Photosensitive resin composition, cured object, cured object manufacturing method, organic el display device, and display device

Abstract

The present invention addresses the problem of providing a photosensitive resin composition that has high sensitivity, that can form patterns without leaving any residues, and that has high storage stability when being frozen and stored.　A photosensitive resin composition according to the present invention contains: an alkali-soluble resin (a); ionic dyes (b) that form ion pairs of organic ions between molecules; and a photosensitive compound (c). There are n types of the ionic dyes (b) included in the photosensitive resin composition. There are (n+1) types of organic ions included in the photosensitive resin composition.

Description

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

[0001] The present invention relates to a photosensitive resin composition that can be suitably used for a planarizing layer, an insulating layer, or the like in an organic EL display device.

[0002] Many products using organic electroluminescence (hereinafter, "organic EL") display devices have been developed for display devices with thin displays, such as smartphones, tablet PCs, and televisions. Generally, organic EL display devices have a driving circuit, a planarization layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode on a substrate, and can emit light by applying a voltage between the opposing first and second electrodes. Among these, photosensitive resin compositions that can be patterned by ultraviolet irradiation are commonly used as materials for the planarization layer and the insulating layer. In particular, photosensitive resin compositions using polyimide-based resins are preferred because they have high heat resistance and generate little gas components from the cured product, allowing for the production of highly reliable organic EL display devices.

[0003] In recent years, with the aim of improving the light extraction efficiency of organic EL display devices, display devices with thinner polarizing plates or no polarizing plates have been developed, and there is a demand for reducing the visible light transmittance of insulating layers and planarizing layers in order to improve contrast.

[0004] Techniques for reducing the visible light transmittance of a cured product and increasing the blackness include adding a colorant such as carbon black, an organic or inorganic pigment, or a dye to a resin composition, as seen in black matrix materials for liquid crystal displays and RGB paste materials. Examples include a method of adding an esterified quinone diazide compound and at least one colorant selected from dyes, inorganic pigments, and organic pigments to an alkali-soluble heat-resistant resin (see Patent Document 1), a method of adding a quinone diazide compound and an acidic dye soluble in both an alkaline developer and an organic solvent to an alkali-soluble resin (see Patent Document 2), and a method of adding a photosensitizer and a yellow, red, or blue dye and / or pigment to an alkali-soluble resin made of polyimide and / or a polyimide precursor (see Patent Document 3).

[0005] JP 2004-145320 A JP 7-261015 A JP 2018-63433 A

[0006] The applicant's investigations revealed that using a nonionic dye as a colorant to increase the blackness results in problems such as reduced sensitivity and generation of residues, while using multiple types of ionic dyes that form intermolecular ion pairs results in problems such as poor storage stability during frozen storage.

[0007] In order to solve the above problems, the photosensitive resin composition of the present invention is a photosensitive resin composition containing an alkali-soluble resin (a), an ionic dye (b) that forms an ion pair between organic ions between its molecules, and a photosensitive compound (c), wherein n types of ionic dye (b) are contained, and the photosensitive resin composition contains (n+1) types of organic ions (n ​​is an integer from 2 to 10).

[0008] The photosensitive resin composition of the present invention has high sensitivity, can form a pattern without leaving any residue, and has high storage stability when stored in a freezer.

[0009] It is a cross-sectional view of an example of an organic EL display device.It is a cross-sectional view of an example of a display device.It is a schematic diagram of a manufacturing procedure of an organic EL display device in an example.

[0010] An embodiment of the present invention will now be described in detail.

[0011] The photosensitive resin composition of the present invention contains an alkali-soluble resin (a), an ionic dye (b) that forms ion pairs between organic ions intermolecularly, and a photosensitive compound (c), wherein the photosensitive resin composition contains n types of ionic dye (b), and the photosensitive resin composition contains (n+1) types of organic ions (n ​​represents an integer from 2 to 10). <Alkali-Soluble Resin (a)> The photosensitive resin composition of the present invention contains an alkali-soluble resin (a). The alkali-solubility of the resin refers to a dissolution rate of 50 nm / min or more, as determined from the film thickness reduction measured when 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 film thickness of 10 μm±0.5 μm, and the prebaked film is immersed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide at 23±1°C for 1 minute and then rinsed with pure water.

[0012] The alkali-soluble resin (a) has alkali solubility and therefore has hydroxyl groups and / or acidic groups in the structural units of the resin and / or at the ends of its main chain. The acidic groups may include, for example, carboxyl groups, phenolic hydroxyl groups, sulfonic acid groups, etc.

[0013] Examples of the alkali-soluble resin (a) include, but are not limited to, polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, polyamideimide precursor, polyamide, polymer of a radically polymerizable monomer having an acidic group, and phenolic resin. The photosensitive resin composition of the present invention may contain two or more of these resins. Among these alkali-soluble resins (a), one or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, polyamideimide precursor, and copolymers thereof are preferred, as they have high development adhesion, excellent heat resistance, and low outgassing at high temperatures, resulting in high long-term reliability when the cured product is used in an organic EL display device. Polyimide, polyimide precursor, polybenzoxazole precursor, or copolymers thereof are more preferred. Furthermore, from the viewpoint of further improving sensitivity, polyimide precursor or polybenzoxazole precursor is even more preferred. Here, the polyimide precursor refers to a resin that can be converted to polyimide by heat treatment or chemical treatment, and may contain, for example, polyamic acid, polyamic acid ester, etc. The polybenzoxazole precursor refers to a resin that can be converted into polybenzoxazole by heat treatment or chemical treatment, and can contain, for example, polyhydroxyamide.

[0014] The polyimide precursor and polybenzoxazole precursor described above have a structural unit represented by the following formula (2), and the polyimide has a structural unit represented by the following formula (3). Two or more of these may be contained, or a resin in which the structural unit represented by formula (2) and the structural unit represented by formula (3) are copolymerized may be contained.

[0015]

[0016] In formula (2), X represents a divalent to octavalent organic group having 4 to 40 carbon atoms, and Y represents a divalent to elevenvalent organic group having 6 to 40 carbon atoms. １１ and R １３ R each independently represents a hydroxyl group or a sulfonic acid group. １２ and R １４each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. t, u, and w represent integers of 0 to 3, and v represents an integer of 0 to 6. However, when the structural unit represented by formula (2) represents a structural unit of a polyimide precursor, u≧2; when the structural unit represented by formula (2) represents a structural unit of a polybenzoxazole precursor, v≧2; and when a plurality of R １３ At least two of these are hydroxyl groups.

[0017]

[0018] In formula (3), E represents a tetravalent to decavalent organic group having 4 to 40 carbon atoms, and G represents a divalent to octavalent organic group having 6 to 40 carbon atoms. １５ and R １６ each independently represents a carboxy group, a sulfonic acid group, or a hydroxyl group, and x and y each independently represent an integer of 0 to 6, provided that x+y>0.

[0019] The polyimide, polyimide precursor, polybenzoxazole precursor, or copolymer thereof preferably has 5 to 100,000 structural units represented by formula (2) or formula (3). In addition to the structural units represented by formula (2) or formula (3), other structural units may be contained. In this case, it is preferable that the structural units represented by formula (2) or formula (3) account for 50 mol % or more of the total structural units. In the above formula (2), X(R １１ ) ｔ (COOR １２ ) ｕ represents an acid residue. X is a divalent to octavalent organic group having 4 to 40 carbon atoms, and is preferably a divalent to octavalent organic group containing an aromatic ring or a cycloaliphatic group.

[0020] X (R １１ ) ｔ (COOR １２ ) ｕExamples of the acid residues represented by the formula (I) include residues of dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, and triphenyl dicarboxylic acid; residues of tricarboxylic acids such as trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, and biphenyl tricarboxylic acid; residues of pyromellitic acid, 3,3',4,4'-biphenyl tetracarboxylic acid, 2,3,3',4'-biphenyl tetracarboxylic acid, 2,2',3,3'-biphenyl tetracarboxylic acid, 3,3',4,4'-benzophenone tetracarboxylic acid, 2,2',3,3'-benzophenone tetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, and 2,2-bis(2,3-dicarboxyl) Examples of the X(R tetracarboxylic acid residue include tetracarboxylic acids such as 1,1-bis(3,4-dicarboxyphenyl)hexafluoropropane, 1,1-bis(3,4-dicarboxyphenyl)ethane, 1,1-bis(2,3-dicarboxyphenyl)ethane, bis(3,4-dicarboxyphenyl)methane, bis(2,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, and aromatic tetracarboxylic acids having the structure represented by the following formula (4) or (5), aliphatic tetracarboxylic acids such as butanetetracarboxylic acid, and aliphatic tetracarboxylic acids containing a cyclic aliphatic group such as 1,2,3,4-cyclopentanetetracarboxylic acid. １１ ) ｔ (COOR １２ ) ｕ may have two or more of these residues.

[0021]

[0022] In formula (4), R ２０ is an oxygen atom, C(CF ３ ) ２ or C(CH ３ ) ２ In addition, in formulas (4) and (5), R ２１ and R２２ each independently represents a hydrogen atom or a hydroxyl group.

[0023] In the case of a tricarboxylic acid or tetracarboxylic acid residue among the acid residues in the above formula (2), one or two carboxy groups are (COOR １２ ) is equivalent to

[0024] In the above formula (3), E(R １５ ) ｘ represents a residue of an acid dianhydride. E is a tetravalent to decavalent organic group having 4 to 40 carbon atoms, and is preferably an organic group containing an aromatic ring or a cycloaliphatic group.

[0025] E(R １５ ) ｘSpecific examples of the residue of the acid dianhydride represented by the formula (I) include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)ether Examples of the dianhydride include aromatic tetracarboxylic dianhydrides such as 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, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, and acid dianhydrides having a structure represented by the following formula (6) or (7), aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic dianhydride, and residues of aliphatic tetracarboxylic dianhydrides containing a cyclic aliphatic group such as 1,2,3,4-cyclopentanetetracarboxylic dianhydride. １５ ) ｘ may have two or more of these residues.

[0026]

[0027] In formula (6), R ２０ is an oxygen atom, C(CF ３ ) ２ or C(CH ３ ) ２ In addition, in formulas (6) and (7), R ２１ and R２２ each independently represents a hydrogen atom or a hydroxyl group.

[0028] Y(R １３ ) ｖ (COOR １４ ) ｗ and G(R １６ ) ｙ represents a residue of a diamine. Y is a di- to eleven-valent organic group having 6 to 40 carbon atoms, and is preferably a di- to eleven-valent organic group containing an aromatic ring or a cycloaliphatic group. G is a di- to octa-valent organic group having 6 to 40 carbon atoms, and is preferably a di- to octa-valent organic group containing an aromatic ring or a cycloaliphatic group.

[0029] Y (R １３ ) ｖ (COOR １４ ) ｗ and G(R １６ ) ｙSpecific examples of the diamine residue represented by the formula (I) include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, and 3,3'-diethyl-4,4'-diaminobiphenyl. The amine compound may contain residues of aromatic diamines such as 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-di(trifluoromethyl)-4,4'-diaminobiphenyl, 9,9-bis(4-aminophenyl)fluorene, 2,2'-bis(trifluoromethyl)-5,5'-dihydroxybenzidine, 3,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, and compounds in which at least a portion of the hydrogen atoms in the aromatic rings of these compounds are substituted with alkyl groups or halogen atoms; residues of aliphatic diamines containing cyclic aliphatic groups such as cyclohexyldiamine and methylenebiscyclohexylamine; and residues of diamines having a structure represented by the following chemical formula group (8). １３ ) ｖ (COOR １４ ) ｗ and G(R １６ ) ｙ may have two or more of these residues.

[0030]

[0031] In chemical formula group (8), R ２０ is an oxygen atom, C(CF ３ ) ２ or C(CH ３ ) ２ In addition, in the chemical formula group (8), R ２１~R ２４ each independently represents a hydrogen atom or a hydroxyl group. The terminals of these resins may be blocked with a known monoamine, acid anhydride, acid chloride, monocarboxylic acid, or active ester compound having an acidic group.

[0032] The alkali-soluble resin (a) may be synthesized by a known method. Examples of methods for producing polyamic acid, a polyimide precursor, include reacting a tetracarboxylic dianhydride with a diamine compound in a solvent at low temperature. Examples of methods for producing polyamic acid esters, which are also polyimide precursors, include the aforementioned method of reacting a polyamic acid with an esterifying agent, as well as methods for obtaining a diester from a tetracarboxylic dianhydride with an alcohol, followed by reaction with an amine in a solvent in the presence of a condensing agent, and methods for obtaining a diester from a tetracarboxylic dianhydride with an alcohol, followed by conversion of the remaining dicarboxylic acid into an acid chloride, followed by reaction with an amine in a solvent. From the perspective of ease of synthesis, it is preferable to include a step of reacting a polyamic acid with an esterifying agent. The esterifying agent is not particularly limited, and known methods can be used, but N,N-dimethylformamide dialkyl acetal is preferred because it facilitates purification of the resulting resin.

[0033] Examples of methods for producing polyhydroxyamide, a polybenzoxazole precursor, include a method of condensing a bisaminophenol compound with a dicarboxylic acid in a solvent. Specifically, examples include a method of reacting a dehydration condensation agent such as dicyclohexylcarbodiimide (DCC) with an acid and then adding a bisaminophenol compound. Examples include a method of adding a dicarboxylic acid dichloride solution dropwise to a solution of a bisaminophenol compound to which a tertiary amine such as pyridine has been added. Examples of methods for producing polyimide include a method of dehydrating and ring-closing the polyamic acid or polyamic acid ester obtained by the above-mentioned method in a solvent. Examples of methods for dehydration and ring-closing include chemical treatment with an acid or base, and heat treatment.

[0034] Examples of methods for producing polybenzoxazole include a method in which polyhydroxyamide obtained by the above-mentioned method is dehydrated and cyclized in a solvent. Examples of methods for dehydration and cyclization include chemical treatment with an acid or a base, and heat treatment. Examples of polyamideimide precursors include polymers of tricarboxylic acids, corresponding tricarboxylic acid anhydrides, tricarboxylic acid anhydride halides, and diamine compounds, with polymers of trimellitic anhydride chloride and aromatic diamine compounds being preferred. Examples of methods for producing polyamideimide precursors include a method in which tricarboxylic acids, corresponding tricarboxylic acid anhydrides, tricarboxylic acid anhydride halides, etc. are reacted with diamine compounds in a solvent at low temperature.

[0035] Examples of methods for producing polyamideimide include a method of reacting trimellitic anhydride with an aromatic diisocyanate in a solvent, and a method of dehydrating and cyclizing the polyamideimide precursor obtained by the above method in a solvent. Examples of methods for dehydrating and cyclizing include chemical treatment with an acid or a base, and heat treatment.

[0036] Examples of polymers of radically polymerizable monomers include acrylic resins and polyhydroxystyrene resins. Known materials can be used as radically polymerizable monomers, including, for example, o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene, as well as alkyl- and alkoxy-substituted derivatives thereof, methacrylic acid and acrylic acid, and derivatives thereof substituted with haloalkyl, alkoxy, halogen, nitro, or cyano at the α-position. Of these, o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene, as well as alkyl- and alkoxy-substituted derivatives thereof, are particularly preferred in terms of sensitivity and resolution during patterning, film remaining rate after development, heat distortion resistance, solvent resistance, adhesion to the base, solution storage stability, and the like. These may be used alone or in combination of two or more.

[0037] Other radical polymerizable monomers that can be used include known materials such as styrene, alkyl, alkoxy, halogen, haloalkyl, nitro, cyano, amide, and ester substitutions at the α-, o-, m-, or p-position of styrene, diolefins such as butadiene and isoprene, and esterified products of methacrylic acid or acrylic acid. These can be used alone or in combination of two or more.

[0038] The polymerization solvent is not particularly limited, and examples thereof include alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether, alkyl acetates such as propyl acetate, butyl acetate and isobutyl acetate, ketones such as methyl isobutyl ketone and methyl propyl ketone, alcohols such as butyl alcohol and isobutyl alcohol, ethyl lactate, butyl lactate, dipropylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, 3-methoxybutyl acetate, ethylene glycol monoethyl ether acetate, gamma butyrolactone, N-methyl-2-pyrrolidone, diacetone alcohol, N-cyclohexyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, di It may contain methyl sulfoxide, propylene glycol monomethyl ether acetate, N,N-dimethylisobutyric acid amide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, 1,3-dimethyl-2-imidazolidinone, N,N-dimethylpropylene urea, delta valerolactone, 2-phenoxyethanol, 2-pyrrolidone, 2-methyl-1,3-propanediol, diethylene glycol butyl ether, triacetin, butyl benzoate, cyclohexylbenzene, bicyclohexyl, o-nitroanisole, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, N-(2-hydroxyethyl)-2-pyrrolidone, N,N-dimethylpropanamide, N,N-dimethylisobutyric acid amide, N,N,N',N'-tetramethylurea, 3-methyl-2-oxazolidinone, and the like.

[0039] <Ionic dye (b) that forms intermolecular ion pairs of organic ions> The photosensitive resin composition of the present invention further contains n types of ionic dye (b) (hereinafter, sometimes referred to as ionic dye (b)) that form intermolecular ion pairs of organic ions, and the photosensitive resin composition contains (n+1) types of organic ions. Here, n represents an integer from 2 to 10, and the organic ion represents an ion of an organic compound containing carbon. When the photosensitive resin composition contains n types of ionic dye (b) whose organic anion moieties and organic cation moieties are different, the photosensitive resin composition contains (n×2) types of organic ions. In this case, the presence of multiple types of organic anions and organic cations in the photosensitive resin composition can lead to ion exchange between the ionic dyes, resulting in an increase in foreign matter during frozen storage and a deterioration in storage stability. On the other hand, the photosensitive resin composition of the present invention contains n types of ionic dye (b) and contains (n+1) types of organic ions, thereby maintaining sensitivity and reducing residues while improving storage stability during frozen storage. This is presumably because the organic ion species for ionic dye (b) are limited, thereby suppressing ion exchange between ionic dyes in the photosensitive resin composition.

[0040] In a first embodiment, n types of ionic dyes (b) are contained, and the photosensitive resin composition contains (n+1) types of organic ions. Examples of such a first embodiment include a case where the organic anion moieties or organic cation moieties of the n types of ionic dyes (b) are all identical. For example, when n is 3, this represents a case where either the organic anion moieties or the organic cation moieties of Ionic Dye 1, Ionic Dye 2, and Ionic Dye 3 are all identical. Furthermore, when n is ≥ 3, a second embodiment includes a case where two or more types of organic anion moieties and organic cation moieties of the n types of ionic dyes (b) are identical. For example, when n is 3, this represents a case where the organic anion moieties of Ionic Dye 1 and Ionic Dye 2 are identical, and the organic cation moieties of Ionic Dye 1 and Ionic Dye 3 are identical. The first embodiment is preferred from the viewpoint of suppressing ion exchange between ionic dyes and improving storage stability during frozen storage. From the viewpoint of improving storage stability, n is preferably 2 to 5, more preferably 2 to 3, and even more preferably 2.

[0041] The ionic dye (b) in the present invention, which forms an ion pair between organic ions between its molecules, refers to a salt-forming compound consisting of an organic anion moiety of an acid dye and an organic cation moiety of a non-dye, a salt-forming compound consisting of an organic cation moiety of a basic dye and an organic anion moiety of a non-dye, or a salt-forming compound consisting of an organic anion moiety of an acid dye and an organic cation moiety of a basic dye.From the viewpoint of improving sensitivity by increasing the proportion of coloring components per molecule and reducing the amount of ionic dye added, it is preferred that the ionic dye of the present invention contains a salt-forming compound consisting of an organic anion moiety of an acid dye and an organic cation moiety of a basic dye.

[0042] A salt-forming compound consisting of an organic anion moiety of an acid dye and an organic cation moiety of a non-dye can be produced by using an acid dye as a raw material and exchanging the counter cation with an organic cation of a non-dye by a known method. A salt-forming compound consisting of an organic cation moiety of a basic dye and an organic anion moiety of a non-dye can be produced by using a basic dye as a raw material and exchanging the counter anion with an organic anion of a non-dye by a known method. A salt-forming compound consisting of an organic anion moiety of an acid dye and an organic cation moiety of a basic dye can be produced by using an acid dye and a basic dye as raw materials and exchanging the counter ions of each dye by a known method.

[0043] Acid dyes, which are raw materials for ionic dye (b), are compounds having acidic substituents such as sulfo or carboxy groups in the dye molecule, or anionic water-soluble dyes that are salts of these. Acid dyes include those that have acidic substituents such as sulfo or carboxy groups and are classified as direct dyes.

[0044] Examples of acid dyes include C.I. Acid Yellow 1, 17, 18, 23, 25, 36, 38, 42, 44, 54, 59, 72, 78, 151; C.I. Acid Orange 7, 10, 12, 19, 20, 22, 28, 30, 52, 56, 74, 127; C.I. Acid Red 1, 3, 4, 6, 8, 11, 12, 14, 18, 26, 27, 33, 37, 53, 57, 88, 106, 108, 111, 114, 131, 137, 138, 151, 154, 158, 159, 173, 184, 186, 215, 257, 266, 296, 337; C.I. Acid Brown 2, 4, 13, 248; C.I. Acid Violet 11, 56, 58; C.I. Azo acid dyes such as Acid Blue 92, 102, 113, 117; C.I. Quinoline acid dyes such as Acid Yellow 2, 3, 5; C.I. Xanthene acid dyes such as Acid Red 50, 51, 52, 87, 91, 92, 93, 94, 289; C.I. Acid Red 82, 92; C.I. Acid Violet 41, 42, 43; C.I. Acid Blue 14, 23, 25, 27, 40, 45, 78, 80, 127:1, 129, 145, 167, 230; C.I. Anthraquinone acid dyes such as Acid Green 25, 27; C.I. Examples of suitable acid dyes include triarylmethane acid dyes such as C.I. Acid Violet 49; C.I. Acid Blue 7, 9, 22, 83, 90; C.I. Acid Green 9, 50; and C.I. Food Green 3; phthalocyanine acid dyes such as C.I. Acid Blue 249; and indigoid acid dyes such as C.I. Acid Blue 74. Among these, the acid dye preferably contains a xanthene acid dye in terms of high heat resistance. The xanthene acid dye more preferably contains a rhodamine acid dye such as C.I. Acid Red 50, 52, or 289.

[0045] The organic cation moiety of the non-dye that is the raw material for the ionic dye (b) is an ammonium ion [N(R) ４ ] ＋ , phosphonium ion [P(R) ４ ] ＋ , iminium ion [(R) ２ -N=C(R) ２ ] ＋, arsonium ion [As(R) ４ ] ＋ , stibonium ion [Sb(R) ４ ] ＋ , oxonium ion [O(R) ３ ] ＋ , sulfonium ion [S(R) ３ ] ＋ , selenonium ion [Se(R) ３ ] ＋ , stannonium ion [Sn(R) ３ ] ＋ , iodonium ion [I(R) ２ ] ＋ , diazonium ion [R-N ＋ From the viewpoint of insulating properties when a cured product made of the photosensitive resin composition of the present invention is used, an ammonium ion [N(R) ４ ] ＋ , phosphonium ion [P(R) ４ ] ＋ , iminium ion [(R) ２ -N=C(R) ２ ] ＋ In the ionic formula, R's each independently represent a hydrocarbon group having 1 to 20 carbon atoms, which may have a substituent and which may have a heteroatom in the carbon chain. From the viewpoint of improving sensitivity by increasing the proportion of coloring component per molecule and reducing the amount of ionic dye added, the molecular weight of the non-dye organic cation moiety is preferably 1,000 or less, more preferably 700 or less, and even more preferably 400 or less. There is no particular restriction on the lower limit of the molecular weight of the non-dye organic cation moiety, but it is preferably 1 or more, and even more preferably 100 or more.

[0046] The basic dye, which is the raw material for the ionic dye (b), is a compound having a basic group such as an amino group or an imino group in the molecule, or a salt thereof, and is a dye that becomes a cation in an aqueous solution.

[0047] Examples of basic dyes include C.I. Basic Red 17, 22, 23, 25, 29, 30, 38, 39, 46, 46:1, 82; C.I. Basic Orange 2, 24, 25; C.I. Basic Violet 18; C.I. Basic Yellow 15, 24, 25, 32, 36, 41, 73, 80; C.I. Basic Brown 1; C.I. Basic Blue 41, 54, 64, 66, 67, 129 and other azo-based basic dyes; C.I. Basic Red 1, 2; C.I. Basic Violet 10, 11 and other xanthene-based basic dyes; C.I. Basic Yellow 11, 13, 21, 23, 28; C.I. Basic Orange 21; C.I. Basic Red 13, 14; C.I. Examples of the basic dye include methine-based basic dyes such as C.I. Basic Violet 16 and 39; anthraquinone-based basic dyes such as C.I. Basic Blue 22, 35, 45 and 47; C.I. Basic Violet 1, 2, 3, 4, 13, 14 and 23; C.I. Basic Blue 1, 5, 7, 8, 11, 15, 18, 21, 24 and 26; C.I. Basic Green 1 and 4; and xanthene-based basic dyes having a structure represented by the following formula (9) or (10).

[0048]

[0049] In formulas (9) and (10), R ２５ ~R ３１ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms which may have a substituent. Among these, the basic dye preferably contains a xanthene basic dye or a triarylmethane basic dye in terms of increasing the blackness of the cured film, and preferably contains a xanthene acid dye in terms of high heat resistance.

[0050] The organic anion moiety of the non-dye that is the raw material for the ionic dye (b) includes aliphatic or aromatic sulfonate ions, aliphatic or aromatic carboxylate ions, and sulfonimide anions [(RSO ２ ) ２ N] ― , borate anion (BR ４ ) ―Examples include: From the viewpoint of suppressing deterioration of electrodes and light-emitting layers of organic EL display devices when a cured product made from the photosensitive resin composition of the present invention is applied, the anion compound is preferably an aliphatic or aromatic sulfonate ion or an aliphatic or aromatic carboxylate ion. Furthermore, from the viewpoint of increasing sensitivity and reducing residues, an aliphatic or aromatic sulfonate ion is preferred. Note that R in the ionic formula is a hydrocarbon group having 1 to 20 carbon atoms, which may each independently have a substituent and may have a heteroatom in the carbon chain. From the viewpoint of improving sensitivity by increasing the proportion of coloring components per molecule and reducing the amount of ionic dye added, the molecular weight of the non-dye organic anion moiety is preferably 1,000 or less, more preferably 700 or less, and even more preferably 400 or less. The lower limit of the molecular weight of the non-dye anion moiety is not particularly limited, but is preferably 1 or more, and even more preferably 100 or more.

[0051] From the viewpoint of high heat resistance, the organic anion moiety and / or the organic cation moiety of the ionic dye (b) preferably have a xanthene skeleton. By using the ionic dye (b) having high heat resistance, the change in OD value can be reduced even when the photosensitive resin composition of the present invention is repeatedly cured.

[0052] Examples of organic anions having a xanthene skeleton include the above-mentioned xanthene acid dyes, and examples of organic cations having a xanthene skeleton include the above-mentioned xanthene basic dyes. Of the n types of ionic dyes (b), it is preferred that at least one has a xanthene skeleton in the organic anion moiety and / or organic cation moiety, and when n≧3, it is more preferred that at least two have a xanthene skeleton in the organic anion moiety and / or organic cation moiety, and it is even more preferred that all of the n types have a xanthene skeleton in the organic anion moiety and / or organic cation moiety.

[0053] The ionic dye (b) preferably has an acidic group, such as at least one selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a sulfonate group, from the viewpoint of increasing alkali solubility during development and improving sensitivity. The acidic group may be, for example, at least one selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a sulfonate group, and a sulfonic acid group and / or a sulfonate group is particularly preferred.

[0054] A salt-forming compound obtained by ion exchange of an acid dye or a basic dye can be produced by a known method. For example, an aqueous solution of an acid dye and an aqueous solution of a basic dye are separately prepared, and the two are slowly mixed with stirring to produce a salt-forming compound consisting of the organic anion moiety of the acid dye and the organic cation moiety of the basic dye as a precipitate. The salt-forming compound can be obtained by recovering the precipitate by filtration. The obtained salt-forming compound is preferably dried at about 60 to 70°C.

[0055] The total content of the two or more ionic dyes (b) contained in the photosensitive resin composition of the present invention is preferably 0.1 to 300 parts by mass, more preferably 0.2 to 200 parts by mass, and particularly preferably 1 to 200 parts by mass, relative to 100 parts by mass of the alkali-soluble resin (a). By making the content of the ionic dye (b) 0.1 parts by mass or more, light of the corresponding wavelength can be absorbed. Furthermore, by making the content 300 parts by mass or less, light of the corresponding wavelength can be absorbed while maintaining the adhesion strength between the photosensitive colored resin film and the substrate, the heat resistance of the film after heat treatment, and the mechanical properties.

[0056] The ionic dye (b) of the present invention preferably includes an ionic dye (b1) (hereinafter, may be referred to as ionic dye (b1)) having a maximum absorption wavelength in the range of 490 nm or more and less than 580 nm in the wavelength range of 350 to 800 nm, and an ionic dye (b2) (hereinafter, may be referred to as ionic dye (b2)) having a maximum absorption wavelength in the range of 580 nm or more and less than 800 nm in the wavelength range of 350 to 800 nm.

[0057] The ionic dye (b1) has a maximum absorption wavelength in the range of 490 nm or more and less than 580 nm in the wavelength range of 350 to 800 nm, and therefore examples thereof include red dyes and violet dyes.

[0058] The ionic dye (b2) has a maximum absorption wavelength in the range of 580 nm or more and 800 nm or less in the range of 350 to 800 nm, and examples thereof include blue dyes and green dyes.

[0059] In the photosensitive resin composition of the present invention, the ionic dye (b) may contain an ionic dye (b3) (hereinafter, sometimes referred to as ionic dye (b3)) having a maximum absorption wavelength in the range of 400 nm or more and less than 490 nm in the wavelength range of 350 to 800 nm. By containing the ionic dye (b3) in addition to the ionic dye (b1) and the ionic dye (b2), the photosensitive resin composition of the present invention can reduce the visible light transmittance of the cured product and produce a black color. Since the ionic dye (b3) has a maximum absorption wavelength in the range of 400 nm or more and less than 490 nm, examples of suitable dyes include yellow dyes and orange dyes.

[0060] <Photosensitive Compound (c)> The photosensitive resin composition of the present invention further contains a photosensitive compound (c). From the viewpoint of achieving high sensitivity, the content of the photosensitive compound (c) is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 10 parts by mass or more, per 100 parts by mass of the alkali-soluble resin (a). On the other hand, from the viewpoint of long-term reliability when the cured product of the present invention is used as a planarization layer and / or insulating layer of an organic EL display device, the content is preferably 100 parts by mass or less. The photosensitive compound (c) may contain a photoacid generator (c1), a photopolymerization initiator (c2), or the like. The photoacid generator (c1) is a compound that generates an acid upon irradiation with light, and the photopolymerization initiator (c2) is a compound that undergoes bond cleavage and / or reaction upon exposure to generate radicals.

[0061] By including a photoacid generator (c1), acid is generated in the light-irradiated areas, increasing the solubility of the light-irradiated areas in an alkaline aqueous solution, thereby obtaining a positive-tone relief pattern in which the light-irradiated areas are dissolved. Furthermore, by including a photoacid generator (c1) and an epoxy compound or a thermal crosslinking agent described below, the acid generated in the light-irradiated areas promotes the crosslinking reaction of the epoxy compound or the thermal crosslinking agent, thereby obtaining a negative-tone relief pattern in which the light-irradiated areas are insolubilized. On the other hand, by including a photopolymerization initiator (c2) and a radically polymerizable compound described below, radical polymerization proceeds in the light-irradiated areas, thereby obtaining a negative-tone relief pattern in which the light-irradiated areas are insolubilized. From the viewpoint of being able to form a fine pattern when the cured product of the present invention is used as a planarizing layer and / or insulating layer in an organic EL display device, it is preferable that the photosensitive compound (c) contains a photoacid generator (c1) capable of obtaining a positive-tone relief pattern.

[0062] The photoacid generator (c1) may include, for example, a quinone diazide compound. The photosensitive resin composition of the present invention preferably includes two or more types of photoacid generator (c1). When two or more types are included, a photosensitive resin composition with higher sensitivity can be obtained.

[0063] The quinone diazide compound may include a compound in which a sulfonic acid of quinone diazide is bonded to a polyhydroxy compound via an ester bond, a compound in which a sulfonic acid of quinone diazide is bonded to a polyamino compound via a sulfonamide bond, or a compound in which a sulfonic acid of quinone diazide is bonded to a polyhydroxypolyamino compound via an ester bond and / or a sulfonamide bond.

[0064] As the quinone diazide structure, either a 5-naphthoquinone diazide sulfonyl group or a 4-naphthoquinone diazide sulfonyl group is preferably used. A naphthoquinone diazide sulfonyl ester compound having a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule may be contained, or a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound may be contained. 4-naphthoquinone diazide sulfonyl ester compounds have absorption in the i-line region of a mercury lamp and are suitable for i-line exposure. 5-naphthoquinone diazide sulfonyl ester compounds have absorption extending to the g-line region of a mercury lamp and are suitable for g-line exposure.

[0065] It is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazide sulfonyl ester compound depending on the wavelength of exposure, but from the viewpoint of increasing sensitivity, it is preferable to include a 4-naphthoquinone diazide sulfonyl ester compound.

[0066] The quinone diazide compound can be synthesized by any esterification reaction of a compound having a phenolic hydroxyl group and a quinone diazide sulfonic acid compound. The use of such a quinone diazide compound further improves resolution, sensitivity, and film retention.

[0067] The content of the photoacid generator (c1) is preferably 0.1 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 25 parts by mass or more, per 100 parts by mass of the alkali-soluble resin (a) from the viewpoint of increasing sensitivity, while being preferably 100 parts by mass or less from the viewpoint of long-term reliability when the cured product of the present invention is used as a planarizing layer and / or insulating layer of an organic EL display device.

[0068] Examples of the photopolymerization initiator (c2) include a benzyl ketal photopolymerization initiator, an α-hydroxyketone photopolymerization initiator, an α-aminoketone photopolymerization initiator, an acylphosphine oxide photopolymerization initiator, an oxime ester photopolymerization initiator, an acridine photopolymerization initiator, a titanocene photopolymerization initiator, a benzophenone photopolymerization initiator, an acetophenone photopolymerization initiator, an aromatic ketoester photopolymerization initiator, and a benzoate ester photopolymerization initiator. The photosensitive resin composition of the present invention may contain two or more types of photopolymerization initiator (c2). From the viewpoint of further improving sensitivity, it is more preferable that the photopolymerization initiator (c2) contains an α-aminoketone photopolymerization initiator, an acylphosphine oxide photopolymerization initiator, or an oxime ester photopolymerization initiator.

[0069] Examples of the α-aminoketone photopolymerization initiator include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-butan-1-one, and 3,6-bis(2-methyl-2-morpholinopropionyl)-9-octyl-9H-carbazole.

[0070] Examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphine oxide.

[0071] Examples of the oxime ester photopolymerization initiator include 1-phenylpropane-1,2-dione-2-(O-ethoxycarbonyl)oxime, 1-phenylbutane-1,2-dione-2-(O-methoxycarbonyl)oxime, 1,3-diphenylpropane-1,2,3-trione-2-(O-ethoxycarbonyl)oxime, 1-[4-(phenylthio)phenyl]octane-1,2-dione-2-(O-benzoyl)oxime, 1-[4-[4-(carboxyphenyl)thio]phenyl]propane-1,2-dione-2-(O-acetyl)oxime, 1-[9- It may contain ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyl)oxime, 1-[9-ethyl-6-[2-methyl-4-[1-(2,2-dimethyl-1,3-dioxolan-4-yl)methyloxy]benzoyl]-9H-carbazol-3-yl]ethanone-1-(O-acetyl)oxime, or 1-(9-ethyl-6-nitro-9H-carbazol-3-yl)-1-[2-methyl-4-(1-methoxypropan-2-yloxy)phenyl]methanone-1-(O-acetyl)oxime.

[0072] From the viewpoint of increasing sensitivity, the content of the photopolymerization initiator (c2) is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 10 parts by mass or more, relative to 100 parts by mass of the total of the alkali-soluble resin (a) and the radically polymerizable compound described below. On the other hand, from the viewpoint of further improving resolution and reducing the taper angle, it is preferably 50 parts by mass or less.

[0073] <Colorant (d)> The photosensitive resin composition of the present invention may contain a colorant (d) other than the ionic dye (b). By incorporating the colorant (d) in addition to the ionic dye (b), the composition can be provided with light-blocking properties, i.e., blocking light of a wavelength absorbed by the colorant (d) from light transmitted through or reflected from a film of the photosensitive resin composition. By providing light-blocking properties, when the cured product of the present invention described below is used as a planarizing layer and / or insulating layer in an organic EL display device, deterioration, malfunction, leakage current, and the like due to light penetration into TFTs can be prevented. Furthermore, external light reflection from wiring and TFTs can be suppressed, and the contrast between light-emitting and non-light-emitting areas can be improved.

[0074] As the colorant (d), it is preferable to use a nonionic dye (d1) and / or a pigment (d2). It is preferable to contain at least one type of colorant (d). For example, it is preferable to contain one type of dye or organic pigment, or two or more types of dyes or pigments, or one or more types of dyes and one or more types of pigments. The nonionic dye (d1) may be, for example, an oil-soluble dye, a disperse dye, or the like. From the viewpoint of solvent solubility, the nonionic dye (d1) is preferred as the colorant (d) in the present invention. On the other hand, from the viewpoint of suppressing fading of the colorant during the heat treatment step of the photosensitive resin composition of the present invention described below, the pigment (d2) is preferred.

[0075] The colorant (d) used in the photosensitive resin composition of the present invention is preferably a colorant (d-1) having a maximum absorption wavelength in the range of 400 nm or more and less than 490 nm in the range of 350 to 800 nm, a colorant (d-2) having a maximum absorption wavelength in the range of 490 nm or more and less than 580 nm, or a colorant (d-3) having a maximum absorption wavelength in the range of 580 nm or more and less than 800 nm, and these may be used in combination.

[0076] In the present invention, from the viewpoints of storage stability and fading during curing and light irradiation, the colorant (d) preferably contains a dye that is soluble in an organic solvent that dissolves the alkali-soluble resin (a) and is compatible with the resin, and a dye that has high heat resistance and light fastness.

[0077] Examples of the skeletal structure of the nonionic dye (d1) include, but are not limited to, anthraquinone-based, azo-based, phthalocyanine-based, methine-based, oxazine-based, quinoline-based, triarylmethane-based, and xanthene-based. Among these, anthraquinone-based, azo-based, methine-based, triarylmethane-based, and xanthene-based are preferred from the viewpoints of solubility in organic solvents and heat resistance. Xanthene-based is more preferred from the viewpoint of high heat resistance.

[0078] The content of the colorant (d) is preferably 0.1 to 300 parts by mass, more preferably 0.2 to 200 parts by mass, and particularly preferably 1 to 200 parts by mass, per 100 parts by mass of the alkali-soluble resin (a). By setting the content of the colorant (d) to 0.1 parts by mass or more, light of the corresponding wavelength can be absorbed. Furthermore, by setting the content to 300 parts by mass or less, light of the corresponding wavelength can be absorbed while maintaining the adhesive strength between the photosensitive colored resin film and the substrate, the heat resistance of the film after heat treatment, and the mechanical properties.

[0079] <Aromatic Hydrocarbon (f) Having at Least One Aromatic C-H Bond and at Least Three Phenolic Hydroxyl Groups in One Aromatic Ring> The photosensitive resin composition of the present invention preferably further comprises an aromatic hydrocarbon (f) (hereinafter, sometimes referred to as compound (f)) having at least one aromatic C-H bond and at least three phenolic hydroxyl groups in one aromatic ring. The photosensitive resin composition of the present invention contains compound (f) and a triazine ring-containing compound (g) (hereinafter, sometimes referred to as compound (g)) represented by formula (1) described below. When the photosensitive resin composition of the present invention contains compound (f) and a triazine ring-containing compound (g) (hereinafter, sometimes referred to as compound (g)) described below, the composition develops color upon heating, regardless of the curing atmosphere, and the transmittance in the wavelength range of 300 nm to 500 nm after curing can be reduced. While the mechanism of this color development is unclear, it is believed that a crosslinking reaction between compound (f) and compound (g) in compound (f) proceeds upon heating, and the crosslinked product adopts a quinone structure, resulting in the generation of a color-developing product with absorption in the wavelength range of 300 nm to 500 nm. Since the crosslinking reaction does not depend on the heating atmosphere during curing, the transmittance in the wavelength region of 300 nm to 500 nm can be reduced after curing without being restricted by the curing conditions. Furthermore, before heating, neither compound (f) nor compound (g) has absorption in the wavelength region of 300 nm to 500 nm, so that before curing, they do not block light in the wavelength region of 350 nm to 450 nm of a mercury lamp, which is commonly used as an exposure light source, and pattern formation can be performed with high sensitivity. Furthermore, by containing ionic dye (b1) and ionic dye (b2), a film with high visible light blocking properties can be obtained after curing.

[0080] The aromatic hydrocarbon structure possessed by compound (f) includes known monocyclic and fused polycyclic structures. Furthermore, the aromatic hydrocarbon has at least one aromatic C-H bond and at least three phenolic hydroxyl groups within one aromatic ring. An aromatic hydrocarbon having at least one aromatic C-H bond within one aromatic ring means that one or more unsubstituted aromatic C-H bonds are present within the aromatic ring. Furthermore, "within one aromatic ring" refers to a specific structure "within a single aromatic ring." For example, a compound having three aromatic rings each having at least one aromatic C-H bond and one phenolic hydroxyl group is not included in the scope of compound (f). Specific examples of compound (f) include, but are not limited to, the structure represented by formula (11) below.

[0081]

[0082] In formula (11), R ７ are independently a monovalent organic group having 1 to 20 carbon atoms, k is an integer of 0 to 2, l is an integer of 0 to 6, and m is an integer of 3 to 9, provided that k, l, and m satisfy the following relational formula: {(2k+6)-(l+m)}≧1 (formula).

[0083] Compound (f) has at least one aromatic C—H bond in one aromatic ring, and thus can form a crosslinked body composed of compound (g), and can reduce the transmittance in the wavelength region of 300 nm to 500 nm after curing.

[0084] When the aromatic C—H bond in one aromatic ring contained in the compound (f) is one or more, preferably two or more, more preferably three or more, the number of crosslinking points with the compound (g) increases, and thus the transmittance in the wavelength region of 300 nm to 500 nm after curing can be more effectively reduced.

[0085] Examples of aromatic hydrocarbons having at least one aromatic C—H bond and three phenolic hydroxyl groups in one aromatic ring include phloroglucinol, pyrogallol, 1,2,4-trihydroxybenzene, 2,4,5-trihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, gallacetophenone, 2,3,4-trihydroxybenzoic acid, gallic acid, methyl gallate, ethyl gallate, propyl gallate, octyl gallate, 2,3,4-trihydroxybenzophenone, and 2,3,4,4′-tetrahydroxybenzophenone.

[0086] Examples of aromatic hydrocarbons having at least one aromatic C—H bond and four or more phenolic hydroxyl groups in one aromatic ring include 1,2,3,4-tetrahydroxybenzene, 1,2,3,5-tetrahydroxybenzene, 1,2,4,5-tetrahydroxybenzene, and leucoquinizarin.

[0087] It is preferable that the substitution position of at least one phenolic hydroxyl group other than any of the phenolic hydroxyl groups in the compound (f) structure is the ortho or para position. By having the substitution position be the ortho or para position, more preferably the para position, the transmittance in the wavelength region of 300 nm to 500 nm after curing can be more effectively reduced. This is presumably because the crosslinked product of compound (f) and compound (g) has an orthoquinone or paraquinone structure, which enhances color development.

[0088] Among the compounds (f), examples of the compound (f1) in which at least one substitution position of a phenolic hydroxyl group other than one of the phenolic hydroxyl groups is the ortho position include pyrogallol, 1,2,4-trihydroxybenzene, 2,4,5-trihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, gallacetophenone, 2,3,4-trihydroxybenzoic acid, gallic acid, methyl gallate, ethyl gallate, propyl gallate, octyl gallate, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 1,2,3,4-tetrahydroxybenzene, 1,2,3,5-tetrahydroxybenzene, and 1,2,4,5-tetrahydroxybenzene.

[0089] Among compounds (f), examples of compounds (f2) in which at least one substitution position of a phenolic hydroxyl group relative to any other phenolic hydroxyl group include 1,2,4-trihydroxybenzene, 2,4,5-trihydroxybenzaldehyde, 1,2,3,4-tetrahydroxybenzene, 1,2,3,5-tetrahydroxybenzene, 1,2,4,5-tetrahydroxybenzene, and leucoquinizarin.

[0090] The molecular weight of the compound (f) is preferably 1000 or less, more preferably 800 or less, and even more preferably 600 or less. The molecular weight of the compound (f) is 126 or more.

[0091] The content of compound (f) is preferably 1 part by mass or more and 50 parts by mass or less per 100 parts by mass of alkali-soluble resin (a). By setting the content to 1 part by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, in combination with compound (g) described below, the transmittance in the wavelength region of 300 nm to 500 nm after curing can be effectively reduced. Furthermore, by setting the content to 50 parts by mass or less, more preferably 40 parts by mass or less, even more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less, the chemical resistance of the cured product can be maintained.

[0092] <Triazine Ring-Containing Compound (g) Represented by Formula (1)> The photosensitive resin composition of the present invention preferably further contains a triazine ring-containing compound (g) represented by Formula (1) (also referred to as compound (g)).

[0093]

[0094] In formula (1), R １ ~R ６ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyl ether group having 2 to 10 carbon atoms, a methylol group, or an alkoxymethyl group. １ ~R ６ At least one of these is a methylol group or an alkoxymethyl group.

[0095] The photosensitive resin composition of the present invention contains compound (g) and compound (f), which develops color upon heating regardless of the atmosphere during curing, and can effectively reduce the transmittance in the wavelength region of 300 nm to 500 nm after curing. That is, the photosensitive resin composition of the present invention contains compound (g) and compound (f) in addition to ionic dye (b1) and ionic dye (b2), and can also reduce the visible light transmittance of the cured product, making it black.

[0096] R １ ~R ６ At least one of the methylol groups or alkoxymethyl groups is a methylol group or an alkoxymethyl group, preferably two or more, more preferably three or more, even more preferably four or more, and most preferably all six are methylol groups or alkoxymethyl groups. The greater the number of methylol groups or alkoxymethyl groups, the more crosslinking points with compound (f) there are, and the more effectively the transmittance in the wavelength region of 300 nm to 500 nm after curing can be reduced.

[0097] Examples of the alkoxymethyl group include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group.

[0098] The content of compound (g) is preferably 1 part by mass or more and 100 parts by mass or less per 100 parts by mass of alkali-soluble resin (a). By setting the content to 1 part by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, in combination with compound (f), the transmittance in the wavelength region of 300 nm to 500 nm after curing can be more effectively reduced. Furthermore, by setting the content to 100 parts by mass or less, more preferably 80 parts by mass or less, even more preferably 50 parts by mass or less, and even more preferably 30 parts by mass or less, the sensitivity of the photosensitive resin composition can be effectively improved.

[0099] <Thermocoloring Compound> The photosensitive resin composition of the present invention may contain a thermocoloring compound. The thermocoloring compound is a thermocoloring compound that develops color upon heat treatment and has a maximum absorption at 350 nm or more and 700 nm or less, more preferably a thermocoloring compound that develops color upon heat treatment and has a maximum absorption at 350 nm or more and 500 nm or less. By including a thermocoloring compound in the photosensitive resin composition of the present invention in addition to the ionic dye (b1) and the ionic dye (b2), the visible light transmittance of the cured product can be reduced and the product can be made black.

[0100] In the present invention, the thermocolorable compound is preferably a compound that develops color at a temperature higher than 120° C., and more preferably a thermocolorable compound that develops color at a temperature higher than 180° C. The higher the color-developing temperature of the thermocolorable compound, the more excellent the heat resistance under high-temperature conditions, and the more excellent the light resistance, with less fading due to long-term irradiation with ultraviolet light and visible light.

[0101] In the present invention, the thermochromic compound may be a general heat-sensitive dye or pressure-sensitive dye, or may be other compounds. Examples of thermochromic compounds include those that develop color by changing their chemical structure or charge state due to the action of acidic groups coexisting in the system during heat treatment, or those that develop color through a thermal oxidation reaction in the presence of oxygen in the air. The thermochromic compound of the present invention does not have a maximum absorption in the range of 350 nm or more and 700 nm or less before heat treatment, and is therefore different from colorant (d). For example, a thermochromic compound having a triarylmethane skeleton is said to develop color when hydrogen from a methine group is eliminated upon heat treatment, resulting in one aryl group becoming a quinone structure. On the other hand, the ionic dye (b) and colorant (d) having a triarylmethane skeleton have a quinone structure before heat treatment, and are therefore different from the thermochromic compound of the present invention.

[0102] The skeletal structure of the thermocolorable compound may contain a triarylmethane skeleton, a diarylmethane skeleton, a fluoran skeleton, a bislactone skeleton, a phthalide skeleton, a xanthene skeleton, a rhodamine lactam skeleton, a fluorene skeleton, a phenothiazine skeleton, a phenoxazine skeleton, a spiropyran skeleton, etc. Among these, a triarylmethane skeleton is preferred because it has a high thermocolorable temperature and excellent heat resistance.

[0103] Specific examples of the triarylmethane skeleton include 2,4',4''-methylidynetrisphenol, 4,4',4''-methylidynetrisphenol, 4,4'-[(4-hydroxyphenyl)methylene]bis(benzenamine), 4,4'-[(4-aminophenyl)methylene]bisphenol, 4,4'-[(4-aminophenyl)methylene]bis[3,5-dimethylphenol], 4,4'-[(2-hydroxyphenyl)methylene]bis[2,3,6-trimethylphenol], 4-[bis (4-hydroxyphenyl)methyl]-2-methoxyphenol, 4,4'-[(2-hydroxyphenyl)methylene]bis[2-methylphenol], 4,4'-[(4-hydroxyphenyl)methylene]bis[2-methylphenol], 4-[bis(4-hydroxyphenyl)methyl]-2-ethoxyphenol, 4,4'-[(4-hydroxyphenyl)methylene]bis[2,6-dimethylphenol], 2,2'-[(4-hydroxyphenyl)methylene]bis[3,5-dimethylphenol] phenol], 4,4'-[(4-hydroxy-3-methoxyphenyl)methylene]bis[2,6-dimethylphenol], 2,2'-[(2-hydroxyphenyl)methylene]bis[2,3,5-trimethylphenol], 4,4'-[(4-hydroxyphenyl)methylene]bis[2,3,6-trimethylphenol], 4,4'-[(2-hydroxyphenyl)methylene]bis[2-cyclohexyl-5-methylphenol], 4,4'-[(4-hydroxyphenyl)methylene]bis[2-cyclohexyl-5-methylphenol] The hydroxyl group-containing compound having a triarylmethane skeleton may be used alone or in combination with other compounds such as 4,4'-[(3-methoxy-4-hydroxyphenyl)methylene]bis[2-cyclohexyl-5-methylphenol], 4,4'-[(3-methoxy-4-hydroxyphenyl)methylene]bis[2-cyclohexyl-5-methylphenol], 4,4'-[(3,4-dihydroxyphenyl)methylene]bis[2-methylphenol], 4,4'-[(3,4-dihydroxyphenyl)methylene]bis[2,6-dimethylphenol], and 4,4'-[(3,4-dihydroxyphenyl)methylene]bis[2,3,6-trimethylphenol]. These compounds may be used alone or in combination. The hydroxyl group-containing compound having a triarylmethane skeleton may be used as a quinone diazide compound by esterifying the compound with the sulfonic acid of naphthoquinone diazide.

[0104] In the present invention, when a thermocoloring compound is contained, the content is preferably 5 to 80 parts by mass, and particularly preferably 10 to 60 parts by mass, per 100 parts by mass of the alkali-soluble resin (a). If the content of the thermocoloring compound is 5 parts by mass or more, the transmittance of the cured product in the ultraviolet-visible region can be reduced. If the content is 80 parts by mass or less, the heat resistance and strength of the cured product can be maintained and the water absorption rate can be reduced.

[0105] <Radical Polymerizable Compound> The photosensitive resin composition of the present invention may contain a radical polymerizable compound. In particular, when the photosensitive resin composition contains a photopolymerization initiator (c2), it is essential that the composition contain a radical polymerizable compound. A radical polymerizable compound refers to a compound having multiple ethylenically unsaturated double bonds in its molecule. During exposure, radicals generated from the photopolymerization initiator (c2) cause radical polymerization of the radical polymerizable compound, insolubilizing the light-irradiated area and thereby obtaining a negative pattern. Furthermore, by containing a radical polymerizable compound, photocuring of the light-irradiated area is promoted, thereby further improving sensitivity. In addition, the crosslinking density after thermal curing is improved, thereby improving the hardness of the cured product.

[0106] The radical polymerizable compound is preferably a compound having a (meth)acrylic group, which facilitates radical polymerization. From the viewpoint of improving sensitivity during exposure and improving hardness of the cured product, a compound having two or more (meth)acrylic groups in the molecule is more preferred. From the viewpoint of improving sensitivity during exposure and improving hardness of the cured product, the double bond equivalent of the radical polymerizable compound is preferably 80 to 400 g / mol.

[0107] Examples of the radical polymerizable compound include trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, 2,2-bis[4-(

[0033] The acrylic acid copolymer may contain, for example, 1,3,5-tris((meth)acryloxyethyl)isocyanuric acid, 1,3-bis((meth)acryloxyethyl)isocyanuric acid, 9,9-bis[4-(2-(meth)acryloxyethoxy)phenyl]fluorene, 9,9-bis[4-(3-(meth)acryloxypropoxy)phenyl]fluorene, 9,9-bis(4-(meth)acryloxyphenyl)fluorene, or acid-modified, ethylene oxide-modified, or propylene oxide-modified products thereof.

[0108] The content of the radical polymerizable compound is preferably 15 parts by mass or more, more preferably 30 parts by mass or more, per 100 parts by mass of the alkali-soluble resin (a) and the radical polymerizable compound in total, from the viewpoints of further improving the sensitivity and reducing the taper angle, while the content is preferably 65 parts by mass or less, more preferably 50 parts by mass or less, per 100 parts by mass of the alkali-soluble resin (a) and the radical polymerizable compound in total, from the viewpoints of further improving the heat resistance of the cured product and reducing the taper angle.

[0109] <Thermal Crosslinking Agent> The photosensitive resin composition of the present invention may contain a thermal crosslinking agent. The thermal crosslinking agent refers to a compound having at least two thermally reactive functional groups in the molecule, such as an alkoxymethyl group, a methylol group, an epoxy group, or an oxetanyl group. By containing a thermal crosslinking agent, crosslinking occurs between the thermal crosslinking agent and the alkali-soluble resin (a) or between the thermal crosslinking agents themselves, thereby improving the heat resistance, chemical resistance, and bending resistance of the cured product after thermal curing.

[0110] Preferred examples of the compound having at least two alkoxymethyl groups or methylol groups include DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, It may contain TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPPHAP, HMOM-TPPHBA, HMOM-TPPHAP (all of which are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), "NIKALAC" (registered trademark) MX-290, "NIKALAC" MX-280, "NIKALAC" MX-270, "NIKALAC" MX-279, "NIKALAC" MW-100LM, "NIKALAC" MX-750LM (all of which are trade names, manufactured by Sanwa Chemical Co., Ltd.), and the like.

[0111] Preferred examples of compounds having at least two epoxy groups include "Epolite" (registered trademark) 40E, "Epolite" 100E, "Epolite" 200E, "Epolite" 400E, "Epolite" 70P, "Epolite" 200P, "Epolite" 400P, "Epolite" 1500NP, "Epolite" 80MF, "Epolite 4000," and "Epolite" 1500NP. "Denacol" (registered trademark) EX-3002 (all manufactured by Kyoeisha Chemical Co., Ltd.), "Denacol" (registered trademark) EX-212L, "Denacol" EX-214L, "Denacol" EX-216L, "Denacol" EX-850L (all manufactured by Nagase ChemteX Corporation), GAN, GOT (all manufactured by Nippon Kayaku Co., Ltd.), "Epicoat" (registered trademark) 828, "Epicoat" 1002, "Epicoat" 1750, "Epicoat" 1007, YX8100-BH30, E1256, E4250, E4275 (all manufactured by Japan Epoxy Resins Co., Ltd.), "Epiclon" (registered trademark) EXA-9583, HP4032 (all manufactured by DIC Corporation), VG3101 (manufactured by Mitsui Chemicals, Inc.), "Tepic" (registered trademark) S, "Tepic" G, "Tepic" P (all manufactured by Nissan Chemical Industries, Ltd.) The present invention may contain, for example, "Denacol" EX-321L (manufactured by Nagase ChemteX Corporation), "Denacol" EX-321L (manufactured by Nagase ChemteX Corporation), NC6000 (manufactured by Nippon Kayaku Co., Ltd.), "Epotohto" (registered trademark) YH-434L (manufactured by Tohto Kasei Co., Ltd.), EPPN502H, NC3000 (manufactured by Nippon Kayaku Co., Ltd.), "Epiclon" (registered trademark) N695, HP7200 (all manufactured by DIC Corporation), and the like.

[0112] Examples of compounds having at least two oxetanyl groups include Ethanacol EHO, Ethanacol OXBP, Ethanacol OXTP, and Ethanacol OXMA (all manufactured by Ube Industries, Ltd.), oxetanized phenol novolac, etc. Two or more types of thermal crosslinking agents may be used in combination.

[0113] When a thermal crosslinking agent is contained, the content thereof is preferably 1 part by mass or more and 30 parts by mass or less, based on 100 parts by mass of the total amount of the photosensitive resin composition excluding the solvent. When the content of the thermal crosslinking agent is 1 part by mass or more, the chemical resistance and bending resistance of the cured product can be further improved. Furthermore, when the content of the thermal crosslinking agent is 30 parts by mass or less, the amount of outgassing from the cured product can be further reduced, the long-term reliability of the organic EL display device can be further improved, and the storage stability of the photosensitive resin composition can also be excellent.

[0114] <Solvent> The photosensitive resin composition of the present invention may contain a solvent. By containing a solvent, the composition can be made into a varnish state, and the coatability can be improved.

[0115] Examples of the solvent include polar aprotic solvents such as γ-butyrolactone, ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tetrahydrofuran, and dioxane, acetone, methyl Ketones such as ethyl ethyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, and diacetone alcohol; esters such as 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, propylene glycol monoethyl ether acetate, and ethyl lactate; ethyl 2-hydroxy-2-methylpropionate, 3- Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate,The solvent may contain other esters such as i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; amides such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N,N-dimethylpropanamide, and N,N-dimethylisobutyramide; and 3-methyl-2-oxazolidinone. The solvent may contain two or more of these.

[0116] The content of the 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 solvent. Furthermore, the proportion of the solvent with a boiling point of 180°C or higher in 100 parts by mass of the total amount of solvent is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less. By keeping the proportion of the solvent with a boiling point of 180°C or higher to 20 parts by mass or less, the amount of outgassing after thermal curing can be further reduced, and the long-term reliability of the organic EL device can be further improved.

[0117] <Adhesion Improver> The photosensitive resin composition of the present invention may contain an adhesion improver. Examples of the adhesion improver include silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane; titanium chelating agents; aluminum chelating agents; and compounds obtained by reacting an aromatic amine compound with an alkoxy group-containing silicon compound. Two or more of these may be contained. By containing these adhesion improvers, when developing a resin film, for example, it is possible to improve the adhesion of the photosensitive resin composition to silicon wafers, indium tin oxide (ITO), SiO ２The adhesion improver can improve the adhesion to the underlying substrate such as silicon nitride during development. It can also improve resistance to oxygen plasma and UV ozone treatments used for cleaning, etc. The content of the adhesion improver is preferably 0.01 to 10 parts by mass per 100 parts by mass of the total amount of the photosensitive resin composition excluding the solvent.

[0118] <Surfactant> The photosensitive resin composition of the present invention may contain an adhesion improver to improve wettability with the substrate. Examples of surfactants that can be used include fluorine-based surfactants such as the SH series, SD series, and ST series from Dow Corning Toray Co., Ltd., the BYK series from BYK Japan K.K., the KP series from Shin-Etsu Chemical Co., Ltd., the Disfoam series from NOF Corporation, the Megafac (registered trademark) series from DIC Corporation, the Fluorad series from Sumitomo 3M Limited, the Surflon (registered trademark) series and Asahi Guard (registered trademark) series from Asahi Glass Co., Ltd., and the Polyfox series from Omnova Solutions, as well as acrylic and / or methacrylic surfactants such as the Polyflow series from Kyoeisha Chemical Co., Ltd. and the Disparlon (registered trademark) series from Kusumoto Chemical Co., Ltd.

[0119] When a surfactant is contained, the content thereof is preferably 0.001 to 1 part by mass in 100 parts by mass of the total amount of the photosensitive resin composition excluding the solvent.

[0120] <Inorganic Particles> The photosensitive resin composition of the present invention may contain inorganic particles. Specific preferred examples of inorganic particles include silicon oxide, titanium oxide, barium titanate, alumina, and talc. The primary particle diameter of the inorganic particles is preferably 100 nm or less, and more preferably 60 nm or less.

[0121] The content of the inorganic particles is preferably 5 to 90 parts by mass in 100 parts by mass of the total amount of the photosensitive resin composition excluding the solvent.

[0122] <Total Chlorine Atoms, Total Bromine Atoms> In the photosensitive resin composition of the present invention, the total mass of all chlorine atoms and all bromine atoms contained in the photosensitive resin composition is preferably 150 ppm or less, more preferably 100 ppm or less, and even more preferably less than 2 ppm, which is the lower detection limit of combustion ion chromatography, relative to the total mass of the solids in the photosensitive resin composition excluding the solvent.

[0123] By setting the total amount of all chlorine atoms and all bromine atoms contained in the photosensitive resin composition to 150 ppm or less relative to the solid content excluding the solvent in the photosensitive resin composition, it is possible to suppress deterioration of the electrodes and light-emitting layers of an organic EL display device having a cured product obtained by curing the photosensitive resin composition, and to improve long-term reliability.

[0124] Furthermore, by setting the total amount of all chlorine atoms and all bromine atoms contained in the photosensitive resin composition to 150 ppm or less based on the solid content excluding the solvent in the photosensitive resin composition, the storage stability of the photosensitive resin composition of the present invention during frozen storage can be improved.

[0125] The total mass of all chlorine atoms and all bromine atoms contained in the photosensitive resin composition can be measured by, for example, combustion ion chromatography, in which the photosensitive resin composition is combusted in a combustion tube of an analyzer, the generated gas is absorbed into a solution, and then a portion of the absorbed solution is analyzed by ion chromatography.

[0126] <Inorganic Ions> In the photosensitive resin composition of the present invention, the total mass of inorganic ions contained in the photosensitive resin composition is preferably 100 ppm or less, more preferably 50 ppm or less, and even more preferably 10 ppm or less, relative to the total mass of the solid content in the photosensitive resin composition, and most preferably less than 5 ppm, which is the lower detection limit of ion chromatography.

[0127] By adjusting the total mass of inorganic ions contained in the photosensitive resin composition to 100 ppm or less, the storage stability of the photosensitive resin composition of the present invention during frozen storage can be improved.

[0128] The inorganic ions refer to ions of inorganic compounds that do not contain carbon, and examples thereof include halogen ions, metal ions, nitrate ions, phosphate ions, sulfate ions, and ammonium ions.

[0129] The total mass of inorganic ions in the photosensitive resin composition can be measured, for example, by suspending the photosensitive resin composition in pure water and analyzing the filtered aqueous solution by ion chromatography.

[0130] <Method for Producing Photosensitive Resin Composition> Next, a method for producing the photosensitive resin composition of the present invention will be described. For example, the photosensitive resin composition of the present invention can be obtained by dissolving an alkali-soluble resin (a), an ionic dye (b) that forms an ion pair of organic ions between molecules, a photosensitive compound (c), and, if necessary, a colorant (d), a thermocoloring compound, a radical-polymerizable compound, a thermal crosslinking agent, a solvent, an adhesion improver, a surfactant, inorganic particles, etc.

[0131] Examples of dissolution methods include stirring and heating. When heating, the heating temperature is preferably set within a range that does not impair the performance of the photosensitive resin composition, and is typically room temperature to 80°C. The order in which the components are dissolved is not particularly limited, and examples include a method in which compounds with low solubility are dissolved in order. For components that tend to generate bubbles when dissolved by stirring, such as surfactants and some adhesion improvers, adding them last after dissolving the other components can prevent poor dissolution of the other components due to the generation of bubbles.

[0132] The obtained photosensitive resin composition is preferably filtered using a filter to remove dust and particles. Examples of filter pore sizes include, but are not limited to, 0.5 μm, 0.2 μm, 0.1 μm, 0.07 μm, 0.05 μm, and 0.02 μm. Examples of filter materials include polypropylene (PP), polyethylene (PE), nylon (NY), and polytetrafluoroethylene (PTFE). Among these, polyethylene and nylon are preferred.

[0133] <Method for Producing a Cured Product> The method for producing a cured product of the present invention includes the steps of forming a resin film made of the photosensitive resin composition of the present invention on a substrate, exposing the resin film to light, developing the exposed resin film, and heat-treating the developed resin film.

[0134] The process of forming a resin film made of the photosensitive resin composition of the present invention on a substrate will now be described. In the present invention, the resin film can be obtained by applying the photosensitive resin composition of the present invention to obtain a coating film of the photosensitive resin composition, and drying the coating film.

[0135] Examples of methods for applying the photosensitive resin composition of the present invention include spin coating, slit coating, dip coating, spray coating, and printing. Among these, slit coating is preferred because it allows application with a small amount of coating liquid, which is advantageous in reducing costs. The amount of coating liquid required for slit coating is, for example, approximately 1 / 5 to 1 / 10 of that required for spin coating. Slit nozzles used for application can be selected from those commercially available from multiple manufacturers, including, for example, the "Linear Coater" manufactured by Dainippon Screen Mfg. Co., Ltd., the "Spinless" manufactured by Tokyo Ohka Kogyo Co., Ltd., the "TS Coater" manufactured by Toray Engineering Co., Ltd., the "Table Coater" manufactured by Chugai Ro Kogyo Co., Ltd., the "CS Series" and "CL Series" manufactured by Tokyo Electron Limited, the "Inline Slit Coater" manufactured by Cermatronics Trading Co., Ltd., and the "Head Coater HC Series" manufactured by Hirata Corporation. The coating speed is generally in the range of 10 mm / s to 400 mm / s. The thickness of the coating film varies depending on the solid content and viscosity of the photosensitive resin composition, but is usually applied so that the thickness after drying is 0.1 to 10 μm, preferably 0.3 to 5 μm.

[0136] Prior to coating, the substrate to which the photosensitive resin composition is to be applied may be pretreated with the adhesion improver described above. Examples of pretreatment methods include treating the substrate surface with a solution prepared by dissolving 0.5 to 20% by mass of an adhesion improver in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, or diethyl adipate. Examples of methods for treating the substrate surface include spin coating, slit die coating, bar coating, dip coating, spray coating, and steam treatment.

[0137] After coating, a reduced-pressure drying treatment is performed as needed. The reduced-pressure drying speed depends on the vacuum chamber volume, the vacuum pump capacity, the piping diameter between the chamber and the pump, etc., but is preferably set, for example, under conditions such that the pressure inside the vacuum chamber is reduced to 40 Pa after 60 seconds without a coated substrate. The typical reduced-pressure drying time is often about 30 to 100 seconds, and the ultimate pressure inside the vacuum chamber at the end of the reduced-pressure drying is usually 100 Pa or less with a coated substrate present. By setting the ultimate pressure to 100 Pa or less, the coating film surface can be dried with reduced stickiness, thereby suppressing surface contamination and particle generation during subsequent substrate transportation.

[0138] After coating or drying under reduced pressure, the coating film is generally heated and dried. This process is also called pre-baking. Drying is performed using a hot plate, oven, infrared rays, or the like. When using a hot plate, the coating film is heated directly on the plate or held on a jig such as a proxy pin placed on the plate. The heating time is preferably from one minute to several hours. The heating temperature varies depending on the type and purpose of the coating film, but from the viewpoint of accelerating solvent drying during pre-baking, it is preferably 80°C or higher, and more preferably 90°C or higher. On the other hand, from the viewpoint of reducing the progress of curing during pre-baking, it is preferably 150°C or lower, and more preferably 140°C or lower.

[0139] Next, the step of exposing the resin film will be described. The resin film of the present invention can be patterned. For example, the resin film can be exposed to actinic radiation through a photomask having a desired pattern, and then developed to form a desired pattern.

[0140] In the step of exposing the resin film, the photomask used during exposure is preferably a halftone photomask having a light-transmitting portion, a light-shielding portion, and a semi-transmitting portion. By exposing using a halftone photomask, a pattern having a stepped shape can be formed after development. When a positive resin film is used, in the pattern having a stepped shape, the portion formed from the light-shielding portion corresponds to a thick film portion, and the portion formed from the half-tone exposed portion irradiated with activated actinic rays through the semi-transmitting portion corresponds to a thin film portion. When the transmittance of the light-transmitting portion of the halftone photomask is taken as 100%, the transmittance of the semi-transmitting portion is preferably 5% or more, more preferably 10% or more. When the transmittance of the semi-transmitting portion is within the above-mentioned range, a clear step between the thick film portion and the thin film portion can be formed. On the other hand, the transmittance of the semi-transmitting portion is preferably 30% or less, more preferably 25% or less, more preferably 20% or less, and most preferably 15% or less. When the transmittance of the semi-transparent portion is within the above-mentioned range, the film thickness of the thin film portion can be made thicker, and even when forming a black cured product with a low optical density in visible light per μm of film thickness, the optical density of the entire film can be increased.

[0141] Examples of actinic radiation used for exposure include ultraviolet light, visible light, electron beams, and X-rays. In the present invention, it is preferable to use i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) from a mercury lamp. When the film has positive photosensitivity, the exposed area dissolves in a developer. When the film has negative photosensitivity, the exposed area hardens and becomes insoluble in a developer.

[0142] Next, the process of developing the exposed resin film will be described. After exposure, the desired pattern is formed by removing the exposed areas in the case of a positive-tone film or the unexposed areas in the case of a negative-tone film using a developer. Examples of the developer include aqueous solutions of alkaline compounds 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. These alkaline aqueous solutions may contain one or more polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone, and dimethylacrylamide; alcohols such as methanol, ethanol, and isopropanol; esters such as ethyl lactate and propylene glycol monomethyl ether acetate; and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone. Examples of the developing method include spray, puddle, immersion, and ultrasonic methods.

[0143] Next, the pattern formed by development is preferably rinsed with distilled water. Alternatively, alcohols such as ethanol and isopropyl alcohol, or esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to the distilled water for rinsing.

[0144] Next, the step of heat-treating the developed resin film will be described. After development, the developed resin film is heat-treated to obtain a cured product. The heat treatment temperature is preferably 180°C or higher, more preferably 200°C or higher, even more preferably 230°C or higher, and particularly preferably 250°C or higher, from the viewpoint of further reducing the amount of outgassing from the cured product. On the other hand, from the viewpoint of improving the film toughness of the cured product, it is preferably 500°C or lower, more preferably 450°C or lower. Within this temperature range, the temperature may be increased stepwise or continuously. The heat treatment time is preferably 30 minutes or longer, from the viewpoint of further reducing the amount of outgassing. Furthermore, from the viewpoint of improving the film toughness of the cured product, it is preferably 3 hours or shorter. For example, a method of heat-treating at 150°C and 250°C for 30 minutes each, or a method of heat-treating while linearly increasing the temperature from room temperature to 300°C over 2 hours, can be used.

[0145] <Cured Product> The cured product of the present invention is a cured product obtained by curing the photosensitive resin composition of the present invention. By heat-treating the photosensitive resin composition of the present invention, components with low heat resistance can be removed, thereby further improving the heat resistance and chemical resistance. In particular, when the photosensitive resin composition of the present invention contains a polyimide precursor, a polybenzoxazole precursor, a copolymer thereof, or a copolymer thereof with a polyimide, imide rings and oxazole rings are formed by heat treatment, thereby further improving the heat resistance and chemical resistance.

[0146] The heat treatment temperature is preferably 180°C or higher, more preferably 200°C or higher, even more preferably 230°C or higher, and particularly preferably 250°C or higher, from the viewpoint of further reducing the amount of outgassing from the cured product. On the other hand, from the viewpoint of improving the film toughness of the cured product, it is preferably 500°C or lower, more preferably 450°C or lower. Within this temperature range, the temperature may be increased stepwise or continuously. The heat treatment time is preferably 30 minutes or longer, from the viewpoint of further reducing the amount of outgassing. Furthermore, from the viewpoint of improving the film toughness of the cured product, it is preferably 3 hours or shorter. For example, a method of heat treatment at 150°C and 250°C for 30 minutes each, or a method of heat treatment while linearly increasing the temperature from room temperature to 300°C over 2 hours may be mentioned.

[0147] The optical density (hereinafter, OD) per μm of film thickness of the cured product of the present invention is preferably 0.5 or more, more preferably 0.7 or more. When the OD value is within the above range, the light-blocking properties can be improved by the cured product, so that in displays such as organic EL displays or liquid crystal displays, the electrode wiring can be visualized and external light reflection can be further reduced, thereby improving the contrast in image display. On the other hand, from the viewpoint of improving the sensitivity during exposure when the photosensitive resin composition containing the photosensitive compound described below is prepared, the OD value is preferably 1.0 or less.

[0148] The OD value of the cured product of the present invention can be controlled by adding, to the photosensitive resin composition of the present invention, an ionic dye (b3), a thermochromic compound, or compound (f) and compound (g) in addition to the ionic dye (b1) and ionic dye (b2). A colorant (d) may also be used in combination.

[0149] <Application Examples of Photosensitive Resin Composition and Cured Product> The photosensitive resin composition and cured product of the present invention are suitable for use as a surface protection layer or interlayer insulating layer for semiconductor elements, an insulating layer for organic electroluminescence (EL) elements, a planarization layer for thin film transistor (TFT) substrates for driving display devices using organic EL elements, a wiring protection insulating layer for circuit boards, an on-chip microlens for solid-state imaging elements, and a planarization layer for various display devices and solid-state imaging elements. For example, they are suitable as a surface protection layer or interlayer insulating layer for MRAM with low heat resistance, polymer memory (Polymer Ferroelectric RAM: PFRAM) and phase change memory (Phase Change RAM: PCRAM, Ovonics Unified Memory: OUM), which are promising next-generation memories. The insulating layer can also be used in a display device including a first electrode formed on a substrate and a second electrode provided opposite the first electrode, such as an LCD, an ECD, an ELD, or a display device using an organic electroluminescent element (organic electroluminescent device). Hereinafter, an organic EL display device, a semiconductor device, and a semiconductor electronic component will be described as examples.

[0150] <Organic EL Display Device> The organic EL display device of the present invention is an organic EL display device having, on a substrate, a driving circuit, a planarizing layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode, and the planarizing layer and / or the insulating layer has the cured product of the present invention.

[0151] When the insulating layer comprises the cured product of the present invention, the insulating layer preferably has an OD value of 0.5 to 1.0 in visible light per 1 μm of film thickness. When the OD value is 0.5 or more, the cured product can improve light-blocking properties, thereby making it possible to visualize electrode wiring and further reduce external light reflection in display devices such as organic electroluminescence (EL) display devices or liquid crystal display devices, thereby improving the contrast of image display. Furthermore, when the OD value is 1.0 or less, the sensitivity upon exposure can be improved when the photosensitive compound is used as a photosensitive resin composition.

[0152] When the insulating layer is a black film, the thickness of the insulating layer is preferably 1.0 to 5.0 μm, more preferably 1.5 μm or more, and even more preferably 2.0 μm or more. By making the thickness of the black insulating layer within the above range, even if the black film has a low optical density in visible light per μm of film thickness, the optical density of the entire film can be increased, and the effect of reducing external light reflection can be improved.

[0153] Taking an active matrix display device as an example, a display device has a TFT and wiring located on the sides of the TFT and connected to the TFT on a substrate such as glass or various plastics, a planarizing layer covering the unevenness thereon, and a display element on the planarizing layer. The display element and wiring are connected via contact holes formed in the planarizing layer. In particular, since flexible organic EL display devices have become mainstream in recent years, it is preferable that the substrate having the aforementioned drive circuit be an organic EL display device containing a resin film. When a cured product obtained by curing the photosensitive resin composition of the present invention is used as an insulating layer or planarizing layer of such a flexible display device, it is particularly preferred because it has excellent bending resistance. From the viewpoint of improving adhesion to the cured product obtained by curing the photosensitive resin composition of the present invention, polyimide is particularly preferred as the resin film.

[0154] In order to enhance the effect of reducing external light reflection, the organic EL display device preferably further includes a color filter having a black matrix. The black matrix preferably contains a resin such as an epoxy resin, an acrylic resin, a urethane resin, a polyester resin, a polyimide resin, a polyolefin resin, or a siloxane resin.

[0155] The black matrix contains a colorant. Examples of colorants that can be used include black organic pigments, mixed-color organic pigments, and inorganic pigments. Examples of black organic pigments include carbon black, perylene black, aniline black, and benzofuranone-based pigments. Examples of mixed-color organic pigments include pseudo-black pigments obtained by mixing two or more pigments, such as red, blue, green, purple, yellow, magenta, and / or cyan. Examples of black inorganic pigments include graphite; fine particles of metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver; metal oxides; metal composite oxides; metal sulfides; metal nitrides; metal oxynitrides; and metal carbides. Among these, carbon black, titanium nitride, titanium carbide, and composite particles of these with metals such as silver, which have high light-shielding properties, are preferred.

[0156] The OD value of the black matrix is ​​preferably 1.5 or more, more preferably 2.5 or more, and even more preferably 4.5 or more.

[0157] FIG. 1 shows a cross-sectional view of an example of an organic EL display device. Bottom-gate or top-gate thin film transistors (TFTs) 1 are arranged in a matrix on a substrate 6. A TFT insulating layer 3 is formed to cover the TFTs 1. Wiring 2 connected to the TFTs 1 is also provided on the TFT insulating layer 3. A planarization layer 4 is further formed on the TFT insulating layer 3, burying the wiring 2. Contact holes 7 are formed in the planarization layer 4, reaching the wiring 2. An ITO (transparent electrode) 5 is formed on the planarization layer 4 and connected to the wiring 2 via the contact holes 7. The ITO 5 serves as an electrode for a display element (e.g., an organic EL element). An insulating layer 8 is formed to cover the periphery of the ITO 5. The organic EL elements may be top-emission types that emit light from the side opposite the substrate 6, or bottom-emission types that extract light from the substrate 6 side. In this manner, an active matrix organic EL display device is obtained, in which TFTs 1 for driving each organic EL element are connected to the corresponding TFTs 1.

[0158] The TFT insulating layer 3, the planarizing layer 4, and / or the insulating layer 8 can be formed by the steps of forming a resin film made of the photosensitive resin composition of the present invention, exposing the resin film to light, developing the exposed resin film, and heat-treating the developed resin film, as described above. An organic EL display device can be obtained by a manufacturing method including these steps.

[0159] <Display Device Other Than Organic EL Display Device> A display device other than an organic EL display device of the present invention is a display device having at least metal wiring, the cured product of the present invention, and a plurality of light-emitting elements, wherein the light-emitting elements are provided with a pair of electrode terminals on either side thereof, the pair of electrode terminals are connected to a plurality of the metal wirings extending in the cured product, and the plurality of the metal wirings maintain electrical insulation due to the cured product.

[0160] The display device will be described with reference to FIG. 2 as an example. In FIG. 2, the display device 11 has a plurality of light-emitting elements 12 arranged on a counter substrate 15, and a cured product 13 arranged on the light-emitting elements 12. "On the light-emitting elements" does not necessarily mean the surface of the light-emitting elements, but may also mean the upper side of a supporting substrate or the light-emitting elements. The embodiment shown in FIG. 2 illustrates a configuration in which a total of three layers are stacked on top of a cured product 13 arranged so as to contact at least a portion of the light-emitting elements 12, but the cured product 13 may also be a single layer. The light-emitting element 12 has a pair of electrode terminals 16 on the surface opposite to the surface contacting the counter substrate 15, and each electrode terminal 16 is connected to a metal wiring 14 extending into the cured product 13. If the plurality of metal wirings 14 extending into the cured product 13 are covered with the cured product 13, the cured product 13 also functions as an insulating layer, thereby maintaining electrical insulation. The phrase "the metal wiring has a structure that maintains electrical insulation" means that the part of the metal wiring that requires electrical insulation is covered with a cured product obtained by curing a photosensitive resin composition containing an alkali-soluble resin (a). In addition, in the present invention, the phrase "the insulating layer has electrical insulation" means that the insulating layer has a volume resistivity of 10 １２ This means a state in which the electrical resistance is Ω cm or more. Furthermore, the light emitting element 12 is electrically connected to a driving element 18 attached to a light emitting element driving substrate 17 provided at a position opposite to the counter substrate 15 via metal wiring 14 or 14c, thereby controlling the light emission of the light emitting element 12. Furthermore, the light emitting element driving substrate 17 is electrically connected to the metal wiring 14 via, for example, solder bumps 20. Furthermore, a barrier metal 19 may be provided to prevent diffusion of metal such as the metal wiring 14.

[0161] The cured product 13 is preferably black and has an OD value of 0.5 to 1.0 in visible light per 1 μm of insulating layer thickness. An OD value of 0.5 or more can improve the light-blocking properties of the cured product, thereby making it possible to visualize electrode wiring and further reduce external light reflection in displays such as organic electroluminescence (EL) displays or liquid crystal display devices, thereby improving the contrast of image displays. Furthermore, an OD value of 1.0 or less can improve the sensitivity upon exposure when the photosensitive compound is used as a photosensitive resin composition.

[0162] The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[0163] [Measurement and Evaluation Methods] (1) Sensitivity and Residue The photosensitive resin compositions obtained in each of the Examples and Comparative Examples were applied onto an 8-inch silicon wafer by spin coating using a coating and developing apparatus (ACT-8 manufactured by Tokyo Electron Limited), and baked at 120°C for 2 minutes to produce a pre-baked film with a thickness of 4.0 μm. The film thickness was measured using a Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd. under the condition of a refractive index of 1.63. Thereafter, using an i-line stepper NSR-2005i9C (manufactured by Nikon Corporation) as an exposure device, the film was exposed to light at an exposure dose of 50 to 300 mJ / cm through a mask having a pattern of 10 μm holes. ２ in the range of 5 mJ / cm ２ After the exposure, the film was developed using the ACT-8 developing device with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as TMAH, manufactured by Tama Chemicals Co., Ltd.) as a developer until the film thickness was reduced to 0.5 μm, and then rinsed with distilled water and spun off to dry, thereby obtaining a pattern.

[0164] The obtained pattern was observed at a magnification of 20 times using an FPD microscope (MX61 manufactured by Olympus Corporation), and the opening diameter of the hole was measured. The minimum exposure dose at which the opening diameter of the contact hole reached 10 μm was determined, and this was taken as the sensitivity. ２ If it was less than 100 mJ / cm, it was marked "S" ２ 120mJ / cm or more ２ If it was less than 120 mJ / cm, it was rated "A"; ２ 150mJ / cm or more ２ If it was less than 150 mJ / cm, it was rated "B"; ２ If the result was above this, it was judged as "C", and if residues occurred in the hole pattern regardless of sensitivity, it was judged as "D".

[0165] (2) OD Value per 1 μm of Film Thickness The photosensitive resin compositions obtained in each Example and Comparative Example were spin-coated onto a 5 cm × 5 cm glass substrate so that the film thickness after heat treatment (curing) would be 2.0 μm, and the substrate was prebaked at 120°C for 120 seconds to produce a prebaked film. The substrate was then cured at 230°C for 60 minutes in an air or nitrogen atmosphere using a high-temperature clean oven (INH-9CD-S, manufactured by Koyo Thermo Systems Co., Ltd.) to produce a cured film. The film thickness of the cured film was measured using a stylus profiler. The OD value of the cured film thus obtained was measured using an optical densitometer (361T, manufactured by X-Rite). The obtained OD value was divided by the film thickness of the cured film to obtain the OD value per 1 μm of film thickness (OD value per 1 μm of film thickness = OD value / film thickness of cured film). An OD value per 1 μm of film thickness of 0.70 or more was rated as "A," a value less than 0.70 and 0.50 or more was rated as "B," and a value less than 0.50 was rated as "C."

[0166] (3) Change in OD Value Due to Repeated Curing The cured film obtained in (2) above was cured again in an air atmosphere at 230°C for 60 minutes using a high-temperature clean oven (INH-9CD-S, manufactured by Koyo Thermo Systems Co., Ltd.) to produce a twice-cured cured film. The film thickness and OD value of the cured film were measured in the same manner as in (2) above, and the obtained OD value was divided by the film thickness of the cured film to calculate the OD value per μm of film thickness after the second cure. The absolute value of the difference between the OD value per μm of film thickness after the first cure and the OD value per μm of film thickness after the second cure was taken as the change in OD value due to repeated curing. A change of less than 0.05 was rated as "A," a change of 0.05 or more but less than 0.15 was rated as "B," and a change of 0.15 or more was rated as "C."

[0167] (4) Frozen Storage Stability Using a coating and developing apparatus (Tokyo Electron Limited, "CLEAN TRACK ACT-12"), each photosensitive resin composition that had been filtered and then stored in a freezer at -18°C for 60 days was applied to a 12-inch Si wafer and dried on a hot plate at 100°C for 3 minutes to obtain a photosensitive resin film with a film thickness of 1000 nm. The number of foreign particles with a size of 0.27 μm or more was counted for the obtained photosensitive resin film using a wafer surface inspection apparatus (Topcon Corporation, "WM-10"). The measurement area was approximately 201 cm2 within a circle with a radius of 8 cm from the center of the wafer. ２ and the coating thickness is 1 cm ２ The defect density per substrate was 0.30 particles / cm. ２ If it was less than 0.30 pieces / cm, it was rated "A"; ２ More than 1.00 pieces / cm ２ If it was less than 1.00 pieces / cm, it was rated "B"; ２ If the result was above this, it was judged as "C".

[0168] (5) Long-Term Reliability of Organic EL Display Devices Figure 3 shows a schematic diagram of the fabrication procedure for organic EL display devices using the photosensitive resin compositions obtained in each Example and Comparative Example. First, a 10-nm thick ITO transparent conductive film was formed over the entire surface of a 38 mm x 46 mm alkali-free glass substrate 21 by sputtering, and then etched to form a first electrode (transparent electrode) 22. Simultaneously, an auxiliary electrode 23 for connecting the second electrode was also formed. The resulting substrate was ultrasonically cleaned for 10 minutes using a cleaning solution (Semicoclean 56 (trade name) manufactured by Furuuchi Chemical Co., Ltd.) and then rinsed with ultrapure water. Next, the photosensitive resin composition obtained in each Example and Comparative Example was applied to the entire substrate by spin coating and prebaked on a hot plate at 120 °C for 2 minutes. The film was exposed to light through a photomask using a high-pressure mercury lamp as a light source at the minimum exposure dose for each photosensitive resin composition, and then developed with a 2.38 wt% TMAH aqueous solution to dissolve unnecessary portions and rinsed with pure water. The obtained resin pattern was heat-treated at 230°C for 60 minutes in an air or nitrogen atmosphere using a high-temperature clean oven (INH-9CD-S, manufactured by Koyo Thermo Systems Co., Ltd.). In this way, an insulating layer 24 was formed in the effective substrate area, with openings 70 μm wide and 260 μm long arranged at a pitch of 155 μm in the width direction and a pitch of 465 μm in the length direction, each opening having a shape that exposes the first electrode. In this way, an insulating layer with an insulating layer aperture ratio of 25% was formed in the effective substrate area, which was a rectangle with one side measuring 16 mm. The thickness of the insulating layer was approximately 1.5 μm in all examples and comparative examples.

[0169] Next, a nitrogen plasma treatment was performed as a pretreatment, and then an organic EL layer 25 including a light-emitting layer was formed by vacuum deposition. Note that the degree of vacuum during deposition was 1×10 －３The pressure was below 1 Pa, and the substrate was rotated relative to the evaporation source during evaporation. First, compound (HT-1) was evaporated to a thickness of 10 nm as a hole injection layer, and compound (HT-2) was evaporated to a thickness of 50 nm as a hole transport layer. Next, compound (GH-1) as a host material and compound (GD-1) as a dopant material were evaporated to a thickness of 40 nm in the emitting layer so that the doping concentration was 10%. Next, compound (ET-1) and compound (LiQ) were laminated to a thickness of 40 nm at a volume ratio of 1:1 as electron transport materials. The structures of the compounds used in the organic EL layer are shown below.

[0170]

[0171] Next, a compound (LiQ) was vapor-deposited to a thickness of 2 nm, followed by vapor deposition of 10 nm of Mg and Ag at a volume ratio of 10:1 to form a second electrode (non-transparent electrode) 26. Finally, a cap-shaped glass plate was sealed by bonding it with an epoxy resin adhesive in a low-humidity nitrogen atmosphere, and four top-emission organic EL display devices, each 5 mm square, were fabricated on one substrate. Note that the film thickness referred to here is the value displayed on a quartz crystal oscillator film thickness monitor.

[0172] By the above method, 20 organic EL display devices were produced for each example and comparative example, and placed on a hot plate heated to 80°C with the light-emitting surface facing up. ２ The organic EL display devices were irradiated with UV light of 1000 hours. Display tests were carried out on the organic EL display devices after 500 hours and 1000 hours had elapsed. After each time period, the organic EL display devices were judged as "A" if there were no unlit devices, "B" if there were 1 to 4 unlit devices, and "C" if there were 5 or more unlit devices.

[0173] (6) Mass of total chlorine and bromine atoms relative to the total mass of the solid content of each raw material and photosensitive resin composition For each ionic dye and the photosensitive resin composition described in each Example and Comparative Example, the mass (ppm) of total chlorine and bromine atoms relative to the total mass of the solid content of each raw material or photosensitive resin composition was quantified by combustion ion chromatography. Combustion and absorption conditions System: AQF-2100H, GA-211 (Mitsubishi Chemical) Electric furnace temperature: Inlet 900°C, Outlet 1000°C Gas: Ar / O２ 200mL / min O ２ 400 mL / min Absorption liquid: H ２ O ２ 0.1% Internal standard P 2 μg / mL Absorption volume: 5 mL Ion chromatography anion analysis conditions System: ICS-1600 (DIONEX) Mobile phase: 2.7 mmol / L Na ２ CO ３ / 0.3 mmol / L NaHCO ３ Flow rate: 1.50 mL / min Detector: electrical conductivity detector Injection volume: 100 μL.

[0174] Synthesis Example 1 Synthesis of Hydroxyl Group-Containing Diamine Compound (α) 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 the solution was cooled to −15°C. To this solution, a solution of 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride dissolved in 100 mL of acetone was added dropwise. After completion of the dropwise addition, the mixture was reacted at −15°C for 4 hours and then returned to room temperature. The precipitated white solid was filtered and dried in vacuo at 50°C.

[0175] 30 g of the solid was placed in a 300 mL stainless steel autoclave and dispersed in 250 mL of methyl cellosolve, followed by the addition of 2 g of 5 mass % palladium on carbon. Hydrogen was introduced into the autoclave using a balloon, and the reduction reaction was carried out at room temperature. After approximately 2 hours, the reaction was terminated after confirming that the balloon no longer deflated. After the reaction was completed, the palladium compound catalyst was removed by filtration, and the mixture was concentrated using a rotary evaporator to obtain a hydroxyl group-containing diamine compound (α) represented by the following formula:

[0176]

[0177] Synthesis Example 2 Synthesis of quinone diazide compound (c-1) Under a dry nitrogen stream, 21.22 g (0.05 mol) of α,α-bis(4-hydroxyphenyl)-4-(4-hydroxy-α,α-dimethylbenzyl)-ethylbenzene (TrisP-PA (trade name) manufactured by Honshu Chemical Industry Co., Ltd.) and 26.87 g (0.10 mol) of 5-naphthoquinone diazide sulfonyl chloride were dissolved in 450 g of 1,4-dioxane at room temperature. To this solution, 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature in the system did not exceed 35°C. After the dropwise addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into water. The precipitate was then collected by filtration. This precipitate was dried in a vacuum dryer to obtain quinone diazide compound (c-1) represented by the following formula:

[0178]

[0179] Synthesis Example 3 Synthesis of Alkali-Soluble Resin (a-1) Under a dry nitrogen stream, 31.0 g (0.10 mol) of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (hereinafter referred to as ODPA) was dissolved in 500 g of N-methylpyrrolidone (hereinafter referred to as NMP). To this solution, 45.35 g (0.075 mol) of the hydroxyl group-containing diamine compound (α) obtained in Synthesis Example 1 and 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane (hereinafter referred to as SiDA) were added along with 50 g of NMP, and the mixture was allowed to react at 40°C for 2 hours. Next, 4.36 g (0.04 mol) of 3-aminophenol (hereinafter referred to as MAP) was added as an end-capping agent along with 5 g of NMP, and the mixture was allowed to react at 50°C for 2 hours. Thereafter, a solution prepared by diluting 32.39 g (0.22 mol) of N,N-dimethylformamide diethyl acetal with 50 g of NMP was added. After addition, the mixture was stirred at 50°C for 3 hours. After stirring was completed, the solution was cooled to room temperature and then added to 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 24 hours to obtain a polyimide precursor (a-1), which is an alkali-soluble resin.

[0180] Synthesis Example 4 Synthesis of Ionic Dye (b2-4) A mixture of 18.46 g (0.05 mol) of the compound represented by (β-1) in the following reaction formula, 120 g of sulfolane, 13.63 g of zinc chloride, and 20.58 g (0.15 mol) of 4-ethoxyaniline was heated and stirred at 170°C for 8 hours. After completion of the reaction, the reaction solution was allowed to cool to room temperature, and then the reaction solution was added dropwise to 450 g of 17.5% by mass hydrochloric acid at 0 to 10°C and stirred for 1 hour. Subsequently, the precipitate was collected by filtration, added to 500 g of a 5% by mass aqueous sodium carbonate solution, and stirred for 1 hour. After filtration, the precipitate was washed with pure water and dried at 60°C for 24 hours to obtain a xanthene compound (β-2) in which two of the nitrogen atoms were substituted with aryl groups.

[0181] Next, a mixture of 22.83 g (0.04 mol) of the obtained compound (β-2), 150 g of 1-methyl-2-pyrrolidone, 1.3 g of copper powder, 8.3 g of potassium carbonate, and 19.84 g (0.08 mol) of 4-iodophenetole was heated and stirred at 150°C for 12 hours. After completion of the reaction, the reaction solution was filtered to remove insoluble matter, and the reaction solution was added dropwise to 450 g of 17.5% by mass hydrochloric acid at 0 to 10°C and stirred for 1 hour. Thereafter, the precipitate was collected by filtration and dried at 60°C for 24 hours to obtain a xanthene compound (β-3) in which four nitrogen atoms were substituted with aryl groups.

[0182] Next, 1.69 g (0.011 mol) of phosphorus oxychloride was added dropwise to a mixture of 8.10 g (0.01 mol) of the obtained compound (β-3), 2.54 g (0.015 mol) of diphenylamine, 10.11 g (0.1 mol) of triethylamine, and 150 g of 1,2-dichloroethane at room temperature, and the mixture was heated and stirred at 85°C for 3 hours. After completion of the reaction, the reaction solution was allowed to cool to room temperature, then added to 300 g of pure water, and extracted with 100 g of chloroform. The organic layer was washed with 150 g of 4 mol / L hydrochloric acid and 150 g of pure water, and the solvent was then distilled off to obtain xanthene compound (β-4) in which xanthene compound (β-3) was amidated.

[0183] Next, 9.98 g (0.01 mol) of the obtained compound (β-4) was dissolved in 150 g of N,N-dimethylformamide (DMF), 2.91 g (0.015 mol) of sodium paratoluenesulfonate was added, and the mixture was heated and stirred at 40 ° C. for 3 hours. After the reaction solution was allowed to cool to room temperature, the reaction solution was poured into 1000 g of pure water, and the precipitated crystals were collected by filtration, washed with water, and then dried at 60 ° C. for 24 hours to obtain ionic dye (b2-4) in which the counter ion of (β-4) was exchanged. The obtained compound was subjected to LC-MS analysis using a liquid chromatograph mass spectrometer (Shimadzu Corporation LC-MS2020) and confirmed to be the target compound. LC-MS (ESI, posi): m / z 963 [M+H] ＋ LC-MS (ESI, nega): m / z 171 [M] － .

[0184]

[0185] Among the compounds used in each example and comparative example, the names or information of those other than those shown in the above synthesis examples are shown below. For the ionic dyes other than the commercially available products and (b2-4), salt-forming compounds consisting of an organic anion moiety of an acid dye and an organic cation moiety of a non-dye were synthesized using known methods. These compounds were salt-forming compounds consisting of an organic cation moiety of a basic dye and an organic anion moiety of a non-dye, and salt-forming compounds consisting of an organic anion moiety of an acid dye and an organic cation moiety of a basic dye. The maximum absorption wavelength of each ionic dye was calculated by measuring the transmission spectrum in a GBL solution from 300 nm to 800 nm using a UV-visible spectrophotometer (Shimadzu Corporation, MultiSpec-1500). d1-3-1: Solvent Blue 45 (a nonionic dye having a maximum absorption wavelength in the range of 580 nm or more and 800 nm or less) e-1: 4,4',4''-methylidynetrisphenol (a thermochromic compound) f12-1: 1,2,4-trihydroxybenzene (a compound (f) that satisfies the conditions that at least one substitution position of a phenolic hydroxyl group other than any one of the phenolic hydroxyl groups is the ortho position and the para position) g-1: 2,4,6-tris[bis(methoxymethyl)amino]-1,3,5-triazine GBL: γ-butyrolactone EL: ethyl lactate PGME: propylene glycol monomethyl ether.

[0186]

[0187] Example 1 10.0 g of polyimide precursor (a-1), 1.1 g of ionic dye (b1-1), 2.4 g of ionic dye (b2-1), 2.0 g of quinone diazide compound (c-1), and 2.0 g of (e-1) were dissolved in 10 g of GBL, 20 g of EL, and 70 g of PGME, and then filtered through a 0.2 μm polytetrafluoroethylene filter to obtain a positive-type photosensitive resin composition AA. Using the obtained photosensitive resin composition, the sensitivity and residue, OD value per 1 μm of film thickness, frozen storage stability, long-term reliability of organic EL display devices, and the mass of total chlorine and total bromine atoms relative to the total mass of the solid content of the photosensitive resin composition were evaluated as described above. However, the evaluation of the OD value and the long-term reliability evaluation of the organic EL display devices used cured films cured under atmospheric conditions.

[0188] [Examples 2 to 5, 7, Comparative Examples 1 to 3] Positive photosensitive resin compositions were obtained in the same manner as in Example 1, except that the types or amounts of the alkali-soluble resin (a), ionic dye (b), other additives, and solvent were changed as shown in Table 2. Using the obtained photosensitive resin compositions, evaluations were made of sensitivity, residue, OD value per 1 μm of film thickness, frozen storage stability, long-term reliability of organic EL display devices, and the masses of total chlorine and total bromine atoms relative to the total mass of the solid content of the photosensitive resin composition. However, evaluations of OD value and long-term reliability of organic EL display devices used cured films cured in an atmospheric atmosphere.

[0189] [Example 6] The photosensitive resin composition AE obtained in Example 5 was used to evaluate the sensitivity, residue, OD value per 1 μm of film thickness, frozen storage stability, long-term reliability of an organic EL display device, and the masses of total chlorine and bromine atoms relative to the total mass of the solid content of the photosensitive resin composition, as described above. However, the evaluation of the OD value and the evaluation of the long-term reliability of an organic EL display device used a cured film cured under a nitrogen atmosphere.

[0190] [Examples 8 and 9] The OD value per μm of film thickness and the amount of change in OD value due to repeated curing were evaluated as described above using the photosensitive resin composition AC obtained in Example 3 and the photosensitive resin composition AF obtained in Example 7. However, the cured films used were cured in the air for both the first and second times.

[0191] The compositions and evaluation results of each of the Examples and Comparative Examples are shown in Tables 2 to 4.

[0192]

[0193]

[0194]

[0195] 1: TFT (thin film transistor) 2: Wiring 3: TFT insulating layer 4: Planarizing layer 5: ITO (transparent electrode) 6: Substrate 7: Contact hole 8: Insulating layer 11: Display device 12: Light-emitting element 13: Cured product 14, 14c: Metal wiring 15: Counter substrate 16: Electrode terminal 17: Light-emitting element driving substrate 18: Driving element 19: Barrier metal 20: Solder bump 21: Non-alkali glass substrate 22: First electrode (transparent electrode) 23: Auxiliary electrode 24: Insulating layer 25: Organic EL layer 26: Second electrode (non-transparent electrode)

Claims

1. A photosensitive resin composition containing an alkali-soluble resin (a), an ionic dye (b) that forms an ion pair between organic ions between its molecules, and a photosensitive compound (c), wherein the photosensitive resin composition contains n types of ionic dye (b) and (n+1) types of organic ions (n ​​represents an integer of 2 to 10).

2. A photosensitive resin composition as described in claim 1, wherein the photosensitive compound (c) contains a photoacid generator (c1).

3. 3. The photosensitive resin composition according to claim 1, wherein the ionic dye (b) comprises an ionic dye (b1) having a maximum absorption wavelength in the range of 490 nm or more and less than 580 nm in the range of 350 to 800 nm, and an ionic dye (b2) having a maximum absorption wavelength in the range of 580 nm or more and less than 800 nm in the range of 350 to 800 nm.

4. The photosensitive resin composition according to claim 3 , wherein the organic anion moiety and / or the organic cation moiety of the ionic dye (b1) and the ionic dye (b2) have a xanthene skeleton.

5. 5. The photosensitive resin composition according to claim 1, wherein the ionic dye (b) has a sulfonic acid group and / or a sulfonate group.

6. The photosensitive resin composition according to any one of claims 1 to 5, wherein the alkali-soluble resin (a) comprises one or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, polyamideimide precursor, and copolymers thereof.

7. 7. The photosensitive resin composition according to claim 1, wherein the ionic dye (b) comprises a salt-forming compound comprising an organic anion moiety of an acid dye and an organic cation moiety of a basic dye.

8. The photosensitive resin composition according to any one of claims 1 to 7, further comprising (f) an aromatic hydrocarbon having at least one aromatic C-H bond and at least three phenolic hydroxyl groups in one aromatic ring, and (g) a triazine ring-containing compound represented by formula (1): 【Chemistry 1】 (In formula (1), R １ ~R ６ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyl ether group having 2 to 10 carbon atoms, a methylol group, or an alkoxymethyl group. １ ~R ６ At least one of these is a methylol group or an alkoxymethyl group.

9. 9. The photosensitive resin composition according to claim 1, wherein the total mass of all chlorine atoms and all bromine atoms contained in the photosensitive resin composition is 150 ppm or less, based on the total mass of solids excluding the solvent in the photosensitive resin composition.

10. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 9.

11. A method for producing a cured product, comprising the steps of: forming a resin film made of the photosensitive resin composition according to any one of claims 1 to 9 on a substrate; exposing the resin film to light; developing the exposed resin film; and heat-treating the developed resin film.

12. An organic EL display device having, on a substrate, a driving circuit, a planarizing layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode, wherein the planarizing layer and / or the insulating layer comprises the cured product according to claim 10.

13. 13. The organic electroluminescence display device according to claim 12, wherein the insulating layer has the cured product, and the optical density of the insulating layer in visible light per 1 μm of film thickness is 0.5 to 1.

0.

14. 14. The organic EL display device according to claim 12, further comprising a color filter having a black matrix.

15. A display device having at least metal wiring, the cured product according to claim 10, and a plurality of light-emitting elements, wherein the light-emitting elements have a pair of electrode terminals on either side thereof, the pair of electrode terminals are connected to a plurality of the metal wirings extending in the cured product, and the plurality of the metal wirings maintain electrical insulation due to the cured product.

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