarization layer contains a cured product of a photosensitive resin composition containing polysiloxane, and the pixel segmentation layer contains the cured product. A cured product of a photosensitive resin composition containing polysiloxane generally improves the performance of flattening unevenness of the TFTs and the wiring located to the sides of the TFTs and connected to the TFTs in an organic EL display device. Therefore, by adopting this second preferred embodiment, the visible light transparency of the organic EL display device can be easily improved, and the flatness of unevenness of the TFTs and the wiring located to the sides of the TFTs and connected to the TFTs in the organic EL display device can be improved.

[0186] In a third preferred embodiment of the organic EL display device of the present invention, the planarization layer and the pixel partitioning layer are each composed of a single layer or multiple layers, and the planarization layer and the pixel partitioning layer contain the hardened material. By including the hardened material in the planarization layer and the pixel partitioning layer, not only is the visible light transmittance of the hardened material high, but also the refractive index difference between the hardened materials forming the stacking interfaces of the layers forming the planarization layer and the pixel partitioning layer can be minimized, thereby improving the visible light transmittance of the organic EL display device. Furthermore, the inclusion of the hardened material in the planarization layer improves the flexibility of the organic EL display device and appropriately improves the flatness of the unevenness of the TFTs and the wiring located on the sides of the TFTs and connected to the TFTs in the organic EL display device.

[0187] The semiconductor device of the present invention includes the cured product of the present invention.

[0188] The semiconductor device of the present invention preferably contains the cured product of the present invention in an insulating film and / or a protective film. Examples of the semiconductor device include those having known structures. The cured product of the present invention is preferably used in the insulating film and / or protective film due to its excellent visible light transmittance.

[0189] Example

[0190] The present invention will be described below with reference to Examples, etc., but the present invention is not limited to these Examples. The photosensitive resin compositions in the Examples were evaluated by the following method.

[0191] (1) Film thickness measurement method

[0192] <Film Thickness Measurement Method>

[0193] The film thickness after prebaking, after development, and after curing was measured using Lambda Ace STM-602 manufactured by Dainippon Screen Co., Ltd. at a refractive index of 1.629.

[0194] (2) Evaluation method of visible light transmittance

[0195] <Production of Hardened Material>

[0196] A photosensitive resin composition (varnish) according to each of the examples and comparative examples described below was spin-coated onto a 50 mm x 50 mm alkali-free glass substrate and pre-baked for 2 minutes on a 120°C hot plate (DIGITAL HOT PLATE HP-18A; manufactured by ASONE Co., Ltd.). The film was developed for 60 seconds using a 2.38 mass% tetramethylammonium aqueous solution (hereinafter referred to as TMAH, manufactured by Tama Chemical Co., Ltd.) and rinsed with pure water. Subsequently, a heat curing step was performed using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermal Systems Co., Ltd.) under a nitrogen atmosphere (oxygen concentration: 100 ppm or less), raising the temperature at 5°C / minute to 250°C. The developed film was then heat-treated at 250°C for 1 hour to produce a cured varnish. The cured product had a thickness of approximately 1.5 μm. In Examples 25 and 26, a heat curing step was performed by increasing the temperature to 230° C. at a rate of 5° C. / min and heating at 230° C. for 1 hour to produce a cured product of the varnish.

[0197] <Visible light transmittance measurement>

[0198] The cured product of the prepared varnish was measured and evaluated using a spectrophotometer (Hitachi, Ltd., "Dual Beam Spectrophotometer U-2900") at wavelengths of 300 nm to 800 nm. Based on the measurement results, the transmittance at a wavelength of 400 nm was read to evaluate visible light transmittance. Unless otherwise specified, the measured results showed that the transmittance at 400 nm was the lowest in the wavelength range of 400 nm to 800 nm, while the transmittance in the range of 401 nm to less than 800 nm was higher than that at 400 nm.

[0199] The obtained transmittance at 400 nm was evaluated according to the following criteria: C or higher was considered good transmittance and was rated as "acceptable", while D or lower was considered "unacceptable".

[0200] A: More than 90%

[0201] B: 85% or more and less than 90%

[0202] C: 80% or more and less than 85%

[0203] D: 75% or more and less than 80%

[0204] E: 70% or more and less than 75%

[0205] F: less than 70%

[0206] (3) Yellowness index determination method

[0207] <Yellowness Index Determination>

[0208] A cured varnish was prepared by the same method as in <Preparation of Cured Product> described in the method for evaluating visible light transmittance. The yellowness index was measured by the C illuminant transmission method using a color computer (Model SM-7-CH) manufactured by SUGA Testing Instruments Co., Ltd.

[0209] (4) Sensitivity evaluation

[0210] <Calculation of Exposure Sensitivity>

[0211] The photosensitive resin composition obtained in each example and comparative example was applied to an 8-inch silicon wafer by spin coating using a coating and developing device ACT-8 (manufactured by Tokyo Electron Co., Ltd.) and baked on a hot plate at 120°C for 3 minutes to prepare a pre-baked film with a film thickness of 3.0 μm. The film thickness was measured by the method described in <Film Thickness Measurement Method>. Subsequently, an exposure machine i-ray stepper NSR-2005i9C (manufactured by Nikon Corporation) was used to expose the film at 60 mJ / cm through a mask having a pattern of 10 μm contact holes. 2 ~300mJ / cm 2 The exposure dose is 10mJ / cm 2 After exposure, the film was developed using the ACT-8 developing device using a 2.38 mass % TMAH aqueous solution until the film was reduced to 0.5 μm during development, rinsed with distilled water, and then shaken to dry to obtain a pattern.

[0212] The resulting developed film pattern was observed at 20x magnification using an FDP microscope MX61 (manufactured by Olympus Corporation). The minimum exposure required to achieve a contact hole opening diameter of 10 μm was determined and used as the exposure sensitivity. Exposure sensitivities of C or higher were considered good and were rated "pass," while those of D or lower were considered "fail."

[0213] A: Below 90

[0214] B: greater than 90 and less than 120

[0215] C: greater than 120 and less than 140

[0216] D: greater than 140 and less than 160

[0217] E: greater than 160 and less than 180

[0218] F: greater than 180

[0219] (5) Chemical resistance evaluation

[0220] <Production of Hardened Material>

[0221] A photosensitive resin composition (varnish) according to each of the Examples and Comparative Examples described below was spin-coated onto a 4-inch silicon wafer and pre-baked for 2 minutes on a 120°C hot plate (DIGITAL HOT PLATE HP-18A; manufactured by ASONE Co., Ltd.). The film was developed using a 2.38% by mass aqueous TMAH solution and rinsed with pure water. Subsequently, a heat curing step was performed using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermal Systems Co., Ltd.) under a nitrogen atmosphere (oxygen concentration: 100 ppm or less), heating the developed film at 250°C for 1 hour. The cured product was produced as a cured product of the varnish. The thickness of the cured product was approximately 2.0 μm. Furthermore, in Examples 25 and 26, a heat curing step was performed by heating the developed film at 230°C for 1 hour at a rate of 5°C / min.

[0222] <Evaluation of Chemical Resistance>

[0223] The resulting cured film was immersed in an organic chemical solution (dimethyl sulfoxide: N-methyl-2-pyrrolidone (NMP): ethanolamine = 70:20:10) at 70°C for 1 minute and observed for peeling or dissolution. A film thickness change of 0.05 μm or less before and after immersion was rated "A," which was considered excellent. A film thickness change of 0.05 μm or more and 0.15 μm or less was rated "B," which was considered excellent. A film thickness change of 0.15 μm or more, or when peeling, dissolution, or cracking was observed, was rated "C," which was considered poor. A smaller film thickness change indicates better chemical resistance.

[0224] (6) Storage stability evaluation

[0225] <Evaluation of Storage Stability>

[0226] The exposure sensitivity of the varnishes obtained in each Example and Comparative Example was determined using the method described in "Calculation of Exposure Sensitivity." The varnishes were stored at 23°C, and the number of days after which the sensitivity changed by 15% or more from the sensitivity on day 0 was measured. A change of 30 days or more was rated "A," which was considered excellent; 15 days or more but less than 30 days was rated "B," which was considered good; and less than 15 days was rated "C," which was considered poor.

[0227] (7) Composition analysis of hardened materials

[0228] Although analysis methods for components contained in the cured product are shown, any method may be used as long as composition analysis can be performed, and the method is not limited to the described method.

[0229] <Preparation of Cured Material for Composition Analysis>

[0230] The photosensitive resin compositions obtained in each of the Examples and Comparative Examples were applied to an 8-inch silicon wafer by spin coating using an ACT-8 coating and developing apparatus (manufactured by Tokyo Electron Co., Ltd.) and baked on a hot plate at 120°C for 3 minutes. Subsequently, the ACT-8 developer was used to develop the film using a 2.38% by mass TMAH aqueous solution, rinsed with distilled water, and then spin-dried. Subsequently, a heat curing step was performed using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermal Systems Co., Ltd.) under a nitrogen atmosphere (oxygen concentration: 100 ppm or less), raising the temperature at 5°C / min to 250°C. The developed film was then heat-treated at 250°C for 1 hour to produce a cured varnish. The cured product had a thickness of approximately 3.0 μm.

[0231] <Composition Analysis by Fourier Transform Infrared Spectroscopy (FT-IR)>

[0232] The obtained cured film was observed using an infrared microscope Nicolet iN10 (manufactured by ThermoFisher SCIENTIFIC) at a wave number of 4000 cm -1 ~650cm -1 The detector uses MCT with a resolution of 8cm -1 The cumulative number of times was 64, and the IR spectrum was obtained by the single reflection ATR method (Ge, 45°) in the measurement mode.

[0233] <Composition Analysis by Pyrolysis GC / MS>

[0234] The obtained hardened film was thermally decomposed at a heating temperature of 600°C using a multi-shot pyrolyzer PY-3030D (manufactured by Frontier Laboratories). A gas chromatograph mass spectrometer JMS-Q1050GC (manufactured by JEOL) was used. A stainless steel capillary column (0.25 mm inner diameter × 30 m, stationary phase; 5% phenyl polydimethylsiloxane) was used as the GC column. The GC temperature was raised from 40°C (held for 3 minutes) to 320°C at a rate of 20°C / min. The injection port temperature was 300°C, the column flow rate was 1.5 mL / min, the ionization method was EI (electron ionization), the mass number range was m / z 10 to 800, and the analysis was performed at a scan rate of 0.5 sec / scan.

[0235] Synthesis Example 1 Synthesis of hydroxyl-containing diamine compounds

[0236] 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. After the addition was complete, the mixture was reacted at -15°C for 4 hours and then returned to room temperature. The precipitated white solid was separated by filtration and vacuum dried at 50°C.

[0237] 30 g of the solid was placed in a 300 mL stainless steel autoclave, dispersed in 250 mL of methyl cellosolve, and 2 g of 5% palladium-carbon was added. Hydrogen was introduced via a balloon, and a reduction reaction was carried out at room temperature. After approximately 2 hours, the balloon was confirmed to have ceased to deflate, indicating the reaction was complete. After completion of the reaction, the palladium compound serving as the catalyst was removed by filtration, and the mixture was concentrated using a rotary evaporator to obtain the hydroxyl-containing diamine compound represented by the following formula.

[0238] [Chemistry 11]

[0239]

[0240] Synthesis Example 2 Synthesis of polyimide precursor (A-1)

[0241] Under a dry nitrogen stream, 31.2 g (0.10 mol) of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (hereinafter referred to as ODPA) was dissolved in 500 g of NMP. 45.35 g (0.075 mol) of the hydroxyl-containing diamine compound obtained in Synthesis Example 1 and 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane were added to the mixture along with 50 g of NMP. The mixture was reacted at 20°C for 1 hour and then at 50°C for 2 hours. Next, 4.36 g (0.04 mol) of 4-aminophenol as a capping agent was added along with 5 g of NMP, and the mixture was reacted at 50°C for 2 hours. A solution of 28.6 g (0.24 mol) of N,N-dimethylformamide dimethyl acetal diluted with 50 g of NMP was then added. After the addition, the mixture was stirred at 50°C for 3 hours. After stirring, the solution was cooled to room temperature and 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 80°C for 24 hours to obtain the target alkali-soluble resin polyimide precursor (A-1).

[0242] Synthesis Example 3 Synthesis of polyimide (A-2)

[0243] Under a dry nitrogen stream, 29.3g (0.08 mol) of BAHF, 1.24g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane, and 3.27g (0.03 mol) of 3-aminophenol as a capping agent were dissolved in 150g of NMP. 31.0g (0.1 mol) of ODPA was added together with 50g of NMP, and the mixture was stirred at 20°C for 1 hour, and then at 50°C for 4 hours. Thereafter, 15g of xylene was added, and while water and xylene were azeotroped together, the mixture was stirred at 150°C for 5 hours. After the stirring was completed, the solution was poured into 3L of water and a white precipitate was collected. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 24 hours to obtain a polyimide (A-2) as an alkali-soluble resin.

[0244] Synthesis Example 4 Synthesis of polybenzoxazole precursor (A-3)

[0245] Under a dry nitrogen stream, 18.3 g (0.05 mol) of BAHF was dissolved in 50 g of NMP and 26.4 g (0.3 mol) of glycidyl methyl ether, and the solution was cooled to -15°C. A solution prepared by dissolving 7.4 g (0.025 mol) of diphenyl ether dicarboxylic acid dichloride (manufactured by Nippon Noyaku Co., Ltd.) and 5.1 g (0.025 mol) of isophthalic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 25 g of γ-butyrolactone (GBL) was added dropwise so that the internal temperature did not exceed 0°C. After the dropwise addition, stirring was continued at -15°C for 6 hours. After the reaction was completed, the solution was poured into 3 L of water containing 10% by mass of methanol, and a white precipitate was collected. The precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 80°C for 24 hours to obtain the target alkali-soluble resin, a polybenzoxazole (PBO) precursor (A-3).

[0246] Synthesis Example 5 Synthesis of polysiloxane (A-4)

[0247] To a 500 ml three-necked flask were added 44.86 g (0.200 mol) of p-phenylphenyltrimethoxysilane (St), 39.66 g (0.200 mol) of phenyltrimethoxysilane (Ph), 6.81 g (0.050 mol) of methyltrimethoxysilane (Me), 13.12 g (0.050 mol) of 3-trimethoxysilylpropylsuccinic anhydride (Suc), 0.522 g of TBC, and 74.58 g of propylene glycol monomethyl ether (hereinafter sometimes referred to as PGME). A phosphoric acid aqueous solution containing 0.448 g of phosphoric acid dissolved in 27.90 g of water (0.50 mass % relative to the added monomers) was added over 30 minutes while stirring at room temperature. The flask was then immersed in a 70°C oil bath and stirred for 90 minutes. The oil bath was then heated to 115°C over 30 minutes. One hour after the start of heating, the internal temperature of the three-necked flask (solution temperature) reached 100°C. The mixture was then heated and stirred for 2 hours (internal temperature 100°C to 110°C) to obtain a polysiloxane solution. Furthermore, nitrogen gas was circulated at 0.05 liters / minute during the heating and stirring. A total of 58.9 g of methanol and water, produced as by-products during the reaction, was distilled off. PGMEA was added to the resulting polysiloxane solution to a solids concentration of 40% by mass, to obtain a polysiloxane (A-4) solution.

[0248] Synthesis Example 6 Synthesis of naphthoquinone diazide-5-sulfonic acid ester compound (B-1)

[0249] Under a dry nitrogen flow, 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 naphthoquinonediazide-5-sulfonyl chloride were dissolved in 450 g of 1,4-dioxane and the temperature was set to room temperature. 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature in the system did not exceed 35°C. After the addition, stirring was performed at 30°C for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the precipitate was collected by filtration. The precipitate was dried using a vacuum dryer to obtain a quinonediazide compound (B-1) represented by the following formula.

[0250] [Chemistry 12]

[0251]

[0252] The compounds used in Examples and Comparative Examples are shown below.

[0253] B-2: PAG-103 (trade name, manufactured by BASF Japan)

[0254] C-1: TekP-4HBPA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.)

[0255] C-2: 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0256] C-3: 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0257] C-4: TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.)

[0258] C-5: Bisphenol P (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0259] C-6: Bisphenol M (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0260] C-7: 1,1,1-tris(4-hydroxyphenyl)ethane (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0261] C-8: 4,4′,4″-trihydroxytriphenylmethane (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0262] C-9: Bisphenol A (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0263] C-10: Bis(4-hydroxyphenyl)sulfone (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0264] [Chemistry 13]

[0265]

[0266] D-1: "Aronix (registered trademark)" M-923 (trade name, manufactured by Toagosei Co., Ltd.)

[0267] D-2: A-9300 (trade name, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0268] D-3: TEPIC-L (trade name, manufactured by Nissan Chemical Industries, Ltd.)

[0269] D-4: TEPIC-VL (trade name, manufactured by Nissan Chemical Industries, Ltd.)

[0270] E-1: HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.)

[0271] E-2: "Techmore (registered trademark)" VG3101L (trade name, manufactured by Printec)

[0272] [Chemistry 14]

[0273]

[0274] Example 1

[0275] 10.0 g of the polyimide precursor (A-1), 1.7 g of (B-1), 0.9 g of (C-7), and 1.5 g of (D-3) obtained in Synthesis Example 2 were dissolved in 56.4 g of PGME and 14.1 g of γ-butyrolactone (hereinafter referred to as GBL), and then filtered through a 0.2 μm polytetrafluoroethylene filter (manufactured by Sumitomo Electric Industries, Ltd.) to obtain a photosensitive resin composition A.

[0276] The obtained photosensitive resin composition was used to determine transmittance at 400 nm, yellowness index, exposure sensitivity, chemical resistance, and storage stability by the methods described in <Measurement of Visible Light Transmittance>, <Measurement of Yellowness Index>, <Evaluation of Chemical Resistance>, and <Evaluation of Storage Stability>, respectively.

[0277] Examples 2 to 26, Comparative Examples 1 to 12

[0278] Varnishes B to Y and a-1 were obtained by the same method as in Example 1, using the types and amounts of the compounds shown in Tables 1 to 3. Furthermore, transmittance at 400 nm (visible light transmittance), yellowness index, exposure sensitivity, chemical resistance, and storage stability were determined by the same method as in Example 1. The evaluation results are shown in Tables 1 to 3.

[0279] [Table 1]

[0280]

[0281] [Table 2]

[0282] [Table 2]

[0283]

[0284] [Table 3]

[0285]

[0286] Example 27

[0287] The IR spectrum of the cured film of the photosensitive resin composition T was measured by the method described in the above <Composition Analysis by FT-IR>. According to the obtained IR spectrum, at 1775 cm -1 ~1780cm -1 and 1720cm -1 ~1725cm -1 The peaks derived from the stretching vibration of the carbonyl group in the imide ring structure were obtained. -1 ~1705cm-1 and 1430cm -1 ~1475cm -1 A peak derived from the stretching vibration of the carbonyl group in the structure represented by formula (1) was obtained.

[0288] The thermal decomposition product of the cured film of the photosensitive resin composition T was analyzed using the method described in the above-mentioned <Composition Analysis by Pyrolysis GC / MS>. The analysis results showed that the structure obtained from the cured film was as follows: a peak attributable to the indene represented by formula (6) (450 seconds to 455 seconds), a peak attributable to the imide ring structure represented by formula (7) (840 seconds to 850 seconds), and a peak attributable to the structure represented by formula (8) (1035 seconds to 1045 seconds).

[0289] [Chemistry 15]

[0290]

[0291] From these results, it was confirmed that the cured film of the photosensitive resin composition T contained an imide ring structure, an indene structure, a structure represented by the formula (2), and a structure represented by the formula (1) in the film.

Claims

1. A photosensitive resin composition comprising: (A) alkali-soluble resin, (B) Photoacid generating materials, and (C) a compound having a phenolic hydroxyl group and having an octanol / water partition coefficient LogP of 4.6 to 20.0, hereinafter referred to as component (C), and The photosensitive resin composition has a transmittance at 400 nm of 80% or more and 99% or less at a thickness of 1.5 μm after thermal curing, and a yellowness index of 0.1 or more and 7.0 or less. The component (C) contains one or more compounds selected from the group consisting of compounds represented by formula (3) and compounds represented by formula (4). In formula (3), R 17 are independently methyl or a group represented by formula (5), and at least one R 17 is a group represented by formula (5), wherein c is an integer from 1 to 4, and * represents a bonding site. In formula (4), R 18 It is a divalent organic group having 1 to 10 carbon atoms, a and b are each independently an integer of 0 to 4, and a+b is 1 or greater.

2. The photosensitive resin composition according to claim 1, further comprising (D) a compound represented by formula (1), R 1 Each independently represents a monovalent organic group having 1 to 20 carbon atoms which may contain a heteroatom. 3 . The photosensitive resin composition according to claim 1 , which is used for a planarization layer and / or a pixel segmentation layer of an organic electroluminescent display device.

4. The photosensitive resin composition according to claim 3, wherein The organic electroluminescent display device is used in a mobile device that includes a camera and / or a sensor directly below the active area of ​​the organic electroluminescent display device. 5 . The photosensitive resin composition according to claim 1 , wherein the component (C) has a LogP of 8.0 to 15.

0. 6 . The photosensitive resin composition according to claim 1 , wherein the component (C) contains a compound having two or more cyclohexane ring structures in its molecule.

7. The photosensitive resin composition according to claim 2, wherein When the contents of the component (C) and the compound represented by the formula (1) (D) relative to 100 parts by mass of the total amount of the alkali-soluble resin (A) are denoted as Cm parts by mass and Dm parts by mass, respectively, the total content (Cm+Dm) is 20 parts by mass or more and 110 parts by mass or less, and the content ratio (Dm / Cm) is 1 / 9 to 9 / 1.

8. The photosensitive resin composition according to claim 2, wherein The compound represented by the formula (D) (1) comprises at least two R 1 is a compound containing a monovalent epoxy group, and / or (Db) at least two R in formula (1) 1 It is a monovalent compound containing an acrylic group and / or a hydroxyl group.

9. The photosensitive resin composition according to claim 2, wherein The compound represented by the formula (D) (1) comprises at least two R 1 is a compound containing a monovalent epoxy group, and (Db) at least two R 1 It is a compound containing a monovalent acrylic group and / or a hydroxyl group, and the mass ratio (Da) / (Db) thereof is 1 / 9 to 9 / 1.

10. The photosensitive resin composition according to claim 1 or 2, wherein The (A) alkali-soluble resin contains one or more alkali-soluble resins selected from the group consisting of polyimide, a polyimide precursor, polybenzoxazole, a polybenzoxazole precursor, and copolymers thereof. 11 . The photosensitive resin composition according to claim 1 , wherein the (B) photoacid generator contains naphthoquinone diazide sulfonic acid ester. 12 . A cured product obtained by curing the photosensitive resin composition according to claim 1 .

13. A method for manufacturing a hardened object, comprising: A step of applying the photosensitive resin composition according to any one of claims 1 to 11 on a substrate to form a resin film; The steps of drying the resin film, exposing the dried resin film to light, developing the exposed resin film, and heating the developed resin film to obtain a cured product are also included.

14. An organic electroluminescent display device comprising the cured product according to claim 12.

15. The organic electroluminescent display device according to claim 14, comprising at least: A substrate, a first electrode, a second electrode, an organic electroluminescent layer, a planarization layer and a pixel division layer, wherein the planarization layer and / or the pixel division layer contain the hardened material.

16. The organic electroluminescent display device according to claim 14 or 15, which is used in a mobile device comprising a camera and / or a sensor directly below the active area of ​​the organic electroluminescent display device.

17. The organic electroluminescent display device according to claim 15, wherein: The planarization layer and the pixel partitioning layer are each composed of a single layer or multiple layers, and at stacking interfaces of hardened materials forming the planarization layer and the pixel partitioning layer, a refractive index difference at a wavelength of 550 nm between the hardened materials forming the stacking interfaces is 0.3 or less at all stacking interfaces.

18. The organic electroluminescent display device according to claim 15 or 17, wherein: The planarization layer and the pixel division layer are each composed of a single layer or multiple layers. The planarization layer contains the cured product, and the pixel division layer contains a cured product of a photosensitive resin composition containing polysiloxane.

19. The organic electroluminescent display device according to claim 15 or 17, wherein: The planarization layer and the pixel division layer are each composed of a single layer or multiple layers. The planarization layer contains a cured product of a photosensitive resin composition containing polysiloxane, and the pixel division layer contains the cured product.

20. The organic electroluminescent display device according to claim 15 or 17, wherein: The planarization layer and the pixel partitioning layer are each composed of a single layer or multiple layers, and the planarization layer and the pixel partitioning layer contain the hardened material.

21. A semiconductor device comprising the hardened article according to claim 12.

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