Positive photosensitive resin composition, cured product, organic el display device, and method for producing cured product

Abstract

The purpose of the present invention is to provide a positive photosensitive resin composition which has high sensitivity, good development adhesion and high heat resistance, while providing a cured product thereof with high folding resistance, and which enables the achievement of high reliability if a cured product thereof is used in an organic EL display device. The present invention provides a positive photosensitive resin composition which contains (A) one or more substances that are selected from the group consisting of a polyimide, a polyimide precursor and a copolymer of those, (B) one or more substances that are selected from the group consisting of a polybenzoxazole, a polybenzoxazole precursor and a copolymer of those, (C) a polyhydroxystyrene and / or a copolymer of a polyhydroxystyrene and a polystyrene, (D) a quinonediazide compound, and (E) a solvent, wherein: the content of the component (B) is 10 parts by mass to 100 parts by mass relative to 100 parts by mass of the component (A); and the content of the component (C) is 1 part by mass to 90 parts by mass relative to 100 parts by mass of the component (A).

Description

Positive photosensitive resin composition, cured product, organic EL display device, and method for producing the cured product

[0001] The present invention relates to a positive photosensitive resin composition, a cured product using the same, an organic EL display device including the cured product, and a method for producing the cured product.

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

[0003] In general, an organic EL display device has a driving circuit, a planarization layer, a first electrode, a pixel division layer, a light-emitting layer, and a second electrode on a substrate, and can emit light by applying a voltage between the opposing first and second electrodes or by passing a current between them. Among these, photosensitive resin compositions that can be patterned by ultraviolet irradiation are generally used as materials for the planarization layer and the pixel division layer. Photosensitive resin compositions using polyimide resins are particularly preferred because they have high heat resistance and generate few gas components from the cured product processed by low-temperature curing at about 200 to 270°C, allowing for the production of highly reliable organic EL display devices (see, for example, Patent Document 1).

[0004] On the other hand, the demand for higher reliability for organic EL display devices is becoming stricter every year, and materials for the planarization layer and the pixel dividing layer are also required to be highly reliable, without causing a decrease in luminance or pixel shrinkage even after reliability tests under accelerated conditions such as high temperature, high humidity, and light irradiation. Here, pixel shrinkage refers to a phenomenon in which luminance decreases or pixels stop lighting from the edge of a pixel.

[0005] Furthermore, in order to shorten exposure time for reasons such as larger substrates and improved productivity, higher sensitivity is required for photosensitive resin compositions. On the other hand, high-sensitivity materials have the problem of poor development adhesion, so better development adhesion is required for photosensitive resin compositions.

[0006] Furthermore, in recent years, there has been active development of flexible organic EL display devices formed on resin film substrates. Flexible organic EL display devices have structurally bendable portions and / or portions that are fixed in a bent state, and bending stress is applied to the planarizing layer and pixel dividing layer at these bent portions. In flexible organic EL display devices that include such bent portions, high bending resistance is required for the materials for the planarizing layer and pixel dividing layer.

[0007] In light of this background, there is a strong demand for the development of a photosensitive resin composition that allows patterning with high sensitivity and that can give a cured product that has high heat resistance and bending resistance and is highly reliable.

[0008] To address these issues, siloxane resins have been investigated as photosensitive resin compositions capable of increasing sensitivity (see, for example, Patent Document 2).Also, the addition of specific phenolic hydroxyl group-containing compounds and phenolic antioxidants to photosensitive resin compositions has been investigated as photosensitive resin compositions capable of imparting high bending resistance (see, for example, Patent Document 3).

[0009] JP 2002-91343 A JP 2006-178436 A International Publication No. 2019-065351

[0010] However, it is difficult to say that the materials proposed in the above-mentioned patent documents have sufficient performance for applications where high reliability is required, such as in-vehicle displays. In view of the above problems, the present invention aims to provide a photosensitive resin composition that has high sensitivity, good development adhesion, high heat resistance, and high bending resistance of the cured product, and that provides high reliability when the cured product is used in an organic EL display device.

[0011] The present invention is as follows: [1] A positive photosensitive resin composition comprising: (A) one or more members selected from the group consisting of polyimides, polyimide precursors, and copolymers thereof; (B) one or more members selected from the group consisting of polybenzoxazoles, polybenzoxazole precursors, and copolymers thereof; (C) polyhydroxystyrenes and / or copolymers of polyhydroxystyrenes and polystyrenes; (D) a quinone diazide compound; and (E) a solvent, wherein the content of component (B) is 10 to 100 parts by mass per 100 parts by mass of component (A); and the content of component (C) is 1 to 90 parts by mass per 100 parts by mass of component (A). [2] The positive photosensitive resin composition according to [1], wherein the mass ratio [PI] / ([PB]+[PH]) is in the range of 0.5≦[PI] / ([PB]+[PH])≦5.0, where [PI] is the content of the component (A), [PB] is the content of the component (B), and [PH] is the content of the component (C). [3] The positive photosensitive resin composition according to [2], wherein the relationship between [PB] and [PH] is [PB]>[PH]. [4] The positive photosensitive resin composition according to [3], wherein the mass ratio between [PB] and [PH] is in the range of 1.01≦[PB] / [PH]≦55.00. [5] The positive photosensitive resin composition according to any one of [1] to [4], wherein the component (C) comprises polyhydroxystyrene. [6] The positive photosensitive resin composition according to any one of [1] to [5], wherein the (E) solvent contains a polar aprotic solvent. [7] The positive photosensitive resin composition according to [6], wherein the content of the polar aprotic solvent is 1 to 30% by mass, relative to 100% by mass of the (E) solvent. [8] The positive photosensitive resin composition according to any one of [1] to [7], wherein the solids concentration of the positive photosensitive resin composition is 3 to 30% by mass. [9] The positive photosensitive resin composition according to any one of [1] to [8], wherein the (B) component contains a resin having a main chain formed from a structural unit represented by formula (1) described below.

[10] The positive photosensitive resin composition according to any one of [1] to [9], further containing (F) a thermal acid generator.

[11] The positive photosensitive resin composition according to

[10] , wherein the (F) thermal acid generator contains a thermal acid generator having a sulfonate ester structure.

[12] The photosensitive resin composition according to

[10] or

[11] , wherein the thermal acid generator (F) contains a compound represented by formula (2) described below.

[13] A cured product obtained by curing the positive photosensitive resin composition according to any one of [1] to

[12] .

[14] A cured product in which, when analyzed by reactive pyrolysis GC / MS, a compound represented by formula (3) described below, a compound represented by formula (4) described below, and a compound represented by formula (5) described below are detected, and the detected peak intensity ratio, when the compound represented by formula (4) is taken as 1, is 0.1 to 1 for the compound represented by formula (3) and 0.1 to 3 for the compound represented by formula (5).

[15] An organic EL display device comprising the cured product according to

[13] or

[14] .

[16] A method for producing a cured product, comprising the steps of: (1) applying the positive photosensitive resin composition according to any one of [1] to

[12] to a substrate to form a positive photosensitive resin film; (2) drying the positive photosensitive resin film; (3) exposing the dried positive photosensitive resin film through a photomask; (4) developing the exposed positive photosensitive resin film; and (5) heat-treating the developed positive photosensitive resin film, in this order.

[0012] The photosensitive resin composition of the present invention has high sensitivity, good development adhesion, high heat resistance, and high bending resistance of the cured product, and it is possible to provide a photosensitive resin composition that has high reliability when the cured product is used in an organic EL display device.

[0013] 1 is a cross-sectional view of an organic EL display device in which a planarizing layer and a pixel dividing layer are formed.

[0014] The positive photosensitive resin composition of the present invention contains (A) one or more compounds selected from the group consisting of polyimides, polyimide precursors, and copolymers thereof (hereinafter, sometimes referred to as component (A)), (B) one or more compounds selected from the group consisting of polybenzoxazoles, polybenzoxazole precursors, and copolymers thereof (hereinafter, sometimes referred to as component (B)), (C) polyhydroxystyrene and / or a copolymer of polyhydroxystyrene and polystyrene (hereinafter, sometimes referred to as component (C)), (D) a quinone diazide compound, and (E) a solvent, wherein the content of component (B) is 10 to 100 parts by mass per 100 parts by mass of component (A), and the content of component (C) is 1 to 90 parts by mass per 100 parts by mass of component (A).

[0015] By adjusting the content of component (B) to 10 to 100 parts by mass per 100 parts by mass of component (A), a cured product with good heat resistance and bending resistance can be obtained. By adjusting the content of component (C) to 1 to 90 parts by mass per 100 parts by mass of component (A), the sensitivity of the resin composition is improved and development adhesion is improved. By containing three components (A), (B), and (C), it is possible to provide a photosensitive resin composition that achieves the desired high sensitivity, good development adhesion, high heat resistance, and high bending resistance of the cured product, and that provides high reliability when used in an organic EL display device.

[0016] The positive photosensitive resin composition of the present invention contains (A) one or more components selected from the group consisting of polyimides, polyimide precursors, and copolymers thereof. Component (A) can contain polyimides containing structural units of known polyimides, polyimide precursors containing structural units of known polyimide precursors, and known copolymers thereof. In the present invention, component (A) is defined as a resin having an imide bond in its main chain. When component (A) contains polybenzoxazole structural units and / or polybenzoxazole precursor structural units in addition to polyimide structural units and / or polyimide precursor structural units, it is referred to as component (A). Component (A) preferably has an alkali-soluble group. The alkali-soluble resin refers to a dissolution rate of 50 nm / min or more, determined from the reduction in film thickness when a solution of a 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, 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.

[0017] In order to impart alkali solubility, it is preferable for the resin to have an acidic group in its structural unit and / or at its main chain terminal. Examples of the acidic group include a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group. Furthermore, it is preferable for component (A) to have a fluorine atom, which can impart water repellency to the interface between the film and the substrate when developing with an alkaline aqueous solution, thereby preventing the alkaline aqueous solution from penetrating into the interface. The fluorine atom content of component (A) is preferably 5% by mass or more from the viewpoint of the effect of preventing the alkaline aqueous solution from penetrating into the interface, and is preferably 20% by mass or less from the viewpoint of solubility in an alkaline aqueous solution.

[0018] The component (A) is synthesized by a known method.

[0019] In the case of polyimide precursors, polyamic acids can be synthesized by, for example, a method of reacting tetracarboxylic dianhydride with a diamine compound at low temperature; and polyamic acid esters can be synthesized by, for example, a method of reacting tetracarboxylic dianhydride with a diamine compound at low temperature and then partially esterifying the amide acid structure with N,N-dimethylformamide dimethyl acetal or the like; a method of obtaining a diester from tetracarboxylic dianhydride and an alcohol and then reacting it with an amine in the presence of a condensing agent; or a method of obtaining a diester from tetracarboxylic dianhydride and an alcohol and then converting the remaining dicarboxylic acid into an acid chloride and reacting it with an amine.

[0020] In the case of polyimide, for example, it can be obtained by heating the polyamic acid or polyamic acid ester obtained by the above-mentioned method in a solvent or by dehydrating and ring-closing the polyamic acid or polyamic acid ester through a chemical treatment with an acid or a base.

[0021] Specific examples of the tetracarboxylic dianhydride used in component (A) 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 Examples of the tetracarboxylic acid dianhydride include aliphatic tetracarboxylic acid dianhydrides such as bis(3,4-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorene dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 2,3,5,6-pyridinetetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, butanetetracarboxylic acid dianhydride, and 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride. Two or more of these tetracarboxylic acid dianhydrides may be used as the tetracarboxylic acid dianhydride used as component (A).

[0022] Specific examples of the diamine compound used in component (A) 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- Examples of the diamine compound include 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-di(trifluoromethyl)-4,4'-diaminobiphenyl, 9,9-bis(4-aminophenyl)fluorene, and compounds in which at least a portion of the hydrogen atoms in these aromatic rings have been substituted with alkyl groups or halogen atoms, as well as aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, and diamines having the structures shown below. Two or more of these diamine compounds may be used.

[0023]

[0024] R ３ and R ６ are each independently an oxygen atom, C(CF ３ ) ２ , or C(CH ３ ) ２ Represents R ４ , R ５ and R ７ ~R １４ each independently represents a hydrogen atom or a hydroxyl group.

[0025] Furthermore, in order to improve the storage stability of the positive-type photosensitive resin composition, it is preferable to cap the main chain ends of these components (A) with a known end-capping agent such as a monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound, etc. For the purpose of improving the chemical resistance of the cured resin obtained by baking, it is also possible to use, as these end-capping agents, monoamines, acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds having at least one alkenyl group or alkynyl group.

[0026] From the viewpoint of improving storage stability, the content of the terminal blocking agent such as a monoamine, an acid anhydride, an acid chloride, or a monocarboxylic acid is preferably 1 mol% or more, more preferably 5 mol% or more, relative to 100 mol% of the total of all monomer components constituting component (A). Furthermore, from the viewpoint of obtaining a resin with good film properties, the content is preferably 40 mol% or less, more preferably 30 mol% or less, relative to 100 mol% of the total of all monomer components constituting component (A). Multiple different terminal groups may be introduced into component (A) by reacting multiple terminal blocking agents.

[0027] The positive-type photosensitive resin composition of the present invention contains (B) one or more components selected from the group consisting of polybenzoxazole, polybenzoxazole precursor, and copolymers thereof. In the present invention, component (B) is defined as a resin that does not contain an imide bond in the main chain. Component (B) may contain a polybenzoxazole containing a structural unit of a known polybenzoxazole, a polybenzoxazole precursor containing a structural unit of a known polybenzoxazole precursor, or a known copolymer thereof.

[0028] In the present invention, component (B) preferably has an alkali-soluble group. To impart alkali solubility, component (B) preferably has an acidic group in its structural unit and / or at its main chain terminal. Examples of acidic groups include a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group. Furthermore, component (B) preferably has a fluorine atom, which can impart water repellency to the interface between the film and the substrate during development with an alkaline aqueous solution and inhibit penetration of the alkaline aqueous solution into the interface. The fluorine atom content in component (B) is preferably 5% by mass or more from the viewpoint of preventing penetration of the alkaline aqueous solution into the interface, and is preferably 20% by mass or less from the viewpoint of solubility in the alkaline aqueous solution.

[0029] The component (B) is synthesized by a known method.

[0030] Polybenzoxazole precursors can be produced by condensation reaction of a bisaminophenol compound with a dicarboxylic acid. Specifically, a method of reacting a dehydration condensation agent such as dicyclohexylcarbodiimide (DCC) with an acid and then adding the bisaminophenol compound thereto, or 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, can be used.

[0031] Polybenzoxazole can be obtained, for example, by heating the polybenzoxazole precursor obtained by the above-mentioned method in a solvent or by dehydrating and ring-closing it by chemical treatment with an acid or a base.

[0032] Examples of dicarboxylic acids used in component (B) include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, and triphenyl dicarboxylic acid. Examples of tricarboxylic acids include trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, and biphenyl tricarboxylic acid. Examples of tetracarboxylic acids include pyromellitic acid, 3,3',4,4'-biphenyl tetracarboxylic acid, 2,3,3',4'-biphenyl tetracarboxylic acid, 2,2',3,3'-biphenyl tetracarboxylic acid, 3,3',4,4'-benzophenone tetracarboxylic acid, 2,2',3,3'-benzophenone tetracarboxylic acid, and 2,2-bis( Examples of the dicarboxylic acid used in component (B) include aliphatic tetracarboxylic acids such as 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, butanetetracarboxylic acid, and 1,2,3,4-cyclopentanetetracarboxylic acid. Two or more of these dicarboxylic acids may be used in combination as the dicarboxylic acid used in component (B).

[0033] Specific examples of the bisaminophenol compound used in component (B) 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'-diaminodi ... Examples of bisaminophenol compounds used in component (B) include methyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-di(trifluoromethyl)-4,4'-diaminobiphenyl, 9,9-bis(4-aminophenyl)fluorene, and compounds in which at least a portion of the hydrogen atoms on these aromatic rings have been substituted with alkyl groups or halogen atoms, as well as aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, and diamines having the structures shown below. Two or more of these bisaminophenol compounds may be used as component (B).

[0034]

[0035] R ３ and R ６ are each independently an oxygen atom, C(CF ３ ) ２ , or C(CH ３ ) ２ Represents R ４ , R ５ and R ７ ~R １４ each independently represents a hydrogen atom or a hydroxyl group.

[0036] Furthermore, in order to improve the storage stability of the positive-type photosensitive resin composition, it is preferable to cap the main chain ends of these components (B) with a known end-capping agent such as a monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound, etc. For the purpose of improving the chemical resistance of the cured resin obtained by baking, it is also possible to use, as these end-capping agents, monoamines, acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds having at least one alkenyl group or alkynyl group.

[0037] From the viewpoint of improving storage stability, the content of the terminal blocking agent such as monoamine, acid anhydride, acid chloride, or monocarboxylic acid is preferably 1 mol% or more, more preferably 5 mol% or more, relative to 100 mol% of the total of all monomer components constituting component (B). Furthermore, from the viewpoint of obtaining a resin with good film properties, the content is preferably 40 mol% or less, more preferably 30 mol% or less, relative to 100 mol% of the total of all monomer components constituting component (B). Multiple different terminal groups may be introduced into component (B) by reacting multiple terminal blocking agents.

[0038] The content of the positive-type photosensitive resin composition component (B) is 10 to 100 parts by mass per 100 parts by mass of the component (A). If the content of the component (B) is less than 10 parts by mass per 100 parts by mass of the component (A), bending resistance decreases. The content of the component (B) is preferably 20 parts by mass or more. On the other hand, if the content of the component (B) exceeds 100 parts by mass per 100 parts by mass of the component (A), heat resistance decreases. The content of the component (B) is preferably 95 parts by mass or less per 100 parts by mass of the component (A).

[0039] The component (B) preferably contains a resin having a structural unit represented by formula (1) in the main chain. By containing a resin having a structural unit represented by formula (1) in the main chain, bending resistance is improved.

[0040]

[0041] In formula (1), R １ and R ２ each independently represents a divalent to octavalent organic group having 2 to 30 carbon atoms, p represents an integer of 0 to 4, and q represents an integer of 1 to 4.

[0042] The positive photosensitive resin composition of the present invention contains (C) polyhydroxystyrene and / or a copolymer of polyhydroxystyrene and polystyrene. "Containing (C) polyhydroxystyrene and / or a copolymer of polyhydroxystyrene and polystyrene" means containing either polyhydroxystyrene or a copolymer of polyhydroxystyrene and polystyrene, or both.

[0043] The component (C) of the present invention is synthesized by a known method.

[0044] Component (C) can be produced by addition polymerization of a phenol derivative having an unsaturated bond. Examples of phenol derivatives having an unsaturated bond include hydroxystyrene, dihydroxystyrene, allylphenol, coumaric acid, 2'-hydroxychalcone, N-hydroxyphenyl-5-norbornene-2,3-dicarboxylic acid imide, resveratrol, and 4-hydroxystilbene, and two or more of these may be used together. Furthermore, the component (C) may be a copolymer with a monomer that does not contain a phenolic hydroxyl group, such as styrene. This facilitates adjustment of the alkali dissolution rate of component (C).

[0045] The content of the component (C) is 1 to 90 parts by mass per 100 parts by mass of the component (A). If the content of the component (C) is less than 1 part by mass per 100 parts by mass of the component (A), sensitivity decreases. The content of the component (C) is preferably 3 parts by mass or more per 100 parts by mass of the component (A). On the other hand, if the content of the component (C) exceeds 90 parts by mass per 100 parts by mass of the component (A), development adhesion decreases. The content of the component (C) is preferably 70 parts by mass or less per 100 parts by mass of the component (A).

[0046] The preferred weight average molecular weight of the component (C) can be determined in polystyrene equivalent terms by gel permeation chromatography (GPC). From the viewpoint of sensitivity, the weight average molecular weight is preferably 1,000 or more, more preferably 3,000 or more, and even more preferably 4,000 or more. From the viewpoint of development adhesion, the weight average molecular weight is preferably 10,000 or less, more preferably 8,000 or less, and even more preferably 7,000 or less.

[0047] From the viewpoint of sensitivity, the component (C) preferably contains polyhydroxystyrene.

[0048] In the positive photosensitive resin composition of the present invention, when the content of the component (A) is [PI] (mass), the content of the component (B) is [PB] (mass), and the content of the component (C) is [PH] (mass), the mass ratio [PI] / ([PB] + [PH]) is preferably in the range of 0.5≦[PI] / ([PB] + [PH])≦5.0. When [PI] / ([PB] + [PH]) is 0.5 or more, heat resistance can be improved. [PI] / ([PB] + [PH]) is more preferably 1 or more. On the other hand, when [PI] / ([PB] + [PH]) is 5 or less, sensitivity can be improved. [PI] / ([PB] + [PH]) is more preferably 4 or less.

[0049] The relationship between [PB] and [PH] is preferably [PB]>[PH]. By satisfying [PB]>[PH], it is possible to improve development adhesion. The relationship between [PI], [PB], and [PH] is preferably [PI]>[PB]>[PH]. By satisfying [PI]>[PB]>[PH], it is possible to improve the heat resistance of a cured product processed by low-temperature curing at about 200 to 270°C.

[0050] The mass ratio of [PB] to [PH] is preferably in the range of 1.01≦[PB] / [PH]≦55.00. When the mass ratio of [PB] / [PH] is 1.01 or more, development adhesion can be improved. The mass ratio of [PB] / [PH] is more preferably 1.50 or more, and even more preferably 2.00 or more. On the other hand, when the mass ratio of [PB] / [PH] is 55.00 or less, sensitivity can be improved. The mass ratio of [PB] / [PH] is more preferably 30.00 or less, and even more preferably 10.00 or less.

[0051] The positive photosensitive resin composition of the present invention contains (D) a quinonediazide compound.

[0052] By including the quinone diazide compound (D), acid is generated in the irradiated areas, increasing the solubility of the irradiated areas in an alkaline aqueous solution, thereby making it possible to obtain a positive relief pattern in which the irradiated areas are dissolved.

[0053] Examples of the (D) quinone diazide compound include a polyhydroxy compound to which quinone diazide sulfonic acid is ester-bonded, a polyamino compound to which quinone diazide sulfonic acid is sulfonamide-bonded, and a polyhydroxy polyamino compound to which quinone diazide sulfonic acid is ester-bonded and / or sulfonamide-bonded. When the total hydroxy or amino groups of the polyhydroxy or polyamino compound in the (D) quinone diazide compound is taken as 100 mol %, it is preferred that 50 mol % or more of the hydroxy or amino groups are esterified or sulfonamide-bonded with quinone diazide sulfonic acid. The positive photosensitive resin composition (D) may contain two or more quinone diazide compounds.

[0054] Among the quinone diazide compounds (D), naphthoquinone diazide sulfonic acid ester compounds can be preferably contained. Naphthoquinone diazide sulfonic acid ester compounds can be synthesized by esterification reaction between a compound having a phenolic hydroxyl group and a quinone diazide sulfonic acid compound, and can be synthesized by a known method. By using these naphthoquinone diazide sulfonic acid ester compounds, resolution, sensitivity, and film retention rate can be further improved.

[0055] The compounds having a phenolic hydroxyl group used herein include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, and BisRS-26X. , DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPH AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl- Preferred examples include compounds such as p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, and BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) to which naphthoquinone diazide-4-sulfonic acid or naphthoquinone diazide-5-sulfonic acid has been introduced via an ester bond, but other compounds can also be used.

[0056] Naphthoquinone diazide sulfonic acid 4-ester compounds have absorption in the i-line region of a mercury lamp and are suitable for i-line exposure, while naphthoquinone diazide-5-sulfonic acid ester compounds have absorption extending to the g-line region of a mercury lamp and are suitable for g-line exposure. The photosensitive resin composition of the present invention may contain either a naphthoquinone diazide-4-sulfonic acid ester compound or a naphthoquinone diazide-5-sulfonic acid ester compound, may contain a naphthoquinone diazide sulfonic acid ester compound containing both a naphthoquinone diazide-4-sulfonyl group and a naphthoquinone diazide-5-sulfonyl group in the same molecule, or may contain a mixture of a naphthoquinone diazide-4-sulfonic acid ester compound and a naphthoquinone diazide-5-sulfonic acid ester compound.

[0057] The content of the quinone diazide compound (D) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, per 100 parts by mass of the polyimide resin (A) from the viewpoint of improving sensitivity during exposure, and is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, per 100 parts by mass of the polyimide resin (A) from the viewpoint of reducing outgassing from the cured product.

[0058] The positive photosensitive resin composition of the present invention contains a solvent (E). By containing the solvent (E), the composition can be made into a varnish state, and the coatability can be improved.

[0059] Examples of the solvent (E) include polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide; ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tetrahydrofuran, and dioxane; acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, and diacetone methyl ether. The solvents may be contained alone or in admixture, such as ketones such as ethanol, 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, other esters such as ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, methyl acetoacetate, and ethyl acetoacetate, and aromatic hydrocarbons such as toluene and xylene.

[0060] From the viewpoint of improving coatability, the solvent (E) preferably contains a polar aprotic solvent, such as N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, or dimethyl sulfoxide.

[0061] The content of the (E) solvent is preferably such that the solids concentration of the positive photosensitive resin composition is 3 to 30% by mass. If the solids concentration is less than 3% by mass, the coatability deteriorates, and a content of 5% by mass or more is more preferable. Furthermore, if the content of the (E) solvent exceeds 30% by mass, the storage stability of the positive photosensitive resin composition deteriorates, and a content of 20% by mass or less is more preferable. Here, the solids concentration refers to the concentration of components other than the (E) solvent in the positive photosensitive resin composition.

[0062] The content of the polar aprotic solvent is preferably 1 to 30% by mass relative to 100% by mass of the (E) solvent. A content of 1% by mass or more can improve the solubility of the (A), (B), and (C) components, thereby improving the linearity of the pattern after development. The content of the polar aprotic solvent is more preferably 3% by mass or more relative to 100% by mass of the (E) solvent. Furthermore, a content of the polar aprotic solvent of 30% by mass or less relative to 100% by mass of the (E) solvent can improve the solvent drying property during pre-baking and improve the development adhesion. The content of the polar aprotic solvent is more preferably 15% by mass or less, and even more preferably 10% by mass or less, relative to 100% by mass of the (E) solvent.

[0063] The positive photosensitive resin composition of the present invention may contain known compounds such as a thermal crosslinking agent.

[0064] Examples of the thermal crosslinking agent include DML-PC, DML-PEP, DMOM-PC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP, and HMOM-TPPA (all of which are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), "NIKALAC" (registered trademark) MX-270, and "NIKA thermal crosslinking agents having a methylol group and / or an alkoxymethyl group, such as "DENACOL" EX-850L, "DENACOL" EX-201-IM (trade names, manufactured by Nagase ChemteX Corporation), VG3101L (trade name, manufactured by Printec Co., Ltd.), "TEPIC" (registered trademark)-S, "TEPIC"-L, "TEPIC"-VL, "TEPIC"-FL, "TEPIC"-UC (trade names, manufactured by Nissan Chemical Industries, Ltd.), and other epoxy group crosslinking agents; thermal crosslinking agents having an oxetane group such as OXT-121, OXT-221, OX-SQ-H, OXT-191, PNOX-1009, and RSOX (all trade names, manufactured by Toagosei Co., Ltd.); bismaleimide thermal crosslinking agents such as 1,2-bis(maleimido)ethane, 1,3-bis(maleimido)propane, 1,4-bis(maleimido)butane, 1,5-bis(maleimido)pentane, 1,6-bis(maleimido)hexane, and 2,2,4-trimethyl-1,6-bis(maleimido)hexane; 4,4'-methylenebis(maleimido)ethane, 1,3-bis(maleimido)propane, 1,4-bis(maleimido)butane, 1,5-bis(maleimido)pentane, 1,6-bis(maleimido)hexane, and 2,2,4-trimethyl-1,6-bis(maleimido)hexane; Examples of suitable thermal crosslinking agents include aromatic polyisocyanates such as bis(phenylene isocyanate) (MDI) and tolylene diisocyanate (TDI); aliphatic polyisocyanates such as hexamethylene diisocyanate (HDI), trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, pentamethylene diisocyanate and lysine diisocyanate; and alicyclic polyisocyanates such as isophorone diisocyanate (IPDI) and 4,4'-methylenebis(cyclohexyl isocyanate) (H12MDI).

[0065] From the viewpoint of improving the chemical resistance of the cured product, the content of the thermal crosslinking agent is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, per 100 parts by mass of the component (A). Furthermore, from the viewpoint of reducing outgassing from the cured product and further improving the reliability of the organic EL display device, the content of the thermal crosslinking agent is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less, per 100 parts by mass of the component (A).

[0066] The positive-type photosensitive resin composition of the present invention may contain a thermal acid generator (F). A thermal acid generator is a compound that generates an acid upon heating. The thermal decomposition onset temperature of the thermal acid generator is preferably 120°C or higher, more preferably 130°C or higher, and even more preferably 140°C or higher. By setting the thermal decomposition temperature to 120°C or higher, it is possible to prevent the generation of acid during the process of heating and drying the applied positive-type photosensitive resin film (sometimes referred to as the pre-baking process) during pattern processing. Furthermore, the thermal decomposition onset temperature of the thermal acid generator (F) is preferably 250°C or lower, more preferably 240°C or lower, and even more preferably 230°C or lower. Setting the thermal decomposition temperature to 250°C or lower allows sufficient acid to be generated during the heating process. In the present invention, generating an acid during the heating process can promote the crosslinking reaction of the thermal crosslinker, thereby significantly reducing the amount of unreacted crosslinkable groups remaining in the cured product. If unreacted crosslinkable groups remain in the cured product, gas components will be generated during reliability testing, causing undesirable phenomena such as a decrease in brightness and pixel shrinkage in the organic EL display device. However, the crosslinking-promoting effect of the acid generated from the thermal acid generator can significantly improve the reliability of the organic EL display device.

[0067] The thermal acid generator (F) in the positive photosensitive resin composition of the present invention may be any compound that has the function of generating an acid upon heating, and also includes compounds that have the function of generating an acid upon exposure to light such as ultraviolet light in addition to heat. However, quinone diazide compounds (D) are not defined as being included in the thermal acid generator (F) even if they generate an acid upon heating.

[0068] The acid generated from the (F) thermal acid generator is preferably a strong acid, for example, an arylsulfonic acid such as p-toluenesulfonic acid or benzenesulfonic acid, an alkylsulfonic acid such as methanesulfonic acid, ethanesulfonic acid or butanesulfonic acid, or camphorsulfonic acid.

[0069] Examples of the thermal acid generator (F) include sulfonium salts and sulfonic acid esters. Two or more of these may be contained. In terms of generating heat by heating, it is preferable that the sulfonium salt contains a compound selected from the group consisting of monoarylsulfonium salts and trialkylsulfonium salts.

[0070] Among the thermal acid generators (F), it is preferable to contain a thermal acid generator having a sulfonate structure, since this has a high effect of improving the reliability of organic EL display devices. For example, methyl methanesulfonate, ethyl methanesulfonate, propyl methanesulfonate, butyl methanesulfonate, phenyl methanesulfonate, methyl ethanesulfonate, ethyl ethanesulfonate, propyl ethanesulfonate, butyl ethanesulfonate, phenyl ethanesulfonate, methyl propanesulfonate, ethyl propanesulfonate, propyl propanesulfonate, butyl propanesulfonate, phenyl propanesulfonate, methyl butanesulfonate, ethyl butanesulfonate, propyl butanesulfonate, butyl butanesulfonate, phenyl butanesulfonate, methyl octanesulfonate, ethyl octanesulfonate, propyl octanesulfonate, butyl octanesulfonate, phenyl octanesulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, propyl p-toluenesulfonate, butyl p-toluenesulfonate, phenyl p-toluenesulfonate, methane Examples of suitable thermal acid generators include methoxyphenyl sulfonate, methoxyethyl methanesulfonate, methoxyethyl p-toluenesulfonate, "Irgacure" (registered trademark), PAG103, PAG121 (trade names, manufactured by BASF Japan Ltd.), PA-411, and PA-480 (trade names, manufactured by Heraeus K.K.). Other examples of thermal acid generators having a sulfonate ester structure include PAI-01, PAI-101, PAI-106, PAI-1001, and PAI-10 02, PAI-1003, PAI-1004 (trade names, manufactured by Midori Chemical Co., Ltd.), SP-082, SP-601, SP-606, SP-607, SP-612 (trade names, manufactured by ADEKA Corporation), NIT, MIN, ILP-110, ILP-110N, ILP-118, ILP-113, PA-223, PA-298 (trade names, manufactured by Heraeus K.K.), NAI-105, NAI-106, NAI-109 (trade names, manufactured by Midori Chemical Co., Ltd.), and the like.

[0071] Furthermore, it is particularly preferable that the (F) thermal acid generator contains a compound represented by formula (2). When the (F) thermal acid generator contains a compound represented by formula (2), the volatility of the (F) thermal acid generator during curing (heat treatment) is reduced, allowing the (F) thermal acid generator to efficiently generate acid during curing, and the crosslinking promotion effect is enhanced, thereby improving the reliability of the organic EL display device. Furthermore, when the (F) thermal acid generator contains a compound represented by formula (2), the solubility in an alkaline developer is more likely to be improved compared to when the (F) thermal acid generator does not contain a compound represented by formula (2), thereby improving exposure sensitivity.

[0072]

[0073] (In formula (2), R １５ is a divalent to tetravalent group having 1 to 10 carbon atoms. １６ each independently represents an alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent. Examples of the substituent include a hydroxyl group, a halogen atom, a cyano group, a vinyl group, an acetylene group, or a linear or cyclic alkyl group having 1 to 10 carbon atoms. a represents an integer of 2 to 4. From the viewpoint of not reducing the exposure sensitivity, in formula (2), R １５ is a divalent to tetravalent group having 1 to 6 carbon atoms which may have a substituent, and R １６ are preferably each independently a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms which may have a substituent.

[0074] Examples of the compound represented by the formula (2) include compounds having a plurality of alcoholic hydroxyl groups (sometimes referred to as polyhydric alcohol compounds), and compounds having a plurality of phenolic hydroxyl groups (sometimes referred to as polyhydric phenol compounds) in which the alcoholic hydroxyl groups or the phenolic hydroxyl groups are sulfonated with methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, octanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, etc. Specific examples of dihydric alcohol compounds among the polyhydric alcohol compounds include methanediol, ethanediol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, and decanediol. Among the polyhydric alcohol compounds, specific examples of trihydric or higher alcohol compounds include propanetriol, butanetriol, pentanetriol, hexanetriol, heptanetriol, octanetriol, nonanetriol, decanetriol, pentaerythritol, etc. Specific examples of polyhydric phenol compounds include dihydroxybenzene, trihydroxybenzene, tetrahydroxybenzene, etc.

[0075] From the viewpoint of easily obtaining the effects of improving exposure sensitivity and improving the reliability of organic EL display devices, the content of the compound represented by formula (2) is preferably 20% by mass or more, more preferably 50% by mass or more, even more preferably 70% by mass or more, and particularly preferably 100% by mass, relative to 100% by mass of the thermal acid generator (F).

[0076] From the viewpoint of further improving the reliability of the organic EL display device, the content of the thermal acid generator (F) is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and even more preferably 3 parts by mass or more, when the total parts by mass of the components (A) and (B) are taken as 100 parts by mass. Also, from the viewpoint of imparting high heat resistance to the cured product, the content of the thermal acid generator (F) is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 8 parts by mass or less, when the total parts by mass of the components (A) and (B) are taken as 100 parts by mass.

[0077] The positive photosensitive resin composition of the present invention may contain a colorant. The colorant refers to a known organic pigment, inorganic pigment, or dye. The colorant is preferably an organic pigment and / or an inorganic pigment.

[0078] Examples of organic pigments include diketopyrrolopyrrole pigments, azo pigments such as azo, disazo or polyazo, copper phthalocyanine, threne pigments, benzofuranone or metal complex pigments.

[0079] Examples of inorganic pigments include titanium oxide, zinc white, zinc sulfide, white lead, calcium carbonate, precipitated barium sulfate, white carbon, manganese violet, and cobalt violet.

[0080] Examples of dyes include azo dyes, anthraquinone dyes, condensed polycyclic aromatic carbonyl dyes, indigoid dyes, carbonium dyes, phthalocyanine dyes, methine or polymethine dyes.

[0081] For the purpose of improving the contrast of an organic EL display device, the colorant is preferably black, which can block visible light across the entire wavelength range. Preferably, the positive-type photosensitive resin composition contains at least one colorant selected from organic pigments, inorganic pigments, and dyes, which will exhibit a black color when cured. To achieve this, the composition may contain the above-mentioned black organic pigments and black inorganic pigments, or two or more organic pigments and dyes may be mixed to produce a pseudo-black color. A pseudo-black color can be obtained by mixing two or more organic pigments and dyes, such as those described above, such as red, orange, yellow, purple, blue, and green. The positive-type photosensitive resin composition of the present invention does not necessarily have to be black; a colorant that changes color upon heat curing to produce a black cured product may also be used.

[0082] Among these, from the viewpoint of ensuring high heat resistance, it is preferable to contain an organic pigment and / or an inorganic pigment and a colorant that will exhibit a black color when cured. Also, from the viewpoint of ensuring high insulating properties, it is preferable to contain an organic pigment and / or a dye and a colorant that will exhibit a black color when cured. In other words, from the viewpoint of achieving both high heat resistance and insulating properties, it is preferable to contain an organic pigment and a colorant that will exhibit a black color when cured.

[0083] The content of the colorant is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, based on the total amount of the positive photosensitive resin composition excluding the solvent, from the viewpoint of obtaining the necessary colorability in the cured product. Also, from the viewpoint of obtaining good storage stability, the content is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less, based on the total amount of the positive photosensitive resin composition excluding the solvent.

[0084] When the positive photosensitive resin composition contains a pigment, it preferably contains a dispersant. The inclusion of a dispersant allows the colorant to be uniformly and stably dispersed in the positive photosensitive resin composition. The dispersant is not particularly limited, but a polymeric dispersant is preferred. Examples of polymeric dispersants include polyester-based polymeric dispersants, acrylic-based polymeric dispersants, polyurethane-based polymeric dispersants, polyallylamine-based polymeric dispersants, and carbodiimide-based dispersants. More specifically, a polymeric dispersant refers to a polymeric compound whose main chain is made of polyamino, polyether, polyester, polyurethane, polyacrylate, or the like, and which has polar groups such as amine, carboxylic acid, phosphoric acid, amine salt, carboxylate salt, and phosphate salt on the side chain or main chain end. The polar groups adsorb to the pigment, and the steric hindrance of the main chain polymer stabilizes the pigment dispersion.

[0085] Dispersants are classified into (polymeric) dispersants having only an amine value, (polymeric) dispersants having only an acid value, (polymeric) dispersants having both an amine value and an acid value, and (polymeric) dispersants having neither an amine value nor an acid value. Of these, (polymeric) dispersants having both an amine value and an acid value and (polymeric) dispersants having only an amine value are preferred, and (polymeric) dispersants having only an amine value are more preferred.

[0086] The content of the dispersant is preferably 1 part by mass or more, more preferably 3 parts by mass or more, per 100 parts by mass of the pigment from the viewpoint of obtaining good dispersion stability, and is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, per 100 parts by mass of the pigment from the viewpoint of maintaining the heat resistance of the cured product.

[0087] The positive photosensitive resin composition used in the present invention may contain an adhesion improver. Examples of adhesion improvers include silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane; zirconia chelating agents, 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 positive photosensitive resin film, for example, it is possible to improve the adhesion of the film to silicon wafers, ITO, SiO ２ The adhesion improver can improve adhesion to the underlying substrate such as silicon nitride. It can also improve resistance to oxygen plasma and UV ozone treatments used for cleaning, etc. The content of the adhesion improver is preferably 0.1 to 10 mass % based on the total amount of the positive photosensitive resin composition excluding the solvent.

[0088] The positive photosensitive resin composition used in the present invention may contain a surfactant for the purpose of improving wettability with the substrate, as necessary. Commercially available surfactants can be used. Specific examples of silicone surfactants include the SH series, SD series, and ST series from Toray Dow Corning Silicones, the BYK series from BYK Japan, the KP series from Shin-Etsu Silicones, the Disfoam series from NOF Corporation, and the TSF series from Toshiba Silicones. Specific examples of fluorine-based surfactants include the Megafac (registered trademark) series from Dainippon Ink Mfg. Co., Ltd., the Fluorad series from Sumitomo 3M, the Surflon (registered trademark) series and Asahi Guard (registered trademark) series from Asahi Glass Co., Ltd., the EF series from Shin-Akita Chemical Co., Ltd., and the Polyfox series from Omnova Solutions. Specific examples of surfactants made from acrylic and / or methacrylic polymers include the Polyflow series from Kyoeisha Chemical Co., Ltd. and the Disparlon (registered trademark) series from Kusumoto Chemical Co., Ltd., but are not limited thereto.

[0089] The content of the surfactant is preferably 0.001 to 1% by mass based on the total amount of the positive photosensitive resin composition excluding the solvent.

[0090] The positive photosensitive resin composition used in the present invention may contain a compound having a phenolic hydroxyl group, if necessary, for the purpose of supplementing the alkaline developability of the photosensitive resin composition. Examples of the compound having a phenolic hydroxyl group include Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP-Z, BisOCR-CP, BisP-MZ, BisP-EZ, Bis26X-CP, BisP-PZ, BisP-IPZ, BisCRIPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, and Bis sOTBP-CP, TekP-4HBPA (tetrakis P-DO-BPA), TrisPHAP, TrisP-PA, TrisP-PHBA, TrisP-SA, TrisOCR-PA, BisOFP- Z, BisRS-2P, BisPG-26X, BisRS-3P, BisOC-OCHP, BisPC-OCHP, Bis25X-OCHP, Bis26X-OCHP, BisOCHP-OC, Bis23 6T-OCHP, Methylene Tris-FR-CR, BisRS-26X, BisRS-OCHP, (product name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, B IR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A (trade name, manufactured by Asahi Yokuzai Kogyo Co., Ltd.), 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, Examples of such compounds include 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,4-dihydroxyquinoline, 2,6-dihydroxyquinoline, 2,3-dihydroxyquinoxaline, anthracene-1,2,10-triol, anthracene-1,8,9-triol, and 8-quinolinol. By incorporating these compounds having a phenolic hydroxyl group, the resulting positive-type photosensitive resin composition is almost insoluble in an alkaline developer before exposure, but readily dissolves in an alkaline developer after exposure, resulting in less film loss due to development and easy development in a short time. This tends to improve sensitivity.

[0091] The content of such a compound having a phenolic hydroxyl group is preferably 1% by mass or more and 20% by mass or less based on the total amount of the positive photosensitive resin composition excluding the solvent.

[0092] The positive photosensitive resin composition used in the present invention may also contain inorganic particles. Preferred examples include, but are not limited to, silicon oxide, titanium oxide, barium titanate, alumina, and talc. The primary particle size of these inorganic particles is preferably 100 nm or less, more preferably 60 nm or less.

[0093] The content of the inorganic particles is preferably 5 to 90% by mass based on the total amount of the positive photosensitive resin composition excluding the solvent.

[0094] Next, a method for producing the positive photosensitive resin composition of the present invention will be described. For example, the positive photosensitive resin composition can be obtained by dissolving the components (A), (B), (C), (D) a quinone diazide compound, and (E) a solvent, and optionally an adhesion improver, a surfactant, a colorant, inorganic particles, and the like.

[0095] 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 positive 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.

[0096] The obtained positive photosensitive resin composition is preferably filtered using a filter to remove dust. The filter pore size is, for example, but not limited to, 0.5 μm, 0.2 μm, 0.1 μm, 0.07 μm, 0.05 μm, 0.02 μm, etc. The filter material may be polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), etc., with polyethylene and nylon being preferred. When the positive photosensitive resin composition contains pigments or particles, it is preferable to use a filter with a pore size larger than the particle size of these pigments or particles.

[0097] The cured product of the present invention is a cured product obtained by curing a positive photosensitive resin composition. The cured product can be obtained by heat-treating the positive photosensitive resin composition. The heat treatment can be performed using a known method such as a hot plate, an oven, or infrared rays. Preferred heat treatment conditions will be described later in the section on the method for producing a cured product (5) - Heat-treating the developed positive photosensitive resin film.

[0098] Next, a method for producing a cured film using the positive photosensitive resin composition of the present invention will be described in detail. The method for producing a cured film includes, in this order, (1) a step of applying the above-mentioned positive photosensitive resin composition to a substrate to form a positive photosensitive resin film, (2) a step of drying the positive photosensitive resin film (pre-baking step), (3) a step of exposing the dried positive photosensitive resin film through a photomask, (4) a step of developing the exposed positive photosensitive resin film, and (5) a step of heat-treating the developed positive photosensitive resin film.

[0099] (1) In the step of applying the above-mentioned positive photosensitive resin composition to a substrate to form a positive photosensitive resin film, the positive photosensitive resin composition of the present invention is applied by a method such as spin coating, slit coating, dip coating, spray coating, or printing to obtain a positive photosensitive resin film of the positive photosensitive resin composition. Prior to application, the substrate to which the positive photosensitive resin composition is to be applied may be pretreated with the above-mentioned adhesion improver.

[0100] For example, the substrate surface may be treated with a solution prepared by dissolving the adhesion improver in a concentration of 0.5 to 20% by mass in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate, etc. Examples of the substrate surface treatment method include spin coating, slit die coating, bar coating, dip coating, spray coating, and steam treatment.

[0101] (2) In the step of drying the positive photosensitive resin film, the applied positive photosensitive resin film is subjected to a reduced pressure drying treatment as needed, and then subjected to a heat treatment at a temperature in the range of 50°C to 180°C for 1 minute to several hours using a hot plate, an oven, infrared rays, or the like, to obtain a positive photosensitive resin film.

[0102] Next, the step (3) of exposing the dried positive photosensitive resin film through a photomask will be described. The positive photosensitive resin film is irradiated with actinic radiation through a photomask having a desired pattern. Actinic radiation used for exposure includes ultraviolet light, visible light, electron beams, and X-rays. In the present invention, it is preferable to use i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) from a mercury lamp.

[0103] After irradiation with actinic radiation, post-exposure baking may be performed. By performing post-exposure baking, effects such as improved resolution after development or an increased tolerance for development conditions can be expected. For post-exposure baking, an oven, a hot plate, infrared radiation, a flash annealing device, a laser annealing device, or the like can be used. The post-exposure baking temperature is preferably 50 to 180°C, more preferably 60 to 150°C. The post-exposure baking time is preferably 10 seconds to several hours. When the post-exposure baking time is within the above range, the reaction proceeds well and the development time can be shortened in some cases.

[0104] (4) In the step of developing the exposed positive photosensitive resin film, the exposed positive photosensitive resin film is developed using a developer to remove areas other than the exposed area. Preferred 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.

[0105] In some cases, polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide, etc., alcohols such as methanol, ethanol, isopropanol, etc., esters such as ethyl lactate, propylene glycol monomethyl ether acetate, etc., ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, methyl isobutyl ketone, etc. may be added to these alkaline aqueous solutions, either alone or in combination. Development methods that can be used include spray, paddle, immersion, ultrasonic, etc.

[0106] Next, the pattern formed by development is preferably rinsed with distilled water. Here, too, alcohols such as ethanol and isopropyl alcohol, or esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to the distilled water for rinsing.

[0107] Next, (5) a step of heat-treating the developed positive photosensitive resin film is carried out. Heat treatment can remove residual solvents and components with low heat resistance, thereby improving heat resistance and chemical resistance. The positive photosensitive resin composition of the present invention can form imide rings and oxazole rings by heat treatment, thereby improving heat resistance and chemical resistance. Furthermore, when a thermal crosslinking agent is contained, heat treatment can promote a thermal crosslinking reaction, improving heat resistance and chemical resistance. From the viewpoint of improving the heat resistance of the cured product, the heat treatment temperature is preferably 200°C or higher, more preferably 220°C or higher, even more preferably 230°C or higher, and particularly preferably 240°C or higher.

[0108] On the other hand, from the viewpoint of avoiding the influence of thermal degradation of the TFT element, the temperature is preferably 400°C or less, more preferably 350°C or less, and even more preferably 270°C or less. Within this temperature range, the temperature may be increased stepwise or continuously. From the viewpoint of improving the heat resistance of the cured product, the heat treatment time is preferably 30 minutes or more, more preferably 45 minutes or more. Furthermore, from the viewpoint of productivity, the heat treatment time is preferably 180 minutes or less, more preferably 120 minutes or less. For example, a method of heat treatment at 150°C and 250°C for 60 minutes each, or a method of heat treatment while linearly increasing the temperature from room temperature to 250°C over 2 hours may be mentioned.

[0109] The cured product of the present invention is preferably a cured product formed from the positive photosensitive resin composition of the present invention. In another embodiment of the cured product of the present invention, when analyzed by reactive pyrolysis GC / MS, the compound represented by formula (3), the compound represented by formula (4), and the compound represented by formula (5) are detected, and the detected peak intensity ratio, when the compound represented by formula (4) is taken as 1, is 0.1 to 1 for the compound represented by formula (3) and 0.1 to 3 for the compound represented by formula (5).

[0110]

[0111] (In formula (3), formula (4) and formula (5), R １７ ~R ２３ each independently represents a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms which may contain a heteroatom.

[0112] In formulas (3), (4), and (5), examples of the monovalent organic group having 1 to 30 carbon atoms and which may contain a heteroatom include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group.

[0113] The alkyl group may be linear, branched, or cyclic. The number of carbon atoms in linear and branched alkyl groups is typically 1 to 30, preferably 1 to 20, and more preferably 1 to 10, from the viewpoints of maintaining high heat resistance and bending resistance of the cured product. The number of carbon atoms in cyclic alkyl groups is typically 3 to 30, preferably 3 to 20, and more preferably 3 to 10, from the viewpoints of maintaining high heat resistance and bending resistance of the cured product. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, and decyl groups.

[0114] The alkenyl group may be linear, branched, or cyclic. The number of carbon atoms in linear and branched alkenyl groups is usually 2 to 30, preferably 2 to 20, and more preferably 2 to 10, from the viewpoints of maintaining high heat resistance and bending resistance of the cured product. The number of carbon atoms in cyclic alkenyl groups is usually 3 to 30, preferably 3 to 20, and more preferably 3 to 10, from the viewpoints of maintaining high heat resistance and bending resistance of the cured product. Examples of alkenyl groups include ethenyl, propenyl, isopropenyl, butenyl, pentenyl, hexenyl, nonenyl, and decenyl groups.

[0115] The alkynyl group may be linear, branched, or cyclic. The number of carbon atoms in linear and branched alkynyl groups is usually 2 to 30, preferably 2 to 20, and more preferably 2 to 10, from the viewpoints of maintaining high heat resistance and high bending resistance of the cured product. The number of carbon atoms in cyclic alkynyl groups is usually 3 to 30, preferably 3 to 20, and more preferably 3 to 10, from the viewpoints of maintaining high heat resistance and high bending resistance of the cured product. Examples of alkynyl groups include ethynyl, propynyl, butynyl, pentynyl, and hexynyl groups.

[0116] The aryl group is an atomic group remaining after removing one hydrogen atom directly bonded to a carbon atom constituting an aromatic ring from an aromatic hydrocarbon, and includes those having a hydroxyl group, the alkyl group, the alkenyl group, or the alkynyl group as a functional group. The number of carbon atoms in the aryl group is typically 6 to 30, preferably 6 to 20. Examples of the aryl group include a phenyl group, a hydroxyphenyl group, an alkylphenyl group, and an alkylhydroxyphenyl group. From the viewpoint of balancing high heat resistance and bending resistance of the cured product, a hydroxyphenyl group or an alkylhydroxyphenyl group is preferred. Examples of the alkylphenyl group include a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a propylphenyl group, a methylethylphenyl group, a propylphenyl group, an isopropylphenyl group, a butylphenyl group, an isobutylphenyl group, a tert-butylphenyl group, a pentylphenyl group, a hexylphenyl group, a cyclohexylphenyl group, a heptylphenyl group, an octylphenyl group, a nonylphenyl group, and a decylphenyl group. Examples of the alkylhydroxyphenyl group include a methylhydroxyphenyl group, an ethylhydroxyphenyl group, a dimethylhydroxyphenyl group, a propylhydroxyphenyl group, a methylethylhydroxyphenyl group, a propylhydroxyphenyl group, an isopropylhydroxyphenyl group, a butylhydroxyphenyl group, an isobutylhydroxyphenyl group, a tert-butylhydroxyphenyl group, a pentylhydroxyphenyl group, a hexylhydroxyphenyl group, a cyclohexylhydroxyphenyl group, a heptylhydroxyphenyl group, an octylhydroxyphenyl group, a nonylhydroxyphenyl group, and a decylhydroxyphenyl group.

[0117] From the viewpoint of balancing high heat resistance and bending resistance of the cured product, ２ , R ３ , R ４ At least one of the groups is preferably an alkyl group, an alkenyl group, an alkynyl group, or an aryl group. More preferably, the group contains both an alkyl group and a hydroxyphenyl group and / or an alkylhydroxyphenyl group.

[0118] When the cured product is analyzed by reactive pyrolysis GC / MS, the compound represented by formula (3), the compound represented by formula (4), and the compound represented by formula (5) are detected, and when the detected peak intensity ratio of the compound represented by formula (4) is 1, the compound represented by formula (3) is 0.1 to 1 and the compound represented by formula (5) is 0.1 to 3, it becomes easier to obtain a cured product that has high heat resistance and high bending resistance.

[0119] The compounds contained in the cured product of the present invention will be explained. The compound represented by formula (3) can be obtained, for example, as a structure derived from (C) polyhydroxystyrene and / or a copolymer of polyhydroxystyrene and polystyrene, or as a residue thereof. The compound represented by formula (4) can be obtained, for example, as a structure derived from (A) polyimide, polyimide precursor, and copolymers thereof, or as a residue thereof. The compound represented by formula (5) can be obtained, for example, as a structure derived from (B) polybenzoxazole, polybenzoxazole precursor, and copolymers thereof, or as a residue thereof.

[0120] A cured product formed from the positive photosensitive resin composition of the present invention can be used in a display device including a first electrode formed on a substrate and a second electrode provided opposite the first electrode, specifically, for example, a planarizing layer in a liquid crystal display device, a planarizing layer and / or a pixel dividing layer in an organic EL display device, etc. Hereinafter, an organic EL display device will be described as an example.

[0121] The organic EL display device of the present invention includes the cured product. Specifically, it is preferable that the organic EL display device has a substrate on which a driving circuit, a planarization layer, a first electrode, a pixel division layer, a light-emitting layer, and a second electrode are disposed, and the planarization layer and / or the pixel division layer contains the cured product. Taking an active matrix display device as an example, a substrate such as glass or a resin film has thin film transistors (hereinafter, TFTs) and wiring located on the sides of the TFTs and connected to the TFTs, a planarization layer is disposed thereon to cover the irregularities, and a display element is further disposed on the planarization layer. The display element and the wiring are connected via contact holes formed in the planarization layer. In particular, flexible organic EL display devices have become mainstream in recent years, and it is preferable that the substrate on which the driving circuit is disposed is made of a resin film.

[0122] In the organic EL display device of the present invention, at least a portion of the portion comprising the cured product preferably has a bendable portion and / or a portion fixed in a bent state. By using a cured product obtained by curing the positive photosensitive resin composition or photosensitive resin sheet of the present invention, an organic EL display device with excellent bending resistance can be obtained. The radius of curvature of the bendable portion and / or the portion fixed in a bent state is preferably 0.1 mm or more and 5 mm or less. A radius of curvature of 0.1 mm or more ensures bending resistance at the bent portion, while a radius of curvature of 5 mm or less ensures design features such as a narrow frame.

[0123] The organic EL display device of the present invention can be bent at any appropriate portion. For example, the organic EL display device may be bent at the center like a foldable display device, or at the edges from the viewpoint of design and maximizing the display screen. Furthermore, the organic EL display device may be bent along its longitudinal direction or along its lateral direction. It is sufficient that a specific portion of the organic EL display device is bendable depending on the application (for example, some or all of the four corners can be bent diagonally).

[0124] 1 shows a cross-sectional view of an example of an organic EL display device in which a planarization layer and a pixel division layer are formed. Bottom-gate or top-gate TFTs 1 are arranged in a matrix on a substrate 6, and 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 provided on the TFT insulating layer 3, burying the wiring 2. A contact hole 7 is provided in the planarization layer 4, reaching the wiring 2. An ITO (transparent electrode) 5 is formed on the planarization layer 4, connected to the wiring 2 via the contact hole 7.

[0125] Here, the ITO 5 serves as an electrode for a display element (e.g., an organic EL element). A pixel division layer 8 is formed to cover the periphery of the ITO 5. The organic EL element may be a top-emission type that emits emitted light from the side opposite the substrate 6, or a bottom-emission type that extracts light from the substrate 6 side. In this way, an active matrix organic EL display device is obtained in which each organic EL element is connected to a TFT 1 for driving it.

[0126] The TFT insulating layer 3, the planarizing layer 4, and / or the pixel dividing layer 8 can be formed by the steps of forming a positive photosensitive resin film made of the positive photosensitive resin composition of the present invention, exposing the positive photosensitive resin film to light, developing the exposed positive photosensitive resin film, and heat-treating the developed positive photosensitive resin film, as described above. An organic EL display device can be obtained by a manufacturing method including these steps.

[0127] Furthermore, cured products formed from the positive photosensitive resin composition of the present invention can be used as insulating films or protective films that constitute electronic components. Examples of electronic components include active components having semiconductors, such as transistors, diodes, integrated circuits (hereinafter referred to as ICs), and memories, as well as passive components, such as resistors, capacitors, and inductors. Electronic components using semiconductors are also referred to as semiconductor devices. Specific examples of cured products suitable for use in electronic components include passivation films for semiconductors, surface protective films for semiconductor elements, TFTs, and the like, interlayer insulating films in multilayer wiring for high-density packaging of 2 to 10 layers, and insulating films and protective films for touch panel displays. However, the present invention is not limited to these and can have a variety of structures.

[0128] The substrate surface on which the cured product is formed can be appropriately selected depending on the application and process, and examples thereof include silicon, ceramics, metal, glass, epoxy resin, etc., and a plurality of these may be arranged on the same surface. Examples of electronic devices having a surface protective film or interlayer insulating film on which the cured product of the present invention is arranged include MRAMs with low heat resistance. That is, the cured product of the present invention is suitable for use as a surface protective film for MRAMs.

[0129] In addition to MRAM, polymer memory (Polymer Ferroelectric RAM: PFRAM) and phase change memory (Phase Change RAM: PCRAM, or Ovonics Unified Memory: OUM), which are promising next-generation memories, are also likely to use new materials that have lower heat resistance than conventional memories. Therefore, the cured product of the present invention is also suitable for use as a surface protection film for these memories.

[0130] It is also suitable for use in fan-out wafer level packages (hereinafter referred to as fan-out WLPs), which are semiconductor packages that secure the required number of terminals by providing an extension section around the semiconductor chip using a sealing resin such as epoxy resin, rewiring from the electrodes on the semiconductor chip to the extension section, and mounting solder balls on the extension section as well.

[0131] In fan-out WLP, wiring is installed across the boundary formed by the main surface of the semiconductor chip and the main surface of the encapsulation resin. That is, an interlayer insulating film is formed on a base material composed of two or more materials, namely, a semiconductor chip with metal wiring and an encapsulation resin, and wiring is then formed on the interlayer insulating film.

[0132] In addition, in a semiconductor package in which a semiconductor chip is embedded in a recess formed in a glass epoxy resin substrate, wiring is provided so as to straddle the boundary between the main surface of the semiconductor chip and the main surface of the printed circuit board. In this embodiment, an interlayer insulating film is formed on a substrate made of two or more materials, and wiring is formed on the interlayer insulating film. The cured product obtained by curing the positive photosensitive resin composition of the present invention has high adhesion to a semiconductor chip provided with metal wiring and also has high adhesion to sealing resins such as epoxy resins, making it suitable for use as an interlayer insulating film provided on a substrate made of two or more materials.

[0133] The present invention will be explained below with reference to examples, but the present invention is not limited to these examples. The positive photosensitive resin compositions in the examples were evaluated by the following methods.

[0134] (1) Sensitivity Evaluation The positive photosensitive resin compositions obtained in each of the Examples and Comparative Examples described below were applied onto an 8-inch silicon wafer by spin coating using an ACT-8 coating and developing apparatus (manufactured by Tokyo Electron Limited), and baked on a hot plate at 120°C for 3 minutes to produce a pre-baked film with a film thickness of 3.0 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.

[0135] Thereafter, using an exposure machine i-line stepper NSR-2005i9C (manufactured by Nikon Corporation), 50 to 300 mJ / cm was applied through a mask having a pattern of 10 μm contact holes. ２ at an exposure dose of 10 mJ / cm ２After the exposure, the film was developed using the ACT-8 developing device with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (hereinafter, TMAH, manufactured by Tama Chemicals Co., Ltd.) for a time period such that the film thickness was reduced to 0.5 μm during development, and then the film was rinsed with distilled water and shaken off to dry, thereby obtaining a pattern.

[0136] The resulting developed film pattern was observed at a magnification of 20 times using an FDP microscope MX61 (manufactured by Olympus Corporation), and the minimum exposure dose required for the contact hole opening diameter to reach 10 μm was determined. This was taken as the exposure sensitivity, and was calculated as 200 mJ / cm ２ The following were judged to be acceptable. The smaller the sensitivity value, the higher the sensitivity, and the more preferable it is.

[0137] (2) Evaluation of Bending Resistance The positive photosensitive resin compositions obtained in each of the Examples and Comparative Examples described below were applied to a polyimide film substrate by spin coating at an arbitrary rotation speed to obtain a positive photosensitive resin film, which was then prebaked for 2 minutes on a hot plate at 120°C as a drying step to obtain a positive photosensitive resin film. Next, using an automatic developing apparatus (AD-2000 manufactured by Takizawa Sangyo Co., Ltd.), the film was shower-developed for 90 seconds with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, and then rinsed with pure water for 30 seconds. The developed substrate with the positive photosensitive resin film was cured (heat-treated) for 60 minutes in an oven at 250°C under a nitrogen atmosphere to obtain a cured product with a film thickness of 2.0 μm.

[0138] Next, 10 polyimide film substrates with a size of 50 mm length x 10 mm width were cut out from the cured product. The cut polyimide films were then stored in an air atmosphere at 100°C for 500 hours. Thereafter, with the cured product facing outward, the polyimide film substrate was folded 180° along a 25 mm vertical line and held in this state for 30 seconds. After 30 seconds, the folded polyimide film substrate was unfolded, and the bent portion along the 25 mm vertical line on the cured product surface was observed using an FPD inspection microscope (MX-61L; manufactured by Olympus Corporation) to evaluate changes in the appearance of the cured product surface. The bending test was performed with a curvature radius ranging from 0.1 to 2.0 mm, and the minimum curvature radius (mm) at which the cured product did not peel from the polyimide film substrate or exhibit changes in appearance such as cracks on the cured product surface was recorded. A smaller minimum curvature radius (mm) is preferable because it has higher bending resistance.

[0139] (3) Reliability Test of Organic EL Display Device <Fabrication of Organic EL Display Device> Figure 2 shows a schematic diagram of the substrate used. First, a 100 nm thick ITO transparent conductive film was formed on the entire surface of a 38 x 46 mm alkali-free glass substrate 11 by sputtering, and then etched to form a first electrode 12. At the same time, an auxiliary electrode 13 was also formed to extract the second electrode. The resulting substrate was ultrasonically cleaned with "Semicoclean 56" (trade name, manufactured by Furuuchi Chemical Co., Ltd.) for 10 minutes and then washed with ultrapure water. Next, a positive-type photosensitive resin composition (varnish) corresponding to each of the Examples and Comparative Examples described below was applied to the entire surface of the substrate by spin coating, and the substrate was prebaked on a hot plate at 120°C for 2 minutes. This film was exposed to UV light through a photomask using a parallel light mask aligner (hereinafter referred to as PLA) (PLA-501F, manufactured by Canon Inc.) and an ultra-high pressure mercury lamp as the light source (a mixture of g-line, h-line, and i-line). The resulting patterned substrate was then developed with a 2.38% TMAH aqueous solution to dissolve only the exposed areas, followed by rinsing with pure water. The resulting patterned substrate was cured for 60 minutes in an inert oven (CLH-21CD-S, manufactured by Koyo Thermo Systems Co., Ltd.) at 250°C under a nitrogen atmosphere. In this way, a pixel dividing layer 14 was formed in the effective area of ​​the substrate, with openings 50 μm wide and 260 μm long arranged at a widthwise pitch of 155 μm and a lengthwise pitch of 465 μm, each of which exposed a portion of the first electrode. In this way, a pixel division layer with an aperture ratio of 18% was provided in the substrate effective area, which was a rectangle with one side measuring 16 mm, and the thickness of the pixel division layer was approximately 2.0 μm.

[0140] Next, a nitrogen plasma treatment was performed as a pretreatment, and then the organic EL layer 15 was formed by vacuum deposition. 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.

[0141]

[0142] Next, a compound (LiQ) was vapor-deposited to a thickness of 2 nm, followed by vapor deposition of 60 nm of Mg and Ag at a volume ratio of 1:10 to form the second electrode 16. Finally, a cap-shaped glass plate was attached using an epoxy resin adhesive in a low-humidity nitrogen atmosphere to seal the substrate, and four light-emitting 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.

[0143] <Reliability Evaluation> The fabricated organic EL display devices were stored in an air atmosphere at 100°C, and were taken out every 100 hours, driven by a direct current at 10 mA / cm2, and the light-emitting area of ​​the light-emitting pixels was measured. The reliability (unit: hours) of the organic EL display device was determined as the minimum time for the light-emitting area to become 50 or less after the UV irradiation treatment test, assuming that the initial light-emitting area before the reliability test was 100, and a reliability of 500 hours or more was determined to pass. A longer minimum time for the light-emitting area to become 50 or less after the UV irradiation treatment test is preferred because it indicates better reliability.

[0144] (4) Heat Resistance Evaluation The positive photosensitive resin compositions obtained in each of the Examples and Comparative Examples described below were applied to an 8-inch silicon wafer by spin coating using an ACT-8 coater / developer (manufactured by Tokyo Electron Limited), and baked on a hot plate at 120°C for 3 minutes to produce a pre-baked film with a film thickness of 3.0 μm. Thereafter, using the ACT-8 developer, the wafer was developed using a 2.38% by mass aqueous solution of tetramethylammonium (hereinafter referred to as TMAH, manufactured by Tama Chemicals Co., Ltd.) for a time until the film thickness was reduced to 0.5 μm. The wafer was then rinsed with distilled water and shaken dry. The wafer was then cured for 60 minutes in an inert oven (CLH-21CD-S manufactured by Koyo Thermo Systems Co., Ltd.) under a nitrogen atmosphere at 250°C. The resulting cured product was peeled off with hydrofluoric acid to obtain a film. 10 mg of the obtained single-layer film was packed into an Al clamp cell to prepare a TGA measurement sample, and thermogravimetric measurement was performed using a TGA-50 (manufactured by Shimadzu Corporation) under a nitrogen atmosphere while raising the temperature by 10°C per minute. A temperature of 320°C or higher at which the weight was reduced by 5% from the weight at 200°C was considered to be acceptable. A higher temperature at which the weight was reduced by 5% from the weight at 200°C indicates higher heat resistance and is therefore preferred.

[0145] (5) Evaluation of Development Adhesion The positive photosensitive resin compositions obtained in each of the Examples and Comparative Examples described below were applied to an 8-inch silicon wafer by spin coating using an ACT-8 coating and developing apparatus (manufactured by Tokyo Electron Limited), and baked on a hot plate at 120°C for 3 minutes to produce a pre-baked film with a film thickness of 3.0 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), the wafer was exposed to light at an exposure dose corresponding to the exposure sensitivity obtained in (1) through a mask having a pattern of many closed portions with a diameter of 3 to 100 μm. 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.) for a time period such that the film thickness was reduced by 0.5 μm during development. The film was then rinsed with distilled water and then shaken off and dried to obtain a pattern.

[0146] The resulting developed film pattern was observed at a magnification of 20 times using an FDP microscope MX61 (manufactured by Olympus Corporation), observing 100 locations per size, and the minimum closed pattern where 90 or more patterns remained without peeling was confirmed. If patterns of 10 μm or less remained without peeling, the pattern was deemed to have passed. A smaller minimum closed pattern where 90 or more patterns remained without peeling is preferred because it indicates excellent development adhesion.

[0147] (6) Evaluation of pattern linearity after development The pattern of the developed film obtained in (5) was observed at a magnification of 20 times using an FDP microscope MX61 (manufactured by Olympus Corporation). 100 50 μm closed patterns were observed, and if 90 or more patterns had no shape abnormality, the result was rated as good (A); if 80 or more patterns had no shape abnormality, the result was rated as fair (B); and if fewer than 80 patterns had no shape abnormality, the result was rated as poor (C).

[0148] <Composition analysis by reactive pyrolysis GC / MS> After adding 3 μL of a reaction reagent (tetramethylammonium hydroxide) to 61 μg of the cured product obtained in (4), a Multi-Shot Pyrolyzer PY-3030D (manufactured by Frontier Labs) was used to perform pyrolysis at a heating temperature of 400 ° C., and a gas chromatograph mass spectrometer JMS-Q1000GC (K9) (manufactured by JEOL Ltd.) was used. The GC column was a stainless steel capillary column (0.25 mm inner diameter × 30 m, stationary phase; 5% phenyl polydimethylsiloxane), and the GC temperature was increased from 40 ° C. (held for 3 minutes) to 320 ° C. at a rate of 20 ° C. / min., the inlet temperature was 300 ° C., the column flow rate was 1.5 mL / min, the ionization method was EI (electron ionization) method, the mass number range was m / z 20 to 800, and the scan speed was 0.5 sec / scan. Analysis was performed.

[0149] The compounds used in the examples and comparative examples are shown below.

[0150] Synthesis Example 1 Synthesis of Hydroxyl Group-Containing Diamine Compound 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. A solution of 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride dissolved in 100 mL of acetone was added dropwise to the solution. After the dropwise addition was completed, 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.

[0151] 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% palladium-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 when it was confirmed that the balloon was no longer deflating. After the reaction was completed, the palladium compound catalyst was removed by filtration, and the mixture was concentrated using a rotary evaporator to obtain a hydroxyl group-containing diamine compound represented by the following formula:

[0152]

[0153] Synthesis Example 2: Synthesis of Polyimide Precursor (P1) Under a dry nitrogen stream, 62.0 g (0.20 mol) of 3,3',4,4'-diphenylethertetracarboxylic dianhydride (hereinafter referred to as ODPA) was dissolved in 500 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP). To this solution, 96.7 g (0.16 mol) of the hydroxyl group-containing diamine compound obtained in Synthesis Example 1 was added together with 100 g of NMP, and the mixture was allowed to react at 20°C for 1 hour, followed by a reaction at 50°C for 2 hours. Next, 8.7 g (0.08 mol) of 3-aminophenol as an end-capping agent was added together with 50 g of NMP, and the mixture was allowed to react at 50°C for 2 hours. Thereafter, a solution prepared by diluting 47.7 g (0.40 mol) of N,N-dimethylformamide dimethyl acetal with 100 g of NMP was added dropwise over 10 minutes. After the dropwise addition, the mixture was stirred at 50°C for 3 hours. After stirring, the solution was cooled to room temperature and then poured into 5 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 24 hours to obtain the target polyimide precursor (P1).

[0154] Synthesis Example 3: Synthesis of Polyimide (P2) Under a dry nitrogen stream, 58.6 g (0.16 mol) of BAHF and 8.7 g (0.08 mol) of 3-aminophenol as an end-capping agent were dissolved in 300 g of N-methyl-2-pyrrolidone (NMP). 62.0 g (0.20 mol) of ODPA was added to the solution along with 100 g of NMP, and the mixture was stirred at 20°C for 1 hour, followed by stirring at 50°C for 4 hours. 15 g of xylene was then added, and the mixture was stirred at 150°C for 5 hours while azeotropically distilling water with the xylene. After stirring, the solution was poured into 5 L of water, and a white precipitate was collected. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 24 hours to obtain the target polyimide (P2).

[0155] Synthesis Example 4: Synthesis of Polybenzoxazole Precursor (P3) Under a dry nitrogen stream, 0.16 mol of a mixture of dicarboxylic acid derivatives obtained by reacting 41.3 g (0.16 mol) of diphenyl ether-4,4'-dicarboxylic acid with 43.2 g (0.32 mol) of 1-hydroxy-1,2,3-benzotriazole was dissolved in 570 g of NMP, and 73.3 g (0.20 mol) of BAHF were dissolved in the mixture and reacted at 75°C for 12 hours. Next, 13.1 g (0.08 mol) of 5-norbornene-2,3-dicarboxylic anhydride dissolved in 70 g of NMP was added, and the mixture was stirred for an additional 12 hours to complete the reaction. The reaction mixture was filtered and then poured into a solution of water / methanol = 3 / 1 (volume ratio), yielding a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 24 hours to obtain the target polybenzoxazole (PBO) precursor (P3). P3 had the structural unit represented by the above formula (1).

[0156] Synthesis Example 5 Synthesis of Polyhydroxystyrene (P4) 2400 g of tetrahydrofuran was mixed with 2.56 g (0.04 mol) of sec-butyllithium as an initiator, and 105.75 g (0.6 mol) of p-t-butoxystyrene was added to the mixture. After polymerization with stirring for 3 hours, 12.82 g (0.4 mol) of methanol was added to carry out a polymerization termination reaction. Next, to purify the polymer, the reaction mixture was poured into 3 L of methanol, and the precipitated polymer was dried. The obtained polymer was dissolved in 1.6 L of acetone, 2 g of concentrated hydrochloric acid was added at 60 ° C., and the mixture was stirred for 7 hours, and p-t-butoxystyrene was deprotected and converted to hydroxystyrene. After completion of the reaction, the solution was poured into water to precipitate the polymer. The obtained precipitate was washed three times with water and then dried in a vacuum dryer at 50 ° C. for 24 hours to obtain the desired polyhydroxystyrene (P4).

[0157] Synthesis Example 6: Synthesis of acrylic resin (P5) A methyl methacrylate / methacrylic acid / styrene copolymer (mass ratio 30 / 40 / 30) was synthesized by a known method (Japanese Patent No. 3120476; Example 1). 40 parts by mass of glycidyl methacrylate was added to 100 parts by mass of the copolymer, and the mixture was reprecipitated in purified water, filtered, and dried to obtain acrylic resin (P5), which is a polymer containing a radical polymerizable monomer.

[0158] Synthesis Example 7 Synthesis of Quinonediazide Compound Under a dry nitrogen stream, 21.22 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 36.27 g (0.135 mol) of 5-naphthoquinone diazide sulfonyl chloride were dissolved in 450 g of 1,4-dioxane and the solution was allowed to reach 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 1 represented by the following formula:

[0159]

[0160] <Thermal crosslinking agent having an epoxy group> TEPIC-VL: "TEPIC" (registered trademark)-VL (an epoxy thermal crosslinking agent containing an isocyanuric ring structure, a compound represented by the following chemical formula, manufactured by Nissan Chemical Industries, Ltd.)

[0161]

[0162] <Thermal Acid Generators> BTS: butyl p-toluenesulfonate (thermal acid generator having a sulfonate ester structure but not satisfying formula (2), manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) F1: 1,3-propanediol di-p-toluenesulfonate (thermal acid generator having a sulfonate ester structure and satisfying formula (2), manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) F2: 1,4-butanediol dimethanesulfonate (thermal acid generator having a sulfonate ester structure and satisfying formula (2), manufactured by Tokyo Chemical Industry Co., Ltd.)

[0163]

[0164] <Solvent> PGME: propylene glycol monomethyl ether GBL: γ-butyrolactone Example 1 Under yellow light, 100 g of (P1) obtained in Synthesis Example 2 as the component (A), 65 g of (P3) obtained in Synthesis Example 4 as the component (B), 25 g of (P4) obtained in Synthesis Example 5 as the component (C), 20 g of quinone diazide compound 1 obtained in Synthesis Example 7 as the quinone diazide compound (D), and 15 g of TEPIC-VL as a thermal crosslinker were weighed out, and these were dissolved in 1,823 g of PGME and 203 g of GBL. The resulting solution was then filtered through a filter with a pore size of 1 μm to obtain a positive-type photosensitive resin composition A. The resulting positive-type photosensitive resin composition was used to perform the evaluations (1) to (6) described above.

[0165] Examples 2 to 19 and Comparative Examples 1 to 7 Positive-type photosensitive resin compositions B to S and positive-type photosensitive resin compositions a to g were obtained in the same manner as in Example 1, using the types and amounts of compounds as shown in Tables 1 and 2. The obtained positive-type photosensitive resin compositions were used to carry out the evaluations (1) to (6) described above.

[0166] The compositions and evaluation results of the examples and comparative examples are shown in Tables 1 and 2.

[0167]

[0168]

[0169]

[0170] In all of Examples 1 to 19, good results were obtained in all of sensitivity, bending resistance, reliability of the organic EL display device, heat resistance, development adhesion, and pattern linearity. In contrast, Comparative Example 1, which did not use the component (A), resulted in poor reliability and heat resistance. Comparative Examples 2 and 7, which contained a large amount of the component (C), resulted in poor development adhesion. Comparative Example 3, which contained a large amount of the component (B), resulted in poor heat resistance. Comparative Examples 4 and 6, which contained a small amount of the component (B), resulted in poor bending resistance. Comparative Example 5, which did not use the component (C), resulted in poor sensitivity.

[0171] Example 20: The pyrolysate of the cured product of photosensitive resin composition O was analyzed by the method described above in <Composition analysis by reactive pyrolysis GC / MS>. As a result of the analysis, the structure obtained in the cured product is shown below, and a peak (1015 to 1025 seconds) assigned to the structure represented by formula (3), a peak (1335 to 1345 seconds) assigned to the structure represented by formula (4), and a peak (1860 to 1870 seconds) assigned to the structure represented by formula (5) were obtained.

[0172]

[0173] From these results, it was confirmed that the compound represented by formula (3), the compound represented by formula (4), and the compound represented by formula (5) were detected in the cured product of photosensitive resin composition O, and that the detected peak intensity ratio was 0.5 for the compound represented by formula (3) and 1 for the compound represented by formula (5), assuming that the compound represented by formula (4) was 1.

[0174] 1: Substrate 2: TFT 3: TFT insulating layer 4: Wiring 5: Planarization layer 6: Contact hole 7: First electrode 8: Pixel dividing layer 9: Organic EL layer 10: Second electrode 11: Glass substrate 12: First electrode 13: Auxiliary electrode 14: Pixel dividing layer 15: Organic EL layer 16: Second electrode

Claims

1. (A) one or more selected from the group consisting of polyimide, polyimide precursor, and copolymers thereof, (B) one or more selected from the group consisting of polybenzoxazole, polybenzoxazole precursor, and copolymers thereof, (C) polyhydroxystyrene, and / or a copolymer of polyhydroxystyrene and polystyrene, (D) a quinone diazide compound, (E) a solvent, and (F) a thermal acid generator, the content of the component (B) is 10 to 100 parts by mass per 100 parts by mass of the component (A), the content of the component (C) is 1 to 90 parts by mass per 100 parts by mass of the component (A), The positive photosensitive resin composition, wherein the thermal acid generator (F) contains a compound represented by formula (2): 【Chemistry 1】 (In formula (2), R 15 is a divalent to tetravalent group having 1 to 10 carbon atoms. R 16 each independently represents an alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent. Examples of the substituent include a hydroxyl group, a halogen atom, a cyano group, a vinyl group, an acetylene group, or a linear or cyclic alkyl group having 1 to 10 carbon atoms. a represents an integer of 2 to 4.)

2. When the content of the component (A) is [PI] (mass), the content of the component (B) is [PB] (mass), and the content of the component (C) is [PH] (mass), 2. The positive photosensitive resin composition according to claim 1, wherein the mass ratio [PI] / ([PB]+[PH]) is in the range of 0.5≦[PI] / ([PB]+[PH])≦5.

0.

3. 3. The positive photosensitive resin composition according to claim 2, wherein the relationship between [PB] and [PH] is [PB]>[PH].

4. 4. The positive photosensitive resin composition according to claim 3, wherein the mass ratio of the [PB] and the [PH] is in the range of 1.01≦[PB] / [PH]≦55.

00.

5. 2. The positive photosensitive resin composition according to claim 1, wherein the component (C) comprises polyhydroxystyrene.

6. 2. The positive photosensitive resin composition according to claim 1, wherein the solvent (E) contains a polar aprotic solvent.

7. 7. The positive photosensitive resin composition according to claim 6, wherein the content of the polar aprotic solvent is 1 to 30% by mass relative to 100% by mass of the solvent (E).

8. 2. The positive photosensitive resin composition according to claim 1, wherein the solid content concentration of the positive photosensitive resin composition is 3 to 30 mass %.

9. 2. The positive photosensitive resin composition according to claim 1, wherein the component (B) comprises a resin having a structural unit represented by formula (1) in the main chain. 【Chemistry 2】 (In formula (1), R １ and R ２ each independently represents a divalent to octavalent organic group having 2 to 30 carbon atoms; p represents an integer of 0 to 4; and q represents an integer of 1 to 4.

10. A cured product obtained by curing the positive photosensitive resin composition according to claim 1.

11. When analyzed by reactive pyrolysis GC / MS, the compound represented by formula (3), the compound represented by formula (4), and the compound represented by formula (5) are detected, and the detected peak intensity ratio of the compound represented by formula (3) is 0.1 to 1, and the compound represented by formula (5) is 0.1 to 3, assuming that the compound represented by formula (4) is 1. 【Transformation 3】 (In formula (3), formula (4) and formula (5), R １７ ~R ２３ each independently represents a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms which may contain a heteroatom.

12. An organic electroluminescence display device comprising the cured product according to claim 10 or 11.

13. (1) A step of applying the positive photosensitive resin composition according to any one of claims 1 to 9 to a substrate to form a positive photosensitive resin film; (2) a step of drying the positive photosensitive resin film; (3) a step of exposing the dried positive photosensitive resin film through a photomask; (4) developing the exposed positive photosensitive resin film; and (5) A step of heat-treating the developed positive photosensitive resin film A method for producing a cured product comprising the steps of:

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