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

Abstract

To provide a photosensitive resin composition that enables pattern formation with a small exposure dose and allows formation of a cured product having a low water absorption rate.SOLUTION: The photosensitive resin composition of the present invention comprises (A) an alkali-soluble resin, (B) a compound represented by formula (1), (C) a phenolic resin represented by formula (3), and (E) a photosensitive compound.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[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 electroluminescence display device. [Background technology]

[0002] Many products using organic electroluminescence (hereinafter "organic EL") display devices have been developed for display devices with thin displays, such as smartphones, tablet PCs, and televisions. 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-based resins are particularly suitable for use in highly reliable organic EL display devices because of their high heat resistance and the low amount of gas components generated from the cured product (see Patent Document 1). In recent years, with the trend toward larger panels for organic EL display devices, there has been a demand for photosensitive resin compositions that can form patterns with a small amount of exposure light from the viewpoint of productivity. One technique for increasing the sensitivity of photosensitive resin compositions using polyimide resins is to add a phenol novolac resin (see Patent Document 2). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2002-91343 [Patent Document 2] Japanese Patent Application Publication No. 7-248626 Summary of the Invention [Problem to be solved by the invention]

[0004] The applicant's investigations have revealed that the photosensitive resin composition described in Patent Document 2 has a high water absorption rate of the phenol novolac resin, and therefore when the cured product is used in the planarizing layer and insulating layer of an organic EL display device, it corrodes the metal electrodes, thereby reducing the light-emitting area of ​​the organic EL display device.

[0005] Therefore, an object of the present invention is to provide a photosensitive resin composition that can form a pattern with a small amount of exposure and can form a cured product with low water absorption. [Means for solving the problem]

[0006] In order to solve the above problems, the photosensitive resin composition of the present invention has the following constitution.

[0007] [1] A photosensitive resin composition containing (A) an alkali-soluble resin, (B) a compound represented by formula (1) (hereinafter, sometimes referred to as component (B)), (C) a phenolic resin represented by formula (3) (hereinafter, sometimes referred to as component (C)), and (E) a photosensitive compound.

[0008] [ka]

[0009] (R 1 is a carboxyl group, an aldehyde group, or a structure represented by formula (2), where a represents an integer of 3 to 5, and b represents an integer of 0 to 2, provided that a+b≦5. L is an ester group, R 2 represents an alkyl group having 1 to 20 carbon atoms. R 3 , R 4 and R 5 each independently represents an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, and R 6 ~R 9each 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, n 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 (4) or a structure represented by formula (5). R 17 and R 18 each independently represents an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, and i and j each independently represent an integer of 0 to 4. * represents a bond. [2] The photosensitive resin composition according to [1], wherein the component (B) contains a compound in which at least one substitution position of a phenolic hydroxyl group other than any one of the phenolic hydroxyl groups in formula (1) is para-positioned.

[0010] [3] The photosensitive resin composition according to [1] or [2], wherein the content of the component (B) is 1 to 50 parts by mass per 100 parts by mass of the alkali-soluble resin (A).

[0011] [4] The photosensitive resin composition according to any one of [1] to [3], wherein the content of the component (C) is 50 to 300 parts by mass per 100 parts by mass of the component (B).

[0012] [5] The photosensitive resin composition according to any one of [1] to [4], wherein the alkali-soluble resin (A) comprises one or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole precursor, and copolymers thereof.

[0013] [6] The photosensitive resin composition according to any one of [1] to [5], further comprising (D) a thermal crosslinking agent.

[0014] [7] The photosensitive resin composition according to [6], wherein the (D) thermal crosslinking agent has an alkoxymethyl group.

[0015] [8] A cured product obtained by curing the photosensitive resin composition according to any one of [1] to [7].

[0016] [9] An organic electroluminescence display device comprising the cured product according to [8]. [Effects of the Invention]

[0017] The photosensitive resin composition of the present invention can form a pattern with a small amount of exposure and can form a cured product with low water absorption. [Brief explanation of the drawings]

[0018] [Figure 1] FIG. 1 is a cross-sectional view of an example of an organic EL display device. DETAILED DESCRIPTION OF THE INVENTION

[0019] An embodiment of the present invention will now be described in detail.

[0020] The photosensitive resin composition of the present invention contains (A) an alkali-soluble resin, (B) a compound represented by formula (1), (C) a phenolic resin represented by formula (3), and (E) a photosensitive compound.

[0021] [ka]

[0022] (R 1 is a carboxyl group, an aldehyde group, or a structure represented by formula (2), where a represents an integer of 3 to 5, and b represents an integer of 0 to 2, provided that a+b≦5. L is an ester group, R 2 represents an alkyl group having 1 to 20 carbon atoms. R 3 , R 4 and R 5 each independently represents an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, and R 6 ~R 9each 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, n 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 (4) or a structure represented by formula (5). R 17 and R 18 each independently represents an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, and i and j each independently represent an integer of 0 to 4. * represents a bond. <(A) Alkali-soluble resin> The photosensitive resin composition of the present invention contains (A) an alkali-soluble resin (hereinafter, sometimes referred to as component (A)). The alkali-soluble resin has a dissolution rate of 50 nm / min or more, as determined from the film thickness reduction when a solution of the resin dissolved in γ-butyrolactone is applied to a silicon wafer and prebaked at 120°C for 4 minutes to form a prebaked film having a thickness of 10 μm±0.5 μm, the prebaked film is immersed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide at 23±1°C for 1 minute, and then rinsed with pure water.

[0023] Component (A) is alkali-soluble and therefore has hydroxyl groups and / or acidic groups in the structural units of the resin and / or at the ends of its main chain. Examples of acidic groups include carboxyl groups, phenolic hydroxyl groups, and sulfonic acid groups.

[0024] Component (A) can include, but is not limited to, known resins that do not fall under component (C), such as polyimides, polyimide precursors, polybenzoxazoles, polybenzoxazole precursors, polyamides, polymers of radically polymerizable monomers having acidic groups, such as acrylic resins and polyhydroxystyrene resins, siloxane resins, and cardo resins. Component (A) may contain two or more of these alkali-soluble resins.

[0025] Among these (A) components, it is preferable that the (A) component contains one or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole precursor, and copolymers thereof, because these components have excellent heat resistance and low outgassing at high temperatures, resulting in high long-term reliability when used in an organic EL display device. Furthermore, from the viewpoint of further improving sensitivity, it is even more preferable that the (A) component contains a polyimide precursor or a polybenzoxazole precursor.

[0026] Here, the polyimide precursor refers to a resin that can be converted into a polyimide by heat treatment or chemical treatment, such as polyamic acid, polyamic acid ester, etc. The polybenzoxazole precursor refers to a resin that can be converted into a polybenzoxazole by heat treatment or chemical treatment, such as polyhydroxyamide, etc.

[0027] The above-mentioned polyimide precursor and polybenzoxazole precursor have a structural unit represented by the following formula (6), and the polyimide has a structural unit represented by the following formula (7). The component (A) may contain two or more types of resins each having a structural unit represented by formula (6) and a structural unit represented by formula (7), or may contain a resin in which the structural unit represented by formula (6) and the structural unit represented by formula (7) are copolymerized.

[0028] [ka]

[0029] In formula (6), X represents a divalent to octavalent organic group having 4 to 40 carbon atoms, and Y represents a divalent to elevenvalent organic group having 6 to 40 carbon atoms. 11 and R 13 R each independently represents a hydroxyl group or a sulfonic acid group. 12 and R 14each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. t, u, and w represent integers of 0 to 3, and v represents an integer of 0 to 6. However, when the structural unit represented by formula (6) represents a structural unit of a polyimide precursor, u≧2; when the structural unit represented by formula (6) represents a structural unit of a polybenzoxazole precursor, v≧2; and when a plurality of R 13 At least two of the R 13 Those having a structural unit represented by formula (6) that does not fall under either the above polyimide precursors or polybenzoxazole precursors are considered to be polyamides.

[0030] [ka]

[0031] In formula (7), E represents a tetravalent to decavalent organic group having 4 to 40 carbon atoms, and G represents a divalent to octavalent organic group having 6 to 40 carbon atoms. 15 and R 16 each independently represents a carboxy group, a sulfonic acid group, or a hydroxyl group, and x and y each independently represent an integer of 0 to 6, provided that x+y>0.

[0032] The polyimide, polyimide precursor, polybenzoxazole precursor, or copolymer thereof preferably has 5 to 100,000 structural units represented by formula (6) or formula (7). Furthermore, other structural units may be contained in addition to the structural units represented by formula (6) or formula (7). In this case, it is preferable that the structural units represented by formula (6) or formula (7) account for 50 mol % or more of the total structural units (100 mol %) of the polyimide, polyimide precursor, polybenzoxazole precursor, or copolymer thereof. In the above formula (6), X(R 11 ) t (COOR 12 ) urepresents an acid residue. X is a divalent to octavalent organic group having 4 to 40 carbon atoms, and among these, a divalent to octavalent organic group containing an aromatic ring or a cycloaliphatic group is preferred.

[0033] 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 (R 2,3-dicarboxyphenyl)hexafluoropropane, 1,1-bis(3,4-dicarboxyphenyl)ethane, 1,1-bis(2,3-dicarboxyphenyl)ethane, bis(3,4-dicarboxyphenyl)methane, bis(2,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, and aromatic tetracarboxylic acids having the structures shown below, aliphatic tetracarboxylic acids such as butanetetracarboxylic acid, and aliphatic tetracarboxylic acids containing a cyclic aliphatic group such as 1,2,3,4-cyclopentanetetracarboxylic acid. 11 ) t (COOR 12 ) u As such, the hydroxyl group may have two or more of these residues.

[0034] [ka]

[0035] R 20 represents an oxygen atom, C(CF3)2 or C(CH3)2. 21 and R 22 each independently represents a hydrogen atom or a hydroxyl group. Among the above acid residues, in the case of a tricarboxylic acid or tetracarboxylic acid residue, one or two carboxy groups are (COOR 12 ) is equivalent to

[0036] In the above formula (7), E(R 15 ) x represents a residue of an acid dianhydride. E is a tetravalent to decavalent organic group having 4 to 40 carbon atoms, and among these, an organic group containing an aromatic ring or a cyclic aliphatic group is preferred.

[0037] 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, bis(3,4-dicarboxyphenyl) Examples of the component (A) include aromatic tetracarboxylic dianhydrides such as ether dianhydrides, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorene dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, and acid dianhydrides having the structures shown below; aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic dianhydride; and residues of aliphatic tetracarboxylic dianhydrides containing cyclic aliphatic groups such as 1,2,3,4-cyclopentanetetracarboxylic dianhydride. Component (A) is a group represented by the formula (7) E(R 15 ) x As such, the aryl group may have two or more of these residues.

[0038] [ka]

[0039] R 20 represents an oxygen atom, C(CF3)2 or C(CH3)2. 21 and R22 each independently represents a hydrogen atom or a hydroxyl group.

[0040] Y(R 13 ) v (COOR 14 ) w and G(R 16 ) y represents a diamine residue. 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 octavalent organic group having 6 to 40 carbon atoms, and is preferably a di- to octavalent organic group containing an aromatic ring or a cycloaliphatic group.

[0041] 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. The component (a) may contain residues of aromatic diamines such as 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 structure shown below. 13 ) v (COOR 14 ) w and G(R 16 ) y As such, the hydroxyl group may have two or more of these residues.

[0042] [ka]

[0043] R 20 represents an oxygen atom, C(CF3)2 or C(CH3)2.21 ~R 24 each independently represents a hydrogen atom or a hydroxyl group. 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.

[0044] The component (A) may be synthesized by a known method.

[0045] Examples of polymers of radically polymerizable monomers having an acidic group include acrylic resins, polyhydroxystyrene resins, etc. Known materials can be used as radically polymerizable monomers having an acidic group, and examples thereof include o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene, as well as alkyl and alkoxy substituted derivatives thereof, methacrylic acid, acrylic acid, and α-position haloalkyl, alkoxy, halogen, nitro, and cyano substituted derivatives thereof.

[0046] Cardo resins include resins with 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.

[0047] Examples of the siloxane resin include known siloxane resins obtained by hydrolyzing and dehydrating condensation of one or more selected from tetrafunctional organosilanes, trifunctional organosilanes, difunctional organosilanes, and monofunctional organosilanes.

[0048] <(B) Compound represented by formula (1) (Component (B))> The photosensitive resin composition of the present invention contains a compound (B) represented by formula (1).

[0049] [ka]

[0050] (R 1is a carboxyl group, an aldehyde group, or a structure represented by formula (2), where a represents an integer of 3 to 5, and b represents an integer of 0 to 2, provided that a+b≦5. L is an ester group, R 2 represents an alkyl group having 1 to 20 carbon atoms, and * represents a bond. By including component (B), the photosensitive resin composition of the present invention can impart excellent alkaline solubility to the exposed area in the step of exposing the resin film in the method for producing a cured product described below, making it possible to form a pattern with a small amount of exposure.It is presumed that the excellent alkaline solubility is achieved because component (B) quickly dissolves in an alkaline developer in the step of developing the exposed resin film described below, thereby dissolving the entangled polymer chains of component (A).

[0051] The photosensitive resin composition of the present invention contains component (B) and component (C), which will be described later. When component (B) alone is contained, the water absorption of the cured product tends to increase, but by using component (C) in combination, it is possible to provide a photosensitive resin composition that can form a pattern with a small amount of exposure and can form a cured product with low water absorption.

[0052] In formula (1), a + b ≦ 5. More preferably, a + b ≦ 4, and even more preferably, a + b ≦ 3. When a + b ≦ 5, the crosslinking reaction with the thermal crosslinking agent (D) described below proceeds efficiently, and the heat resistance of the cured product can be improved.

[0053] From the viewpoint of forming a pattern with a small amount of exposure, it is preferable that component (B) contains a compound in which at least one substitution position of a phenolic hydroxyl group other than one of the phenolic hydroxyl groups in formula (1) is para-positioned. By including component (B) in a compound in which at least one substitution position of a phenolic hydroxyl group other than one of the phenolic hydroxyl groups in formula (1) is para-positioned, excellent alkaline solubility can be imparted to the exposed area. This is presumably because, in the step of developing the exposed resin film described below, the steric hindrance of component (B) makes component (B) more likely to dissolve rapidly in an alkaline developer, thereby rapidly dissolving the entangled polymer chains of component (A).

[0054] Specific examples of component (B) include phloroglucinol, pyrogallol, 1,2,4-trihydroxybenzene, 2,4,5-trihydroxybenzaldehyde, 2,3,4-trihydroxybenzoic acid, gallic acid, methyl gallate, ethyl gallate, propyl gallate, octyl gallate, 1,2,3,4-tetrahydroxybenzene, 1,2,3,5-tetrahydroxybenzene, and 1,2,4,5-tetrahydroxybenzene.

[0055] Among the components (B), examples of compounds in which at least one substitution position of a phenolic hydroxyl group relative to any other phenolic hydroxyl group include 1,2,4-trihydroxybenzene, 2,4,5-trihydroxybenzaldehyde, 1,2,3,4-tetrahydroxybenzene, 1,2,3,5-tetrahydroxybenzene, and 1,2,4,5-tetrahydroxybenzene.

[0056] In the present invention, the content of component (B) 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 ensuring that the content of component (B) is 1 part by mass or more per 100 parts by mass of component (A), excellent alkali solubility can be imparted to the exposed areas in the step of exposing the resin film in the method for producing a cured product described below, thereby enabling pattern formation with a small amount of exposure. Furthermore, the content of component (B) is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less, per 100 parts by mass of component (A). By ensuring that the content of component (B) is 50 parts by mass or less per 100 parts by mass of component (A), the alkali solubility of the unexposed areas is reduced, allowing for the formation of a thick cured product.

[0057] The parts by mass of component (B) per 100 parts by mass of component (A) can be determined by calculating "parts by mass of component (B) / parts by mass of component (A) × 100" and rounding off to one decimal place. <(C) Phenolic resin represented by formula (3) (component (C))> The photosensitive resin composition of the present invention contains (C) a phenolic resin represented by formula (3).

[0058] [ka]

[0059] (R 3 , R 4 and R 5 each independently represents an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, and R 6 ~R 9 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, n 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 (4) or a structure represented by formula (5). R 17 and R 18 each independently represents an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, and i and j each independently represent an integer of 0 to 4. * represents a bond. In formula (3), T and U each independently represent a divalent organic group having 1 to 30 carbon atoms. When at least one of T and U has a structure represented by formula (4) or formula (5), a cured product with low water absorption can be formed in the cured product manufacturing method described below. A cured product with low water absorption can suppress corrosion of metal electrodes when used in the planarizing layer and insulating layer of an organic EL display device. Furthermore, from the viewpoint of heat resistance of the cured product, it is more preferable that at least one of T and U has a structure represented by formula (5).

[0060] In formula (3), c, d, and e each independently represent 1 or 2, and are preferably 1 in order to impart appropriate alkali solubility.

[0061] In formula (3), R6 ~R 9 each independently represents a direct bond or an alkylene group having 1 to 20 carbon atoms, and is more preferably a direct bond or methylene in order to impart appropriate alkali solubility.

[0062] The photosensitive resin composition of the present invention, when used in combination with component (B) and component (C), can provide a photosensitive resin composition that can form a pattern with a small amount of exposure and can form a cured product with low water absorption.

[0063] In formula (3), at least one of T and U preferably contains the following structure as a phenolic resin having a structure represented by formula (4), but is not limited to this.

[0064] [ka]

[0065] (n represents an integer between 0 and 100.) Specific examples of phenolic resins in which at least one of T and U in formula (3) is represented by formula (4) include, but are not limited to, the J-DPP series (manufactured by JFE Chemical Corporation).

[0066] In formula (3), at least one of T and U preferably contains the following structure as a phenol resin having a structure represented by formula (5), but is not limited to this.

[0067] [ka]

[0068] (n represents an integer between 0 and 100.) Specific examples of phenolic resins in which at least one of T and U in formula (3) is represented by formula (5) include, but are not limited to, the MEHC-7851 series (manufactured by Meiwa Chemical Industry Co., Ltd.).

[0069] The weight-average molecular weight of component (C) can be measured using a GPC (gel permeation chromatography) device, Waters 2690-996 (manufactured by Nihon Waters Co., Ltd.), using tetrahydrofuran as the developing solvent, and calculated in terms of polystyrene. The weight-average molecular weight of component (C) is preferably 300 to 10,000, more preferably 350 to 2,000. Within this range, a pattern can be formed with a small amount of exposure.

[0070] In the present invention, the content of component (C) is preferably 50 parts by weight or more, more preferably 70 parts by weight or more, and even more preferably 100 parts by weight or more, per 100 parts by weight of component (B). By ensuring that the content of component (C) is 50 parts by weight or more per 100 parts by weight of component (B), a cured product with low water absorption can be formed, thereby suppressing corrosion of metal electrodes when used in the planarization layer and insulating layer of an organic electroluminescence display device. Furthermore, the content of component (C) is preferably 300 parts by weight or less, more preferably 250 parts by weight or less, and even more preferably 200 parts by weight or less, per 100 parts by weight of component (B). By ensuring that the content of component (C) is 300 parts by weight or less per 100 parts by weight of component (B), a pattern can be formed with a small amount of exposure light in the method for producing a cured product described below.

[0071] The parts by mass of component (C) per 100 parts by mass of component (B) can be determined by calculating "parts by mass of component (C) / parts by mass of component (B) × 100" and rounding off to one decimal place. <(D) Thermal crosslinking agent> The photosensitive resin composition of the present invention preferably contains a (D) thermal crosslinking agent. The (D) thermal crosslinking agent refers to a compound having at least two functional groups in the molecule, each of which is one or more types selected from the group consisting of an alkoxymethyl group, a methylol group, an epoxy group, and an oxetanyl group. The inclusion of the (D) thermal crosslinking agent can crosslink between the (D) thermal crosslinking agent and component (B) or with other components, thereby improving the heat resistance, chemical resistance, and bending resistance of the cured product after thermal curing. From the viewpoint of the heat resistance of the cured product and the storage stability of the photosensitive resin composition, the (D) thermal crosslinking agent preferably contains an alkoxymethyl group.

[0072] The content of the (D) thermal crosslinking agent is preferably 1% by mass or more and 30% by mass or less, based on 100% by mass of the total amount of the resin composition excluding the solvent. If the content of the (D) thermal crosslinking agent is 1% by mass or more, the chemical resistance and bending resistance of the cured product can be further improved. Furthermore, if the content of the (D) thermal crosslinking agent is 30% by mass or less, the amount of outgassing from the cured product can be further reduced, the long-term reliability of the organic EL display device can be further improved, and the storage stability of the photosensitive resin composition can also be excellent.

[0073] <(E) Photosensitive compound> The photosensitive resin composition of the present invention further contains (E) a photosensitive compound (hereinafter, sometimes referred to as component (E)). From the viewpoint of achieving high sensitivity, the content of the component (E) is preferably at least 0.1 parts by mass, more preferably at least 1 part by mass, and even more preferably at least 10 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 component (E) is preferably no more than 100 parts by mass per 100 parts by mass of the component (A).

[0074] The component (E) preferably contains a photoacid generator, which is a compound that generates an acid upon irradiation with light.

[0075] By including a photoacid generator, acid is generated in the light-irradiated area, increasing the solubility of the light-irradiated area in an alkaline aqueous solution, and a positive relief pattern in which the light-irradiated area dissolves can be obtained. Therefore, when the cured product of the present invention is used as a planarizing layer and / or insulating layer in an organic EL display device, a fine pattern can be formed.

[0076] The photoacid generator may contain, for example, a quinone diazide compound. The photosensitive resin composition of the present invention preferably contains two or more types of photoacid generators, and when two or more types are contained, a photosensitive resin composition with higher sensitivity can be obtained.

[0077] The quinone diazide compound may include a polyhydroxy compound to which a sulfonic acid of quinone diazide is bonded via an ester bond, a polyamino compound to which a sulfonic acid of quinone diazide is bonded via a sulfonamide bond, or a polyhydroxypolyamino compound to which a sulfonic acid of quinone diazide is bonded via an ester bond and / or a sulfonamide bond.

[0078] As the quinone diazide structure, either a 5-naphthoquinone diazide sulfonyl group or a 4-naphthoquinone diazide sulfonyl group is preferably used. A naphthoquinone diazide sulfonyl ester compound having both a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule may be contained, or a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound may be contained. 4-naphthoquinone diazide sulfonyl ester compounds have absorption in the i-line region of a mercury lamp and are suitable for i-line exposure. 5-naphthoquinone diazide sulfonyl ester compounds have absorption extending into the g-line region of a mercury lamp and are suitable for g-line exposure.

[0079] It is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazide sulfonyl ester compound depending on the wavelength of exposure, but from the viewpoint of increasing sensitivity, it is preferable to include a 4-naphthoquinone diazide sulfonyl ester compound.

[0080] 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.

[0081] <Solvent> The photosensitive resin composition of the present invention may contain a solvent. By containing a solvent, the composition can be made into a varnish state, and the coatability can be improved.

[0082] 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 ethyl Ketones such as 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, 2-hydroxy-2-methylpropionate, 3-methoxypropionate, and methylpropionate. Methyl pionate, 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-methoxybutyl propionate, 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, i-propyl butyrate,Other esters such as n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate may be included; 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.

[0083] 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 solvents with a boiling point of 180°C or higher in 100 parts by mass of the total amount of solvent is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less. By keeping the proportion of solvents with a boiling point of 180°C or higher to 20 parts by mass or less, the amount of outgassing after thermal curing can be further reduced, and the long-term reliability of the organic EL device can be further improved.

[0084] <Adhesion improver> The photosensitive resin composition of the present invention may contain an adhesion improver. Examples of adhesion improvers 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 including these adhesion improvers, the development adhesion to the base substrate, such as a silicon wafer, indium tin oxide (ITO), SiO2, or silicon nitride, can be improved when developing a resin film. Furthermore, the resistance to oxygen plasma and UV ozone treatments used for cleaning can be improved. 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.

[0085] <Surfactant> The photosensitive resin composition of the present invention may contain a surfactant to improve wettability with the substrate. The surfactant may include known silicone surfactants, fluorine surfactants, acrylic and / or methacrylic surfactants, etc.

[0086] 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.

[0087] <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 components (A), (B), (C), and (E), and optionally, component (D), a solvent, an adhesion improver, a surfactant, etc.

[0088] Methods for dissolving 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 usually room temperature to 80° C. The order in which the components are dissolved is not particularly limited, and examples include a method in which the components are dissolved in order starting with the least soluble compound.

[0089] The photosensitive resin composition thus obtained is preferably filtered through 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).

[0090] <Method of manufacturing the 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.

[0091] The process of forming a resin film made of the photosensitive resin composition of the present invention on a substrate will now be described. In the present invention, the resin film can be obtained by applying the photosensitive resin composition of the present invention to obtain a coating film of the photosensitive resin composition, and drying the coating film. The substrate may be a known substrate such as a glass substrate.

[0092] 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 for cost reduction. 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, such as 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 film thickness after drying is 0.1 to 10 μm, preferably 0.3 to 5 μm.

[0093] Prior to coating, the substrate to which the photosensitive resin composition is to be applied may be pretreated with the above-mentioned adhesion promoter. Examples of pretreatment methods include treating the substrate surface with a solution prepared by dissolving 0.5 to 20% by mass of an adhesion promoter 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.

[0094] After application, a reduced pressure drying treatment is carried out as necessary. 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 piping between the chamber and the pump, but is preferably set so that, for example, 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.

[0095] After coating or vacuum drying, the coating film is generally heated and dried. This process is also called pre-baking. Drying is performed using a hot plate, oven, infrared light, 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 slowing down the progress of curing during pre-baking, it is preferably 150°C or lower, and more preferably 140°C or lower.

[0096] Next, the step of exposing the resin film will be described. The resin film 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.

[0097] 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.

[0098] Next, the process of developing the exposed resin film will be described. After exposure, in the case of a positive-tone film, the exposed areas are removed with a developer to form the desired pattern. Preferred developers include aqueous solutions of alkaline compounds such as tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine. These alkaline aqueous solutions may contain one or more polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone, and dimethylacrylamide; alcohols such as methanol, ethanol, and isopropanol; esters such as ethyl lactate and propylene glycol monomethyl ether acetate; and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone. Development methods include spray, paddle, immersion, and ultrasonic.

[0099] Next, the pattern formed by development is preferably rinsed with distilled water. Alternatively, alcohols such as ethanol and isopropyl alcohol, or esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to the distilled water for rinsing.

[0100] Next, the step of heat treating the developed resin film will be described. After development, the developed resin film is subjected to a heat treatment to obtain a cured product. The heat treatment temperature is preferably 180°C or higher, more preferably 200°C or higher, even more preferably 230°C or higher, and particularly preferably 250°C or higher, from the viewpoint of further reducing the amount of outgassing from the cured product. On the other hand, from the viewpoint of improving the film toughness of the cured product, it is preferably 500°C or lower, more preferably 450°C or lower. Within this temperature range, the temperature may be increased stepwise or continuously. The heat treatment time is preferably 30 minutes or longer from the viewpoint of further reducing the amount of outgassing. Furthermore, from the viewpoint of improving the film toughness of the cured product, it is preferably 3 hours or shorter. Examples of the heat treatment method include a method in which heat treatment is performed at 150°C and 250°C for 30 minutes each, and a method in which the temperature is increased linearly from room temperature to 300°C over 2 hours. When the photosensitive resin composition of the present invention is used in an organic electroluminescence 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 electroluminescence 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%.

[0101] <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 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 heat resistance and chemical resistance. Furthermore, by including component (C), the photosensitive resin composition of the present invention can form a cured product with low water absorption.

[0102] The heat treatment temperature is preferably 180°C or higher, more preferably 200°C or higher, even more preferably 230°C or higher, and particularly preferably 250°C or higher, from the viewpoint of further reducing the amount of outgassing from the cured product. On the other hand, from the viewpoint of improving the film toughness of the cured product, it is preferably 500°C or lower, more preferably 450°C or lower. Within this temperature range, the temperature may be increased stepwise or continuously. The heat treatment time is preferably 30 minutes or longer from the viewpoint of further reducing the amount of outgassing. Furthermore, from the viewpoint of improving the film toughness of the cured product, it is preferably 3 hours or shorter. For example, a method of heat treatment at 150°C and 250°C for 30 minutes each, or a method of heat treatment while linearly increasing the temperature from room temperature to 300°C over 2 hours may be used.

[0103] <Application examples of photosensitive resin compositions and cured products> The photosensitive resin composition and cured product of the present invention are suitable for use as surface protection layers and interlayer insulating layers for semiconductor devices, insulating layers for organic electroluminescent devices, planarization layers for thin film transistor (TFT) substrates used in display devices using organic electroluminescent devices, wiring protection insulating layers for circuit boards, on-chip microlenses for solid-state imaging devices, and planarization layers for various display devices and solid-state imaging devices. For example, they are suitable as surface protection layers and interlayer insulating layers for MRAM, which has low heat resistance, polymer memory (Polymer Ferroelectric RAM: PFRAM) and phase change memory (Phase Change RAM: PCRAM, Ovonics Unified Memory: OUM), which are promising next-generation memories. They can also be used as insulating layers for display devices including a first electrode formed on a substrate and a second electrode disposed opposite the first electrode, such as LCDs, ECDs, ELDs, and display devices using organic electroluminescent elements (organic electroluminescent devices). The following description will be given using an organic electroluminescent display device as an example.

[0104] <Organic EL display device> The organic EL display device of the present invention comprises the cured product of the present invention.

[0105] 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, and a TFT insulating layer 3 is formed to cover the TFTs 1. Wiring 2 connected to the TFTs 1 is also formed 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. A first electrode 5 is formed on the planarization layer 4, connected to the wiring 2 via the contact holes 7. An insulating layer 8 is then formed to cover the periphery of the first electrode 5. An organic EL light-emitting layer and a second electrode are then formed on the first electrode 5 and insulating layer 8, in this order, to obtain an organic EL display device. The organic EL display device may be a top-emission type, in which emitted light is emitted from the side opposite the substrate 6, or a bottom-emission type, in which light is extracted from the substrate 6 side.

[0106] The planarization layer 4 and / or 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. Because the cured product of the present invention has low water absorption, when used in the planarization layer 4 and / or insulating layer 8 of an organic EL display device, corrosion of the first electrode 5 and the second electrode can be suppressed. [Example]

[0107] 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. (1) Evaluation of remaining film rate during development The varnish obtained in each example and comparative example was spin-coated onto an 8-inch silicon wafer using an ACT-8 coater / developer (Tokyo Electron Limited), followed by baking at 120°C for 2 minutes to produce a pre-baked film with a thickness of 4.0 μm. The film thickness was measured using a stylus profiler (P-15; KLA-Tencor Corporation). The film was then developed for 60 seconds using the ACT-8 developer with a 2.38% by mass aqueous solution of tetramethylammonium (TMAH, Tama Chemicals Co., Ltd.) as the developer. The film was then rinsed with distilled water and dried to obtain a developed film. The thickness of the film after development was measured, and "thickness of the film after development / thickness of the pre-baked film x 100" was calculated, and the result was rounded to one decimal place to determine the "remaining film rate at development." If the remaining film rate at development was 90.0% or more, it was judged as "A," if it was 80.0% or more but less than 90.0%, it was judged as "B," and if it was less than 80.0%, it was judged as "C." (2) Sensitivity evaluation (1) Using the same method as in the evaluation of the remaining film rate during development, a pre-baked film with a film thickness of 4.0 μm was prepared from the varnish obtained in each Example and Comparative Example. Then, using an i-line stepper NSR-2005i9C (manufactured by Nikon Corporation) as an exposure device, the film was exposed to light at a dose of 50 to 500 mJ / cm through a mask with a 10 μm hole pattern. 2 in the range of 5 mJ / cm 2 After exposure, Using the ACT-8 developing device, the resist was developed for 60 seconds using a 2.38% by mass aqueous solution of TMAH as a developer, and then rinsed with distilled water and spun off to dry, obtaining a pattern.

[0108] Furthermore, the obtained pattern was observed at a magnification of 20 times using an FPD microscope MX61 (manufactured by Olympus Corporation), and the opening diameter of the hole was measured. The minimum exposure dose at which the opening diameter of the contact hole reached 10 μm was determined, and this was taken as the "sensitivity." When the sensitivity was 150 mJ / cm 2 If it is less than 150mJ / cm, it is rated "A" 2 More than 200mJ / cm 2 If it was less than 200mJ / cm, it was rated "B" 2 More than 250mJ / cm 2 If it is less than 250mJ / cm, it is marked "C" 2 If it was above this, it was judged as "D". (3) Water absorption rate of the cured product (1) The developed film obtained in the evaluation of the remaining film rate during development was heated using an inert oven CLH-21CD-S (manufactured by Koyo Thermo Systems Co., Ltd.) at an oxygen concentration of 20 ppm or less, with the temperature increasing rate of 5°C / min up to 250°C, and then further baked at 250°C for 1 hour to produce an 8-inch silicon wafer laminated with a cured product of the photosensitive resin composition.

[0109] The 8-inch silicon wafer on which the cured product was laminated was immersed in 45% by mass hydrofluoric acid for 5 minutes, and the cured product was then peeled off from the 8-inch silicon wafer. The resulting cured product 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 TGA-50 thermogravimetric analyzer (Shimadzu Corporation). The 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 the weight (W2) was measured. The "water absorption of the cured product" was calculated by "(W1 - W2) / W1 x 100" and rounded to the nearest tenth. A cured product with a water absorption of less than 3.0% was rated "A," a value of 3.0% to less than 3.5% was rated "B," a value of 3.5% to less than 4.0% was rated "C," and a value of 4.0% or greater was rated "D." (4) Heat resistance evaluation (3) To evaluate the water absorption of the cured product, W2 was measured, and the temperature was raised to 250°C at a rate of 10°C / min. After holding at 250°C for 60 minutes, the weight (W3) was measured. "W3 / W2 x 100" was calculated and rounded to the nearest tenth to determine the weight change rate. The "heat resistance of the cured product" was evaluated as follows: a weight change rate of 99.0% or more was assigned an "A," a weight change rate of 98.0% or more but less than 99.0% was assigned a "B," and a weight change rate of less than 98.0% was assigned a "C."

[0110] 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 cooled to -15°C. A solution of 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride dissolved in 100 mL of acetone was added dropwise to the solution. After the addition was completed, the mixture was reacted at -15°C for 4 hours and then returned to room temperature. The precipitated white solid was filtered and dried in vacuo at 50°C.

[0111] 30 g of the solid was placed in a 300 mL stainless steel autoclave and dispersed in 250 mL of methyl cellosolve, followed by 2 g of 5% by 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 by confirming that the balloon no longer deflated. After the reaction was completed, the palladium compound catalyst was removed by filtration, and the mixture was concentrated using a rotary evaporator to obtain the hydroxyl group-containing diamine compound (α) represented by the following formula:

[0112] [ka]

[0113] 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'-diphenylethertetracarboxylic 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 (hereinafter referred to as MAP) was added as an end-capping agent along with 5 g of NMP, and the mixture was allowed to react at 50°C for 2 hours. Subsequently, a solution of 32.39 g (0.22 mol) of N,N-dimethylformamide diethyl acetal diluted with 50 g of NMP was added. After addition, the mixture was stirred at 50°C for 3 hours. After stirring, the solution was cooled to room temperature and then poured into 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 24 hours to obtain a polyimide precursor (A-1), which is an alkali-soluble resin.

[0114] Synthesis Example 3: Synthesis of alkali-soluble resin (A-2) A methyl methacrylate / methacrylic acid / styrene copolymer (mass ratio 30 / 40 / 30) was synthesized by a known method (Japanese Patent No. 3120476; Example 1), and then 40 parts by mass of glycidyl methacrylate was added to 100 parts by mass of the copolymer to obtain an acrylic resin (A-2).

[0115] Synthesis Example 4: Synthesis of quinone diazide compound (E-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 5-naphthoquinone diazide sulfonyl chloride were dissolved in 450 g of 1,4-dioxane at room temperature. To this solution, 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature in the system did not exceed 35°C. After the addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into water. The precipitate was then collected by filtration. This precipitate was dried in a vacuum dryer to obtain quinone diazide compound (E-1) represented by the following formula:

[0116] [ka]

[0117] The names of the compounds used in each of the Examples and Comparative Examples are shown below. Component (D) other than commercially available products was synthesized using a known method. GBL: gamma-butyrolactone EL: Ethyl lactate PGME: Propylene glycol monomethyl ether B-1: Pyrogallol (component (B) that does not satisfy the condition that at least one substitution position of a phenolic hydroxyl group relative to any other phenolic hydroxyl group is para-position) B-2: 1,2,4-trihydroxybenzene (component (B) that satisfies the condition that at least one substitution position of a phenolic hydroxyl group other than any other phenolic hydroxyl group is para-positioned) B'-1: Hexahydroxybenzene J-DPP-95 (manufactured by JFE Chemical Corporation)

[0118] [ka]

[0119] (n represents an integer between 0 and 100.) MEHC-7851SS (manufactured by Meiwa Kasei Co., Ltd.)

[0120] [ka]

[0121] (n represents an integer between 0 and 100.) VG-3101-L (Printec Co., Ltd.)

[0122] [ka]

[0123] (D-1) Compound

[0124] [ka]

[0125] (Me represents a methyl group.) Example 1 70 g of polyimide precursor (A-1), 8 g of compound (B-2), 10 g of J-DPP-95, 10 g of compound (D-1), and 30 g of compound (E-1) were dissolved in a mixture of 100 g of GBL, 200 g of EL, and 700 g of PGME. The solution was then filtered through a 0.2 μm polytetrafluoroethylene filter to obtain a photosensitive resin composition varnish W1. The resulting varnish was used to evaluate the residual film rate during development, sensitivity, water absorption rate of the cured product, and heat resistance of the cured product as described above. The evaluation results are shown in Table 2.

[0126] The parts by mass of component (B) per 100 parts by mass of component (A) was calculated by "parts by mass of component (B) / parts by mass of component (A) × 100" and rounded to the nearest tenth. The calculation results are shown in Table 2.

[0127] The parts by mass of component (C) per 100 parts by mass of component (B) was calculated by "parts by mass of component (C) / parts by mass of component (B) × 100" and rounded to the nearest tenth. The calculation results are shown in Table 2.

[0128] Examples 2 to 14, Comparative Examples 1 to 3 A varnish of a photosensitive resin composition was obtained in the same manner as in Example 1, except that components (A), (B), (C), (D), (E), other components, and the solvent were changed as shown in Table 1. Using the obtained varnish, the residual film rate at development, sensitivity, water absorption rate of the cured product, and heat resistance of the cured product were evaluated as described above.

[0129] The compositions of the examples and comparative examples are shown in Table 1, and the evaluation results are shown in Table 2.

[0130] The parts by mass of component (B) per 100 parts by mass of component (A) was calculated by "parts by mass of component (B) / parts by mass of component (A) × 100" and rounded to the nearest tenth. The calculation results are shown in Table 2.

[0131] The parts by mass of component (C) per 100 parts by mass of component (B) was calculated by "parts by mass of component (C) / parts by mass of component (B) × 100" and rounded to the nearest tenth. The calculation results are shown in Table 2.

[0132] [Table 1]

[0133] [Table 2] [Explanation of symbols]

[0134] 1: TFT (thin film transistor) 2: Wiring 3: TFT insulating layer 4: Flattening layer 5:First electrode 6: Circuit board 7: Contact hole 8: Insulating layer

Claims

1. A photosensitive resin composition containing (A) an alkali-soluble resin, (B) a compound represented by formula (1) (hereinafter referred to as component (B)), (C) a phenolic resin represented by formula (3) (hereinafter referred to as component (C)), and (E) a photosensitive compound. 【Chemical 1】 (R １ is a carboxyl group, an aldehyde group, or a structure represented by formula (2), where a represents an integer of 3 to 5, and b represents an integer of 0 to 2, provided that a+b≦5. L is an ester group, R ２ represents an alkyl group having 1 to 20 carbon atoms. R ３ , R ４ and R ５ each independently represents an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms; R ６ ~R ９ 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, n 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 (4) or a structure represented by formula (5). R １７ and R １８ each independently represents an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, and i and j each independently represent an integer of 0 to 4. * represents a bond.

2. 2. The photosensitive resin composition according to claim 1, wherein the component (B) comprises a compound in which at least one substitution position of a phenolic hydroxyl group other than any one of the phenolic hydroxyl groups in formula (1) is para-positioned.

3. 3. The photosensitive resin composition according to claim 1, wherein the content of the component (B) is 1 to 50 parts by mass per 100 parts by mass of the alkali-soluble resin (A).

4. 3. The photosensitive resin composition according to claim 1, wherein the content of the component (C) is 50 to 300 parts by mass per 100 parts by mass of the component (B).

5. 3. The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (A) comprises at least one selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole precursor, and copolymers thereof.

6. The photosensitive resin composition according to claim 1 or 2, further comprising (D) a thermal crosslinking agent.

7. The photosensitive resin composition according to claim 6, wherein the thermal crosslinking agent (D) has an alkoxymethyl group.

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

9. An organic electroluminescence display device comprising the cured product according to claim 8 .

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