Photosensitive resin composition, cured product, and organic el display device

Abstract

The present invention addresses the problem of providing a photosensitive resin composition which is capable of forming a cured product that has a low transmittance around the wavelength of 450 nm after curing even under low oxygen concentration circumstances in which the heating atmosphere at the time of curing has an oxygen concentration of less than 5%, and which is capable of forming a cured product that has a small amount of outgas after curing.　A photosensitive resin composition according to the present invention contains an alkali-soluble resin (A), a photosensitive compound (B), a phenolic compound (C) that has a structure represented by formula (C1), and a phenolic compound (D) that has a structure represented by formula (D1) and has a phenolic hydroxyl group equivalent of 100-500 g / Eq. In formula (C1), n represents an integer of 2 to 4 and * represents an atomic bond. In formula (D1), R1 represents an alkyl group having 1 to 20 carbon atoms, a represents an integer of 1 or 2, b represents an integer of 0 to 2, and * represents an atomic bond.

Description

Photosensitive resin composition, cured product, organic EL display device

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

[0002] Many products using organic electroluminescence (hereinafter referred to as "organic EL") display devices have been developed for display devices with thin displays, such as smartphones, tablet PCs, and televisions. Organic EL display devices generally have a drive circuit, a planarization layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode on a substrate, and can emit light by applying a voltage between the opposing first and second electrodes. Among these, photosensitive resin compositions that can be patterned by ultraviolet light irradiation are commonly used as materials for the planarization layer and the insulating layer. Photosensitive resin compositions using polyimide resins are particularly suitable for achieving highly reliable organic EL display devices because of their high heat resistance and the low outgassing generated from the cured product when the display device is operated. In organic EL display devices, if the cured product used as the planarization layer material and / or the insulating layer material contains a large amount of outgassing, the luminance of the light-emitting layer may decrease.

[0003] In recent years, with the application of driving thin film transistors (hereinafter referred to as TFTs) using oxide semiconductor layers to organic EL display devices, there has been a demand for low transmittance of insulating layers and planarizing layers at wavelengths around 450 nm to prevent malfunctions due to light entering the TFTs. On the other hand, high transmittance of ultraviolet light is required when patterning a photosensitive resin composition during manufacturing. To satisfy these conflicting demands, there is a method of adding a novolac resin, a photosensitizer, and a polymer other than the novolac resin to a cured product by heat curing after pattern formation, which method involves adding a photosensitizer and a polymer other than the novolac resin (see Patent Document 1).

[0004] Furthermore, as a technique for reducing the transmittance of the entire visible light as well as the transmittance at a wavelength of around 450 nm and increasing the degree of blackness, there is a method of adding, to an alkali-soluble resin, a quinone diazide compound and a thermochromic compound that develops color upon heating and has an absorption maximum in the range of 350 nm to 700 nm, or a compound that does not have an absorption maximum in the range of 350 nm to less than 500 nm but has an absorption maximum in the range of 500 nm to 750 nm (see Patent Document 2).

[0005] International Publication No. 2015 / 129092 Japanese Patent Application Laid-Open No. 2004-326094

[0006] The applicant's investigations have revealed that the resin compositions described in Patent Documents 1 and 2 reduce transmittance at wavelengths around 450 nm by utilizing oxidation by oxygen in the atmosphere during heat curing, and therefore the transmittance does not decrease under low oxygen concentrations of less than 5%, placing limitations on the curing conditions. Furthermore, when these resin compositions are used in organic EL display devices and the like, if they are heat cured in an atmosphere with an oxygen concentration of 5% or more, the outgassing generated during heat curing contaminates the electrodes, deteriorating the current-voltage characteristics.

[0007] Therefore, an object of the present invention is to provide a photosensitive resin composition which, even when the heating atmosphere during curing is a low oxygen concentration of less than 5%, gives a cured product with low transmittance at a wavelength of around 450 nm after curing, and which generates little outgassing after curing, making it suitable for use in organic EL display devices and the like.

[0008] In order to solve the above problems, the photosensitive resin composition of the present invention has the following constitution.

[0009] [1] A photosensitive resin composition comprising: component (A): an alkali-soluble resin; component (B): a photosensitive compound; component (C): a phenolic compound having a structure represented by formula (C1); and component (D): a phenolic compound having a structure represented by formula (D1) and not having a structure represented by formula (C1), and having a phenolic hydroxyl group equivalent of 100 to 500 g / Eq.

[0010]

[0011] In formula (C1), n ​​represents an integer of 2 to 4, and * represents a bond. １represents an alkyl group having 1 to 20 carbon atoms, a represents an integer of 1 or 2, and b represents an integer of 0 to 2. * represents a bond.

[0012] [2] The photosensitive resin composition according to [1] above, wherein the component (C) contains a phenol compound that satisfies the following condition (C′1):

[0013] Condition (C'1): The substitution position of at least one phenolic hydroxyl group other than any one of the phenolic hydroxyl groups in formula (C1) is the para position. [3] The photosensitive resin composition according to the above item [1] or [2], wherein the component (C) contains one or more compounds selected from the group consisting of the following components (C3), (C4), and (C5): Component (C3): a phenolic compound having a structure represented by formula (C3): Component (C4): a phenolic compound having a structure represented by formula (C4): Component (C5): a phenolic compound having a structure represented by formula (C5):

[0014]

[0015] In formula (C3), formula (C4), and formula (C5), n and m each independently represent an integer of 2 to 4, p represents an integer of 0 to 2, q represents an integer of 0 to 4, and 2≦p+m≦4 is satisfied; and X is —NR ２８ represents -, -O-, -S-, and R ２８ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; R ２ each independently represents a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; R ３ and R ４ are each independently OR ２９ , -SR ２９ , -N(R ２９ ) ２ , an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms; R ２９ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

[0016] [4] The photosensitive resin composition according to any one of [1] to [3] above, wherein the component (D) is a phenol compound having a structure represented by formula (D2):

[0017]

[0018] In formula (D2), R ５ , R ６ and R ７ each independently represents an alkyl group having 1 to 20 carbon atoms; R ８ ~R １１ each independently represents a direct bond or an alkylene group having 1 to 20 carbon atoms. c, d, and e each independently represent 1 or 2, f, g, and h each independently represent an integer of 0 to 2, and i represents an integer of 0 to 100. T and U each independently represent a divalent organic group having 1 to 30 carbon atoms, and at least one of T and U is a structure represented by formula (D3) or a structure represented by formula (D4). R １２ and R １３ each independently represents an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, and j and k each independently represent an integer of 0 to 4. * represents a bond.

[0019] [5] The photosensitive resin composition according to any one of [1] to [4], wherein the content of the component (C) is 1 to 60 parts by mass per 100 parts by mass of the component (A).

[0020] [6] The photosensitive resin composition according to any one of [1] to [5], wherein the content of the component (D) is 10 to 300 parts by mass per 100 parts by mass of the component (C).

[0021] [7] The photosensitive resin composition according to any one of [1] to [6], wherein the component (B) is a naphthoquinone diazide compound having a conversion rate of 70% or more but less than 90%.

[0022] [8] The photosensitive resin composition according to any one of [1] to [7] above, wherein the component (A) comprises one or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole precursor, and copolymers thereof.

[0023] [9] A cured product obtained by curing the photosensitive resin composition according to any one of [1] to [8] above.

[0024]

[10] The cured product according to [9], wherein the transmittance of the cured product at a wavelength of 450 nm is less than 30%.

[0025]

[11] An organic EL display device comprising the cured product according to [9] or

[10] above.

[0026]

[12] An organic EL display device, wherein a planarization layer and / or an insulating layer comprises the cured product according to [9] or

[10] above, and the planarization layer and / or the insulating layer has a transmittance of less than 30% at a wavelength of 450 nm.

[0027] The photosensitive resin composition of the present invention can form a cured product that has low transmittance at a wavelength around 450 nm and low outgassing after curing, even when the heating atmosphere during curing is one with an oxygen concentration of less than 5%.

[0028] 1 is a cross-sectional view of an example of an organic EL display device;

[0029] An embodiment of the present invention will now be described in detail.

[0030] The photosensitive resin composition of the present invention is a photosensitive resin composition containing: component (A): an alkali-soluble resin; component (B): a photosensitive compound; component (C): a phenolic compound having a structure represented by formula (C1); and component (D): a phenolic compound having a structure represented by formula (D1) and not having a structure represented by formula (C1), and having a phenolic hydroxyl group equivalent of 100 to 500 g / Eq.

[0031]

[0032] In formula (C1), n ​​represents an integer of 2 to 4, and * represents a bond. １ represents an alkyl group having 1 to 20 carbon atoms, a represents an integer of 1 or 2, and b represents an integer of 0 to 2. * represents a bond.

[0033] <Component (A): Alkali-Soluble Resin> The photosensitive resin composition of the present invention contains an alkali-soluble resin as component (A). In this application, alkali-solubility refers to a dissolution rate of 50 nm / min or more per immersion time in the tetramethylammonium hydroxide aqueous solution, which is calculated by: applying a solution of the resin dissolved in γ-butyrolactone onto a silicon wafer and prebaking at 120°C for 4 minutes to form a prebaked film with a film thickness of 10 μm±0.5 μm; immersing the prebaked film in a 2.38 mass% aqueous tetramethylammonium hydroxide solution at 23±1°C for 1 minute, rinsing with pure water, and drying with an air blow for 30 seconds; measuring the film thickness after immersion; and determining the difference (amount of film thickness reduction) between the film thickness (actual measured value) of the prebaked film before and after immersion.

[0034] Since component (A) is alkali-soluble, it preferably has hydroxyl groups and / or acidic groups in the structural units of the resin and / or at the ends of its main chain. Examples of acidic groups include carboxyl groups, phenolic hydroxyl groups, and sulfonic acid groups.

[0035] Examples of component (A) include, but are not limited to, polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamide, polymers of radically polymerizable monomers having an acidic group such as acrylic resin, cardo resin, and siloxane resin, etc. Component (A) may contain two or more of these alkali-soluble resins.

[0036] Among these components (A), the component (A) preferably contains one or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, and copolymers thereof, and more preferably contains one or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole precursor, and copolymers thereof, because the component (A) has high development adhesion, excellent heat resistance, and a small amount of outgassing at high temperatures, resulting in high long-term reliability when the cured product is used in an organic EL display device.

[0037] From the viewpoints of promoting color development by heating of the phenol compound (C) having a structure represented by formula (C1) described below and reducing the transmittance at a wavelength of 450 nm after curing, it is preferable that the component (A) contains one or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, and polyamide. In addition, from the viewpoint of further improving sensitivity, it is even more preferable that the component (A) contains a polyimide precursor or a polybenzoxazole precursor.

[0038] Here, the polyimide precursor refers to a resin that can be converted into polyimide by heat treatment or chemical treatment, such as polyamic acid or polyamic acid ester.

[0039] The polybenzoxazole precursor refers to a resin that can be converted into polybenzoxazole by heat treatment or chemical treatment, such as polyhydroxyamide.

[0040] The above-mentioned polyimide precursor, polybenzoxazole precursor and polyamide have a structural unit represented by the following formula (1), and the polyimide has a structural unit represented by the following formula (2).

[0041] The component (A) may contain two or more types of resins each having a structural unit represented by formula (1) and two or more types of resins having a structural unit represented by formula (2), or may contain a resin in which the structural unit represented by formula (1) and the structural unit represented by formula (2) are copolymerized.

[0042]

[0043] In formula (1), X represents a divalent to octavalent organic group having 4 to 40 carbon atoms, and Y represents a divalent to elevenvalent organic group having 6 to 40 carbon atoms. １４ and R １６ R each independently represents a hydroxyl group or a sulfonic acid group. １５ and R １７each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. t, u, and w represent integers of 0 to 3, and v represents an integer of 0 to 6. However, when the structural unit represented by formula (1) represents a structural unit of a polyimide precursor, u≧2; when the structural unit represented by formula (1) represents a structural unit of a polybenzoxazole precursor, v≧2; and when a plurality of R １６ At least two of the structural units are hydroxyl groups. A compound having a structural unit represented by formula (1) that does not fall under the category of the polyimide precursor or polybenzoxazole precursor is considered to be a polyamide.

[0044]

[0045] In formula (2), E represents a tetravalent to decavalent organic group having 4 to 40 carbon atoms, and G represents a divalent to octavalent organic group having 6 to 40 carbon atoms. １８ and R １９ each independently represents a carboxy group, a sulfonic acid group, or a hydroxyl group, and x and y each independently represent an integer of 0 to 6, provided that x+y>0.

[0046] The polyimide, polyimide precursor, polybenzoxazole precursor, or copolymer thereof preferably has 5 to 100,000 structural units represented by formula (1) or formula (2). Furthermore, in addition to the structural units represented by formula (1) or formula (2), other structural units may be contained. In this case, it is preferable that the structural units represented by formula (1) or formula (2) account for 50 mol % or more of 100 mol % of all structural units.

[0047] In the above formula (1), X(R １４ ) ｔ (COOR １５ ) ｕ represents an acid residue. X is a divalent to octavalent organic group having 4 to 40 carbon atoms, and is preferably a divalent to octavalent organic group containing an aromatic ring or a cycloaliphatic group.

[0048] Examples of acid residues include residues of dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, and triphenyl dicarboxylic acid; residues of tricarboxylic acids such as trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, and biphenyl tricarboxylic acid; residues of pyromellitic acid, 3,3',4,4'-biphenyl tetracarboxylic acid, 2,3,3',4'-biphenyl tetracarboxylic acid, 2,2',3,3'-biphenyl tetracarboxylic acid, 3,3',4,4'-benzophenone tetracarboxylic acid, 2,2',3,3'-benzophenone tetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, and 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane. Examples of component (A) include residues of tetracarboxylic acids such as X(R hexafluoropropane), 1,1-bis(3,4-dicarboxyphenyl)ethane, 1,1-bis(2,3-dicarboxyphenyl)ethane, bis(3,4-dicarboxyphenyl)methane, bis(2,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, and aromatic tetracarboxylic acids having the structures shown below, aliphatic tetracarboxylic acids such as butanetetracarboxylic acid, and aliphatic tetracarboxylic acids containing a cyclic aliphatic group such as 1,2,3,4-cyclopentanetetracarboxylic acid. １４ ) ｔ (COOR １５ ) ｕ As the hydroxyl group, two or more of these residues may be contained.

[0049]

[0050] R ２０ is an oxygen atom, C(CF ３ ) ２ or C(CH ３ ) ２ Represents R ２１ and R ２２each independently represents a hydrogen atom or a hydroxyl group.

[0051] Among the above acid residues, in the case of a tricarboxylic acid or tetracarboxylic acid residue, one or two carboxy groups are (COOR) in formula (1). １５ ) is equivalent to

[0052] In the above formula (2), E(R １８ ) ｘ represents a residue of an acid dianhydride. E is a tetravalent to decavalent organic group having 4 to 40 carbon atoms, and is preferably an organic group containing an aromatic ring or a cyclic aliphatic group.

[0053] Specific examples of the acid dianhydride residue include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, and bis(3,4-dicarboxyphenyl). Examples of the component (A) include aromatic tetracarboxylic acid dianhydrides such as ether dianhydrides, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorene dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 2,3,5,6-pyridinetetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, and acid dianhydrides having the structures shown below; aliphatic tetracarboxylic acid dianhydrides such as butanetetracarboxylic acid dianhydride; and residues of aliphatic tetracarboxylic acid dianhydrides containing a cyclic aliphatic group such as 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride. １８ ) ｘ As the hydroxyl group, two or more of these residues may be contained.

[0054]

[0055] R ２０ is an oxygen atom, C(CF ３ ) ２ or C(CH ３ ) ２ Represents R ２１ and R ２２each independently represents a hydrogen atom or a hydroxyl group.

[0056] Y(R １６ ) ｖ (COOR １７ ) ｗ and G(R １９ ) ｙ represents a residue of a diamine. Y is a di- to eleven-valent organic group having 6 to 40 carbon atoms, and is preferably a di- to eleven-valent organic group containing an aromatic ring or a cycloaliphatic group. G is a di- to octa-valent organic group having 6 to 40 carbon atoms, and is preferably a di- to octa-valent organic group containing an aromatic ring or a cycloaliphatic group.

[0057] Specific examples of the diamine residue include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, and 3,3'-diethyl-4,4'-diaminobiphenyl. phenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-di(trifluoromethyl)-4,4'-diaminobiphenyl, 9,9-bis(4-aminophenyl)fluorene, 2,2'-bis(trifluoromethyl)-5,5'-dihydroxybenzidine, 3,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, and compounds in which at least a portion of the hydrogen atoms in these aromatic rings are substituted with alkyl groups or halogen atoms; residues of aliphatic diamines containing cyclic aliphatic groups such as cyclohexyldiamine and methylenebiscyclohexylamine; and residues of diamines having the structures shown below. Component (A) is a compound represented by the formula (1) where Y(R １６ ) ｖ (COOR １７ ) ｗ and G(R １９ ) ｙ As the hydroxyl group, two or more of these residues may be contained.

[0058]

[0059] R ２０ is an oxygen atom, C(CF ３ ) ２ or C(CH ３ ) ２ Represents R ２１ ~R２４ each independently represents a hydrogen atom or a hydroxyl group.

[0060] The terminals of these resins may also be blocked with known monoamines, acid anhydrides, acid chlorides, monocarboxylic acids, or active ester compounds having an acidic group.

[0061] The component (A) may be synthesized by a known method.

[0062] Examples of polymers of radically polymerizable monomers having an acidic group include acrylic resins, etc. Known materials can be used as radically polymerizable monomers having an acidic group, and examples thereof include acrylic acid, (meth)acrylic acid, mono(2-acryloyloxyethyl) succinate, 1-(2-methacryloyloxyethyl) succinate, and 6-(4-carboxyphenoxy)hexyl acrylate.

[0063] Cardo resins include resins having a cardo structure, i.e., a backbone structure in which two rings are bonded to a quaternary carbon atom that constitutes a ring. A typical cardo structure is a fluorene ring bonded to a benzene ring.

[0064] Examples of the siloxane resin include known siloxane resins obtained by hydrolyzing and dehydrating condensation of one or more organosilanes selected from tetrafunctional organosilanes, trifunctional organosilanes, difunctional organosilanes, and monofunctional organosilanes.

[0065] <Component (B): Photosensitive Compound> The photosensitive resin composition of the present invention further contains a photosensitive compound as component (B). From the viewpoint of achieving high sensitivity, the content of component (B) is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 10 parts by mass or more, per 100 parts by mass of component (A). On the other hand, from the viewpoint of long-term reliability when the cured product of the present invention is used as a planarizing layer and / or insulating layer of an organic EL display device, the content of component (B) is preferably 100 parts by mass or less, per 100 parts by mass of component (A).

[0066] The component (B) may contain a photoacid generator (B1), a photopolymerization initiator (B2), etc. The photoacid generator (B1) is a compound that generates an acid upon irradiation with light, and the photopolymerization initiator (B2) is a compound that undergoes bond cleavage and / or reaction upon exposure to generate radicals.

[0067] By containing the photoacid generator (B1), an acid is generated in the light-irradiated areas, increasing the solubility of the light-irradiated areas in an alkaline aqueous solution, thereby obtaining a positive-tone relief pattern in which the light-irradiated areas are dissolved. Furthermore, by containing the photoacid generator (B1) and a thermal crosslinking agent described below, the acid generated in the light-irradiated areas promotes the crosslinking reaction of the thermal crosslinking agent, thereby obtaining a negative-tone relief pattern in which the light-irradiated areas are insolubilized.

[0068] By including the photopolymerization initiator (B2) and the radically polymerizable compound described below, radical polymerization proceeds in the irradiated areas, and a negative relief pattern can be obtained in which the irradiated areas are insolubilized.

[0069] From the viewpoint of being able to form a fine pattern when the cured product of the present invention is used as a planarizing layer and / or insulating layer in an organic EL display device, it is preferable that the component (B) contains a photoacid generator (B1) that can obtain a positive relief pattern.

[0070] The photoacid generator (B1) may contain, for example, a quinone diazide compound. The photosensitive resin composition of the present invention may contain two or more types of photoacid generators (B1).

[0071] The quinone diazide compound may include a compound in which a sulfonic acid of quinone diazide is bonded to a polyhydroxy compound via an ester bond, a compound in which a sulfonic acid of quinone diazide is bonded to a polyamino compound via a sulfonamide bond, or a compound in which a sulfonic acid of quinone diazide is bonded to a polyhydroxypolyamino compound via an ester bond and / or a sulfonamide bond.

[0072] As the quinone diazide structure, either a 5-naphthoquinone diazide sulfonic acid group or a 4-naphthoquinone diazide sulfonic acid group is preferably used. A naphthoquinone diazide compound having both a 4-naphthoquinone diazide sulfonic acid group and a 5-naphthoquinone diazide sulfonic acid group in the same molecule may be contained, or both a 4-naphthoquinone diazide sulfonic acid ester compound and a 5-naphthoquinone diazide sulfonic acid ester compound may be contained. 4-naphthoquinone diazide sulfonic acid ester compounds have absorption in the i-line region of a mercury lamp and are suitable for i-line exposure. 5-naphthoquinone diazide sulfonic acid ester compounds have absorption extending to the g-line region of a mercury lamp and are suitable for g-line exposure.

[0073] It is preferable to select a 4-naphthoquinone diazide sulfonic acid ester compound or a 5-naphthoquinone diazide sulfonic acid ester compound depending on the wavelength of exposure.

[0074] The quinone diazide compound can be synthesized by any esterification reaction of a compound having a phenolic hydroxyl group and a quinone diazide sulfonic acid compound. The use of such a quinone diazide compound further improves resolution, sensitivity, and film retention.

[0075] The quinone diazide compound preferably has a conversion rate of 70% or more but less than 90%, and more preferably 75% or more but less than 85%. A conversion rate of 70% or more can further reduce the water absorption rate of the cured product of the present invention. A low water absorption rate of the cured product reduces the amount of water-derived outgassing after curing, and can further suppress corrosion of metal electrodes when used in the planarization layer and / or insulating layer of an organic EL display device. Furthermore, a conversion rate of less than 90% can enable pattern formation with higher sensitivity.

[0076] In the present invention, the conversion rate can be calculated, for example, in the case of a polyhydroxy compound, as "(molar number of naphthoquinone diazide sulfonic acid groups) / (molar number of hydroxy groups of the polyhydroxy compound before esterification) × 100," in the case of a polyamino compound, as "(molar number of naphthoquinone diazide sulfonic acid groups) / (molar number of amino groups of the polyamino compound before sulfonamidation) × 100," and in the case of a polyhydroxypolyamino compound, as "(molar number of naphthoquinone diazide sulfonic acid groups) / {(molar number of hydroxy groups of the polyhydroxypolyamino compound before esterification or sulfonamidation) + (molar number of ester groups or amino groups of the polyhydroxypolyamino compound before esterification)} × 100." The mole number of hydroxy groups of the polyhydroxy compound before esterification can be obtained from the sum of the mole number of naphthoquinone diazide sulfonic acid groups and the mole number of hydroxy groups remaining in the polyhydroxy compound after esterification, and the same concept can be applied to the case of a polyamino compound.

[0077] The present invention may contain two or more naphthoquinone diazide compounds. In this case, the conversion rate is calculated as an average conversion rate by multiplying the conversion rate of each naphthoquinone diazide compound by its ratio to all naphthoquinone diazide compounds, as shown in the following formula: Σ((conversion rate of a certain naphthoquinone diazide compound) × (ratio of a certain naphthoquinone diazide compound to all naphthoquinone diazide compounds)) Furthermore, the number of moles of naphthoquinone diazide sulfonic acid groups, the number of moles of amino groups, and the number of moles of hydroxyl groups used to calculate the conversion rate of naphthoquinone diazide compounds in the photosensitive resin composition can be obtained by removing the resin component of the photosensitive resin composition using a reprecipitation method or the like, separating the contained components using a column fractionation method or the like, and identifying their chemical structures using NMR or IR.

[0078] From the viewpoint of achieving high sensitivity, the content of the photoacid generator (B1) is preferably at least 0.1 parts by mass, more preferably at least 10 parts by mass, and even more preferably at least 20 parts by mass, per 100 parts by mass of the component (A). On the other hand, from the viewpoint of long-term reliability when the cured product of the present invention is used as a planarizing layer and / or insulating layer in an organic EL display device, the content of the photoacid generator (B1) is preferably no more than 100 parts by mass, per 100 parts by mass of the component (A).

[0079] Examples of the photopolymerization initiator (B2) that can be used in the photosensitive resin composition of the present invention include benzyl ketal-based photopolymerization initiators, α-hydroxyketone-based photopolymerization initiators, α-aminoketone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, oxime ester-based photopolymerization initiators, acridine-based photopolymerization initiators, titanocene-based photopolymerization initiators, benzophenone-based photopolymerization initiators, acetophenone-based photopolymerization initiators, aromatic ketoester-based photopolymerization initiators, and benzoate ester-based photopolymerization initiators. The photosensitive resin composition of the present invention may contain two or more types of photopolymerization initiators (B2). From the viewpoint of further improving sensitivity, the photopolymerization initiator (B2) preferably contains an α-aminoketone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, or an oxime ester-based photopolymerization initiator.

[0080] Examples of the α-aminoketone photopolymerization initiator include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-butan-1-one, and 3,6-bis(2-methyl-2-morpholinopropionyl)-9-octyl-9H-carbazole.

[0081] Examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphine oxide.

[0082] Examples of the oxime ester photopolymerization initiator include 1-phenylpropane-1,2-dione-2-(O-ethoxycarbonyl)oxime, 1-phenylbutane-1,2-dione-2-(O-methoxycarbonyl)oxime, 1,3-diphenylpropane-1,2,3-trione-2-(O-ethoxycarbonyl)oxime, 1-[4-(phenylthio)phenyl]octane-1,2-dione-2-(O-benzoyl)oxime, 1-[4-[4-(carboxyphenyl)thio]phenyl]propane-1,2-dione-2-(O-acetyl)oxime, 1-[9 -ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyl)oxime, 1-[9-ethyl-6-[2-methyl-4-[1-(2,2-dimethyl-1,3-dioxolan-4-yl)methyloxy]benzoyl]-9H-carbazol-3-yl]ethanone-1-(O-acetyl)oxime, 1-(9-ethyl-6-nitro-9H-carbazol-3-yl)-1-[2-methyl-4-(1-methoxypropan-2-yloxy)phenyl]methanone-1-(O-acetyl)oxime, and the like.

[0083] From the viewpoint of increasing sensitivity, the content of the photopolymerization initiator (B2) is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 10 parts by mass or more, per 100 parts by mass of the total of the component (A) and the radical polymerizable compound described below. On the other hand, from the viewpoint of further improving resolution and reducing the taper angle, the content of the photopolymerization initiator (B2) is preferably 50 parts by mass or less, per 100 parts by mass of the total of the component (A) and the radical polymerizable compound described below.

[0084] <Component (C): Phenolic Compound Having a Structure Represented by Formula (C1)> The photosensitive resin composition of the present invention contains, as the component (C), a phenolic compound having a structure represented by formula (C1).

[0085]

[0086] In formula (C1), n ​​represents an integer of 2 to 4, and * represents a bond.

[0087] By including component (C), the photosensitive resin composition of the present invention develops color upon heating, even in a curing atmosphere with a low oxygen concentration of less than 5%, and can reduce the transmittance at a wavelength of 450 nm after curing. While the color-developing mechanism is unclear, it is believed that component (C) assumes a quinone structure upon heating, resulting in the formation of a color-developing substance with absorption in the 300 nm to 500 nm range. While oxygen is typically required for phenolic compounds to assume a quinone structure upon heating, component (C) possesses three or more phenolic hydroxyl groups in the same aromatic ring and is electron-rich, and therefore readily assumes a quinone structure upon heating, even in a low oxygen concentration of less than 5%, thereby reducing the transmittance at 450 nm after curing. Furthermore, before heating, component (C) does not absorb light in the 300 nm to 500 nm range, and therefore does not block the 350 nm to 450 nm exposure wavelength range of mercury lamps, which are commonly used as exposure light sources, allowing for highly sensitive pattern formation.

[0088] In formula (C1), n ​​represents an integer of 2 to 4, and from the viewpoint of availability of raw materials, n is preferably 2 to 3, and n is more preferably 2.

[0089] Furthermore, the component (C) may have multiple structures represented by formula (C1) per molecule, and from the viewpoint of further reducing the transmittance at a wavelength of 450 nm after curing, the component (C) preferably has two or more structures represented by formula (C1) per molecule. There is no particular upper limit to the number of structures represented by formula (C1) contained in one molecule, but it is preferably 10 or less, and more preferably 5 or less.

[0090] From the perspective of further reducing the transmittance at a wavelength of 450 nm after curing, it is preferable that component (C) contains a phenolic compound that satisfies the following condition (C'1): Condition (C'1): The substitution position of at least one phenolic hydroxyl group other than any phenolic hydroxyl group in formula (C1) is para-positioned. By containing a phenolic compound (hereinafter sometimes referred to as component (C'1)) that satisfies condition (C'1), the transmittance at a wavelength of 450 nm after curing can be further reduced. This is presumably because component (C) has a phenolic hydroxyl group that is para-positioned relative to the phenolic hydroxyl group in formula (C1), which allows component (C) to assume a paraquinone structure upon heating, thereby further enhancing the color development properties of component (C). Specifically, component (C'1) preferably contains one or more phenolic compounds selected from the group consisting of phenolic compounds having a structure represented by any of the following formulas (C'1a) to (C'1d), and it is particularly preferable to contain a phenolic compound having a structure represented by formula (C'1a).

[0091]

[0092] In the formula, * represents a bond.

[0093] In the partial structure represented by Formula (C1), the substituent bonded to the benzyl position may be an optionally substituted amino group, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkenyl group, an optionally substituted alkenyl ether group, an optionally substituted aryl group, an optionally substituted aryloxy group, or an optionally substituted heteroaryl group. From the viewpoint of further reducing the transmittance at a wavelength of 450 nm after curing, the substituent bonded to the benzyl position is preferably an optionally substituted amino group, an optionally substituted aryl group, or an optionally substituted heteroaryl group, with an optionally substituted amino group or an optionally substituted aryl group being more preferred. Examples of the substituent include a phenolic hydroxyl group, a sulfo group, a carboxy group, an alkoxy group, and a hydrocarbon group having 1 to 10 carbon atoms, with a phenolic hydroxyl group being preferred. Below, examples of component (C) in which the substituent bonded to the benzyl position in the partial structure represented by Formula (C1) is an optionally substituted aryl group are given, but are not limited to these.

[0094]

[0095] n's each independently represent an integer of 2 to 4; R ２５ each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; L represents a single bond, an oxygen atom, or C(CF ３ ) ２ , C(CH ３ ) ２ , S.O. ２ or CO. M represents a nitrogen atom, CH or CCH ３ Represents.

[0096] In the partial structure represented by formula (C1), component (C) in which the substituent bonded to the benzyl position is an optionally substituted aryl group preferably satisfies condition (C'1) from the viewpoint of further reducing the transmittance at a wavelength of 450 nm after curing. Specifically, component (C) more preferably contains at least one phenol compound selected from the group consisting of the following phenol compounds:

[0097]

[0098] From the viewpoint of reducing the transmittance at a wavelength of 500 nm after curing in addition to the transmittance at a wavelength of 450 nm after curing, it is preferable that the component (C) contains a phenol compound that satisfies the following condition (C'2): Condition (C'2): The substituent bonded to the benzyl position in formula (C1) is an amino group that may have a substituent.Specific examples of the component (C) that satisfy condition (C'2) include phenol compounds having a structure represented by formula (C2).

[0099]

[0100] In formula (C2), n represents an integer of 2 to 4, and * represents a bond.

[0101] The phenol compound having the structure represented by the formula (C2) preferably satisfies the condition (C'1).

[0102] When component (C) has a structure represented by formula (C2), it is possible to reduce the transmittance at a wavelength of 500 nm after curing, in addition to the transmittance at a wavelength of 450 nm after curing. Although the mechanism is unclear, it is thought that this is because the substituent bonded to the benzyl position in formula (C1) is an amino group which may have a substituent, and electrons are donated from the amino group to the quinone structure generated by heating component (C), thereby shifting the wavelength of the absorption band of the quinone structure to a longer wavelength.

[0103] In the partial structure represented by formula (C2), the substituent adjacent to the nitrogen atom can be an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent, and examples of phenol compounds having the structure shown below include, but are not limited to, these.

[0104]

[0105] n's each independently represent an integer of 2 to 4; R ３１ and R ３２ each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; L represents a single bond, an oxygen atom, or C(CF３ ) ２ , C(CH ３ ) ２ , S.O. ２ or CO. M represents a nitrogen atom, CH or CCH ３ Represents.

[0106] From the viewpoint of reducing the transmittance at a wavelength of 500 nm after curing in addition to the transmittance at a wavelength of 450 nm after curing, it is preferable that, as the substituent adjacent to the nitrogen atom in formula (C2), at least one of an optionally substituted aryl group or an optionally substituted heteroaryl group is adjacent to the nitrogen atom.

[0107] From the viewpoint of further reducing the transmittance at a wavelength of 450 nm after curing and also reducing the transmittance at a wavelength of 500 nm after curing, it is preferable that component (C) contain a phenol compound that satisfies conditions (C'1) and (C'2). Specifically, component (C) preferably contains one or more phenol compounds selected from the group consisting of phenol compounds having a structure represented by any of the following formulas (C'2a) to (C'2d), and it is particularly preferable that component (C) contain a phenol compound having a structure represented by formula (C'2a).

[0108]

[0109] From the viewpoint of further reducing the transmittance at a wavelength of 550 nm after curing in addition to the transmittance at a wavelength of 500 nm after curing, it is preferable that the component (C) contains one or more selected from the group consisting of the following components (C3), (C4), and (C5): Component (C3): a phenolic compound having a structure represented by the following formula (C3) Component (C4): a phenolic compound having a structure represented by the following formula (C4) Component (C5): a phenolic compound having a structure represented by the following formula (C5)

[0110]

[0111] In formula (C3), formula (C4), and formula (C5), n and m each independently represent an integer of 2 to 4, p represents an integer of 0 to 2, q represents an integer of 0 to 4, and 2≦p+m≦4 is satisfied; and X is —NR ２８ represents -, -O-, -S-, and R ２８represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; R ２ each independently represents a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; R ３ and R ４ are each independently OR ２９ , -SR ２９ , -N(R ２９ ) ２ , an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms; R ２９ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

[0112] The mechanism by which the transmittance at a wavelength of 550 nm after curing is further reduced is not clear, but it is thought that when component (C) takes on a quinone structure upon heating, it is able to take on a broad conjugated structure throughout the molecule, which causes the absorption band of the quinone structure to shift to longer wavelengths.

[0113] From the viewpoint of reducing the transmittance at a wavelength of 550 nm after curing, the component (C) preferably contains the component (C3) and / or the component (C4), and more preferably contains the component (C3).

[0114] From the viewpoint of reducing the transmittance at a wavelength of 550 nm after curing, the component (C3) is a compound represented by the formula (C3), wherein X is —NR ２８ It is preferable to contain a phenolic compound in which X is — or —O—, and it is more preferable to contain a phenolic compound in which X is —O—.

[0115] From the viewpoint of reducing the transmittance at a wavelength of 550 nm after curing, it is preferable that one or more selected from the group consisting of component (C3), component (C4), and component (C5) have two structures that satisfy condition (C'1) in the same molecule.

[0116] Specific examples of the above include components (C3) to (C5) that contain at least two structures represented by any of the above formulas (C'1a) to (C'1d) in the same molecule, and it is particularly preferred that the same molecule contain at least two structures represented by formula (C'1a).

[0117] Preferred specific examples of components (C3), (C4), and (C5) are shown below, but are not limited to these.

[0118]

[0119] Each n independently represents an integer of 2 to 4. Me represents a methyl group.

[0120] The component (C3) preferably contains one or more compounds selected from the group consisting of phenol compounds having a structure represented by any one of formulas (C3a) to (C3f), and particularly preferably contains a phenol compound having a structure represented by formula (C3a).

[0121]

[0122] n's each independently represent an integer of 2 to 4, p' represents an integer of 0 to 2, and X's represents -NR ３０ represents -, -O-, -S-, and R ３０ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; R ２６ each independently represents a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; R ２７ represents a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

[0123] The photosensitive resin composition of the present invention may contain two or more types of component (C). By containing two or more types of component (C), the transmittance of any wavelength can be reduced.

[0124] The upper limit of the molecular weight of component (C) is not particularly limited, but is preferably not more than 1000, more preferably not more than 800, and even more preferably not more than 600. The lower limit of the molecular weight of component (C) is preferably 126 or more.

[0125] Component (C) can be synthesized by a known method. For example, a known method involves reacting a compound substituted with a methylol group or an alkoxymethyl group with a polyhydric phenol compound selected from a trihydroxybenzene compound, a tetrahydroxybenzene compound, and a pentahydroxybenzene compound under acidic conditions. From the viewpoint of raw material availability, it is preferable to use a trihydroxybenzene compound.

[0126] Examples of trihydroxybenzene compounds include phloroglucinol, pyrogallol, and 1,2,4-trihydroxybenzene, and examples of tetrahydroxybenzene compounds include 1,2,3,4-tetrahydroxybenzene and 1,2,3,5-tetrahydroxybenzene. Component (C) that satisfies condition (C'1) can be obtained by using any of 1,2,4-trihydroxybenzene, 1,2,3,4-tetrahydroxybenzene, 1,2,3,5-tetrahydroxybenzene, and pentahydroxybenzene as the polyhydric phenol compound.

[0127] On the other hand, by using a compound in which a methylol group or an alkoxymethyl group is substituted on the nitrogen atom, a component (C) that satisfies the condition (C'2) can be obtained, and further by using any one of 1,2,4-trihydroxybenzene, 1,2,3,4-tetrahydroxybenzene, 1,2,3,5-tetrahydroxybenzene, and pentahydroxybenzene as the polyhydric phenol compound, a component (C) that satisfies the conditions (C'1) and (C'2) can be obtained.

[0128] A compound in which a methylol group is substituted on the nitrogen atom can be obtained, for example, by reacting a primary amino group- or secondary amino group-containing compound with formaldehyde under basic conditions, and a compound in which an alkoxymethyl group is substituted on the nitrogen atom can be obtained by further reacting the compound with an alcohol under acidic conditions.

[0129] Furthermore, component (C3) can be obtained by using a compound in which at least two methylol groups are substituted on one or more rings selected from the group consisting of pyrrole rings, furan rings, and thiophene rings. Component (C4) and component (C5) can be obtained by using a compound in which methylol groups are substituted on the 1- and 4-positions and the 1- and 2-positions of the benzene skeleton, respectively. Furthermore, components (C3) to (C5) can be obtained by using any one of 1,2,4-trihydroxybenzene, 1,2,3,4-tetrahydroxybenzene, 1,2,3,5-tetrahydroxybenzene, and pentahydroxybenzene as the polyhydric phenol compound, into which a structure represented by any one of formulas (C'1a) to (C'1d) has been introduced.

[0130] In the present invention, the content of component (C) is preferably 1 part 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 component (A). By making the content of component (C) 1 part by mass or more per 100 parts by mass of component (A), the transmittance at a wavelength of 450 nm after curing can be further reduced. Furthermore, the content of component (C) is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 40 parts by mass or less, per 100 parts by mass of component (A). By making the content of component (C) 60 parts by mass or less per 100 parts by mass of component (A), an increase in the water absorption rate of the cured product can be further suppressed, and the chemical resistance of the cured product can be maintained.

[0131] <Component (D): Phenolic Compound Having a Structure Represented by Formula (D1) and Having a Phenolic Hydroxyl Group Equivalent of 100 to 500 g / Eq> The photosensitive resin composition of the present invention includes, as the component (D), a phenolic compound having a structure represented by Formula (D1) and having a phenolic hydroxyl group equivalent of 100 to 500 g / Eq.

[0132]

[0133] In formula (D1), R １ represents an alkyl group having 1 to 20 carbon atoms, a represents an integer of 1 or 2, and b represents an integer of 0 to 2. * represents a bond.

[0134] In the present invention, the phenolic hydroxyl group equivalent means a value measured by a method according to JIS K 0070:1992.

[0135] In the present invention, the component (D) is a phenol compound having a structure represented by formula (D1) but not having a structure represented by formula (C1). For example, a phenol compound having both a structure represented by formula (C1) and a structure represented by formula (D1) is referred to as the component (C).

[0136] The inclusion of component (D) can reduce the water absorption of the cured product of the present invention. The low water absorption of the cured product reduces the amount of water-derived outgassing after curing, and can inhibit corrosion of metal electrodes when used in a planarizing layer and / or insulating layer of an organic EL display device.

[0137] By using the aforementioned components (C) and (D) in combination, it is possible to suppress an increase in the water absorption rate of the cured product due to the phenolic hydroxyl groups of component (C), thereby further reducing the amount of outgassing derived from water after curing.

[0138] From the viewpoint of imparting appropriate alkali solubility during development and improving sensitivity, the phenolic hydroxyl group equivalent of component (D) is 500 g / Eq or less, preferably 300 g / Eq or less, and more preferably 200 g / Eq or less. From the viewpoint of reducing the water absorption of the cured product and reducing the amount of outgassing derived from water after curing, the phenolic hydroxyl group equivalent of component (D) is 100 g / Eq or more, preferably 110 g / Eq or more, and more preferably 120 g / Eq or more. The component (D) is preferably a phenolic compound having a structure represented by formula (D2).

[0139]

[0140] In formula (D2), R ５ , R ６ and R ７ each independently represents an alkyl group having 1 to 20 carbon atoms; R ８ ~R １１each independently represents a direct bond or an alkylene group having 1 to 20 carbon atoms. c, d, and e each independently represent 1 or 2, f, g, and h each independently represent an integer of 0 to 2, and i represents an integer of 0 to 100. T and U each independently represent a divalent organic group having 1 to 30 carbon atoms, and at least one of T and U is a structure represented by formula (D3) or a structure represented by formula (D4). R １２ and R １３ each independently represents an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, and j and k each independently represent an integer of 0 to 4. * represents a bond.

[0141] In formula (D2), R ８ ~R １１ each independently represents a direct bond or an alkylene group having 1 to 20 carbon atoms, and is more preferably a direct bond, a methylene group, or an ethylene group in order to impart appropriate alkali solubility.

[0142] In formula (D2), c, d, and e each independently represent 1 or 2, but from the viewpoint of simultaneously imparting appropriate alkali solubility and reducing the water absorption of the cured product, 1 is more preferable.

[0143] In formula (D2), at least one of T and U is preferably a structure represented by formula (D3) or formula (D4), because this allows for the formation of a cured product with a lower water absorption rate in the method for producing the cured product described below. The lower water absorption rate of the cured product further reduces the amount of water-derived outgassing after curing, and when used in a planarizing layer and / or insulating layer of an organic EL display device, corrosion of metal electrodes can be further suppressed. Furthermore, from the viewpoint of the heat resistance of the cured product, it is more preferable that at least one of T and U is a structure represented by formula (D4). Formula (D2) containing a structure represented by formula (D4) further reduces the amount of outgassing after curing.

[0144] Furthermore, the component (D) may have a structure represented by formula (D3) and a structure represented by formula (D4) in one molecule.

[0145] In formula (D2), the phenol compound in which at least one of T and U has a structure represented by formula (D3) preferably has the following structure, but is not limited to this.

[0146]

[0147] i represents an integer of 0 to 100.

[0148] Specific examples of the phenol compound having a structure in which at least one of T and U in formula (D2) is represented by formula (D3) include, but are not limited to, the J-DPP series (manufactured by JFE Chemical Corporation).

[0149] In formula (D2), the phenol compound in which at least one of T and U has a structure represented by formula (D4) preferably has the following structure, but is not limited to this.

[0150]

[0151] i represents an integer of 0 to 100.

[0152] Specific examples of the phenol compound in which at least one of T and U in formula (D2) is represented by formula (D4) include, but are not limited to, MEHC-7851 series (manufactured by Meiwa Kasei Co., Ltd.), GPH-65, and GPH-103 (manufactured by Nippon Kayaku Co., Ltd.).

[0153] The photosensitive resin composition of the present invention may contain two or more types of component (D).

[0154] The weight average molecular weight of component (D) can be measured using a GPC (gel permeation chromatography) device, Waters 2690-996 (manufactured by Nippon Waters Co., Ltd.), using tetrahydrofuran as the developing solvent, and calculated in terms of polystyrene. The weight average molecular weight of component (D) is preferably 300 to 10,000, and more preferably 350 to 2,000. Within this range, the water absorption of the cured product can be reduced, while a better pattern can be formed in the method for producing the cured product described below.

[0155] In the present invention, the content of the (D) component is preferably 1 part 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 (A) component. By making the content of the (D) component 1 part by mass or more per 100 parts by mass of the (A) component, the water absorption of the cured product can be further reduced. Furthermore, the content of the (D) component is preferably 100 parts by mass or less, more preferably 60 parts by mass or less, and even more preferably 50 parts by mass or less, per 100 parts by mass of the (A) component. By making the content of the (D) component 100 parts by mass or less per 100 parts by mass of the (A) component, a good pattern can be formed in the method for producing a cured product described below, and a cured product with a lower amount of outgassing after curing can be obtained.

[0156] The content of the (D) component is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and even more preferably 40 parts by mass or more, per 100 parts by mass of the (C) component. By making the content of the (D) component 10 parts by mass or more, per 100 parts by mass of the (C) component, the water absorption of the cured product can be further reduced. The content of the (D) component is preferably 300 parts by mass or less, more preferably 250 parts by mass or less, and even more preferably 200 parts by mass or less, per 100 parts by mass of the (C) component. By making the content of the (D) component 100 parts by mass or less, per 100 parts by mass of the (C) component, it is possible to impart appropriate alkali solubility during development and to obtain a cured product with a lower amount of outgassing after curing.

[0157] By using the photosensitive resin composition of the present invention in combination with the component (C) and the component (D), it is possible to form a cured product that has reduced transmittance at a wavelength of around 450 nm after curing and that also has a small amount of outgassing after curing, even when the heating atmosphere during curing is at a low oxygen concentration of less than 5%.

[0158] <Radical Polymerizable Compound> The photosensitive resin composition of the present invention may contain a radical polymerizable compound. In particular, when the photosensitive resin composition contains a photopolymerization initiator (B2), it is essential that the composition contain a radical polymerizable compound. The radical polymerizable compound used when the photopolymerization initiator (B2) is contained in the present invention refers to a compound having multiple ethylenically unsaturated double bonds in its molecule and forming a crosslinked structure upon polymerization. During exposure, radicals generated from the photopolymerization initiator (B2) cause radical polymerization of the radical polymerizable compound to form a crosslinked structure, thereby insolubilizing the light-irradiated area and obtaining a negative pattern. Furthermore, the inclusion of a radical polymerizable compound promotes photocuring of the light-irradiated area, thereby further improving sensitivity. Additionally, the crosslink density after thermal curing is improved, thereby improving the hardness of the cured product.

[0159] As the radical polymerizable compound, from the viewpoints of improving sensitivity during exposure and improving hardness of the cured product, a compound having two or more (meth)acrylic groups in the molecule, which facilitates radical polymerization, is preferred. From the viewpoints of improving sensitivity during exposure and improving hardness of the cured product, the double bond equivalent of the radical polymerizable compound is preferably 80 to 400 g / mol.

[0160] From the viewpoints of further improving sensitivity and reducing the taper angle, the content of the radical polymerizable compound is preferably 15 parts by mass or more, and more preferably 30 parts by mass or more, per 100 parts by mass of the total of the component (A) and the radical polymerizable compound. On the other hand, from the viewpoints of further improving heat resistance of the cured product and reducing the taper angle, the content of the radical polymerizable compound is preferably 65 parts by mass or less, and more preferably 50 parts by mass or less, per 100 parts by mass of the total of the component (A) and the radical polymerizable compound.

[0161] <Thermal Crosslinking Agent> The photosensitive resin composition of the present invention preferably contains a thermal crosslinking agent. The thermal crosslinking agent refers to a compound having at least two thermally reactive functional groups in the molecule, such as a known alkoxymethyl group, a methylol group, an epoxy group, or an oxetanyl group, and may contain known compounds that do not fall under the category of components (C) and (D), but is not limited thereto.

[0162] The inclusion of a thermal crosslinking agent can crosslink between the thermal crosslinking agent and the alkali-soluble resin (A) or between the thermal crosslinking agents themselves, improving the heat resistance of the cured product after thermal curing and further reducing the outgassing components generated from the cured product. It can also improve chemical resistance and bending resistance. From the perspective of reducing the transmittance in the 300-500 nm range after curing, the thermal crosslinking agent is preferably a compound with low reactivity with phenolic hydroxyl groups, and an alkoxymethyl group is preferred. This is presumably because the reaction of the phenolic hydroxyl groups of component (C) with the thermal crosslinking agent makes it difficult for the crosslinked product to form a quinone structure.

[0163] When a thermal crosslinking agent is contained, its content is preferably 1 part by mass or more and 30 parts by mass or less per 100 parts by mass of the total amount of the resin composition excluding the solvent. If the content of the thermal crosslinking agent is 1 part by mass or more, the chemical resistance and bending resistance of the cured product can be further improved. Furthermore, if the content of the thermal crosslinking agent is 30 parts by mass or less, the water absorption rate after curing can be reduced, and the storage stability of the resin composition is also excellent.

[0164] <Solvent> The photosensitive resin composition of the present invention may contain a solvent. By containing a solvent, the composition can be made into a varnish state, and the coatability can be further improved.

[0165] Examples of the solvent include polar aprotic solvents such as γ-butyrolactone, ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tetrahydrofuran, and dioxane, acetone, methyl Ketones such as ethyl ethyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, and diacetone alcohol; esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and ethyl lactate; ethyl 2-hydroxy-2-methylpropionate, 3- Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate,The solvent may contain esters such as i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; amides such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N,N-dimethylpropanamide, and N,N-dimethylisobutyramide; and 3-methyl-2-oxazolidinone. The solvent may contain two or more of these.

[0166] The content of the solvent is not particularly limited, but is preferably 100 to 3,000 parts by mass, and more preferably 150 to 2,000 parts by mass, relative to 100 parts by mass of the total amount of the photosensitive resin composition excluding the solvent. Furthermore, the proportion of the solvent having a boiling point of 180°C or higher in 100 parts by mass of the total amount of solvent is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less. By keeping the proportion of the solvent having a boiling point of 180°C or higher to 20 parts by mass or less, the amount of outgassing after curing can be further reduced, and the long-term reliability of the organic EL device can be further improved.

[0167] <Colorant> The photosensitive resin composition of the present invention may further contain a colorant. By including component (C) and a colorant in the photosensitive resin composition of the present invention, a film with higher visible light blocking properties can be obtained after curing. By imparting light blocking properties, when the cured product of the present invention described below is used as a planarizing layer and / or insulating layer in an organic EL display device, deterioration, malfunction, leakage current, and the like due to light penetration into TFTs can be more effectively prevented. Furthermore, external light reflection from wiring and TFTs can be suppressed, and the contrast between light-emitting areas and non-light-emitting areas can be further improved.

[0168] The colorant preferably contains a dye and / or a pigment, and two or more of these may be contained.

[0169] From the viewpoint of solvent solubility, it is preferable to contain a dye as the colorant. Furthermore, from the viewpoint of increasing sensitivity and reducing residues, it is preferable to contain an ionic dye that forms an ion pair between organic ions as the dye. On the other hand, it is preferable to contain a pigment from the viewpoint of suppressing fading of the colorant in the heat treatment step of the photosensitive resin composition described below.

[0170] The content of the colorant is preferably 0.1 to 300 parts by mass, more preferably 0.2 to 200 parts by mass, and particularly preferably 1 to 200 parts by mass, per 100 parts by mass of component (A). By setting the content of the colorant to 0.1 parts by mass or more per 100 parts by mass of component (A), it is possible to better absorb light of the corresponding wavelength. Furthermore, by setting the content to 300 parts by mass or less, it is possible to better absorb light of the corresponding wavelength while maintaining the adhesive strength between the resin film and the substrate, the heat resistance of the film after heat treatment, and the mechanical properties.

[0171] <Adhesion improver> The photosensitive resin composition of the present invention may contain an adhesion improver. Examples of the adhesion improver include known silane coupling 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 resin film, for example, it is possible to improve adhesion between the silicon wafer, indium tin oxide (ITO), SiO ２ The adhesion improver can improve the adhesion to the underlying substrate such as silicon nitride during development. It can also improve resistance to oxygen plasma and UV ozone treatments used for cleaning, etc. The content of the adhesion improver is preferably 0.01 to 10 parts by mass per 100 parts by mass of the total amount of the photosensitive resin composition excluding the solvent.

[0172] <Surfactant> The photosensitive resin composition of the present invention may contain a surfactant, which can improve wettability with the substrate. The surfactant may include known silicone surfactants, fluorine surfactants, acrylic and / or methacrylic surfactants, etc.

[0173] When a surfactant is contained, the content thereof is preferably 0.001 to 1 part by mass in 100 parts by mass of the total amount of the photosensitive resin composition excluding the solvent.

[0174] <Inorganic Particles> The photosensitive resin composition of the present invention may contain inorganic particles. Specific preferred examples of inorganic particles include silicon oxide, titanium oxide, barium titanate, alumina, and talc. The primary particle diameter of the inorganic particles is preferably 100 nm or less, and more preferably 60 nm or less.

[0175] The content of the inorganic particles is preferably 5 to 90 parts by mass in 100 parts by mass of the total amount of the photosensitive resin composition excluding the solvent.

[0176] <Method for producing photosensitive resin composition> Next, a method for producing the photosensitive resin composition of the present invention will be described. For example, the photosensitive resin composition of the present invention can be obtained by dissolving the components (A), (B), (C), and (D), and optionally a radical polymerizable compound, a thermal crosslinking agent, a solvent, a colorant, an adhesion improver, a surfactant, inorganic particles, etc.

[0177] Examples of dissolution methods include stirring and heating. When heating, the heating temperature is preferably set within a range that does not impair the performance of the photosensitive resin composition, and is typically room temperature to 80°C. The order in which the components are dissolved is not particularly limited, and examples include a method in which compounds with low solubility are dissolved in order. For components that tend to generate bubbles when dissolved by stirring, such as surfactants and some adhesion improvers, adding them last after dissolving the other components can prevent poor dissolution of the other components due to the generation of bubbles.

[0178] The obtained photosensitive resin composition is preferably filtered using a filter to remove dust and particles. Examples of filter pore sizes include, but are not limited to, 0.5 μm, 0.2 μm, 0.1 μm, 0.07 μm, 0.05 μm, and 0.02 μm. Examples of filter materials include polypropylene (PP), polyethylene (PE), nylon (NY), and polytetrafluoroethylene (PTFE). Among these, polyethylene and nylon are preferred.

[0179] <Method for Producing a Cured Product> The method for producing a cured product of the present invention includes the steps of forming a resin film made of the photosensitive resin composition of the present invention on a substrate, exposing the resin film to light, developing the exposed resin film, and heat-treating the developed resin film.

[0180] The process for forming a resin film made of the photosensitive resin composition of the present invention on a substrate will now be described. In the method for producing a cured product of the present invention, the resin film can be obtained by applying the photosensitive resin composition of the present invention to obtain a coating film of the photosensitive resin composition, and drying the coating film.

[0181] The substrate may be a known substrate such as a glass substrate.

[0182] Examples of methods for applying the photosensitive resin composition of the present invention include spin coating, slit coating, dip coating, spray coating, and printing. Among these, slit coating is preferred because it allows application with a small amount of coating liquid, which is advantageous in reducing costs. The amount of coating liquid required for slit coating is, for example, approximately 1 / 5 to 1 / 10 of that required for spin coating. Slit nozzles used for application can be selected from those commercially available from multiple manufacturers, including, for example, the "Linear Coater" manufactured by Dainippon Screen Mfg. Co., Ltd., the "Spinless" manufactured by Tokyo Ohka Kogyo Co., Ltd., the "TS Coater" manufactured by Toray Engineering Co., Ltd., the "Table Coater" manufactured by Chugai Ro Kogyo Co., Ltd., the "CS Series" and "CL Series" manufactured by Tokyo Electron Limited, the "Inline Slit Coater" manufactured by Cermatronics Trading Co., Ltd., and the "Head Coater HC Series" manufactured by Hirata Corporation. The coating speed is generally in the range of 10 mm / s to 400 mm / s. The thickness of the coating film varies depending on the solid content and viscosity of the photosensitive resin composition, but is usually applied so that the thickness after drying is 0.1 to 10 μm, preferably 0.3 to 5 μm.

[0183] Prior to coating, the substrate to which the photosensitive resin composition is to be applied may be pretreated with the adhesion improver described above. Examples of pretreatment methods include treating the substrate surface with a solution prepared by dissolving 0.5 to 20% by mass of an adhesion improver in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, or diethyl adipate. Examples of methods for treating the substrate surface include spin coating, slit die coating, bar coating, dip coating, spray coating, and steam treatment.

[0184] After application, a reduced pressure drying treatment is carried out as necessary.

[0185] The reduced-pressure drying speed depends on factors such as the volume of the vacuum chamber, the capacity of the vacuum pump, and the diameter of the pipes between the chamber and the pump, but is preferably set, for example, under conditions such that the pressure inside the vacuum chamber is reduced to 40 Pa after 60 seconds without a coated substrate present. Typical reduced-pressure drying times are often around 30 to 100 seconds, and the ultimate pressure inside the vacuum chamber at the end of reduced-pressure drying is usually 100 Pa or less with a coated substrate present. By setting the ultimate pressure to 100 Pa or less, it is possible to achieve a dry state with reduced stickiness on the surface of the coating film, thereby suppressing surface contamination and particle generation during subsequent substrate transport.

[0186] After coating or drying under reduced pressure, the coating film is generally heated and dried. This process is also called pre-baking. Drying is performed using a hot plate, oven, infrared rays, or the like. When using a hot plate, the coating film is heated directly on the plate or held on a jig such as a proxy pin placed on the plate. The heating time is preferably from one minute to several hours. The heating temperature varies depending on the type and purpose of the coating film, but from the viewpoint of accelerating solvent drying during pre-baking, it is preferably 80°C or higher, and more preferably 90°C or higher. On the other hand, from the viewpoint of reducing the progress of curing during pre-baking, it is preferably 150°C or lower, and more preferably 140°C or lower.

[0187] Next, the step of exposing the resin film will be described.

[0188] The resin film obtained from the photosensitive resin composition of the present invention can be patterned, for example, by exposing the resin film to actinic radiation through a photomask having a desired pattern, and then developing the film to form a desired pattern.

[0189] Examples of actinic radiation used for exposure include ultraviolet light, visible light, electron beams, and X-rays. In the present invention, it is preferable to use i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) from a mercury lamp. When the film has positive photosensitivity, the exposed area dissolves in a developer. When the film has negative photosensitivity, the exposed area hardens and becomes insoluble in a developer.

[0190] Next, the process of developing the exposed resin film will be described.

[0191] After exposure, the exposed areas are removed with a developer in the case of a positive-tone film, and the unexposed areas are removed with a developer in the case of a negative-tone film, to form a desired pattern. Examples of the developer include aqueous solutions of alkaline compounds such as tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine. These alkaline aqueous solutions may contain one or more polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, and dimethylacrylamide; alcohols such as methanol, ethanol, and isopropanol; esters such as ethyl lactate and propylene glycol monomethyl ether acetate; and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone. Examples of the developing method include spray, puddle, immersion, and ultrasonic methods.

[0192] Next, the pattern formed by development is preferably rinsed with pure water. Alternatively, alcohols such as ethanol and isopropyl alcohol, or esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to the pure water for rinsing.

[0193] Next, the step of heat treating the developed resin film will be described.

[0194] After development, the developed resin film is subjected to a heat treatment to obtain a cured product.

[0195] The heat treatment temperature is preferably 180°C or higher, more preferably 200°C or higher, even more preferably 230°C or higher, and particularly preferably 250°C or higher, from the viewpoint of further reducing the amount of outgassing from the cured product. On the other hand, from the viewpoint of improving the film toughness of the cured product, it is preferably 500°C or lower, more preferably 450°C or lower. Within this temperature range, the temperature may be increased stepwise or continuously. The heat treatment time is preferably 30 minutes or longer, from the viewpoint of further reducing the amount of outgassing after curing. Furthermore, from the viewpoint of improving the film toughness of the cured product, it is preferably 3 hours or shorter. For example, a method of heat treatment at 150°C and 250°C for 30 minutes each, or a method of heat treatment while linearly increasing the temperature from room temperature to 300°C over 2 hours may be mentioned.

[0196] When the photosensitive resin composition of the present invention is used in an organic EL display device or the like, the atmosphere during the heat treatment is preferably a low oxygen concentration of less than 5% in order to prevent contamination of electrodes by outgassing components during heat curing and deterioration of current-voltage characteristics. Preventing deterioration of current-voltage characteristics can further reduce the driving voltage of the organic EL display device, thereby further improving the luminous efficiency and durability. Specific examples of inert gases for achieving an oxygen concentration of less than 5% include nitrogen and argon. The oxygen concentration in the inert gas atmosphere is preferably less than 5%, more preferably less than 1%, even more preferably less than 0.5%, and particularly preferably less than 0.01%.

[0197] <Cured Product> The cured product of the present invention is a cured product obtained by curing the photosensitive resin composition of the present invention. By heat-treating the photosensitive resin composition of the present invention, components with low heat resistance can be removed, thereby further improving the heat resistance and chemical resistance. In particular, when the photosensitive resin composition of the present invention contains a polyimide precursor, a polybenzoxazole precursor, a copolymer thereof, or a copolymer thereof with a polyimide, imide rings and oxazole rings are formed by heat treatment, thereby further improving the heat resistance and chemical resistance.

[0198] Furthermore, by including component (C), the photosensitive resin composition of the present invention can reduce the ultraviolet light transmittance of the cured product. The heat treatment temperature is preferably 180°C or higher, more preferably 200°C or higher, even more preferably 230°C or higher, and particularly preferably 250°C or higher, from the viewpoint of further reducing the amount of outgassing from the cured product. On the other hand, from the viewpoint of improving the film toughness of the cured product, it is preferably 500°C or lower, more preferably 450°C or lower. Within this temperature range, the temperature may be increased stepwise or continuously. The heat treatment time is preferably 30 minutes or longer, from the viewpoint of further reducing the amount of outgassing after curing. Furthermore, from the viewpoint of improving the film toughness of the cured product, it is preferably 3 hours or shorter. For example, a method of heat treatment at 150°C and 250°C for 30 minutes each, or a method of heat treatment while linearly increasing the temperature from room temperature to 300°C over 2 hours, can be mentioned.

[0199] The transmittance of the cured product at a wavelength of 450 nm is preferably less than 30%, more preferably less than 20%, and even more preferably less than 15%. The lower limit of the transmittance at a wavelength of 450 nm is not particularly limited, but is preferably 0.01% or more.

[0200] The water absorption of the cured product is preferably less than 4.0%, more preferably less than 3.5%, and even more preferably less than 3.0%. A low water absorption of the cured product can better suppress corrosion of metal electrodes when used in a planarizing layer and / or insulating layer of an organic EL display device. In the present invention, the water absorption refers to a value measured by the method described in (3) Evaluation of the Water Absorption of a Cured Product below.

[0201] The outgassing amount of the cured product is preferably less than 2.0%, more preferably less than 1.0%. A low outgassing amount of the cured product can further improve the long-term reliability of an organic EL display device when the cured product is used in the device. In the present invention, the outgassing amount refers to a value measured by the method described in (4) Evaluation of outgassing of cured product below.

[0202] <Application Examples of Photosensitive Resin Composition and Cured Product> The photosensitive resin composition and cured product of the present invention are suitably used for surface protection layers and interlayer insulating layers of semiconductor elements, insulating layers of organic electroluminescence (hereinafter referred to as EL) elements, planarizing layers of thin film transistor (hereinafter referred to as TFT) substrates for driving display devices using organic EL elements, wiring protection insulating layers of circuit boards, on-chip microlenses of solid-state imaging elements, and planarizing layers for various display devices and solid-state imaging elements. For example, the film is suitable as a surface protection layer or an interlayer insulating layer for a magnetoresistive random access memory (MRAM) having low heat resistance, a polymer memory (PFRAM) which is a promising next-generation memory, a phase change memory (PCRAM) which is an Ovonics Unified Memory (OUM), etc. It can also be used as an insulating layer for a display device including a first electrode formed on a substrate and a second electrode provided opposite the first electrode, such as a liquid crystal display (LCD), an electrochromic display (ECD), an electroluminescent display (ELD), or a display device using an organic electroluminescent element (organic electroluminescent device). Hereinafter, an organic EL display device will be described as an example.

[0203] <Organic EL Display Device> The organic EL display device of the present invention has the cured product of the present invention. Preferably, the organic EL display device of the present invention is an organic EL display device having, on a substrate, a drive circuit, a planarizing layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode, wherein the planarizing layer and / or the insulating layer has the cured product of the present invention.

[0204] When the planarization layer and / or insulating layer contains the cured product of the present invention, the planarization layer and / or insulating layer preferably has a transmittance of less than 30% at a wavelength of 450 nm. When the transmittance at a wavelength of 450 nm is less than 30%, malfunctions due to the penetration of ultraviolet light into the TFT can be prevented in organic EL display devices using oxide semiconductor layer TFTs. To prevent ultraviolet light from penetrating the TFT, the transmittance at a wavelength of 450 nm is preferably less than 30%, more preferably less than 20%, and even more preferably less than 15%. The lower limit of the transmittance at a wavelength of 450 nm is not particularly limited, but is preferably 0.01% or more.

[0205] The transmittance of the planarizing layer and / or insulating layer at a wavelength of 500 nm is preferably less than 35%, more preferably less than 25%, and even more preferably less than 20%.

[0206] Furthermore, the transmittance of the planarizing layer and / or insulating layer at a wavelength of 550 nm is preferably less than 35%, more preferably less than 25%, and even more preferably less than 20%.

[0207] Taking an active matrix display device as an example, a display device has a TFT and wiring located on the sides of the TFT and connected to the TFT on a substrate such as glass or various plastics, a planarizing layer covering the unevenness thereon, and a display element on the planarizing layer. The display element and wiring are connected via contact holes formed in the planarizing layer. In particular, since flexible organic EL display devices have become mainstream in recent years, it is preferable that the substrate having the aforementioned drive circuit be an organic EL display device containing a resin film. When a cured product obtained by curing the photosensitive resin composition of the present invention is used as an insulating layer or planarizing layer of such a flexible display device, it is particularly preferred because it has excellent bending resistance. From the viewpoint of improving adhesion to the cured product obtained by curing the photosensitive resin composition of the present invention, polyimide is particularly preferred as the resin film.

[0208] In order to enhance the effect of reducing external light reflection, the organic EL display device preferably further includes a color filter having a black matrix. The black matrix preferably contains a resin such as an epoxy resin, an acrylic resin, a urethane resin, a polyester resin, a polyimide resin, a polyolefin resin, or a siloxane resin.

[0209] The black matrix contains a colorant. Examples of colorants that can be used include black organic pigments, mixed-color organic pigments, and inorganic pigments. Examples of black organic pigments include carbon black, perylene black, aniline black, and benzofuranone-based pigments. Examples of mixed-color organic pigments include pseudo-black pigments obtained by mixing two or more pigments, such as red, blue, green, purple, yellow, magenta, and / or cyan. Examples of black inorganic pigments include graphite; fine particles of metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver; metal oxides; metal composite oxides; metal sulfides; metal nitrides; metal oxynitrides; and metal carbides. Among these, carbon black, titanium nitride, titanium carbide, and composite particles of these with metals such as silver, which have high light-shielding properties, are preferred.

[0210] FIG. 1 shows a cross-sectional view of an example of an organic EL display device. Bottom-gate or top-gate thin film transistors (TFTs) 1 are arranged in a matrix on a substrate 6. A TFT insulating layer 3 is formed to cover the TFTs 1. Wiring 2 connected to the TFTs 1 is also provided on the TFT insulating layer 3. A planarization layer 4 is further formed on the TFT insulating layer 3, burying the wiring 2. Contact holes 7 are formed in the planarization layer 4, reaching the wiring 2. An ITO (transparent electrode) 5 is formed on the planarization layer 4 and connected to the wiring 2 via the contact holes 7. The ITO 5 serves as an electrode for a display element (e.g., an organic EL element). An insulating layer 8 is formed to cover the periphery of the ITO 5. The organic EL elements may be top-emission types that emit light from the side opposite the substrate 6, or bottom-emission types that extract light from the substrate 6 side. In this manner, an active matrix organic EL display device is obtained, in which TFTs 1 for driving each organic EL element are connected to the corresponding TFTs 1.

[0211] The TFT insulating layer 3, the planarizing layer 4, and / or the insulating layer 8 can be formed by the steps of forming a resin film made of the photosensitive resin composition of the present invention, exposing the resin film to light, developing the exposed resin film, and heat-treating the developed resin film, as described above. An organic EL display device can be obtained by a manufacturing method including these steps.

[0212] <Display Device Other Than Organic EL Display Device> A display device other than an organic EL display device of the present invention is a display device having at least metal wiring, the cured product of the present invention, and a plurality of light-emitting elements, wherein the light-emitting elements are provided with a pair of electrode terminals on either side thereof, the pair of electrode terminals are connected to a plurality of the metal wirings extending in the cured product, and the plurality of the metal wirings maintain electrical insulation due to the cured product.

[0213] The display device will be described with reference to FIG. 2 as an example of one embodiment.

[0214] In FIG. 2 , the display device 9 has a plurality of light-emitting elements 10 arranged on a counter substrate 13, and a cured product 11 arranged on the light-emitting elements 10. "On the light-emitting elements" does not necessarily mean the surface of the light-emitting elements, but may also mean the upper side of the support substrate or the light-emitting elements. The embodiment shown in FIG. 2 illustrates a configuration in which a total of three layers are stacked, with multiple cured products 11 stacked on top of a cured product 11 arranged so as to contact at least a portion of the light-emitting elements 10, but the cured product 11 may also be a single layer. The light-emitting element 10 has a pair of electrode terminals 14 on the surface opposite to the surface contacting the counter substrate 13, and each electrode terminal 14 is connected to a metal wiring 12 extending into the cured product 11. If the multiple metal wiring 12 extending into the cured product 11 are covered with the cured product 11, the cured product 11 also functions as an insulating layer, thereby maintaining electrical insulation. The term "metal wiring maintaining electrical insulation" means that the portions of the metal wiring that require electrical insulation are covered with a cured product obtained by curing a photosensitive resin composition containing an alkali-soluble resin (A). In the present invention, the insulating layer is in an electrically insulating state when the volume resistivity of the insulating layer is 10 １２ This means a state in which the electrical resistance is Ω·cm or more. Furthermore, the light emitting element 10 is electrically connected to a driving element 16 attached to a light emitting element driving substrate 15 provided at a position opposite to the counter substrate 13 via metal wiring 12 and 12c, thereby controlling the light emission of the light emitting element 10. Furthermore, the light emitting element driving substrate 15 is electrically connected to the metal wiring 12 via, for example, solder bumps 18. Furthermore, a barrier metal 17 may be provided to prevent diffusion of metal such as the metal wiring 12.

[0215] The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Evaluations in the examples were carried out by the following methods.

[0216] (1) Evaluation of Light-Shielding Properties at 450 nm and 500 nm (Transmittance at 450 nm and 500 nm) The varnishes obtained in each Example and Comparative Example were applied to a 5 cm square glass substrate by spin coating so that the film thickness after heat treatment (curing) was 3.0 μm, and the substrate was prebaked at 120°C for 120 seconds to produce a prebaked film. The substrate was then developed with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide for 60 seconds and rinsed with pure water. The substrate was then cured at 250°C for 60 minutes in a nitrogen atmosphere with an oxygen concentration of approximately 1% using a high-temperature clean oven INH-9CD-S (manufactured by Koyo Thermo Systems Co., Ltd.) to produce a cured film (hereinafter, the cured film may be referred to as the cured film). The film thickness of the cured film was measured using a stylus profiler P-15 (manufactured by KLA Tencor Corporation). The cured film thus obtained was measured for its transmission spectrum at wavelengths of 300 nm to 800 nm using a UV-visible spectrophotometer MultiSpec-1500 (manufactured by Shimadzu Corporation), and the transmittance at a wavelength of 450 nm at a film thickness of 3.0 μm after curing (hereinafter referred to as T%) was calculated. ４５０ ) and transmittance at 500 nm (hereinafter referred to as T% ５００ The T% at a film thickness of 3.0 μm after curing was determined. ４５０ is less than 15% and T% ５００ If it is less than 20%, it is marked as "S", and T% ４５０ is less than 15% and T% ５００ If it is 20% or more but less than 25%, it is marked "A", and if it is T%, it is marked "A". ４５０ is less than 15% and T% ５００ is 25% or more but less than 35% and T% ４５０ is 15% or more and less than 30% and T% ５００ If it is less than 35%, it is marked "B", T% ５００ Regardless of T% ４５０ When T% is 30% or more ４５０ Regardless of T% ５００ When the value was 35% or more, it was judged as "C".

[0217] (2) Evaluation of light-shielding ability at 550 nm (transmittance at 550 nm) For the cured film obtained in the same manner as in (1), the transmission spectrum at wavelengths of 300 nm to 800 nm was measured using a UV-visible spectrophotometer MultiSpec-1500 (manufactured by Shimadzu Corporation), and the transmittance at a wavelength of 550 nm (hereinafter referred to as T%) at a film thickness of 3.0 μm after curing was evaluated. ５５０ The T% at a film thickness of 3.0 μm after curing was determined. ５５０ If it is less than 20%, it is marked as "S", and T% ５５０ If it is 20% or more but less than 25%, it is marked "A", and if it is T%, it is marked "A". ５５０ If it is 25% or more but less than 35%, it is "B", T% ５５０ When the value was 35% or more, it was judged as "C".

[0218] (3) Evaluation of Water Absorption of Cured Product The varnishes obtained in each Example and Comparative Example were spin-coated onto an 8-inch silicon wafer so that the film thickness after heat treatment (cure) would be 3.0 μm, and the wafer was pre-baked at 120°C for 120 seconds to produce a pre-baked film. The wafer was then developed with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide for 60 seconds and rinsed with pure water. The wafer was then cured at 250°C for 60 minutes in a nitrogen atmosphere with an oxygen concentration of approximately 1% using a high-temperature clean oven INH-9CD-S (manufactured by Koyo Thermo Systems Co., Ltd.) to produce a cured film. The film thickness of the cured film was measured using a stylus profiler P-15 (manufactured by KLA Tencor Corporation).

[0219] An 8-inch silicon wafer with a cured film laminated thereon was immersed in 45% by mass hydrofluoric acid for 5 minutes to peel the cured film from the 8-inch silicon wafer. The resulting cured film was thoroughly washed with pure water and then dried in an oven at 60°C for 5 hours to obtain a film. The film was cut into 2 cm squares and placed in a thermogravimetric analyzer TGA-50 (Shimadzu Corporation), and its weight (W1) was measured before starting the measurement. The temperature was then raised from room temperature to 100°C under a nitrogen atmosphere, and the sample was then held at 100°C for 60 minutes, after which its weight (W2) was measured. The "water absorption of the cured product" was calculated by rounding to the nearest tenth (1 / 2) decimal place. A cured product with a water absorption of less than 3.0% was rated "S," a product with a water absorption of 3.0% or more but less than 3.5% was rated "A," a product with a water absorption of 3.5% or more but less than 4.0% was rated "B," and a product with a water absorption of 4.0% or more was rated "C."

[0220] (4) Evaluation of outgassing of the cured product After measuring W2 in (3) Evaluation of water absorption of the cured product, the temperature was raised to 250°C at a rate of 10°C / min, and then the product was held at 250°C for 60 minutes, after which the weight (W3) was measured. The weight change rate was calculated by rounding off to the nearest tenth to determine "(W2 - W3) / W2 x 100." The weight change rate was defined as "outgassing of the cured product" and was evaluated as follows: A weight change rate of less than 1.0% was assigned an "A," a weight change rate of 1.0% or more but less than 2.0% was assigned a "B," and a weight change rate of 2.0% or more was assigned a "C."

[0221] Synthesis Example 1 Synthesis of Hydroxyl Group-Containing Diamine Compound (α) 18.3 g (0.05 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was dissolved in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide, and the solution was cooled to −15°C. To this solution, a solution of 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride dissolved in 100 mL of acetone was added dropwise. After completion of the dropwise addition, the mixture was reacted at −15°C for 4 hours and then returned to room temperature. The precipitated white solid was filtered and dried in vacuo at 50°C.

[0222] After filtering and vacuum-drying, 30 g of the white solid was placed in a 300 mL stainless steel autoclave and dispersed in 250 mL of methyl cellosolve, followed by the addition of 2 g of 5 mass % 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 after confirming that the balloon no longer deflated. After the reaction was completed, the palladium-carbon catalyst was removed by filtration, and the resulting mixture was concentrated using a rotary evaporator to obtain a hydroxyl group-containing diamine compound (α) represented by the following formula:

[0223]

[0224] Synthesis Example 2: Synthesis of Alkali-Soluble Resin (a-1) Under a dry nitrogen stream, 31.0 g (0.10 mol) of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride was dissolved in 500 g of N-methylpyrrolidone (hereinafter referred to as NMP). To this solution, 45.35 g (0.075 mol) of the hydroxyl group-containing diamine compound (α) obtained in Synthesis Example 1 and 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane were added along with 50 g of NMP, and the mixture was allowed to react at 40°C for 2 hours. Next, 4.36 g (0.04 mol) of 3-aminophenol as an end-capping agent was added along with 5 g of NMP, and the mixture was allowed to react at 50°C for 2 hours. Thereafter, a solution prepared by diluting 32.39 g (0.22 mol) of N,N-dimethylformamide diethyl acetal with 50 g of NMP was added. After the addition, the mixture was stirred at 50°C for 3 hours. After the stirring was completed, the solution was cooled to room temperature and then added to 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 24 hours to obtain a polyimide precursor (a-1), which is an alkali-soluble resin.

[0225] Synthesis Example 3 Synthesis of Alkali-Soluble Resin (a-2) Under a dry nitrogen stream, 31.1 g (0.085 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 2.18 g (0.02 mol) of 3-aminophenol were dissolved in 150 g of NMP and 52.8 g (0.6 mol) of glycidyl methyl ether, and the solution was cooled to -15°C. To this solution, 29.5 g (0.10 mol) of diphenyl ether dicarboxylic acid dichloride (manufactured by Nihon Nohyaku Co., Ltd.) dissolved in 50 g of NMP was added dropwise so that the internal temperature did not exceed 0°C. After completion of the dropwise addition, stirring was continued at -15°C for 6 hours. After completion of the reaction, the solution was poured into 3 L of water containing 10 wt% methanol, and the 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 polyhydroxyamide (a-2), an alkali-soluble resin.

[0226] Synthesis Example 4 Synthesis of Alkali-Soluble Resin (a-3) Under a dry nitrogen stream, 8 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 220 g of propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA). Next, 15 g of methacrylic acid, 25 g of glycidyl methacrylate, 10 g of p-isopropenylphenol, 25 g of methyl methacrylate, 5 g of lauryl methacrylate, and 20 g of N-(cyclohexyl)maleimide were added and stirred at 70 °C for 5 hours. After stirring, PGMEA was added to the resin solution until the solids concentration reached 30% by mass, and a 30% by mass solution of acrylic resin (a-3), an alkali-soluble resin, was obtained.

[0227] Synthesis Example 5 Synthesis of Photosensitive Compound (b-1) Under a dry nitrogen stream, 21.22 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 26.87 g (0.10 mol) of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride were dissolved in 450 g of 1,4-dioxane at room temperature. 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise thereto 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 photosensitive compound (b-1) represented by the following formula: In the following formula (b-1), "2:1" indicates that the molar ratio of naphthoquinone diazide sulfonic acid groups to hydrogen in Q in the structure of (b-1) is 2:1. The conversion rate of (b-1) was 67%.

[0228]

[0229] Synthesis Example 6: Synthesis of photosensitive compound (b-2)

[0063] A photosensitive compound (b-2) having a molar ratio of naphthoquinone diazide sulfonic acid groups to hydrogen of Q in the structure of (b-1) of 5:1 was obtained in the same manner as in Synthesis Example 5, except that the amount of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride was 33.59 g (0.125 mol). The conversion rate of (b-2) was 83%.

[0230] Synthesis Example 7 Synthesis of Photosensitive Compound (b-3) A naphthoquinone diazide compound (b-3) in which the molar ratio of naphthoquinone diazide sulfonic acid groups to hydrogen for Q in the structure of (b-1) was 9:1 was obtained in the same manner as in Synthesis Example 5, except that the amount of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride was 36.27 g (0.135 mol). The conversion rate of this naphthoquinone diazide compound was 90%.

[0231] Synthesis Example 8 Synthesis of phenol compound (c-1) Under a dry nitrogen stream, 1.68 g (0.01 mol) of 2,6-bis(hydroxymethyl)-p-cresol (hereinafter referred to as 26DPMC), 12.61 g (0.10 mol) of 1,2,4-trihydroxybenzene, and 0.29 g of p-toluenesulfonic acid monohydrate were dissolved in 40 g of water at room temperature, and the mixture was allowed to react for 4 hours at 65° C. Thereafter, the solid that precipitated upon cooling in an ice bath was collected by filtration, washed three times with water, and then dried for 24 hours in a vacuum dryer at 50° C. to obtain phenol compound (c-1) that satisfies condition (C′1).

[0232] The obtained compound was subjected to LC-MS analysis using an LC-MS2020 (Shimadzu Corporation) and was confirmed to be the target compound. LC-MS (ESI, negative): m / z 383 [M-H] －

[0233]

[0234] Synthesis Example 9 Synthesis of phenol compound (c-2) A phenol compound (c-2) satisfying the condition (C′1) was obtained in the same manner as in Synthesis Example 8, except that 1.68 g (0.01 mol) of 26DPMC was replaced with 2.88 g (0.01 mol) of 3,3′-methylenebis(2-hydroxy-5-methylbenzenemethanol).

[0235] The obtained compound was subjected to LC-MS analysis using an LC-MS2020 (Shimadzu Corporation) and was confirmed to be the target compound. LC-MS (ESI, negative): m / z 503 [M-H] －

[0236]

[0237] Synthesis Example 10: Synthesis of phenol compound (c-3) Under a dry nitrogen stream, 16.72 g (0.10 mol) of carbazole and 12.99 g (0.16 mol) of a 37% aqueous formaldehyde solution were dissolved in 120 g of tetrahydrofuran at room temperature, and 0.5 g of a 50% aqueous sodium hydroxide solution was added thereto, followed by a reaction at room temperature for 8 hours. The solution was then poured into 1 L of water to obtain a yellow-white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 40°C for 24 hours to obtain an N-methylolated carbazole.

[0238] Subsequently, a phenol compound (c-3) satisfying the conditions (C'1) and (C2) was obtained in the same manner as in Synthesis Example 8, except that 3.94 g (0.02 mol) of the obtained N-methylolated carbazole was used instead of 1.68 g (0.01 mol) of 26DPMC.

[0239] The obtained compound was subjected to LC-MS analysis using an LC-MS2020 (Shimadzu Corporation) and was confirmed to be the target compound. LC-MS (ESI, negative): m / z 304 [M-H] －

[0240]

[0241] Synthesis Example 11 Synthesis of phenol compound (c-4) A phenol compound (c-4) satisfying the conditions (C′1) and (C2) was obtained in the same manner as in Synthesis Example 8, except that 4.56 g (0.01 mol) of a dimethylol derivative of bisindolefluorene synthesized with reference to JP 2004-145320 A was used instead of 1.68 g (0.01 mol) of 26DPMC.

[0242] The obtained compound was subjected to LC-MS analysis using an LC-MS2020 (Shimadzu Corporation) and was confirmed to be the target compound. LC-MS (ESI, negative): m / z 671 [M-H] －

[0243]

[0244] Synthesis Example 12 Synthesis of Phenol Compound (c-5) Under a dry nitrogen stream, 27.64 g (0.20 mol) of potassium carbonate was dissolved in 63 g of water, and nitrogen bubbling was performed for 30 minutes. Subsequently, 8.11 g (0.1 mol) of 1-methylpyrrole and 17.86 g (0.22 mol) of a 37% aqueous formaldehyde solution were added, and the reaction was carried out at room temperature under a nitrogen atmosphere for 7 days. Thereafter, the solution was filtered, and the resulting solid was dissolved in acetone, dehydrated by adding anhydrous sodium sulfate, concentrated using a rotary evaporator, and dried in a vacuum dryer at 50°C for 24 hours to obtain a 2,5-dimethylolated 1-methylpyrrole.

[0245] Subsequently, a phenol compound (c-5) having a structure represented by formula (C3) that satisfied condition (C'1) was obtained in the same manner as in Synthesis Example 8, except that 1.41 g (0.01 mol) of the 2,5-dimethylol derivative of the obtained 1-methylpyrrole was used instead of 1.68 g (0.01 mol) of 26DPMC.

[0246] The obtained compound was subjected to LC-MS analysis using an LC-MS2020 (Shimadzu Corporation) and was confirmed to be the target compound. LC-MS (ESI, negative): m / z 356 [M-H] －

[0247]

[0248] Synthesis Example 13: Synthesis of phenol compound (c-6) A phenol compound (c-6) having a structure represented by formula (C3) and satisfying condition (C′1) was obtained in the same manner as in Synthesis Example 8, except that 1.28 g (0.01 mol) of 2,5-bis(hydroxymethyl)furan was used instead of 1.68 g (0.01 mol) of 26DPMC.

[0249] The obtained compound was subjected to LC-MS analysis using an LC-MS2020 (Shimadzu Corporation) and was confirmed to be the target compound. LC-MS (ESI, negative): m / z 343 [M-H] －

[0250]

[0251] Synthesis Example 14 Synthesis of phenol compound (c-7) Phenol compound (c-7) was obtained in the same manner as in Synthesis Example 8, except that 12.61 g (0.10 mol) of pyrogallol was used instead of 12.61 g (0.10 mol) of 1,2,4-trihydroxybenzene.

[0252] The obtained compound was subjected to LC-MS analysis using an LC-MS2020 (Shimadzu Corporation) and was confirmed to be the target compound. LC-MS (ESI, negative): m / z 383 [M-H] －

[0253]

[0254] The names of the compounds used in each example and comparative example are shown below. The phenol compounds (c-8) and (c-9) were synthesized with reference to the specification of U.S. Pat. No. 4,992,596, and other compounds that were not commercially available were synthesized using known methods.

[0255]

[0256] (d-1) J-DPP-95 (phenolic hydroxyl group equivalent: 171 g / Eq, manufactured by JFE Chemical Corporation)

[0257]

[0258] i represents an integer of 0 to 100.

[0259] (d-2) MEHC-7851SS (phenolic hydroxyl group equivalent: 198 g / Eq, manufactured by Meiwa Chemical Industry Co., Ltd.)

[0260]

[0261] i represents an integer of 0 to 100.

[0262] (d-3) SPI (phenolic hydroxyl group equivalent: 154 g / Eq, manufactured by JFE Chemical Corporation)

[0263]

[0264] (d-4) S-TPM130 (phenolic hydroxyl group equivalent: 101 g / Eq, manufactured by JFE Chemical Corporation)

[0265]

[0266] l represents an integer of 0 to 100.

[0267] (d-5) BPFL (phenolic hydroxyl group equivalent: 176 g / Eq, manufactured by JFE Chemical Corporation)

[0268]

[0269] (d-6) Cresol novolak resin KA-1160 (phenolic hydroxyl group equivalent weight 117 g / Eq, manufactured by DIC Corporation) Structural formula: omitted (d-7) Biphenol (phenolic hydroxyl group equivalent weight 93 g / Eq, manufactured by Honshu Chemical Industry Co., Ltd.)

[0270]

[0271] (e-1) HMOM-TPHAP (manufactured by Honshu Chemical Industry Co., Ltd.)

[0272]

[0273] GBL: γ-butyrolactone EL: ethyl lactate PGME: propylene glycol monomethyl ether Example 1 10.0 g of polyimide precursor (a-1), 3.0 g of photosensitive compound (b-1), 2.0 g of phenolic compound (c-1), 2.0 g of phenolic compound (d-1), and 1.0 g of thermal crosslinker (e-1) were dissolved in a mixture of 10 g of GBL, 20 g of EL, and 70 g of PGME, and then filtered through a 0.2 μm polytetrafluoroethylene filter to obtain positive-type photosensitive resin composition AA. The resulting varnish was used to evaluate the light-shielding properties at 450 nm and 500 nm, the water absorption rate of the cured product, and the outgassing of the cured product, as described above. For each evaluation, a cured film cured in a nitrogen atmosphere with an oxygen concentration of approximately 1% was used.

[0274] Examples 2 to 27, Examples 33 to 44, Comparative Examples 1 to 9 Varnishes of positive-type photosensitive resin compositions were obtained in the same manner as in Example 1, except that the components (A), (B), (C), (D), other components, and solvents were changed as shown in Tables 1 and 2. Using the obtained varnishes, the light-shielding properties at 450 nm and 500 nm, the water absorption of the cured product, and the outgassing of the cured product were evaluated as described above. For each evaluation, a cured film cured in a nitrogen atmosphere with an oxygen concentration of approximately 1% was used.

[0275] Examples 28 to 32 The light-shielding ability at 550 nm was evaluated as described above using the positive-type photosensitive resin compositions AJ to AN obtained in Examples 10 to 14. For each evaluation, a cured film cured in a nitrogen atmosphere with an oxygen concentration of approximately 1% was used.

[0276] The compositions and evaluation results of each of the Examples and Comparative Examples are shown in Tables 1 to 3.

[0277]

[0278]

[0279]

[0280]

[0281]

[0282]

[0283] 1: TFT (thin film transistor) 2: Wiring 3: TFT insulating layer 4: Planarizing layer 5: ITO (transparent electrode) 6: Substrate 7: Contact hole 8: Insulating layer 9: Display device 10: Light-emitting element 11: Cured product 12, 12c: Metal wiring 13: Counter substrate 14: Electrode terminal 15: Light-emitting element driving substrate 16: Driving element 17: Barrier metal 18: Solder bump

Claims

1. A photosensitive resin composition comprising: component (A): an alkali-soluble resin; component (B): a photosensitive compound; component (C): a phenolic compound having a structure represented by formula (C1); and component (D): a phenolic compound having a structure represented by formula (D1) and not having a structure represented by formula (C1), and having a phenolic hydroxyl group equivalent of 100 to 500 g / Eq. In formula (C1), n ​​represents an integer of 2 to 4, and * represents a bond. １ represents an alkyl group having 1 to 20 carbon atoms, a represents an integer of 1 or 2, and b represents an integer of 0 to 2. * represents a bond.

2. The photosensitive resin composition according to claim 1, wherein the component (C) contains a phenolic compound that satisfies the following condition (C'1): Condition (C'1): At least one substitution position of a phenolic hydroxyl group other than any of the phenolic hydroxyl groups in the formula (C1) is para-position.

3. The photosensitive resin composition according to claim 1 or 2, wherein the component (C) contains one or more selected from the group consisting of the following components (C3), (C4), and (C5): Component (C3): a phenol compound having a structure represented by the following formula (C3) Component (C4): a phenol compound having a structure represented by the following formula (C4) Component (C5): a phenol compound having a structure represented by the following formula (C5) In formula (C3), formula (C4), and formula (C5), n and m each independently represent an integer of 2 to 4, p represents an integer of 0 to 2, q represents an integer of 0 to 4, and 2≦p+m≦4 is satisfied; and X is —NR ２８ represents -, -O-, -S-, and R ２８ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; R ２ each independently represents a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; R ３ and R ４ are each independently OR ２９ , -SR ２９ , -N(R ２９ ) ２ , an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms; R ２９ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

4. The photosensitive resin composition according to claim 1 or 2, wherein the component (D) is a phenol compound having a structure represented by formula (D2). In formula (D2), R ５ , R ６ and R ７ each independently represents an alkyl group having 1 to 20 carbon atoms; R ８ ~R １１ each independently represents a direct bond or an alkylene group having 1 to 20 carbon atoms. c, d, and e each independently represent 1 or 2, f, g, and h each independently represent an integer of 0 to 2, and i represents an integer of 0 to 100. T and U each independently represent a divalent organic group having 1 to 30 carbon atoms, and at least one of T and U is a structure represented by formula (D3) or a structure represented by formula (D4). R １２ and R １３ each independently represents an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, and j and k each independently represent an integer of 0 to 4. * represents a bond.

5. The photosensitive resin composition according to claim 1 or 2, wherein the content of the component (C) is 1 to 60 parts by mass per 100 parts by mass of the component (A).

6. The photosensitive resin composition according to claim 1 or 2, wherein the content of the component (D) is 10 to 300 parts by mass per 100 parts by mass of the component (C).

7. The photosensitive resin composition according to claim 1 or 2, wherein component (B) is a naphthoquinone diazide compound having a conversion rate of 70% or more but less than 90%.

8. The photosensitive resin composition according to claim 1 or 2, wherein component (A) comprises one or more members selected from the group consisting of polyimides, polyimide precursors, polybenzoxazole precursors, and copolymers thereof.

9. A cured product obtained by curing the photosensitive resin composition according to claim 1 or 2.

10. The cured product according to claim 9, wherein the transmittance of the cured product at a wavelength of 450 nm is less than 30%.

11. An organic EL display device comprising the cured product according to claim 9.

12. An organic EL display device, wherein the planarizing layer and / or insulating layer comprises the cured product according to claim 9, and the transmittance of the planarizing layer and / or insulating layer at a wavelength of 450 nm is less than 30%.

Images