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

Abstract

Provided is a photosensitive resin composition which has high sensitivity, good development adhesion, high chemical resistance, high bending resistance of a cured product, and high reliability when the cured product is used in an organic EL display device. A photosensitive resin composition containing (A) one or more substances selected from the group consisting of polyimides, polyimide precursors, and copolymers thereof, (B) one or more substances selected from the group consisting of polybenzoxazoles, polybenzoxazole precursors, and copolymers thereof, (C) polyhydroxystyrene, and / or a copolymer of polyhydroxystyrene and polystyrene, and (D) a quinonediazide compound; the component (B) is more than 100 parts by mass but not more than 2000 parts by mass with respect to 100 parts by mass of the component (A), and the component (C) is 5-500 parts by mass with respect to 100 parts by mass of the component (A).

Description

Technical Field

[0001] This invention relates to photosensitive resin compositions and cured products using the same, organic EL display devices having cured products, and methods for manufacturing cured products. Background Technology

[0002] In display devices with thin displays such as smartphones, tablets, and televisions, many products using organic electroluminescent (hereinafter referred to as "organic EL") display devices have been developed.

[0003] Typically, organic EL display devices have a driving circuit, a planarization layer, a first electrode, a pixel segmentation layer, a light-emitting layer, and a second electrode on a substrate. They emit light by applying a voltage between the opposing first and second electrodes or by passing a current. In recent years, the development of flexible organic EL display devices formed on resin film substrates has been actively pursued. Flexible organic EL display devices structurally have bendable portions and / or portions fixed in a bent state, where bending stress is applied to the planarization layer and pixel segmentation layer. In flexible organic EL display devices including such bent portions, high bending resistance is required for the materials used in the planarization layer and pixel segmentation layer. Among these, photosensitive resin compositions capable of being patterned by ultraviolet light irradiation are commonly used as materials for the planarization layer and pixel segmentation layer. Photosensitive resin compositions using polybenzoxazole-based resins are preferred due to their high bending resistance, resulting in flexible organic display devices with good productivity (see, for example, Patent Document 1).

[0004] On the other hand, the requirements for high reliability in organic EL display devices are becoming increasingly stringent each year. For materials used in planarization layers and pixel separation layers, there is a demand for highly reliable materials that do not exhibit reduced brightness or pixel shrinkage even after reliability tests under accelerated conditions such as high temperature, high humidity, and light irradiation. Here, pixel shrinkage refers to the phenomenon where the brightness decreases or becomes completely dim from the edge of the pixel.

[0005] Furthermore, due to reasons such as the increasing size of substrates and improved productivity, higher sensitivity is required for photosensitive resin compositions in order to shorten exposure time. On the other hand, high-sensitivity materials suffer from deterioration in development adhesion, requiring photosensitive resin compositions to have even better development adhesion.

[0006] In addition, in recent years, the structure of organic EL display devices has become increasingly complex, with an increase in the number of processes. Therefore, high chemical resistance is required for materials used in planarization layers and pixel segmentation layers.

[0007] Against this backdrop, there is a strong desire to develop photosensitive resin compositions that can be patterned with high sensitivity and produce cured products with high flexural strength, chemical resistance, and excellent reliability.

[0008] To address this issue, siloxane resins have been investigated as photosensitive resin compositions capable of achieving high sensitivity (see, for example, Patent Document 2). Furthermore, as photosensitive resin compositions capable of imparting high chemical resistance, the addition of specific end-capped isocyanate compounds to the photosensitive resin composition has been investigated (see, for example, Patent Document 3).

[0009] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 2022-34533 Patent Document 2: Japanese Patent Application Publication No. 2006-178436 Patent Document 3: Japanese Patent Application Publication No. 2013-242511 Summary of the Invention

[0010] The problem that the invention aims to solve However, it is difficult to say that the materials proposed in the patent documents listed above have sufficient performance for applications with more stringent bending requirements, such as flexible organic EL display devices in recent years. In view of the above problems, the present invention aims to provide a photosensitive resin composition with high sensitivity, good development adhesion, high bending resistance and chemical resistance of the cured product, and high reliability when the cured product is used in organic EL display devices.

[0011] Methods for solving problems The present invention is described below.

[0012] [1] A photosensitive resin composition comprising: (A) one or more selected from the group consisting of polyimides, polyimide precursors and copolymers thereof; (B) one or more selected from the group consisting of polybenzoxazole, polybenzoxazole precursors and copolymers thereof; (C) polyhydroxystyrene and / or copolymers of polyhydroxystyrene and polystyrene; (D) a quinone diazide compound. Compared to 100 parts by mass of component (A) mentioned above, component (B) mentioned above is greater than 100 parts by mass and less than 2000 parts by mass. Compared to 100 parts by mass of component (A) mentioned above, component (C) mentioned above is 5 parts by mass or more and 500 parts by mass or less.

[0013] [2] The photosensitive resin composition as described in [1] further contains (E) a heat-generating acid agent.

[0014] [3] The photosensitive resin composition as described in [2], wherein the aforementioned (E) heat-generating acid agent contains the compound represented by formula (3) described later.

[0015] [4] The photosensitive resin composition as described in any one of [1] to [3], wherein when the content of the aforementioned component (A) is set to [PI] (mass), the content of the aforementioned component (B) is set to [PB] (mass), and the content of the aforementioned component (C) is set to [PH] (mass), The quality ratio [PB] / ([PI]+[PH]) is in the range of 0.5≤[PB] / ([PI]+[PH])≤10.0.

[0016] [5] The photosensitive resin composition as described in [4], wherein the mass ratio of the aforementioned [PI] and [PH] is in the range of 0.1 ≤ [PI] / [PH] ≤ 6.

[0017] [6] The photosensitive resin composition as described in [5], wherein the mass ratio of the aforementioned [PI] and [PH] is in the range of 1 < [PI] / [PH] ≤ 6.

[0018] [7] The photosensitive resin composition as described in any one of [1] to [6], wherein at least a portion of the aforementioned component (B) has the structure shown in formula (9) described later.

[0019] [8] The photosensitive resin composition as described in any one of [1] to [7], wherein at least a portion of the aforementioned component (B) has the structure shown in formula (1) described later.

[0020] [9] The photosensitive resin composition as described in any one of [1] to [8], wherein at least a portion of the aforementioned component (B) has the structure shown in formula (2) described later.

[0021]

[10] The photosensitive resin composition as described in any one of [1] to [9], wherein the aforementioned component (C) comprises polyhydroxystyrene.

[0022]

[11] The photosensitive resin composition as described in any one of [1] to

[10] further contains (F) one or more compounds selected from the group (F-1) below, wherein the aforementioned (F) component is contained in 0.001 to 2.00 parts by mass relative to 100 parts by mass of the aforementioned photosensitive resin composition.

[0023] Group (F-1): 1,3-Dimethyl-2-imidazoline, N,N'-dimethylpropylene urea, 3-methoxy-N,N-dimethylpropionamide, 3-n-butoxy-N,N-dimethylpropionamide, N,N-dimethylisobutylamide, and tetramethylurea

[12] A cured product obtained by curing any one of the photosensitive resin compositions described in [1] to

[11] .

[0024]

[13] The solidified product as described in

[12] , wherein when analyzed by reactive thermal pyrolysis GC / MS, the compounds shown in formula (4) (described later), the compounds shown in formula (5) (described later) and the compounds shown in formula (6) (described later) are detected. In terms of the ratio of their detected peak intensities, if the compound shown in formula (5) is set to 1, then the compound shown in formula (4) is 0.1 or more and 1 or less, and the compound shown in formula (6) is 0.1 or more and 3 or less.

[0025]

[14] An organic EL display device having the cured material described in

[12] or

[13] .

[0026]

[15] A method for manufacturing a cured product, comprising the following steps in sequence: (1) a step of coating a photosensitive resin composition as described in any one of [1] to

[11] onto a substrate to form a photosensitive resin film; (2) a step of drying the aforementioned photosensitive resin film; (3) a step of exposing the dried photosensitive resin film through a photomask; (4) a step of developing the exposed photosensitive resin film; and (5) a step of heat-treating the developed photosensitive resin film.

[0027] Invention Effects The photosensitive resin composition of the present invention provides high sensitivity, good development adhesion, and high flexural strength and chemical resistance of the cured product, making it highly reliable when used in organic EL display devices. Attached Figure Description

[0028] [ Figure 1 This is a cross-sectional view of an organic EL display device that has formed a planarization layer and a pixel segmentation layer.

[0029] [ Figure 2 [This is a schematic diagram of the substrate for an organic EL display device.] Detailed Implementation

[0030] The embodiments of the present invention will be described in detail.

[0031] The photosensitive resin composition of the present invention comprises: (A) one or more selected from the group consisting of polyimides, polyimide precursors and copolymers thereof (hereinafter, sometimes referred to as component (A)); (B) one or more selected from the group consisting of polybenzoxazole, polybenzoxazole precursors and copolymers thereof (hereinafter, sometimes referred to as component (B)); (C) polyhydroxystyrene, and / or copolymers of polyhydroxystyrene and polystyrene (hereinafter, sometimes referred to as component (C)); and (D) a quinone diazide compound; Compared to 100 parts by mass of component (A) mentioned above, component (B) mentioned above is greater than 100 parts by mass and less than 2000 parts by mass. Compared to 100 parts by mass of component (A) mentioned above, component (C) mentioned above is 5 or more but less than 500 parts by mass.

[0032] By making the content of component (B) greater than 100 parts by mass and less than 2000 parts by mass relative to 100 parts by mass of component (A), a cured product with good bending resistance and chemical resistance can be obtained. By making the content of component (C) greater than 5 parts by mass and less than 500 parts by mass relative to 100 parts by mass of component (A), the sensitivity of the resin composition is improved and the development adhesion is improved. By containing these three components (A) to (C), a photosensitive resin composition with high sensitivity, good development adhesion, high bending resistance and chemical resistance of the cured product, and high reliability when used in organic EL display devices can be provided.

[0033] The photosensitive resin composition of the present invention contains (A) one or more selected from the group consisting of polyimides, polyimide precursors and copolymers thereof.

[0034] (A) The component may contain known polyimides containing structural units of polyimides, known polyimide precursors containing structural units of polyimides, and known copolymers thereof.

[0035] It should be noted that, in the case of a copolymer formed from the structural units of polyimide and / or the structural units of the polyimide precursor together with the structural units of polybenzoxazole and / or the structural units of the polybenzoxazole precursor, component (A) is defined.

[0036] (A) The preferred component is alkali-soluble. "Alkali-soluble" means that: a solution obtained by dissolving resin in γ-butyrolactone is coated on a silicon wafer, and a pre-baked film with a thickness of 10μm±0.5μm is formed by pre-baking at 120°C for 4 minutes. After immersing the pre-baked film in a 2.38% by mass tetramethylammonium hydroxide aqueous solution at 23±1°C for 1 minute, it is rinsed with pure water. The dissolution rate, calculated based on the reduction in film thickness at this time, is 50nm / min or higher.

[0037] To impart alkali solubility, it is preferable to have 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, sulfonic acid groups, and thiol groups.

[0038] (A) The components can be synthesized using known methods.

[0039] In the case of a polyimide precursor, if it is a polyamic acid, it can be synthesized, for example, by reacting a tetracarboxylic dianhydride with a diamine compound at low temperature. If it is a polyamic ester, it can be synthesized, for example, by the following methods: reacting a tetracarboxylic dianhydride with a diamine compound at low temperature and then partially esterifying the amic acid structure using N,N-dimethylformamide dimethyl acetal or the like; obtaining a diester from a tetracarboxylic dianhydride and an alcohol, and then reacting it in the presence of an amine and a condensing agent; obtaining a diester from a tetracarboxylic dianhydride and an alcohol, and then acyl-chlorinating the remaining dicarboxylic acid to react it with an amine; and so on.

[0040] In the case of polyimide, it can be obtained, for example, by dehydrating and cyclically closing the polyamic acid or polyamic ester obtained by the aforementioned method in a solvent by heating or chemical treatment with acids, alkalis, etc.

[0041] As a tetracarboxylic acid dianhydride used in component (A), specifically, examples 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'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic 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, Aliphatic tetracarboxylic acid dianhydrides, such as 4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorenic acid dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorenic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 2,3,5,6-pyridinetetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, butanetetracarboxylic acid dianhydride, and 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, may be used as a tetracarboxylic acid dianhydride used as component (A).

[0042] Specific examples of diamine compounds used in component (A) include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthylenediamine, 2,6-naphthylenediamine, 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 Diamines include '-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 9,9-bis(4-aminophenyl)fluorene, or compounds obtained by substituting at least a portion of the hydrogen atoms of their aromatic rings with alkyl or halogen atoms, aliphatic cyclohexyldiamines, methylenebicyclohexylamine, and diamines with the structures shown below. Two or more of these diamine compounds may be used.

[0043] [Chemical Formula 1] R 12 and R 15 Each can independently represent an oxygen atom, C(CF3)2, or C(CH3)2. R 13 R 14 and R 16 ~R 23 Each can be used independently to represent a hydrogen atom or a hydroxyl group.

[0044] Furthermore, to improve the storage stability of the photosensitive resin composition, it is preferable to use known end-capping agents such as monoamines, acid anhydrides, monocarboxylic acids, monoacyl chlorides, and monoactive esters to block the main chain ends of these (A) components. For the purpose of improving the chemical resistance of the cured resin obtained after firing, monoamines, acid anhydrides, monocarboxylic acids, monoacyl chlorides, and monoactive esters having at least one alkenyl or alkynyl group may also be used as these end-capping agents.

[0045] Regarding the content of end-capping agents such as monoamines, acid anhydrides, monoacyl chlorides, and monocarboxylic acids, from the viewpoint of improving storage stability, it is preferably 1 mol% or more, more preferably 5 mol% or more, relative to 100 mol% of the total monomer components constituting component (A). Furthermore, from the viewpoint of obtaining a resin with good film properties, it is preferably 40 mol% or less, more preferably 30 mol% or less, relative to 100 mol% of the total monomer components constituting component (A). It is also possible to introduce various different terminal groups into component (A) by reacting various end-capping agents.

[0046] The photosensitive resin composition of the present invention contains (B) one or more selected from the group consisting of polybenzoxazole, polybenzoxazole precursors and copolymers thereof.

[0047] (B) The component may contain known polybenzoxazole containing structural units of polybenzoxazole, known polybenzoxazole precursors containing structural units of polybenzoxazole precursors, and known copolymers thereof.

[0048] In this invention, component (B) preferably has alkali solubility. To impart alkali solubility, it is preferable that the structural units of component (B) and / or the ends of its main chain have acidic groups. Examples of acidic groups include carboxyl groups, phenolic hydroxyl groups, sulfonic acid groups, thiol groups, etc.

[0049] (B) The components can be synthesized using known methods.

[0050] In the case of polybenzoxazole precursors, as a manufacturing method, they can be obtained by reacting a bisaminophenol compound with a dicarboxylic acid, tricarboxylic acid, or tetracarboxylic acid, which are acids. From the viewpoint of improving the mechanical strength of the cured product described in this invention, it is preferable to react the bisaminophenol compound with a dicarboxylic acid to obtain the polybenzoxazole precursor. Specifically, as a manufacturing method for polybenzoxazole precursors, there are methods such as: reacting a dehydrating condensing agent such as dicyclohexylcarbodiimide (DCC) with an acid and adding a bisaminophenol compound thereto; adding a solution of dicarboxylic acid diacyl chloride dropwise to a solution of the bisaminophenol compound; adding an active dicarboxylic acid ester to a solution of the bisaminophenol compound; and so on.

[0051] In the case of polybenzoxazole, it can be obtained, for example, by dehydrating and cyclizing the polybenzoxazole precursor obtained by the aforementioned method in a solvent by heating or chemical treatment with acids, alkalis, etc.

[0052] Examples of dicarboxylic acids used in component (B) include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, triphenyl dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 2,6-dicarboxynaphthalene, etc.; examples of tricarboxylic acids include trimellitic acid, pyromellitic acid, diphenyl ether tricarboxylic acid, biphenyl tricarboxylic acid, etc.; examples of tetracarboxylic acids include pyromellitic tetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 3,3',4, 4'-Benzophenone tetracarboxylic acid, 2,2',3,3'-Benzophenone tetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 2,2-bis(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-naphthalene tetracarboxylic acid, 2,3,6,7-naphthalene tetracarboxylic acid, 2,3,5,6-pyridine tetracarboxylic acid, 3,4,9,10-perylene tetracarboxylic acid, butane tetracarboxylic acid, 1,2,3,4-cyclopentane tetracarboxylic acid, and other aliphatic tetracarboxylic acids. (B) Two or more of the dicarboxylic acids, tricarboxylic acids, and tetracarboxylic acids used in the ingredients may be used.

[0053] Specific examples of diaminophenol compounds used in component (B) include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BAHF), bis(3-amino-4-hydroxyphenyl)sulfone, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, 2,2-bis(3-amino-4-hydroxyphenyl)propane, and 1,1,1-trifluoro-2,2-bis(3-amino-4-hydroxyphenyl)ethane (BIS-AP-EF). Two or more of these diaminophenol compounds may be used in component (B).

[0054] Furthermore, to improve the storage stability of the photosensitive resin composition, it is preferable to use a known end-capping agent such as a monoamine, acid anhydride, monocarboxylic acid, monoacyl chloride compound, or monoactive ester compound to seal the ends of the main chain in at least a portion of these (B) components. Among these, end-capping agents having crosslinking groups or phenolic hydroxyl groups are preferred. By using end-capping agents with crosslinking groups, the crosslinking reaction is carried out in the heat curing process, thus obtaining a cured product with excellent chemical resistance and bending resistance. As end-capping agents with crosslinking groups, from the viewpoint of a high crosslinking reaction rate and rapid curing reaction, it is preferable to use end-capping agents containing the structure represented by formula (9) to seal the ends of the main chain.

[0055] [Chemical Formula 2] In equation (9), R 24 R 25 R 26 Each can be independently represented by a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. This indicates the bonding site with the nitrogen atom.

[0056] Polybenzoxazole precursors having a structure including the structure represented by formula (9) can be obtained, for example, by condensing a bisaminophenol compound or a derivative thereof, a dicarboxylic acid or a derivative thereof, with a monocarboxylic acid or a derivative thereof having a structure including the structure represented by formula (9).

[0057] Examples of monocarboxylic acids that include the structure represented by formula (9) include methacrylic acid, acrylic acid, crotonic acid, tigrinic acid, and 3-ethoxyacrylic acid.

[0058] R 24 R 25 R 26 Each is independently a hydrogen atom, an alkyl group with 1 to 3 carbon atoms, or an alkoxy group with 1 to 3 carbon atoms, but from the viewpoint of developing adhesion and storage stability, R 24 R 25 R 26 Each is preferably a hydrogen atom or a methyl group, with R being particularly preferred. 24 It is a hydrogen atom or a methyl group, and R 25 and R 26 It is a hydrogen atom. That is, it is particularly preferred that at least a portion of the aforementioned component (B) has the structure shown in formula (1).

[0059] [Chemical Formula 3] In equation (1), R 1 It represents a hydrogen atom or a methyl group. This indicates the bonding site with the nitrogen atom.

[0060] Polybenzoxazole precursors having a structure including the end-capping agent represented by formula (1) can be obtained, for example, by condensing a diaminophenol compound or a derivative thereof, a dicarboxylic acid or a derivative thereof, with acrylic acid and / or methacrylic acid or a derivative thereof.

[0061] Furthermore, by using a capping agent having a phenolic hydroxyl group, the (D) quinone diazide compound described later can interact strongly with component (B), thus achieving high sensitivity, which is therefore preferred. Specifically, it is preferable to use a capping agent containing the structure represented by formula (2) for blocking.

[0062] [Chemical Formula 4] In equation (2), R 2 represents a methyl, methoxy, or fluorine atom, and 'a' represents 0 or 1. This indicates the bonding site with the nitrogen atom.

[0063] Polybenzoxazole precursors having a capping agent comprising the structure represented by formula (2) can be obtained, for example, by condensing a bisaminophenol compound or a derivative thereof, a dicarboxylic acid or a derivative thereof, with a monoamine compound or a derivative thereof represented by formula (7).

[0064] [Chemical Formula 5] In equation (7), R 2 represents a methyl, methoxy, or fluorine atom, and 'a' represents 0 or 1.

[0065] As the compound represented by formula (7), the compound represented by formula (8) is particularly preferred. Since the amino group and the phenolic hydroxyl group are located in the ortho position, the oxazole ring closure occurs during the heat curing process and the phenolic hydroxyl group disappears, thus obtaining a cured product with low water absorption.

[0066] [Chemical Formula 6] In equation (8), R 2 represents a methyl, methoxy, or fluorine atom, and 'a' represents 0 or 1.

[0067] Regarding the content of end-capping agents such as monoamines, acid anhydrides, monoacyl chlorides, and monocarboxylic acids, from the viewpoint of improving storage stability, it is preferably 1 mol% or more, more preferably 5 mol% or more, relative to 100 mol% of the total monomer components constituting component (B). Furthermore, from the viewpoint of obtaining a resin with good film properties, it is preferably 40 mol% or less, more preferably 30 mol% or less, relative to 100 mol% of the total monomer components constituting component (B). It is also possible to introduce various different terminal groups into component (B) by reacting various end-capping agents.

[0068] In the photosensitive resin composition of the present invention, the content of component (B) is greater than 100 parts by mass and less than 2000 parts by mass relative to 100 parts by mass of component (A). If the content of component (B) is less than 100 parts by mass relative to 100 parts by mass of component (A), the bending resistance decreases. The content of component (B) is preferably 150 parts by mass or more. On the other hand, if the content of component (B) is greater than 2000 parts by mass relative to 100 parts by mass of component (A), the chemical resistance decreases. The content of component (B) is preferably less than 1000 parts by mass relative to 100 parts by mass of component (A).

[0069] The photosensitive resin composition of the present invention contains (C) polyhydroxystyrene and / or a copolymer of polyhydroxystyrene and polystyrene.

[0070] The term "containing (C) polyhydroxystyrene, and / or copolymers of polyhydroxystyrene and polystyrene" refers to any one or both of polyhydroxystyrene, and copolymers of polyhydroxystyrene and polystyrene.

[0071] The (C) component of this invention can be synthesized using known methods.

[0072] As a method for manufacturing component (C), it can be obtained by addition polymerization of a phenolic derivative having unsaturated bonds. Examples of phenolic derivatives having unsaturated bonds include hydroxystyrene, dihydroxystyrene, allylphenol, coumaric acid, 2'-hydroxychalcone, N-hydroxyphenyl-5-norbornene-2,3-dicarboximide, resveratrol, and 4-hydroxystyrene; two or more of these can be used. Alternatively, copolymers formed with monomers such as styrene that do not contain phenolic hydroxyl groups can also be used. In this way, the alkali dissolution rate of component (C) becomes easy to adjust.

[0073] The content of component (C) is 5 parts by mass or more and 500 parts by mass or less relative to 100 parts by mass of component (A). If the content of component (C) is less than 5 parts by mass relative to 100 parts by mass of component (A), the sensitivity decreases. The content of component (C) is preferably 10 parts by mass or more relative to 100 parts by mass of component (A). On the other hand, if the content of component (C) is greater than 500 parts by mass relative to 100 parts by mass of component (A), the development adhesion decreases. The content of component (C) is preferably 300 parts by mass or less relative to 100 parts by mass of component (A).

[0074] (C) The preferred weight-average molecular weight of the component can be determined by gel permeation chromatography (GPC) based on polystyrene. From the viewpoint of sensitivity, it is preferably 1,000 or more, more preferably 3,000 or more, and even more preferably 4,000 or more. From the viewpoint of imaging adhesion, it is preferably 10,000 or less, more preferably 8,000 or less, and even more preferably 7,000 or less.

[0075] From a sensitivity point of view, component (C) preferably contains polyhydroxystyrene.

[0076] In the photosensitive resin composition of the present invention, when the content of the aforementioned component (A) is set to [PI] (mass), the content of the aforementioned component (B) is set to [PB] (mass), and the content of the aforementioned component (C) is set to [PH] (mass), the mass ratio [PB] / ([PI]+[PH]) is preferably in the range of 0.5 ≤ [PB] / ([PI]+[PH]) ≤ 10.0. If [PB] / ([PI]+[PH]) is 0.5 or more, the bending resistance can be improved. [PB] / ([PI]+[PH]) is more preferably 1 or more. On the other hand, if [PB] / ([PI]+[PH]) is 10.0 or less, the sensitivity can be improved. [PB] / ([PI]+[PH]) is more preferably 5.0 or less.

[0077] The aforementioned mass ratio of [PI] and [PH] is preferably 0.1 ≤ [PI] / [PH] ≤ 6. By making [PI] / [PH] 0.1 or higher, the development adhesion can be improved. [PI] / [PH] is more preferably greater than 1. By making [PI] / [PH] 6 or lower, the sensitivity can be improved.

[0078] The photosensitive resin composition of the present invention contains (D) quinone diazide compound.

[0079] By using a (D)quinone diazide compound, an acid is generated in the light-irradiated part, increasing the solubility of the light-irradiated part in an alkaline aqueous solution, thus enabling the production of a positive relief pattern that dissolves in the light-irradiated part.

[0080] Examples of (D)quinone diazide compounds include compounds formed by ester bonding of quinone diazidesulfonic acid with a polyhydroxy compound, compounds formed by sulfonamide bonding of quinone diazidesulfonic acid with a polyamino compound, and compounds formed by ester bonding and / or sulfonamide bonding of quinone diazidesulfonic acid with a polyhydroxy-polyamino compound. When the total hydroxyl or amino group of these polyhydroxy or polyamino compounds in the (D)quinone diazide compound is set to 100 mol%, it is preferable that 50 mol% or more has been esterified or sulfonated using quinone diazidesulfonic acid. Furthermore, the photosensitive resin composition may contain two or more (D)quinone diazide compounds.

[0081] (D) Among quinone diazide compounds, naphthoquinone diazide sulfonates may be appropriately contained. Naphthoquinone diazide sulfonates can be synthesized by esterification of a compound having a phenolic hydroxyl group with a quinone diazide sulfonate compound, and can be synthesized using known methods. By using these naphthoquinone diazide sulfonates, resolution, sensitivity, and residual film yield are further improved.

[0082] Examples of compounds containing phenolic hydroxyl groups used herein include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, MethyleneTris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, T... ML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (trade name, manufactured by Asahi Kasei Corporation) Compounds obtained by introducing diazidonaphthoquinone-4-sulfonic acid or diazidonaphthoquinone-5-sulfonic acid through ester bonds in compounds such as those manufactured by Kizai Kogyo Co., Ltd., 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, and BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) are preferred examples, but other compounds may also be used.

[0083] The diazidonaphthoquinone-4-sulfonate compound exhibits absorption in the i-line region of a mercury lamp, making it suitable for i-line exposure. The absorption of the diazidonaphthoquinone-5-sulfonate compound extends to the g-line region of the mercury lamp, making it suitable for g-line exposure. The photosensitive resin composition of the present invention may contain any compound selected from the diazidonaphthoquinone-4-sulfonate compound and the diazidonaphthoquinone-5-sulfonate compound. It may also contain a naphthoquinone diazidosulfonate compound in which diazidonaphthoquinone-4-sulfonyl and diazidonaphthoquinone-5-sulfonyl groups are combined in the same molecule. Alternatively, it may be a mixture containing both diazidonaphthoquinone-4-sulfonate compound and diazidonaphthoquinone-5-sulfonate compound.

[0084] Regarding the content of (D) quinone diazide compound, from the viewpoint of improving sensitivity during exposure, it is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, relative to 100 parts by mass of the aforementioned component (A). Furthermore, from the viewpoint of reducing gas escape from the cured product, it is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, relative to 100 parts by mass of the aforementioned component (A).

[0085] The photosensitive resin composition of the present invention may contain an (E) thermal acid-generating agent. An (E) thermal acid-generating agent is a compound that generates acid upon heating. The thermal decomposition initiation temperature of the (E) thermal acid-generating agent is preferably 120°C or higher, more preferably 130°C or higher, and even more preferably 140°C or higher. By setting the thermal decomposition temperature to 120°C or higher, acid generation can be prevented during the patterning process in the drying step (sometimes described as a pre-baking step) where heat is applied to the coated photosensitive resin film. Furthermore, the thermal decomposition initiation temperature of the (E) thermal acid-generating agent is preferably 250°C or lower, more preferably 240°C or lower, and even more preferably 230°C or lower. By setting the thermal decomposition temperature to 250°C or lower, sufficient acid can be generated during the heating step. In the present invention, by generating acid during the heating step, the crosslinking reaction of the thermal crosslinking agent can be promoted, resulting in a significant reduction in unreacted crosslinking groups remaining in the cured product. If unreacted crosslinking groups remain in the cured material, gaseous components will be generated during reliability testing, resulting in undesirable phenomena such as reduced brightness and pixel shrinkage in organic EL display devices. However, by utilizing the crosslinking-promoting effect based on the acid generated by the (E) heat-generating acid agent, the reliability of organic EL display devices can be significantly improved.

[0086] In this invention, the (E) thermal acid-producing agent in the photosensitive resin composition only needs to have the function of producing acid by heating. Compounds that can produce acid by light such as ultraviolet light in addition to heat are also included in the definition of thermal acid-producing agents. However, (D) quinone diazide compounds are defined as compounds not included in the (E) thermal acid-producing agent even when they produce acid by heating.

[0087] The acid produced by the (E) heat-generating acid agent is preferably a strong acid, for example, preferably an aryl sulfonic acid such as p-toluenesulfonic acid or benzenesulfonic acid, an alkyl sulfonic acid such as methanesulfonic acid or ethanesulfonic acid, a butyric acid, or camphor sulfonic acid.

[0088] Examples of (E) heat-generating acid agents include sulfonate salts and sulfonates. Two or more of these may be contained. Among sulfonate salts, from the viewpoint of generating heat through heating, compounds selected from the group consisting of monoaryl sulfonate salts and trialkyl sulfonate salts are preferred.

[0089] (E) Among the heat-generating acid agents, considering the high reliability improvement effect of organic EL display devices, it is preferable to contain a heat-generating acid agent with a sulfonate structure. Examples include methyl methanesulfonate, ethyl methanesulfonate, propyl methanesulfonate, butyl methanesulfonate, phenyl methanesulfonate, methyl ethanesulfonate, ethyl ethanesulfonate, propyl ethanesulfonate, butyl ethanesulfonate, phenyl ethanesulfonate, methyl propanesulfonate, ethyl propanesulfonate, propyl propanesulfonate, butyl propanesulfonate, phenyl propanesulfonate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, phenyl butyrate, methyl octyl sulfonate, ethyl octyl sulfonate, propyl octyl sulfonate, butyl octyl sulfonate, phenyl octyl sulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, propyl p-toluenesulfonate, butyl p-toluenesulfonate, phenyl p-toluenesulfonate, methoxyphenyl methanesulfonate, methoxyethyl methanesulfonate, methoxyethyl p-toluenesulfonate, "Irgacure" (registered trademark) PAG103, PAG121 (trade name, BASF) Products manufactured in Japan (by Heraeus Co., Ltd.), PA-411, PA-480 (trade name, manufactured by Heraeus Co., Ltd.), etc. In addition, other heat-generating acid agents with sulfonate structures include PAI-01, PAI-101, PAI-106, PAI-1001, PAI-1002, PAI-1003, PAI-1004 (trade name, manufactured by Midori Kagaku Co., Ltd.), SP-082, SP-601, SP-606, SP-607, SP-612 (trade name, manufactured by ADEKA Co., Ltd.), NIT, MIN, ILP-110, ILP-110N, ILP-118, ILP-113, PA-223, PA-298 (trade name, manufactured by Heraeus Co., Ltd.), NAI-105, NAI-106, and NAI-109 (trade name, manufactured by Midori Kagaku Co., Ltd.).

[0090] Furthermore, the (E) thermal acid-generating agent is particularly preferably a compound represented by formula (3). By including the compound represented by formula (3) in the (E) thermal acid-generating agent, the volatility of the (E) thermal acid-generating agent during curing (heat treatment) is reduced, and acid can be efficiently generated from the (E) thermal acid-generating agent during curing, resulting in a greater crosslinking promotion effect, thereby improving the reliability of the organic EL display device. In addition, by including the compound represented by formula (3) in the (E) thermal acid-generating agent, its solubility in alkaline developing solution is easily improved compared to the case without the compound represented by formula (3), thus improving exposure sensitivity.

[0091] [Chemical Formula 7] (In equation (3), R) 3 It is a divalent to tetravalent group with 1 to 10 carbon atoms. R 4 Each can independently represent an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms, which may have substituents. Examples of such substituents include hydroxyl, halogen, cyano, vinyl, ethynyl, or a straight-chain or cyclic alkyl group having 1 to 10 carbon atoms. 'a' represents an integer from 2 to 4. From the perspective of not reducing exposure sensitivity, in equation (3), R is preferred. 3 R is a divalent to tetravalent group with 1 to 6 carbon atoms that can have substituents. 4 Each can be an alkyl group having 1 to 6 carbon atoms that is straight-chain, branched, or cyclic, or an aryl group having 6 to 10 carbon atoms that is substituent.

[0092] Examples of compounds described in formula (3) above include compounds obtained by sulfonating the alcoholic or phenolic hydroxyl groups of compounds having multiple alcoholic hydroxyl groups (sometimes referred to as "polyol compounds") or compounds having multiple phenolic hydroxyl groups (sometimes referred to as "polyphenol compounds") with methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, octylsulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, etc. Among polyol compounds, specific examples of binary alcohol compounds include methanethiol, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, etc. Among polyol compounds, specific examples of trivalent or more alcohol compounds include glycerol, butylene glycerol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, pentaerythritol, etc. Among polyphenol compounds, specific examples include dihydroxybenzene, trihydroxybenzene, tetrahydroxybenzene, etc.

[0093] Regarding the content of the compound shown in formula (3), from the viewpoint of easily obtaining the effect of improving exposure sensitivity and improving the reliability of organic EL display devices, it is preferable to contain 20% by mass or more in 100% by mass of the thermally generated acid agent (E). More preferably, it is 50% by mass or more, even more preferably 70% by mass or more, and particularly preferably 100% by mass.

[0094] From the viewpoint of further improving the reliability of the organic EL display device, the content of the thermally generated acid agent (E) is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and even more preferably 3 parts by mass or more, relative to the total 100 parts by mass of the aforementioned components (A) and (B). Furthermore, from the viewpoint of improving sensitivity, the content of the thermally generated acid agent (E) is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 8 parts by mass or less, relative to the total 100 parts by mass of the aforementioned components (A) and (B).

[0095] The photosensitive resin composition of the present invention may contain (F) one or more compounds selected from the group (F-1) below, and when the aforementioned photosensitive resin composition is set to 100 parts by mass, it contains 0.001 to 2.00 parts by mass of the aforementioned (F) component.

[0096] Group (F-1): 1,3-Dimethyl-2-imidazoline, N,N'-dimethylpropylene urea, 3-methoxy-N,N-dimethylpropionamide, 3-n-butoxy-N,N-dimethylpropionamide, N,N-dimethylisobutylamide, and tetramethylurea In the photosensitive resin composition of the present invention, the content of component (F) is preferably 0.001 to 2.00 parts by weight relative to 100 parts by weight of the aforementioned photosensitive resin composition. If the content of component (F) is less than 0.001 parts by weight relative to 100 parts by weight of the aforementioned photosensitive resin composition, the storage stability decreases. The content of component (F) is more preferably 0.003 parts by weight or more, and even more preferably 0.01 parts by weight or more. On the other hand, if the content of component (F) is greater than 2.00 parts by weight relative to 100 parts by weight of the aforementioned photosensitive resin composition, the sensitivity decreases. The content of component (F) is more preferably 1.50 parts by weight or less relative to 100 parts by weight of the aforementioned photosensitive resin composition, and even more preferably 1.00 parts by weight or less.

[0097] The photosensitive resin composition of the present invention may contain a solvent. By containing a solvent, it is possible to produce a varnish-like state, which improves coatability.

[0098] The aforementioned solvents may contain, alone or in combination, polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol mono-n-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether; tetrahydrofuran; dioxane ethers; acetone; methyl ethyl ketone; diisobutyl ketone; cyclohexanone; 2-heptanone; 3-heptanone; and diacetone alcohol. Solvents include ketones, 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, ethyl lactate, etc., ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, methyl acetoacetate, ethyl acetoacetate, and other esters, as well as aromatic hydrocarbons such as toluene and xylene.

[0099] From the viewpoint of improving coatability, the solvent is preferably a polar aprotic solvent. Preferred polar aprotic solvents include N-methyl-2-pyrrolidone and γ-butyrolactone.

[0100] The solvent content is preferably 3 to 30% by mass, which is the concentration of the solid component in the photosensitive resin composition. If the solid component concentration is less than 3% by mass, the coatability deteriorates; more preferably, it is 5% by mass or more. Furthermore, if the solvent content is greater than 30% by mass, the storage stability of the photosensitive resin composition deteriorates; more preferably, it is 20% by mass or less. Here, the solid component concentration refers to the concentration of components other than the solvent in the photosensitive resin composition.

[0101] The photosensitive resin composition of the present invention may contain known compounds such as thermal crosslinking agents.

[0102] Examples of thermal crosslinking agents include DML-PC, DML-PEP, DMOM-PC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP, HMOM-TPPA (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), "NIKALAC" (registered trademark) MX-270, "NIKALAC" (registered trademark) MW-100LM (trade names, manufactured by Sanwa Chemical Co., Ltd.), and thermal crosslinking agents containing hydroxymethyl and / or alkoxymethyl groups, such as "Denacol" EX-850L and "Denacol" EX-201-IM (trade names, manufactured by Nagase). Chemical crosslinking agents with epoxy groups, such as Chemtex (manufactured by Chemtex Corporation), VG3101L (trade name, manufactured by PRINTEX Corporation), "TEPIC" (registered trademark)-S, "TEPIC"-L, "TEPIC"-VL, "TEPIC"-FL, "TEPIC"-UC (trade names, manufactured by Nissan Chemical Industries, Ltd.), OXT-121, OXT-221, OX-SQ-H, OXT-191, PNOX-1009, RSOX (trade names, manufactured by Toa Synthetic), and oxetane, 1,2-bis(maleimide)ethane, 1,3-bis(maleimide)propane, 1,4-bis(maleimide)propane, etc. Bismaleimide thermal crosslinking agents such as bis(maleimide)butane, 1,5-bis(maleimide)pentane, 1,6-bis(maleimide)hexane, and 2,2,4-trimethyl-1,6-bis(maleimide)hexane; aromatic polyisocyanates such as 4,4'-methylene bis(phenylene isocyanate) (MDI) and toluene diisocyanate (TDI); aliphatic polyisocyanates such as hexamethylene diisocyanate (HDI), trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, pentamethylene diisocyanate, and lysine diisocyanate; and alicyclic polyisocyanate thermal crosslinking agents such as isophorone diisocyanate (IPDI) and 4,4'-methylene bis(cyclohexyl isocyanate) (H12MDI).

[0103] From the viewpoint of improving the chemical resistance of the cured product, the content of the thermal crosslinking agent is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, relative to a total of 100 parts by mass of components (A) and (B). Furthermore, from the viewpoint of reducing gas escape from the cured product and further improving the reliability of the organic EL display device, the content of the thermal crosslinking agent is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less, relative to a total of 100 parts by mass of components (A) and (B).

[0104] The photosensitive resin composition of the present invention may contain a colorant. A colorant refers to a known organic pigment, inorganic pigment, or dye. Preferably, the colorant is an organic pigment and / or an inorganic pigment.

[0105] Examples of organic pigments include, for example, pyrrolopyrrole dione pigments, azo, diazo or polyazo pigments, copper phthalocyanine, vat pigments, benzofuranone pigments or metal complex pigments.

[0106] Examples of inorganic pigments include titanium dioxide, zinc white, zinc sulfide, lead white, calcium carbonate, precipitated barium sulfate, silica, manganese violet, or cobalt violet.

[0107] Examples of dyes include, for example, azo dyes, anthraquinone dyes, fused polycyclic aromatic carbonyl dyes, indigo dyes, carbomon dyes, phthalocyanine dyes, methine or polymethyst dyes.

[0108] For the purpose of improving the contrast of organic EL display devices, the colorant is preferably black, capable of blocking visible light across the entire wavelength range. Preferably, the photosensitive resin composition contains one or more selected from organic pigments, inorganic pigments, and dyes, and contains a colorant that is black when the cured product is formed. Therefore, it can contain the aforementioned black organic pigments and black inorganic pigments, or it can be approximately blackened by mixing two or more organic pigments and dyes. In the case of approximately blackening, it can be obtained by mixing two or more organic pigments and dyes such as red, orange, yellow, purple, blue, and green. It should be noted that the photosensitive resin composition of the present invention does not necessarily need to be black; a colorant that makes the cured product black by color change during heat curing can also be used.

[0109] From the viewpoint of ensuring high heat resistance, it is preferable that these contain organic pigments and / or inorganic pigments, and a colorant that is black when the cured product is formed. Furthermore, from the viewpoint of ensuring high insulation, it is preferable that these contain organic pigments and / or dyes, and a colorant that is black when the cured product is formed. That is, from the viewpoint of simultaneously achieving high heat resistance and insulation, it is preferable that these contain organic pigments, and a colorant that is black when the cured product is formed.

[0110] Regarding the content of the colorant, from the viewpoint of obtaining the desired colorability of the cured product, it is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, relative to the total amount of the photosensitive resin composition excluding the solvent. Furthermore, from the viewpoint of obtaining good storage stability, it is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less, relative to the total amount of the photosensitive resin composition excluding the solvent.

[0111] When a photosensitive resin composition contains pigments, it is preferable to include a dispersant. By including a dispersant, the colorant can be uniformly and stably dispersed in the photosensitive resin composition. There are no particular limitations on the dispersant, but a polymeric dispersant is preferred. Examples of polymeric dispersants include polyester-based, acrylic-based, polyurethane-based, polyallylamine-based, or carbodiimide-based dispersants. More specifically, a polymeric dispersant refers to a polymeric compound whose main chain is formed of polyamine, polyether, polyester, polyurethane, polyacrylate, etc., and which has polar groups such as amines, carboxylic acids, phosphoric acids, amine salts, carboxylates, and phosphates at the side chains or ends of the main chain. The polar groups adsorb onto the pigment, utilizing the steric hindrance of the main chain polymer to stabilize the dispersion of the pigment.

[0112] Dispersants can be classified as (polymer) dispersants having only amine value, (polymer) dispersants having only acid value, (polymer) dispersants having both amine value and acid value, or (polymer) dispersants having neither amine value nor acid value, but preferably (polymer) dispersants having both amine value and acid value, (polymer) dispersants having only amine value, and more preferably (polymer) dispersants having only amine value.

[0113] Regarding the content of the dispersant, from the viewpoint of obtaining good dispersion stability, it is preferably 1 part by mass or more, more preferably 3 parts by mass or more, relative to 100 parts by mass of pigment. Furthermore, from the viewpoint of maintaining the heat resistance of the cured product, it is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, relative to 100 parts by mass of pigment.

[0114] The photosensitive resin composition of the present invention may contain an adhesion modifier. Examples of adhesion modifiers include vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, silane coupling agents, zirconium oxide chelating agents, titanium chelating agents, aluminum chelating agents, and compounds obtained by reacting aromatic amine compounds with alkoxy-containing silicon compounds. Two or more of these may be contained. By containing these adhesion modifiers, adhesion to substrates such as silicon wafers, ITO, SiO2, and silicon nitride can be improved when developing the photosensitive resin film. Furthermore, resistance to oxygen plasma and UV ozone treatment used in washing and other processes can be improved. The content of the binding modifier is preferably 0.1 to 10% by mass relative to the total amount of the photosensitive resin composition excluding the solvent.

[0115] The photosensitive resin composition of the present invention may contain surfactants as needed for the purpose of improving wettability with the substrate. Surfactants can be commercially available compounds. Specifically, examples of silicone-based surfactants include the SH, SD, and ST series from Dow Corning Toray Silicone Co., Ltd., the BYK series from BYK Chemie Japan KK, the KP series from Shin-Etsu Silicone Co., Ltd., the DISFOAM series from Nippon Yushi Co., Ltd., and the TSF series from Toshiba Silicones Co., Ltd. Examples of fluorinated surfactants include the MEGAFACE (registered trademark) series from Dai Nippon Ink Industries Co., Ltd., the Fluorad series from Sumitomo 3M Ltd., the Surflon (registered trademark) series and the Asahi Guard (registered trademark) series from Asahi Glass Co., Ltd., the EF series from Shin-Akita Chemical Co., Ltd., and the PolyFox series from OMNOVA Solutions Inc. Examples of surfactants formed from acrylic and / or methacrylic polymers include the Polyflow series from Kyoeisha Chemical Co., Ltd., and the DISPARLON (registered trademark) series from Kusumoto Chemical Co., Ltd., but these are not limited to these examples.

[0116] The surfactant content is preferably 0.001 to 1% by mass relative to the total amount of the photosensitive resin composition excluding the solvent.

[0117] The photosensitive resin composition of the present invention may contain compounds having phenolic hydroxyl groups as needed to compensate for the alkaline developability of the photosensitive resin composition. Examples of compounds having phenolic hydroxyl groups include, for example, Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP-Z, BisOCR-CP, BisP-MZ, BisP-EZ, Bis26X-CP, BisP-PZ, BisP-IPZ, BisCRIPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, and TekP-4HBPA (Tetrakis). P-DO-BPA), TrisPHAP, TrisP-PA, TrisP-PHBA, TrisP-SA, TrisOCR-PA, BisOFP-Z, BisRS-2P, BisPG-26X, BisRS-3P, BisOC-OCHP, BisPC-OCHP, Bis25X-OCHP, Bis26X-OCHP, BisOCHP-OC, Bis236T-OCHP, MethyleneTris-FR-CR, BisRS-26X, BisRS-OCHP (trade name, Honshu Chemical Industry Co., Ltd.) The photosensitive resin compositions containing these compounds (manufactured by Asahi Organic Materials Co., Ltd.) are almost insoluble in alkaline developers before exposure, but readily soluble in alkaline developers upon exposure. Therefore, film loss due to development is minimal, and development is facilitated in a short time. Therefore, it is easy to increase sensitivity.

[0118] The content of such a compound having phenolic hydroxyl groups is preferably 1% by mass or more and 20% by mass or less relative to the total amount of the photosensitive resin composition excluding the solvent.

[0119] Furthermore, the photosensitive resin composition of the present invention may contain inorganic particles. Preferred examples include silicon dioxide, titanium dioxide, barium titanate, aluminum oxide, talc, etc., but are not limited thereto. The primary particle size of these inorganic particles is preferably 100 nm or less, more preferably 60 nm or less.

[0120] The content of inorganic particles is preferably 5 to 90% by mass relative to the total amount of the photosensitive resin composition excluding the solvent.

[0121] Next, a method for manufacturing the photosensitive resin composition of the present invention will be described. For example, the photosensitive resin composition can be obtained by dissolving component (A), component (B), component (C), (D) quinone diazide compound, optional (E) thermal acid-producing agent, component (F), and, as needed, a binding modifier, surfactant, colorant, inorganic particles, etc., in a solvent.

[0122] Examples of dissolution methods include stirring and heating. When heating is used, the heating temperature is preferably set within a range that does not impair the performance of the photosensitive resin composition, typically room temperature to 80°C. Furthermore, the order in which the components are dissolved is not particularly limited; for example, a method of dissolving compounds with low solubility sequentially can be used. Additionally, for components such as surfactants and certain adhesion modifiers that are prone to generating bubbles during stirring, other components can be dissolved first and then added last, thereby preventing poor dissolution of other components due to bubble formation.

[0123] The resulting photosensitive resin composition is preferably filtered to remove foreign matter. Filter pore sizes include, for example, 0.5 μm, 0.2 μm, 0.1 μm, 0.07 μm, 0.05 μm, and 0.02 μm, but are not limited to these. Filter materials include polypropylene (PP), polyethylene (PE), nylon (NY), and polytetrafluoroethylene (PTFE), with polyethylene and nylon being preferred. When the photosensitive resin composition contains pigments or particles, a filter with a pore size larger than their particle size is preferred.

[0124] The cured product of the present invention is a cured product obtained by curing a photosensitive resin composition. The cured product can be obtained by heat treatment of the photosensitive resin composition. The heat treatment method can be any known method, such as using a heating plate, an oven, or infrared radiation. Preferred heat treatment conditions will be described in the step of heat treatment of the developed photosensitive resin film in the method for manufacturing the cured product (5) described later.

[0125] Next, a method for manufacturing a cured product using the photosensitive resin composition of the present invention will be described in detail.

[0126] The method for manufacturing a cured product includes the following steps in sequence: (1) The step of coating the above-mentioned photosensitive resin composition onto a substrate to form a photosensitive resin film, (2) The process of drying the aforementioned photosensitive resin film (pre-baking process). (3) The process of exposing the dried photosensitive resin film through a light mask. (4) The process of developing the exposed photosensitive resin film, and (5) The process of heat-treating the developed photosensitive resin film.

[0127] In step (1), which involves coating the above-mentioned photosensitive resin composition onto a substrate to form a photosensitive resin film, the photosensitive resin composition of the present invention is coated using methods such as spin coating, slot coating, dip coating, spray coating, and printing to obtain a photosensitive resin film of the photosensitive resin composition. Before coating, the substrate to which the photosensitive resin composition is to be coated can be pretreated using the aforementioned adhesion modifier.

[0128] For example, the following method can be used to treat the surface of a substrate using a solution obtained by dissolving 0.5 to 20% by mass of a bonding modifier in solvents such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and diethyl adipate. Examples of substrate surface treatment methods include spin coating, stencil coating, bar coating, dip coating, spray coating, and steam treatment.

[0129] In the process of drying the photosensitive resin film in (2), the coated photosensitive resin film is subjected to reduced pressure drying treatment as needed, and then heat treatment is carried out in the range of 50℃~180℃ for 1 minute to several hours using a heating plate, oven, infrared, etc., to obtain the dried photosensitive resin film.

[0130] Next, in the step of exposing the dried photosensitive resin film through a photomask (3), chemical rays are irradiated onto the photosensitive resin film through a photomask having the desired pattern. Chemical rays used in the exposure include ultraviolet light, visible light, electron beams, X-rays, etc. In this invention, the i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp are preferably used.

[0131] After irradiation with chemical rays, post-exposure baking can be performed. Post-exposure baking can be expected to improve the resolution after development or increase the allowable range of development conditions. Post-exposure baking can be performed using an oven, heated plate, infrared radiation, rapid annealing device, or laser annealing device. The preferred post-exposure baking temperature is 50~180℃, more preferably 60~150℃. The preferred post-exposure baking time is 10 seconds to several hours. If the post-exposure baking time is within the above range, the reaction proceeds well, and sometimes the development time can be shortened.

[0132] In step (4), which involves developing the exposed photosensitive resin film, a developing solution is used to develop the exposed photosensitive resin film and remove the portion other than the exposed portion. The developing solution is preferably an aqueous solution (alkaline aqueous solution) of a compound exhibiting alkalinity, such as tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, or hexamethylenediamine.

[0133] Alternatively, depending on the circumstances, solutions can be obtained by adding one or more of the following to these alkaline aqueous solutions: polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, and dimethacrylamide; 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 can include spraying, immersion, soaking, and ultrasonication.

[0134] Next, the pattern formed by development is preferably rinsed with distilled water. Alternatively, alcohols such as ethanol and isopropanol, or esters such as ethyl lactate and propylene glycol monomethyl ether acetate, can be added to the distilled water for rinsing.

[0135] Next, step (5) of heat-treating the developed photosensitive resin film is performed. Heat treatment removes residual solvents and components with low heat resistance, thereby improving heat resistance and chemical resistance. The photosensitive resin composition of the present invention can form imide rings and oxazole rings through heat treatment, thus improving heat resistance and chemical resistance. Furthermore, in the case of a thermal crosslinking agent, a thermal crosslinking reaction can be performed through heat treatment, further improving heat resistance and chemical resistance. From the viewpoint of improving the heat resistance of the cured product, the heat treatment temperature is preferably 200°C or higher, more preferably 220°C or higher, even more preferably 230°C or higher, and particularly preferably 240°C or higher.

[0136] On the other hand, from the viewpoint of avoiding the effects of thermal degradation of TFT elements, the temperature is preferably below 400°C, more preferably below 350°C, and even more preferably below 270°C. Within this temperature range, the temperature can be increased in stages or continuously. Regarding the heat treatment time, from the viewpoint of improving the heat resistance of the cured product, it is preferably 30 minutes or more, more preferably 45 minutes or more. In addition, from the viewpoint of productivity, it is preferably 180 minutes or less, more preferably 120 minutes or less. For example, the following methods can be cited: a method of heat treatment at 150°C and 250°C for 60 minutes each; a method of heat treatment while linearly increasing the temperature from room temperature to 250°C over 2 hours; and so on.

[0137] The cured product of the present invention is preferably a cured product formed from the photosensitive resin composition of the present invention. In addition, in other embodiments of the cured product of the present invention, when analyzed by reactive thermal pyrolysis GC / MS, if the compounds shown in formula (4), formula (5), and formula (6) are detected, in terms of the peak intensity ratio, if the compound shown in formula (5) is set to 1, then the compound shown in formula (4) is 0.1 or more and 1 or less, and the compound shown in formula (6) is 0.1 or more and 3 or less.

[0138] [Chemical Formula 8] (In equations (4), (5) and (6), R) 5 ~R 11 Each of these groups independently represents a hydrogen atom or a monovalent organic group containing 1 to 30 carbon atoms, which may include heteroatoms.

[0139] In formulas (4), (5) and (6), the monovalent organic groups with 1 to 30 carbon atoms that may contain heteroatoms can be exemplified by alkyl, alkenyl, alkynyl, aryl and the like.

[0140] The aforementioned alkyl group can be linear, branched, or cyclic. The linear and branched alkyl groups typically have 1 to 30 carbon atoms, and from the viewpoint of high heat resistance and maintaining high flexural strength of the cured product, 1 to 20 carbon atoms are preferred, and more preferably 1 to 10 carbon atoms. Cyclic alkyl groups typically have 3 to 30 carbon atoms, and from the viewpoint of high heat resistance and maintaining high flexural strength of the cured product, 3 to 20 carbon atoms are preferred, and more preferably 3 to 10 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, and decyl.

[0141] The aforementioned alkenyl groups can be linear, branched, or cyclic. Linear and branched alkenyl groups typically have 2 to 30 carbon atoms, and from the viewpoint of high heat resistance and maintaining high flexural strength of the cured product, 2 to 20 carbon atoms are preferred, and more preferably 2 to 10 carbon atoms. Cyclic alkenyl groups typically have 3 to 30 carbon atoms, and from the viewpoint of high heat resistance and maintaining high flexural strength of the cured product, 3 to 20 carbon atoms are preferred, and more preferably 3 to 10 carbon atoms. Examples of alkenyl groups include vinyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, hexenyl, nonenyl, and decenyl.

[0142] The aforementioned alkynyl group can be linear, branched, or cyclic. The number of carbon atoms in linear and branched alkynyl groups is typically 2 to 30, and preferably 2 to 20, more preferably 2 to 10, from the viewpoint of high heat resistance and maintaining high flexural strength of the cured product. The number of carbon atoms in cyclic alkynyl groups is typically 3 to 30, and preferably 3 to 20, more preferably 3 to 10, from the viewpoint of high heat resistance and maintaining high flexural strength of the cured product. Examples of alkynyl groups include ethynyl, propynyl, butynyl, pentynyl, and hexynyl.

[0143] The aforementioned aryl group is the remaining atomic group obtained by removing one hydrogen atom directly bonded to the carbon atom constituting the aromatic ring from an aromatic hydrocarbon, including aryl groups having hydroxyl, the aforementioned alkyl, the aforementioned alkenyl, or the aforementioned alkynyl as functional groups. The number of carbon atoms in the aryl group is typically 6 to 30, preferably 6 to 20. Examples of aryl groups include phenyl, hydroxyphenyl, alkylphenyl, and alkylhydroxyphenyl. From the viewpoint of achieving a balance between high heat resistance and the bending resistance of the cured product, hydroxyphenyl and alkylhydroxyphenyl are preferred. Examples of alkylphenyl groups include methylphenyl, ethylphenyl, dimethylphenyl, propylphenyl, methylethylphenyl, isopropylphenyl, butylphenyl, isobutylphenyl, tert-butylphenyl, pentylphenyl, hexylphenyl, cyclohexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, and decylphenyl. Examples of alkyl hydroxyphenyl compounds include, for example, methyl hydroxyphenyl, ethyl hydroxyphenyl, dimethyl hydroxyphenyl, propyl hydroxyphenyl, methyl ethyl hydroxyphenyl, isopropyl hydroxyphenyl, butyl hydroxyphenyl, isobutyl hydroxyphenyl, tert-butyl hydroxyphenyl, pentyl hydroxyphenyl, hexyl hydroxyphenyl, cyclohexyl hydroxyphenyl, heptyl hydroxyphenyl, octyl hydroxyphenyl, nonyl hydroxyphenyl, decyl hydroxyphenyl, etc.

[0144] When analyzing the cured product using reactive thermal pyrolysis GC / MS, compounds shown in formula (4), formula (5), and formula (6) were detected. In terms of the peak intensity ratio, if the compound shown in formula (5) is set to 1, then the compound shown in formula (4) is 0.1 or more and 1 or less, and the compound shown in formula (6) is 0.1 or more and 3 or less. Thus, it is easy to obtain a cured product with high bending resistance and chemical resistance.

[0145] The compounds contained in the cured products of the present invention will be described. The compound represented by formula (4) can be obtained, for example, as a structure or residue thereof derived from (C) polyhydroxystyrene, and / or a copolymer of polyhydroxystyrene and polystyrene. The compound represented by formula (5) can be obtained, for example, as a structure or residue thereof derived from (A) polyimide, a polyimide precursor, and copolymers thereof. The compound represented by formula (6) can be obtained, for example, as a structure or residue thereof derived from (B) polybenzoxazole, a polybenzoxazole precursor, and copolymers thereof.

[0146] The cured product formed from the photosensitive resin composition of the present invention can be used in a display device comprising a first electrode formed on a substrate and a second electrode disposed opposite to the first electrode, specifically, for example, a planarization layer of a liquid crystal display device, a planarization layer and / or a pixel segmentation layer of an organic EL display device. Hereinafter, an organic EL display device will be used as an example for explanation.

[0147] The organic EL display device of the present invention includes the aforementioned cured material. Specifically, an organic EL display device having a driving circuit, a planarization layer, a first electrode, a pixel segmentation layer, a light-emitting layer, and a second electrode on a substrate, and wherein the planarization layer and / or the pixel segmentation layer contains the aforementioned cured material, is preferred. Taking an active matrix type display device as an example, a thin-film transistor (hereinafter TFT) is provided on a substrate such as glass or a resin film, and wiring located on the side of the TFT and connected to the TFT is provided, and a planarization layer is provided thereon in a manner that covers the unevenness, and a display element is further provided on the planarization layer. The display element and the wiring are connected via contact holes formed in the planarization layer. In particular, in recent years, the flexibility of organic EL display devices has become mainstream, and the aforementioned organic EL display device with a driving circuit whose substrate is formed of a resin film is preferred.

[0148] Regarding the organic EL display device of the present invention, it is preferable that at least a portion of the cured portion preferably has a bendable portion and / or a portion fixed in a bendable state. By using the cured product obtained by curing the photosensitive resin composition or photosensitive resin sheet of the present invention, an organic EL display device with excellent bending resistance can be obtained. The radius of curvature of the aforementioned bendable portion and / or portion fixed in a bendable state is preferably 0.1 mm or more, and preferably 5 mm or less. If the radius of curvature is 0.1 mm or more, the bending resistance of the bent portion can be ensured; if it is 5 mm or less, the appearance design such as a narrow bezel can be ensured.

[0149] The organic EL display device of the present invention can be bent at any suitable location. For example, the organic EL display device can be bent at the center like a folding display device, and from the viewpoint of maximizing the appearance and display image, it can also be bent at the ends. Furthermore, the organic EL display device can be bent along its long side or along its short side. Depending on the application, specific parts of the organic EL display device can be bent (e.g., part or all of the four corners can be bent along an inclined direction).

[0150] Figure 1 This is a cross-sectional view of an example of an organic EL display device in which a planarization layer and a pixel segmentation layer are formed. On a substrate 1, bottom-gate or top-gate TFTs 2 are arranged in rows and columns, and a TFT insulating layer 3 is formed to cover the TFTs 2. Furthermore, wiring 4 connected to the TFTs 2 is provided on the TFT insulating layer 3. Next, a planarization layer 5 is provided on the TFT insulating layer 3 to embed the wiring 4. Contact holes 6 leading to the wiring 4 are provided in the planarization layer 5. Then, ITO (first electrode) 7 is formed on the planarization layer 5 through the contact holes 6 to connect with the wiring 4.

[0151] Here, ITO7 serves as the electrode for the display element (e.g., an organic EL element). Then, a pixel segmentation layer 8 is formed covering the periphery of ITO7. The organic EL element can be a top-emitting type that emits light from the side opposite to the substrate 1, or a bottom-emitting type that extracts light from the substrate 1 side. As described above, an active matrix type organic EL display device with an organic EL layer 9 and a second electrode 10, in which TFTs 2 for driving each organic EL element are connected to it, can be obtained.

[0152] The TFT insulating layer 3, planarization layer 5, and / or pixel segmentation layer 8 can be formed as described above through the following steps: a step of forming a photosensitive resin film formed from the photosensitive resin composition of the present invention; a step of exposing the aforementioned photosensitive resin film; a step of developing the exposed photosensitive resin film; and a step of heat-treating the developed photosensitive resin film. By means of this manufacturing method having these steps, an organic EL display device can be obtained.

[0153] Furthermore, the cured product formed from the photosensitive resin composition of the present invention can be used as an insulating film or protective film constituting electronic components. Here, examples of electronic components include active components having semiconductors such as transistors, diodes, integrated circuits (hereinafter ICs), and memory, as well as passive components such as resistors, capacitors, and inductors. Electronic components using semiconductors are also referred to as semiconductor devices. Specific examples of the cured product within electronic components include suitable applications such as passivation films for semiconductors, surface protective films for semiconductor elements and TFTs, interlayer insulating films in multilayer wiring for high-density mounting of 2 to 10 layers, insulating films for touch panel displays, and protective films, but are not limited to these applications; various structures can be employed.

[0154] Furthermore, the substrate surface on which the cured material is formed can be appropriately selected according to the application and process, and examples include silicon, ceramics, metals, glass, epoxy resins, etc., and multiple of these materials can be disposed on the same surface. Examples of electronic devices having a surface protective film, interlayer insulating film, etc., disposed with the cured material of the present invention include, for example, MRAM (magnetoresistive random access memory) with low heat resistance. In other words, the cured material of the present invention is suitable for use as a surface protective film for MRAM.

[0155] In addition to MRAM, polymeric memory (Polymer Ferroelectric RAM: PFRAM) and phase change memory (Phase Change RAM: PCRAM, or Ovonics Unified Memory: OUM), which are expected to be next-generation memories, are also more likely to use new materials with lower heat resistance compared to conventional memories. Therefore, the cured products of this invention are also suitable for their surface protective film applications.

[0156] Additionally, it can be appropriately used for fan-out wafer-level packaging (hereinafter referred to as fan-out WLP). Fan-out WLP is a semiconductor package in which an expansion portion is provided around the semiconductor chip using a sealing resin such as epoxy resin, and redistribution is performed from the electrodes on the semiconductor chip to the expansion portion. Solder balls are also mounted on the expansion portion, thereby ensuring the necessary number of terminals.

[0157] In a fan-out type WLP, wiring is arranged such that it spans the boundary line formed between the main surface of the semiconductor chip and the main surface of the sealing resin. That is, an interlayer insulating film is formed on a substrate made of two or more materials, namely a semiconductor chip to which metal wiring is applied and a sealing resin, and wiring is formed on the interlayer insulating film.

[0158] In addition, in semiconductor packages where a semiconductor chip is embedded in a recess formed on a glass epoxy resin substrate, wiring is also provided across the boundary line between the main surface of the semiconductor chip and the main surface of the printed circuit board. In this method, an interlayer insulating film is formed on a substrate made of two or more materials, and wiring is formed on this interlayer insulating film. The cured product formed by curing the photosensitive resin composition of the present invention has high adhesion to the semiconductor chip with metal wiring applied, and also has high adhesion to sealing resins such as epoxy resin. Therefore, it can be suitably used as an interlayer insulating film provided on a substrate made of two or more materials.

[0159] Example The present invention will now be described with reference to examples, but the present invention is not limited to these examples. It should be noted that the evaluation of the photosensitive resin compositions in the examples was performed using the following methods.

[0160] (1) Sensitivity evaluation Using an ACT-8 coating and developing apparatus (manufactured by Tokyo Electron Co., Ltd.), the photosensitive resin compositions obtained in the examples and comparative examples described below were coated onto an 8-inch silicon wafer using a spin coating method. The wafers were then baked at 120°C for 3 minutes using a hot plate to produce a pre-baked film with a thickness of 3.0 μm. It should be noted that the film thickness was measured using a Lambda Ace STM-602 (manufactured by Dainippon ScreenMfg. Co., Ltd.) at a refractive index of 1.63.

[0161] Then, using an exposure machine (Nikon) with an i-line stepper NSR-2005i9C, through a mask with a pattern of 10μm contact holes, at 50~300mJ / cm²... 2 The exposure amount, in 10mJ / cm 2 Exposure was performed using a step size. After exposure, the aforementioned ACT-8 developing apparatus was used, and a 2.38% by mass tetramethylammonium aqueous solution (hereinafter TMAH, manufactured by Tama Chemical Co., Ltd.) was used for development at a time when the film loss was 0.5 μm. After rinsing with distilled water, the mixture was spin-dried to obtain the pattern.

[0162] The pattern of the developed film was observed using an FDP microscope MX61 (manufactured by Olympus Corporation) at 20x magnification. The minimum required exposure for the contact hole opening diameter to reach 10μm was determined and used as the exposure sensitivity, with 200mJ / cm² as the threshold. 2 The following are considered acceptable. The lower the sensitivity value, the higher the sensitivity, and the better.

[0163] (2) Evaluation of bending resistance Using a spin coating method, the photosensitive resin compositions obtained in the examples and comparative examples described below were coated onto a polyimide film substrate at an arbitrary rotation speed to obtain a photosensitive resin film. As a drying step, the film was pre-baked on a heated plate at 120°C for 2 minutes to obtain the photosensitive resin film. Next, using an automatic developing apparatus (AD-2000 manufactured by Takizawa Sangyo Co., Ltd.), the film was spray-developed with a 2.38% by mass tetramethylammonium hydroxide aqueous solution for 90 seconds, followed by rinsing with pure water for 30 seconds. Under a nitrogen atmosphere, the developed substrate with the photosensitive resin film was cured (heat treatment) in an oven at 250°C for 60 minutes to obtain a cured product with a film thickness of 2.0 μm.

[0164] Next, ten polyimide film substrates with cured material were cut out, each measuring 50 mm x 10 mm. The cut polyimide films were then stored at 100°C for 500 hours in air. Then, with the cured side facing outwards, the polyimide film substrate was bent 180° along a 25 mm longitudinal line and held for 30 seconds. After 30 seconds, the bent polyimide film substrate was opened, and the bent portion along the 25 mm longitudinal line on the surface of the cured material was observed using an FPD inspection microscope (MX-61L; Olympus Co., Ltd.). The changes in the appearance of the cured surface were evaluated. The bending test was conducted within a radius of curvature ranging from 0.1 to 2.0 mm, and the minimum radius of curvature (mm) at which no peeling of the cured material from the polyimide film substrate or cracking of the cured surface occurred was recorded. The smaller the minimum radius of curvature (mm), the higher the bending resistance, and the better. Values ​​below 1.5mm are considered acceptable.

[0165] (3) Reliability test of organic EL display device <Fabrication of Organic EL Display Devices> Figure 2A schematic diagram of the substrate used is shown. First, an ITO transparent conductive film of 100 nm was formed on the entire surface of a 38×46 mm alkali-free glass substrate 11 by sputtering, and the first electrode 12 was etched. Simultaneously, an auxiliary electrode 13 was formed to remove the second electrode. The obtained substrate was ultrasonically cleaned for 10 minutes using "Semico Clean56" (trade name, manufactured by Furuuchi Chemical Co., Ltd.), and then washed with ultrapure water. Next, the photosensitive resin composition (varnish) according to the embodiments and comparative examples described later was coated onto the entire surface of the substrate by spin coating, and pre-baked on a heated plate at 120°C for 2 minutes. For this film, a parallel light mask aligner (hereinafter referred to as PLA) (Canon Corporation PLA-501F) was used, with an ultra-high pressure mercury lamp as the light source (a mixed line of g, h, and i lines). After UV exposure through the light mask, development was performed using a 2.38% by mass TMAH aqueous solution, dissolving only the exposed portion, followed by rinsing with pure water. The resulting patterned substrate was cured in an inert oven (Koyo Thermo Systems Co., Ltd. CLH-21CD-S) at 250°C for 60 minutes under a nitrogen atmosphere. As described above, openings with a width of 50μm and a length of 260μm were arranged at a spacing of 155μm in the width direction and 465μm in the length direction, with each opening ensuring that the pixel segmentation layer 14, shaped to expose the first electrode 12, is formed only in the effective area of ​​the substrate. As described above, a pixel segmentation layer 14 with an aperture ratio of 18% is provided in the effective area of ​​a quadrilateral substrate with each side of 16 mm, and the thickness of the pixel segmentation layer 14 is approximately 2.0 μm.

[0166] Next, as a pretreatment, nitrogen plasma treatment was performed, followed by the formation of an organic EL layer 15 using vacuum evaporation. It should be noted that the vacuum level during evaporation was 1×10⁻⁶. -3 Below Pa, during evaporation, the substrate is rotated relative to the evaporation source. First, a 10 nm layer of compound (HT-1) is deposited as a hole injection layer, and a 50 nm layer of compound (HT-2) is deposited as a hole transport layer. Next, on the light-emitting layer, a 40 nm thick layer is deposited using a compound (GH-1) as the host material and a compound (GD-1) as the dopant material at a doping concentration of 10%. Next, a 40 nm thick layer is formed by stacking compounds (ET-1) and (LiQ) at a 1:1 volume ratio as electron transport materials. The structures of the compounds used in the organic EL layer are shown below.

[0167] [Chemical Formula 9] Next, after depositing a 2nm layer of compound (LiQ), Mg and Ag were deposited at a volume ratio of 1:10 to a depth of 60nm to form the second electrode 16. Finally, under a low-humidity nitrogen atmosphere, an epoxy resin adhesive was used to bond the cap-shaped glass plate, thereby sealing it and fabricating four light-emitting devices (quadrilaterals with each side measuring 5mm) on a single substrate. It should be noted that the film thickness referred to here is the value displayed in a quartz oscillating film thickness monitor.

[0168] <Reliability Evaluation> The fabricated organic EL display device was stored at 100°C in an air atmosphere. Every 100 hours, the device was removed and driven to emit light using a DC current at 10 mA / cm², and the luminous area of ​​the luminous pixels was measured. With the initial luminous area before the reliability test set at 100, the shortest time it took for the luminous area to fall below 50 after the heating test was defined as the reliability (in hours) of the organic EL display device. Reliability was considered acceptable if it exceeded 500 hours. The longer the shortest time for the luminous area to fall below 50 after the heating test, the better the reliability, and therefore, the preferred device.

[0169] (4) Evaluation of chemical resistance Using an ACT-8 coating and developing apparatus (manufactured by Tokyo Electron Co., Ltd.), the photosensitive resin compositions obtained in the examples and comparative examples described below were coated onto an 8-inch silicon wafer using a spin coating method. The wafer was then baked at 120°C for 3 minutes using a hot plate to produce a pre-baked film with a thickness of 3.0 μm. Next, using the aforementioned ACT-8 developing apparatus, a 2.38% by mass tetramethylammonium aqueous solution (hereinafter TMAH, manufactured by Tama Chemical Co., Ltd.) was developed for a time with a film loss of 0.5 μm. After rinsing with distilled water, the film was spin-dried. Finally, the film was cured in an inert oven (CLH-21CD-S manufactured by Koyo Thermo Systems Co., Ltd.) at 250°C under a nitrogen atmosphere for 60 minutes to obtain the cured product. The cured material was immersed in an organic solvent (dimethyl sulfoxide: N-methyl-2-pyrrolidone (NMP): ethanolamine = 70:20:10) at 70°C for 1 minute, and the presence or absence of peeling and dissolution was observed. A film thickness change of less than 0.05 μm before and after immersion was considered extremely good and rated "A"; a film thickness change of 0.05 μm or more but less than 0.15 μm was considered good and rated "B"; and a film thickness change of 0.15 μm or more, or the observation of peeling, dissolution, or cracks, was considered poor and rated "C".

[0170] (5) Evaluation of the tightness of the development Using an ACT-8 coating and developing apparatus (manufactured by Tokyo Electron Co., Ltd.), the photosensitive resin compositions obtained in the examples and comparative examples described below were coated onto an 8-inch silicon wafer by spin coating. The wafer was then baked at 120°C for 3 minutes using a hot plate to produce a pre-baked film with a thickness of 3.0 μm. It should be noted that the film thickness was measured using a Lambda Ace STM-602 manufactured by Dainippon ScreenMfg. Co., Ltd. at a refractive index of 1.63. Then, an exposure machine, an i-line stepper NSR-2005i9C (manufactured by Nikon Corporation), was used to expose the wafer through a mask with a pattern of numerous closed portions with diameters of 3 to 100 μm, at the exposure amount with the exposure sensitivity obtained in (1). After exposure, the aforementioned ACT-8 developing apparatus was used, and a 2.38% by mass tetramethylammonium aqueous solution (hereinafter TMAH, manufactured by Tama Chemical Industry Co., Ltd.) was used for development at a time when the film loss during development was 0.5 μm. After rinsing with distilled water, the mixture was spin-dried to obtain the pattern.

[0171] The pattern of the developed film was observed using an FDP microscope MX61 (manufactured by Olympus Corporation) at 20x magnification. 100 areas were observed per unit size. The smallest diameter (μm) of the closed-end patterns that remained intact after 90 or more patterns was confirmed. Patterns smaller than 10 μm that remained intact were considered acceptable. The smaller the smallest closed-end pattern remaining after 90 or more patterns, the better the development adhesion, and therefore the preferred option.

[0172] (6) Evaluation of preservation stability For the photosensitive resin compositions obtained through the examples and comparative examples described below, the exposure sensitivity was determined using the method described in (1). The aforementioned photosensitive resin compositions were stored at 23°C, and the number of days in which the exposure sensitivity changed by more than 15% from day 0 was investigated. If the number of days with the change was 30 days or more, it was considered extremely good and rated as "A"; if it was 15 days or more but less than 30 days, it was considered good and rated as "B"; and if it was less than 15 days, it was considered poor and rated as "C".

[0173] Compositional Analysis Based on Reactive Thermolysis GC / MS Add 3 μL of the reaction reagent (tetramethylammonium hydroxide) to 61 μg of the cured product obtained in (4), and then perform thermal pyrolysis using a Multi Shot Pyrolyzer PY-3030D (Frontier Labs) at a heating temperature of 400 °C. The gas chromatograph-mass spectrometer was JMS-Q1000GC (K9) (JEOL Ltd.). The GC column was a stainless steel capillary column (0.25 mm inner diameter × 30 m, stationary phase: 5% phenyl polydimethylsiloxane). The GC temperature was increased from 40 °C (held for 3 minutes) to 320 °C at a rate of 20 °C / min. The injection port temperature was 300 °C. The column flow rate was 1.5 mL / min. The ionization method was EI (electron ionization). The mass number range was set to m / z 20~800. The scan rate was set to 0.5 sec / scan. The analysis was performed.

[0174] The following examples and comparative examples show the compounds used.

[0175] Synthesis Example 1: Synthesis of diamine compounds containing hydroxyl groups 18.3 g (0.05 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter referred to as BAHF) was dissolved in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide, and the solution was cooled to -15 °C. A solution obtained by dissolving 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride in 100 mL of acetone was added dropwise. After the addition was complete, the reaction was carried out at -15 °C for 4 hours, and then allowed to return to room temperature. The precipitated white solid was separated by filtration and dried under vacuum at 50 °C.

[0176] 30g of vacuum-dried solid was placed in a 300mL stainless steel autoclave and dispersed in 250mL of methyl cellosolve. 2g of 5% palladium-carbon was added. 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 considered complete when the balloon was confirmed to be deflating. After the reaction, the palladium compound acting as a catalyst was removed by filtration, and the product was concentrated using a rotary evaporator to obtain a diamine compound containing a hydroxyl group, as shown in the following formula.

[0177] [Chemical Formula 10] Synthesis Example 2: Synthesis of Polyimide Precursor (P1) Under a dry nitrogen stream, 62.0 g (0.20 mol) of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (hereinafter referred to as ODPA) was dissolved in 500 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP). 96.7 g (0.16 mol) of the hydroxyl-containing diamine compound obtained in Synthesis Example 1 was added together with 100 g of NMP, and the reaction was carried out at 20°C for 1 hour, followed by a reaction at 50°C for 2 hours. Next, 8.7 g (0.08 mol) of 3-aminophenol as a capping agent was added together with 50 g of NMP, and the reaction was carried out at 50°C for 2 hours. Then, a solution obtained by diluting 47.7 g (0.40 mol) of N,N-dimethylformamide dimethyl acetal with 100 g of NMP was added dropwise over 10 minutes. After the addition, the mixture was stirred at 50°C for 3 hours. After stirring, the solution was cooled to room temperature and then added to 5 L of water, resulting in a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80 °C for 24 hours to obtain the target polyimide precursor (P1). P1 is formed from a copolymer of the structural units of the polyimide precursor and the structural units of the polybenzoxazole precursor, and is therefore defined as component (A).

[0178] Synthesis Example 3: Synthesis of polybenzoxazole precursor (P2) Under a dry nitrogen stream, 0.16 mol of a mixture of dicarboxylic acid derivatives obtained by reacting 41.3 g (0.16 mol) of diphenyl ether-4,4'-dicarboxylic acid with 43.2 g (0.32 mol) of 1-hydroxy-1,2,3-benzotriazole and 73.3 g (0.20 mol) of BAHF were dissolved in 570 g of NMP, and the reaction was carried out at 75 °C for 12 hours. Next, 13.1 g (0.08 mol) of 5-norbornene-2,3-dicarboxylic anhydride dissolved in 70 g of NMP was added, and the reaction was stirred for another 12 hours until the reaction was complete. After filtering the reaction mixture, the mixture was added to a solution of water / methanol = 3 / 1 (volume ratio), resulting in a white precipitate. The precipitate was collected by filtration, washed three times with water, and dried in a vacuum dryer at 80 °C for 24 hours to obtain the target polybenzoxazole (PBO) precursor (P2).

[0179] Synthesis Example 4: Synthesis of polybenzoxazole precursor (P3) Under a dry nitrogen stream, 73.3 g (0.20 mol) of BAHF was dissolved in 300 g of NMP, and the solution was cooled to -15 °C. A solution obtained by dissolving 47.2 g (0.16 mol) of diphenyl ether dicarboxylic acid diacyl chloride in 100 g of γ-butyrolactone was added dropwise, keeping the internal temperature below 0 °C. After the addition was complete, the mixture was stirred continuously at -15 °C for 30 minutes. Next, a solution obtained by dissolving 8.36 g (0.08 mol) of methacryloyl chloride in 100 g of γ-butyrolactone was added dropwise, keeping the internal temperature below 0 °C. After the addition was complete, the mixture was stirred continuously at -15 °C for 60 minutes, and then stirred at room temperature for 120 minutes. After the reaction was complete, the solution was added to 5 L of pure water, and a white precipitate was collected. The precipitate was collected by filtration, washed three times with pure water, and then dried using a vacuum dryer at 80 °C for 24 hours to obtain the target polybenzoxazole (PBO) precursor (P3).

[0180] Synthesis Example 5: Synthesis of polybenzoxazole precursor (P4) Under a dry nitrogen stream, 69.6 g (0.19 mol) of BAHF and 10.4 g (0.095 mol) of 2-aminophenol were dissolved in 500 g of NMP, and the solution was cooled to -15°C. A solution obtained by dissolving 70.1 g (0.24 mol) of diphenyl ether dicarboxylic acid diacyl chloride in 100 g of γ-butyrolactone was added dropwise, keeping the internal temperature below 0°C. After the addition was complete, the mixture was stirred continuously at -15°C for 60 minutes, and then stirred at room temperature for 120 minutes. After the reaction was complete, the solution was added to 5 L of pure water, and a white precipitate was collected. The precipitate was collected by filtration, washed three times with pure water, and then dried using a vacuum dryer at 80°C for 24 hours to obtain the target polybenzoxazole (PBO) precursor (P4).

[0181] Synthesis Example 6: Synthesis of Polyhydroxystyrene (P5) To a mixture obtained by adding 2.56 g (0.04 mol) of sec-butyllithium as an initiator to 2400 g of tetrahydrofuran, 105.75 g (0.6 mol) of p-tert-butoxystyrene was added. Polymerization was carried out while stirring for 3 hours, followed by the addition of 12.82 g (0.4 mol) of methanol to stop the polymerization. Next, to purify the polymer, the reaction mixture was injected into 3 L of methanol to dry the precipitated polymer. The resulting polymer was dissolved in 1.6 L of acetone, and 2 g of concentrated hydrochloric acid was added at 60 °C. The mixture was stirred for 7 hours to deprotect the p-tert-butoxystyrene, converting it to hydroxystyrene. After the reaction was complete, the solution was injected into water to precipitate the polymer. The precipitate was washed three times with water and then dried using a vacuum dryer at 50 °C for 24 hours to obtain the target polyhydroxystyrene (P5).

[0182] Synthesis Example 7: Synthesis of Acrylic Resin (P6) A methyl methacrylate / methacrylic acid / styrene copolymer (mass ratio 30 / 40 / 30) was synthesized using a known method (Japanese Patent No. 3120476; Example 1). 40 parts by mass of glycidyl methacrylate were added to 100 parts by mass of the copolymer, and the mixture was reprecipitated using purified water, filtered, and dried to obtain an acrylic resin (P6) that is a polymer containing free radical polymerizable monomers.

[0183] Synthesis Example 8: Synthesis of Quinone Diazide Compounds Under a dry nitrogen stream, 21.22 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 36.27 g (0.135 mol) of diazidonaphthoquinone-5-sulfonyl chloride were dissolved in 450 g of 1,4-dioxane, and the solution was brought to room temperature. 15.18 g of triethylamine, mixed with 50 g of 1,4-dioxane, was added dropwise without raising the temperature above 35°C. After addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered, and the filtrate was added to water. The precipitate was then collected by filtration. The precipitate was dried using a vacuum dryer to obtain quinone diazide compound 1 represented by the following formula.

[0184] [Chemical Formula 11] Synthesis Example 9: Synthesis of polybenzoxazole precursor (P7) Instead of BAHF, 51.7 g (0.20 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)propane (hereinafter referred to as BAP) was used, and instead of methacryloyl chloride, 8.36 g (0.08 mol) of crotonyl chloride was used. Otherwise, the same procedure as in Synthesis Example 4 was followed to obtain the target polybenzoxazole (PBO) precursor (P7).

[0185] Synthesis Example 10: Synthesis of polyimide precursor (P8) Instead of the hydroxyl-containing diamine compound obtained in Synthesis Example 1, 41.36 g (0.16 mol) of BAP was used, and the same procedure as in Synthesis Example 2 was followed to obtain the target polyimide precursor (P8).

[0186] <Thermocrosslinking agents with epoxy groups> TEPIC-VL: "TEPIC" (registered trademark) -VL (an epoxy thermal crosslinking agent containing an isocyanuric acid ring structure, a compound shown in the following chemical formula, manufactured by Nissan Chemical Industries, Ltd.) [Chemical Formula 12] <Heat-generating acid agents> BTS: Butyl p-toluenesulfonate (a thermal acid-producing agent with a sulfonate structure but not satisfying formula (3), manufactured by FUJIFILMWako Pure Chemical Corporation) E1: 1,3-Propanediol di-p-toluenesulfonate (a thermal acid-producing agent with a sulfonate structure and satisfying formula (3), manufactured by FUJIFILM Wako Pure Chemical Corporation) E2: 1,4-Butanediol dimethanesulfonate (a thermal acid-producing agent with a sulfonate structure and satisfying formula (3), manufactured by Tokyo Chemical Industry Co., Ltd.) [Chemical Formula 13] Solvent PGME: Propylene Glycol Monomethyl Ether GBL: γ-Butyrolactone Example 1 Under a yellow light, 100g of (P1) obtained in Synthesis Example 2 as component (A), 200g of (P3) obtained in Synthesis Example 4 as component (B), 40g of (P5) obtained in Synthesis Example 6 as component (C), 20g of quinone diazide compound 1 obtained in Synthesis Example 8 as component (D), and 5g of 1,3-propanediol di-p-toluenesulfonate (E1) as a thermal acid-producing agent (E) were weighed and dissolved in a 1:1 solution of PGME and GBL to achieve a solid component concentration of 10%. The resulting solution was then filtered using a filter with a pore size of 1 μm to obtain photosensitive resin composition A. The evaluations described in (1) to (6) above were performed using the obtained photosensitive resin composition.

[0187] Examples 2-21, Comparative Examples 1-7 Using the same method as in Example 1, and with the types and amounts of compounds as described in Tables 1 and 2, photosensitive resin compositions B to U and a to g were obtained. The evaluations described in (1) to (6) above were performed using the obtained photosensitive resin compositions.

[0188] The composition and evaluation results of the embodiments and comparative examples are shown in Tables 1 and 2.

[0189] [Table 1-1] [Table 1-2] [Table 2] Examples 1-21 all achieved good results in all aspects of sensitivity, flexural strength, reliability of the organic EL display device, chemical resistance, development adhesion, and storage stability. In contrast, Comparative Examples 1 and 4, which did not use component (B), showed poor flexural strength and reliability of the organic EL display device. Comparative Examples 2 and 7, which used a high amount of component (C), showed poor development adhesion. Comparative Example 3, which used a high amount of component (B), showed poor sensitivity and chemical resistance. Comparative Example 6, which used a low amount of component (B), showed poor flexural strength and reliability of the organic EL display device. Comparative Example 5, which did not use component (C), showed poor sensitivity.

[0190] Example 22 The pyrolysis product of the cured photosensitive resin composition A of Example 1 was analyzed using the method described in the aforementioned <Compositional Analysis Based on Reactive Pyrolysis GC / MS>. The results of the analysis are shown below, with peaks belonging to the structure shown in formula (4) (1015~1025 sec), peaks belonging to the structure shown in formula (5) (1335~1345 sec), and peaks belonging to the structure shown in formula (6) (1860~1870 sec).

[0191] [Chemical Formula 14] These results confirm that, for the cured product of photosensitive resin composition A, compounds represented by formula (4), formula (5) and formula (6) were detected in the cured product. In terms of the ratio of their detected peak intensities, if the compound represented by formula (5) is set to 1, then the compound represented by formula (4) is 0.3 and the compound represented by formula (6) is 1.5.

[0192] Explanation of reference numerals in the attached figures 1: Substrate 2: TFT 3: TFT insulating layer 4: Wiring 5: Planarization layer 6: Contact hole 7: First electrode 8: Pixel segmentation layer 9: Organic EL layer 10: Second electrode 11: Glass substrate 12: First electrode 13: Auxiliary electrode 14: Pixel Segmentation Layer 15: Organic EL layer 16: Second electrode

Claims

1. A photosensitive resin composition comprising: (A) Selected from one or more of the group consisting of polyimides, polyimide precursors and copolymers thereof. (B) Select one or more from the group consisting of polybenzoxazole, polybenzoxazole precursors and their copolymers. (C) Polyhydroxystyrene, and / or copolymers of polyhydroxystyrene and polystyrene, and (D) Quinone diazide compounds; Relative to 100 parts by mass of component (A), component (B) is greater than 100 parts by mass and less than 2000 parts by mass. The amount of component (C) is 5 or more but less than 500 parts by mass relative to 100 parts by mass of component (A).

2. The photosensitive resin composition of claim 1, further comprising (E) a thermally generated acid agent.

3. The photosensitive resin composition according to claim 2, wherein, The (E) thermal acid-producing agent contains the compound shown in formula (3). [Chemical Formula 1] In equation (3), R 3 It is a divalent to tetravalent group with 1 to 10 carbon atoms; R 4 Each of the following can independently represent an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms that may have substituents; the substituent is one or more groups selected from the group consisting of hydroxyl, halogen atom, cyano, vinyl, ethynyl or a straight-chain or cyclic alkyl group having 1 to 10 carbon atoms; b represents an integer from 2 to 4.

4. The photosensitive resin composition of claim 1, wherein, When the content of component (A) is set to [PI] (mass), the content of component (B) is set to [PB] (mass), and the content of component (C) is set to [PH] (mass), The quality ratio [PB] / ([PI]+[PH]) is in the range of 0.5≤[PB] / ([PI]+[PH])≤10.

0.

5. The photosensitive resin composition of claim 4, wherein, The mass ratio of [PI] and [PH] is in the range of 0.1 ≤ [PI] / [PH] ≤ 6.

6. The photosensitive resin composition of claim 5, wherein, The mass ratio of [PI] and [PH] is in the range of 1 < [PI] / [PH] ≤ 6.

7. The photosensitive resin composition of claim 1, wherein, At least a portion of component (B) has the structure shown in formula (9). [Chemical Formula 2] In equation (9), R 24 R 25 R 26 Each can independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms; This indicates the bonding site with the nitrogen atom.

8. The photosensitive resin composition of claim 7, wherein, At least a portion of component (B) has the structure shown in formula (1). [Chemical Formula 3] In equation (1), R 1 Indicates a hydrogen atom or a methyl group; This indicates the bonding site with the nitrogen atom.

9. The photosensitive resin composition of claim 1, wherein, At least a portion of component (B) has the structure shown in formula (2). [Chemical Formula 4] In equation (2), R 2 represents a methyl, methoxy, or fluorine atom, and 'a' represents 0 or 1; This indicates the bonding site with the nitrogen atom.

10. The photosensitive resin composition of claim 1, wherein, The component (C) contains polyhydroxystyrene.

11. The photosensitive resin composition of claim 1, further comprising (F) one or more compounds selected from the group (F-1), in, The photosensitive resin composition contains 0.001 to 2.00 parts by weight of component (F) relative to 100 parts by weight. Group (F-1): 1,3-dimethyl-2-imidazoline, N,N'-dimethylpropylene urea, 3-methoxy-N,N-dimethylpropionamide, 3-n-butoxy-N,N-dimethylpropionamide, N,N-dimethylisobutylamide, and tetramethylurea.

12. A cured product obtained by curing the photosensitive resin composition of claim 1.

13. The cured product as claimed in claim 12, wherein, When analyzed using reactive thermal pyrolysis GC / MS, compounds represented by formula (4), (5), and (6) were detected. In terms of their peak intensity ratios, if the compound represented by formula (5) is set to 1, then the compound represented by formula (4) has an intensity of 0.1 or higher and 1 or lower, and the compound represented by formula (6) has an intensity of 0.1 or higher and 3 or lower. [Chemical Formula 5] In equations (4), (5), and (6), R 5 ~R 11 Each of these groups independently represents a hydrogen atom or a monovalent organic group containing 1 to 30 carbon atoms, which may include heteroatoms.

14. An organic EL display device comprising the cured material as described in claim 12 or 13.

15. A method for manufacturing a cured material, comprising the following steps in sequence: (1) The step of coating the photosensitive resin composition according to any one of claims 1 to 11 onto a substrate to form a photosensitive resin film, (2) The step of drying the photosensitive resin film, (3) The process of exposing the dried photosensitive resin film through a light mask. (4) The process of developing the exposed photosensitive resin film, and (5) The process of heat-treating the developed photosensitive resin film.

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