Photosensitive resin composition, cured product, and display device

Abstract

A photosensitive resin composition according to the present invention realizes a low-outgassing cured product having high bending resistance and provides a display device which has good bending resistance and good long-term reliability. The photosensitive resin composition contains (A) an alkali-soluble resin, (B) a quinone diazide compound, (C) a crosslinking agent, (D) a thermal acid generator, and (E) a compound represented by formula (1). (In formula (1), T represents a group having a divalent to tetravalent C7-20 alicyclic structure. Each R1 independently represents a monovalent C1-10 group. Each of a and b independently represents an integer of 1-3, and each of c and d independently represents an integer of 0-2. 1 ≤ (a + c) ≤ 4 and 1 ≤ (b + d) ≤ 4.)

Description

Photosensitive resin composition, cured product, display device

[0001] The present invention relates to a photosensitive resin composition, a cured product using the same, and a display device equipped with the cured product.

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

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

[0004] On the other hand, it has been reported that adding a thermal acid generator to a photosensitive resin composition can promote the crosslinking reaction of the crosslinking agent during curing, thereby improving the mechanical properties of the cured product (see, for example, Patent Document 2).

[0005] JP 2002-91343 A JP 2013-190699 A

[0006] In recent years, there has been active development of flexible organic EL display devices formed on a resin film substrate. Flexible organic EL display devices have structurally bendable portions and / or portions that are fixed in a bent state, and bending stress is applied to the planarizing layer and pixel division layer at these bent portions. Flexible organic EL display devices that include such bent portions are required to have high mechanical properties and bending resistance, as cracks may occur in the planarizing layer and pixel division layer due to bending operations. To address this issue, Patent Document 2 investigates the addition of a thermal acid generator to promote the crosslinking reaction of the crosslinking agent, thereby improving the mechanical properties of the cured product.

[0007] Meanwhile, demands for higher reliability for organic EL display devices are becoming more stringent every year, and materials for planarization layers and pixel division layers are also required to have long-term reliability that prevents a decrease in luminance or pixel shrinkage even after reliability tests under accelerated conditions such as high temperature, high humidity, and light exposure. Here, pixel shrinkage refers to a phenomenon in which luminance decreases or pixels stop lighting from the edge of a pixel. Factors that reduce reliability include gas components generated from the materials and the release of moisture contained in the materials, and the eluted components corrode wiring and pixels, causing a decrease in reliability.

[0008] Our research has revealed that although the mechanical properties of the cured product of a photosensitive resin composition using the aforementioned thermal acid generator are significantly improved, the strong acid component generated by the thermal acid generator during the curing process damages the structure of the composition, significantly deteriorating the heat resistance of the cured product. This deterioration in heat resistance leads to increased outgassing under accelerated conditions such as high temperature, high humidity, and light exposure, which has an adverse effect on long-term reliability after reliability testing.

[0009] In view of the above problems, an object of the present invention is to provide a cured product that has high bending resistance and low outgassing, and to provide an organic EL display device that has good bending resistance and long-term reliability.

[0010] In order to solve the above problems, the present invention has the following configuration: [1] A photosensitive resin composition comprising (A) an alkali-soluble resin, (B) a quinone diazide compound, (C) a crosslinking agent, (D) a thermal acid generator, and (E) a compound represented by formula (1).

[0011]

[0012] (In formula (1), T represents a divalent to tetravalent group containing an alicyclic structure having 7 to 20 carbon atoms. R １each independently represent a monovalent group having 1 to 10 carbon atoms. a and b each independently represent an integer of 1 to 3, and c and d each independently represent an integer of 0 to 2. 1≦(a+c)≦4, and 1≦(b+d)≦4. [2] The photosensitive resin composition according to [1], wherein T in the compound represented by formula (1) (E) contains a polycyclic alicyclic structure. [3] The photosensitive resin composition according to [1] or [2], wherein T in the compound represented by formula (1) (E) contains a structure represented by formula (2) or formula (3).

[0013]

[0014] (In formula (2), each e independently represents an integer of 0 to 5. In formula (3), R ２ each independently represents a hydrogen atom or a group having 1 to 10 carbon atoms. * represents a bonding position.) [4] The photosensitive resin composition according to any one of [1] to [3], wherein the mass ratio γ2 / γ1 is in the range of 0.50≦γ2 / γ1≦3.00 and the mass ratio γ3 / (γ1+γ2) is in the range of 0.05≦γ3 / (γ1+γ2)≦0.20, where γ1, γ2, and γ3 are the contents (mass) of the (C) crosslinking agent, (E) compound represented by formula (1), and (D) thermal acid generator, respectively. [5] The photosensitive resin composition according to any one of [1] to [4], wherein the (C) crosslinking agent comprises a compound having a methylol group and / or an alkoxymethyl group. [6] The photosensitive resin composition according to any one of [1] to [5], wherein the (D) thermal acid generator comprises a compound represented by formula (4).

[0015]

[0016] (In formula (4), R ３ is a monovalent to tetravalent group having 1 to 10 carbon atoms. ４each independently represents an alkyl group having 1 to 10 carbon atoms, which may have a substituent, or an aryl group having 6 to 20 carbon atoms, which may have a substituent. f represents an integer of 1 to 4. [7] The photosensitive resin composition according to any one of [1] to [6], wherein the alkali-soluble resin (A) comprises one or more selected from the group consisting of polyimide precursors, polyimides, polybenzoxazole precursors, polybenzoxazoles, and copolymers thereof. [8] The photosensitive resin composition according to [7], wherein the alkali-soluble resin (A) has a terminal structure represented by formula (5).

[0017]

[0018] (In formula (5), R ５ are each independently a hydrogen atom or a monovalent group having 1 to 10 carbon atoms. * indicates a bonding position.) [9] The photosensitive resin composition according to [7] or [8], wherein the alkali-soluble resin (A) has a structure represented by formula (6).

[0019]

[0020] (In formula (6), U is a divalent hydrocarbon group having 4 to 20 carbon atoms, R ６ are each independently a hydrocarbon group having 1 to 4 carbon atoms or a hydroxyl group, and each g is independently an integer of 0 to 4. * indicates a bonding position.

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

[11] A display device comprising the cured product according to

[10] .

[0021] The photosensitive resin composition of the present invention realizes a cured product that has high bending resistance and low outgassing, and can provide a display device that has good bending resistance and long-term reliability.

[0022] 1 is a cross-sectional view of a TFT substrate on which a planarization layer and a pixel division layer are formed.

[0023] The present invention will be described in detail below with reference to the preferred embodiments. However, the present invention should not be limited to the preferred embodiments described below.

[0024] The photosensitive resin composition of the present invention is a photosensitive resin composition comprising (A) an alkali-soluble resin, (B) a quinone diazide compound, (C) a crosslinking agent, (D) a thermal acid generator, and (E) a compound represented by formula (1).

[0025]

[0026] In formula (1), T represents a divalent to tetravalent group containing an alicyclic structure having 7 to 20 carbon atoms. １ each independently represents a monovalent group having 1 to 10 carbon atoms. a and b each independently represent an integer of 1 to 3, and c and d each independently represent an integer of 0 to 2. 1≦(a+c)≦4, and 1≦(b+d)≦4.

[0027] As a result of extensive research, the present inventors have discovered that, even when a thermal acid generator is used, the use of a compound represented by formula (E) (1) makes it possible to obtain a cured product that has high bending resistance and little outgassing. More specifically, it has been clarified that by combining a compound represented by formula (E) (1), which easily forms a crosslinked structure with a crosslinking agent and is not susceptible to damage by the strong acid component generated by the thermal acid generator during curing treatment, a photosensitive resin composition can be obtained that has high bending resistance and is highly reliable when used in an organic EL display device.

[0028] <Alkali-Soluble Resin> The photosensitive resin composition of the present invention contains (A) an alkali-soluble resin (hereinafter, sometimes referred to as component (A)). In the present invention, alkali-soluble refers to a dissolution rate of 50 nm / min or more, determined from the film thickness reduction when a solution of a resin dissolved in γ-butyrolactone is applied to a silicon wafer and dried at 120°C for 4 minutes (the process of drying a coated resin film by applying heat is sometimes referred to as prebaking) to form a dried photosensitive resin film having a film thickness of 10 μm±0.5 μm (the dried photosensitive resin film obtained by prebaking is sometimes referred to as a prebaked film), the prebaked film is immersed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide at 23±1°C for 1 minute, and then rinsed with pure water.

[0029] Examples of the alkali-soluble resin (A) include polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, and copolymers thereof, as well as polyamide, polymers obtained by polymerizing radically polymerizable monomers, phenolic resins, and siloxane resins, but are not particularly limited as long as they have the alkali-solubility described above. Two or more of these alkali-soluble resins may be used in combination. Among the alkali-soluble resins described above, those having excellent heat resistance, low outgassing at high temperatures, and excellent film properties such as elongation are preferred. Specifically, the alkali-soluble resin (A) preferably contains one or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, and copolymers thereof.

[0030] In the present invention, one or more alkali-soluble resins selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles, polybenzoxazole precursors, and copolymers thereof that can be used as the alkali-soluble resin (A) preferably have acidic groups in the structural units of the resin and / or at the ends of its main chain to impart the alkali-solubility. Examples of the acidic groups include carboxyl groups, phenolic hydroxyl groups, sulfonic acid groups, and thiol groups.

[0031] On the other hand, polymers having fluorine-containing residues, such as hexafluoroisopropylidene groups, may generate fluorine-containing hydrocarbons due to decomposition of the residues during the thermal curing process. These fluorine-containing hydrocarbon groups may adhere to patterned openings and contaminate the openings. If this phenomenon occurs in an organic EL display device, the fluorine-containing hydrocarbons adhering to the openings may cause deterioration in the contact resistance and reliability of the organic EL display device. Therefore, it is preferable that the alkali-soluble resin (A) does not contain any fluorine-containing residues.

[0032] The one or more alkali-soluble resins used in the photosensitive resin composition of the present invention, which are selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles, polybenzoxazole precursors, and copolymers thereof, can be synthesized by known methods.

[0033] In the case of polyimide precursors, polyamic acids can be synthesized by, for example, a method of reacting tetracarboxylic dianhydride with a diamine compound at low temperature, while polyamic acid esters can be synthesized by, for example, a method of reacting tetracarboxylic dianhydride with a diamine compound at low temperature and then partially esterifying the amide acid structure with N,N-dimethylformamide dimethyl acetal or the like, a method of obtaining a diester from tetracarboxylic dianhydride with an alcohol and then reacting it with an amine in the presence of a condensing agent, or a method of obtaining a diester from tetracarboxylic dianhydride with an alcohol and then converting the remaining dicarboxylic acid into an acid chloride and reacting it with an amine.

[0034] In the case of polyimide, for example, it can be obtained by heating the polyamic acid or polyamic acid ester obtained by the above-mentioned method in an organic solvent or by dehydrating and ring-closing the polyamic acid or polyamic acid ester by chemical treatment with an acid or a base.

[0035] The polybenzoxazole precursor can be produced by a condensation reaction of a bisaminophenol compound with a dicarboxylic acid. Specifically, there are a method of reacting a dehydration condensation agent such as dicyclohexylcarbodiimide (DCC) with an acid and then adding the bisaminophenol compound thereto, and a method of adding a dicarboxylic acid dichloride solution dropwise to a solution of a bisaminophenol compound to which a tertiary amine such as pyridine has been added.

[0036] Polybenzoxazole can be obtained, for example, by heating the polybenzoxazole precursor obtained by the above-mentioned method in an organic solvent or by dehydrating and ring-closing it by chemical treatment with an acid or a base.

[0037] Specific examples of tetracarboxylic dianhydrides used as raw materials for polyimides, polyimide precursors, and copolymers thereof include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3- Examples of the tetracarboxylic acid dianhydride include aromatic tetracarboxylic acid dianhydrides such as bis(3,4-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 2,3,5,6-pyridinetetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, and 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorene dianhydride; aliphatic tetracarboxylic acid dianhydrides such as butanetetracarboxylic acid dianhydride and 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride; and tetracarboxylic acid dianhydrides having the structure shown below. Two or more of these may be used.

[0038]

[0039] R ７ is an oxygen atom, SO ２ , S, cyclo ring, alkyl group, C(CF ３ ) ２ , or C(CH ３ ) ２ Represents R ８~R １１ each independently represents a hydrogen atom or a hydroxyl group.

[0040] Specific examples of diamine compounds used as raw materials for polyimides, polyimide precursors, and copolymers containing them include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl Examples of such compounds include fluorene, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-di(trifluoromethyl)-4,4'-diaminobiphenyl, 9,9-bis(4-aminophenyl)fluorene, and compounds in which at least a portion of the hydrogen atoms in these aromatic rings have been substituted with alkyl groups or halogen atoms, as well as aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, and diamine compounds having the structure shown below. Two or more of these compounds may be used.

[0041]

[0042] R １２ , R １５ , R １８ , is an oxygen atom, SO ２ , S, cyclo ring, alkyl group, C(CF ３ ) ２ , or C(CH ３ ) ２ Represents R １３ , R １４ , R １６ , R １７ , R １９ , R ２０ , R２１ ~R ２６ each independently represents a hydrogen atom or a hydroxyl group.

[0043] Examples of the acid component used in polybenzoxazole, polybenzoxazole precursor, and copolymers thereof include dicarboxylic acids, tricarboxylic acids, and tetracarboxylic acids. Examples of dicarboxylic acids include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, and triphenyl dicarboxylic acid. Examples of tricarboxylic acids include trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, and biphenyl tricarboxylic acid. Examples of tetracarboxylic acids include pyromellitic acid, 3,3',4,4'-biphenyl tetracarboxylic acid, 2,3,3',4'-biphenyl tetracarboxylic acid, 2,2',3,3'-biphenyl tetracarboxylic acid, 3,3',4,4'-benzophenone tetracarboxylic acid, 2,2',3,3'-benzophenone tetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)propane, 2,2-bis(2,3-dicarboxyphenyl)propane, and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane. Examples of the tetracarboxylic acid include aromatic tetracarboxylic acids such as fluoropropane, 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-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 9,9-bis(3,4-dicarboxyphenyl)fluorene, and 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorene; and aliphatic tetracarboxylic acids such as butanetetracarboxylic acid and 1,2,3,4-cyclopentanetetracarboxylic acid. Two or more of these may be used.

[0044] Specific examples of bisaminophenol compounds used in polybenzoxazole, polybenzoxazole precursors, and copolymers thereof 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, 1,1,1-trifluoro-2,2-bis(3-amino-4-hydroxyphenyl)ethane (BIS-AP-EF), etc. Two or more of these may be used.

[0045] When polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, or a copolymer thereof is used, it is preferable that the alkali-soluble resin (A) has a structure represented by formula (6). Having the structure of formula (6) improves the fluidity of the resin during curing (heat treatment), facilitates the crosslinking reaction between the crosslinking agent (C) (hereinafter sometimes referred to as component (C)) and the compound represented by formula (1) (E) (hereinafter sometimes referred to as component (E)), facilitates the formation of a crosslinked structure with high acid resistance formed by the component (C) and the component (E) described below, and facilitates the achievement of the effects of the present invention.

[0046]

[0047] In formula (6), U is a divalent hydrocarbon group having 4 to 20 carbon atoms, R ６ each independently represents a hydrocarbon group having 1 to 4 carbon atoms or a hydroxyl group, and each g independently represents an integer of 0 to 4. * indicates a bonding position.

[0048] In the formula (6), preferred specific examples of the structure of U include, but are not limited to, structures represented by the following formulas:

[0049]

[0050] * indicates the bond position.

[0051] Furthermore, in order to improve the storage stability of the photosensitive resin composition, it is preferable to cap the main chain ends of one or more alkali-soluble resins selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles, polybenzoxazole precursors, and copolymers thereof with an end-capping agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, a monoactive ester compound, etc. For the purpose of improving the chemical resistance of a cured product obtained by heating the photosensitive resin composition, a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound having at least one alkenyl or alkynyl group can also be used as the end-capping agent.

[0052] From the viewpoint of improving storage stability, the content of the terminal blocking agent such as monoamine, acid anhydride, acid chloride, or monocarboxylic acid is preferably 1 mol% or more, more preferably 5 mol% or more, relative to 100 mol% of the total of all monomer components constituting the resin. Furthermore, from the viewpoint of obtaining a resin with good film properties, the content is preferably 60 mol% or less, more preferably 40 mol% or less, relative to 100 mol% of the total of all monomer components constituting the resin. Multiple different terminal groups may be introduced by reacting multiple terminal blocking agents.

[0053] When a polyimide, a polyimide precursor, a polybenzoxazole, a polybenzoxazole precursor, or a copolymer thereof is used, the alkali-soluble resin (A) preferably has a terminal structure represented by formula (5). By having the terminal structure of formula (5), part of the resin terminal is incorporated into part of the highly acid-resistant crosslinked structure formed by components (C) and (E), which will be described later, and the effects of the present invention can be more easily achieved.

[0054]

[0055] In formula (5), R ５ are each independently a hydrogen atom or a monovalent group having 1 to 10 carbon atoms. * indicates the bonding position.

[0056] Preferred specific examples of the formula (5) include, but are not limited to, structures represented by the following formulas:

[0057]

[0058] * indicates the bond position.

[0059] Examples of polyamides include polycondensates of dibasic acid and diamine, ring-opening polymerization products of cyclic lactam, polycondensates of aminocarboxylic acid, and copolymers and blends thereof.More specifically, aliphatic polyamides such as polyamide 6, polyamide 10, polyamide 11, polyamide 12, polyamide 46, polyamide 66, polyamide 610, and polyamide 612, aromatic polyamides such as polymetaxylene adipamide (polyamide MXD6), polyhexamethylene terephthalamide (polyamide 6T), and polyhexamethylene isophthalamide (polyamide 6I), and copolymers and blends such as polyamide 6 / 6I, polyamide 66 / 6I, polyamide 6 / 6T, polyamide 66 / 6T, polyamide 6 / 66 / 6T, polyamide 6 / 66 / 6I, polyamide 9T, and polyamide 10T can be used.

[0060] The polymer obtained by polymerizing a radically polymerizable monomer is preferably a polymer obtained by radically polymerizing (meth)acrylic acid or a (meth)acrylic acid ester. Examples of the (meth)acrylic acid ester include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, cyclopropyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, cyclohexenyl (meth)acrylate, 4-methoxycyclohexyl (meth)acrylate, 2-cyclopropyloxycarbonylethyl (meth)acrylate, 2-cyclopentyloxycarbonylethyl (meth)acrylate, and 2-cyclohexyloxycarbonyl (meth)acrylate. Known (meth)acrylates such as ethyl (meth)acrylate, 2-cyclohexenyloxycarbonylethyl (meth)acrylate, 2-(4-methoxycyclohexyl)oxycarbonylethyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, tetracyclodecanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, adamantyl (meth)acrylate, adamantylmethyl (meth)acrylate, and 1-methyladamantyl (meth)acrylate can be used. Here, "(meth)acrylic acid" collectively refers to methacrylic acid and acrylic acid, and the same applies to the compounds described herein, including the above series of compounds. Aromatic vinyl compounds such as styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, and α-methylstyrene may also be copolymerized with the above-mentioned (meth)acrylic acid or (meth)acrylic acid esters. Furthermore, an ethylenically unsaturated double bond group can be introduced by addition reaction of an epoxy compound having an ethylenically unsaturated double bond group with (meth)acrylic acid.

[0061] Phenolic resins include novolak phenolic resins and resol phenolic resins, which can be obtained by polycondensing various phenols alone or a mixture of multiple phenols with aldehydes such as formalin.

[0062] Examples of phenols constituting novolak phenolic resins and resol phenolic resins include phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2,4,5-trimethylphenol, methylenebisphenol, and methylenebisp-cresol. phenol, resorcinol, catechol, 2-methylresorcinol, 4-methylresorcinol, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichlorophenol, m-methoxyphenol, p-methoxyphenol, p-butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3-diethylphenol, 2,5-diethylphenol, p-isopropylphenol, α-naphthol, β-naphthol, and the like, which can be used alone or as a mixture of two or more thereof.

[0063] In addition, examples of aldehydes include formaldehyde (used in the form of formalin), paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, and chloroacetaldehyde, and these can be used alone or in combination.

[0064] Examples of siloxane resins (hereinafter sometimes referred to as polysiloxanes) include siloxane resins obtained by hydrolyzing one or more selected from tetrafunctional organosilanes, trifunctional organosilanes, difunctional organosilanes, and monofunctional organosilanes (these may be referred to as siloxane resin monomers) and partially condensing them by a dehydration reaction. Partial condensation by a dehydration reaction may also be simply referred to as partial condensation.

[0065] Specific examples of organosilanes include tetrafunctional organosilanes such as tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, and tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, and 1-(p-hydroxyphenyl)trimethoxysilane. (p-hydroxyphenyl)ethyltrimethoxysilane, 2-(p-hydroxyphenyl)ethyltrimethoxysilane, 4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyltrimethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,trifunctional organosilanes such as (4-epoxycyclohexyl)ethyltriethoxysilane, (3-ethyl-3-oxetanyl)methoxy]propyltrimethoxysilane, (3-ethyl-3-oxetanyl)methoxy]propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic acid, 1-naphthyltrimethoxysilane, 1-naphthyltriethoxysilane, 1-naphthyltri-n-propoxysilane, and 2-naphthyltrimethoxysilane; dimethyldimethoxysilane; dimethyldiethoxysilane; Examples of suitable organosilanes include bifunctional organosilanes such as silane, dimethyldiacetoxysilane, di-n-butyldimethoxysilane, diphenyldimethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, di(1-naphthyl)dimethoxysilane, and di(1-naphthyl)diethoxysilane; and monofunctional organosilanes such as trimethylmethoxysilane, tri-n-butylethoxysilane, (3-glycidoxypropyl)dimethylmethoxysilane, and (3-glycidoxypropyl)dimethylethoxysilane. Two or more of these organosilanes may be used. Furthermore, silicate compounds such as Methyl Silicate 51 manufactured by Fuso Chemical Co., Ltd. and M Silicate 51 manufactured by Tama Chemical Co., Ltd. may also be copolymerized.

[0066] Siloxane resins are synthesized by hydrolysis and partial condensation of siloxane resin monomers such as organosilanes. Here, partial condensation refers to leaving some Si-OH groups in the resulting polysiloxane, rather than condensing all of the Si-OH groups in the hydrolyzate. Conventional methods can be used for hydrolysis and partial condensation. For example, an organic solvent, water, and optionally a catalyst are added to an organosilane mixture, followed by heating and stirring at 50 to 150°C for approximately 0.5 to 100 hours. During stirring, hydrolysis by-products (alcohols such as methanol) and condensation by-products (water) may be removed by distillation, if necessary.

[0067] The catalyst used for hydrolysis and partial condensation of siloxane resin monomers such as organosilanes is not particularly limited, but acid catalysts and base catalysts are preferably used.Specific examples of acid catalysts include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acids or their anhydrides, and acidic cation exchange resins.Specific examples of base catalysts include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, sodium hydroxide, potassium hydroxide, alkoxysilanes having amino groups, and basic anion exchange resins.

[0068] <Quinone diazide compound> The photosensitive resin composition of the present invention contains (B) a quinone diazide compound (hereinafter, sometimes referred to as component (B)). By containing the quinone diazide compound (B), an acid is generated in the light-irradiated areas, which increases the solubility of the light-irradiated areas in an alkaline aqueous solution, thereby forming a positive relief pattern in which the light-irradiated areas are dissolved.

[0069] Examples of quinone diazide compounds include those in which the sulfonic acid of quinone diazide is bonded to a polyhydroxy compound via an ester bond, those in which the sulfonic acid of quinone diazide is bonded to a polyamino compound via a sulfonamide bond, and those in which the sulfonic acid of quinone diazide is bonded to a polyhydroxy polyamino compound via an ester bond and / or a sulfonamide bond. It is preferred that 50 mol % or more of the functional groups of these polyhydroxy compounds or polyamino compounds are substituted with quinone diazide. The photosensitive resin composition may also contain two or more quinone diazide compounds (B).

[0070] Among the quinone diazide compounds (B), naphthoquinone diazide sulfonic acid ester compounds are preferably used, and can be synthesized by an esterification reaction between a compound having a phenolic hydroxyl group and a naphthoquinone diazide sulfonic acid compound, and can be synthesized by a known method. By using these naphthoquinone diazide sulfonic acid ester compounds, resolution, sensitivity, and film retention rate can be further improved.

[0071] The compounds having a phenolic hydroxyl group used herein include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, and BisP-MZ. Cilentris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-E P, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TM L-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (all product names, 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 (the above product names, Asahi Yukizai Kogyo) Examples of naphthoquinone diazide sulfonate ester compounds include those obtained by introducing naphthoquinone diazide-4-sulfonic acid or naphthoquinone diazide-5-sulfonic acid into the above compounds via an ester bond, although other compounds may also be used.

[0072] Naphthoquinone diazide sulfonic acid 4-ester compounds have absorption in the i-line region of a mercury lamp and are suitable for i-line exposure, while naphthoquinone diazide-5-sulfonic acid ester compounds have absorption extending to the g-line region of a mercury lamp and are suitable for g-line exposure. The photosensitive resin composition of the present invention may contain either a naphthoquinone diazide-4-sulfonic acid ester compound or a naphthoquinone diazide-5-sulfonic acid ester compound, may contain a naphthoquinone diazide sulfonic acid ester compound containing both a naphthoquinone diazide-4-sulfonyl group and a naphthoquinone diazide-5-sulfonyl group in the same molecule, or may contain a mixture of a naphthoquinone diazide-4-sulfonic acid ester compound and a naphthoquinone diazide-5-sulfonic acid ester compound.

[0073] The content of the (B) component relative to 100 parts by mass of the (A) alkali-soluble resin is preferably 3 parts by mass or more and 50 parts by mass or less. 3 parts by mass or more improves exposure sensitivity, and 50 parts by mass or less further improves visible light transmittance. The content of the (B) component is more preferably 5 parts by mass or more and 40 parts by mass or less, even more preferably 7 parts by mass or more and 40 parts by mass or less, and particularly preferably 10 parts by mass or more and 35 parts by mass or less.

[0074] <Crosslinking Agent> The photosensitive resin composition of the present invention contains a crosslinking agent (C). The crosslinking agent (C) used in the present invention is a component that crosslinks with the phenolic hydroxyl group in the compound represented by formula (E) (1) and can improve the chemical resistance and heat resistance of the cured product. In addition, as will be described in detail below, in the present invention, the highly acid-resistant crosslinked structure formed by components (C) and (E) makes it easier to achieve the effects of the present invention. Specific examples of component (C) include compounds having a methylol group, an alkoxymethyl group, an epoxy group, an oxetanyl group, a bismaleimide structure, an isocyanate structure, or an oxazine structure. Compounds having both the above groups or structures and a phenolic hydroxyl group are defined as crosslinking agents (C). Furthermore, the component (C) used in the present invention preferably has a low molecular weight, from the viewpoint of increasing conformational diversity during the curing process and facilitating the formation of a crosslinked structure with component (E). Specifically, the molecular weight is preferably 1,500 g / mol or less, more preferably 1,200 g / mol or less, even more preferably 1,000 g / mol or less, and particularly preferably 800 g / mol or less.

[0075] Examples of those having a methylol group and / or an alkoxymethyl group 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- Examples of such compounds include TPHAP, HMOM-TPPA (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A (all trade names, manufactured by Asahi Organic Chemicals Co., Ltd.), and "NIKALAC" (registered trademark) MX-290, MX-280, MX-270, MX-279, MW-100LM, MX-750LM (all trade names, manufactured by Sanwa Chemical Co., Ltd.), each of which is available from the respective companies.

[0076] Examples of epoxy group-containing resins include "Epikote" (registered trademark) 807, 828, 1002, 1750, 1007, YX8100-BH30, E1256, E4250, and E4275 (all trade names, manufactured by Japan Epoxy Co., Ltd.), "Epiclon" (registered trademark) EXA-4880, EXA-4822, EXA-9583, HP4032, and HP4770 (all trade names, manufactured by Dainippon Ink and Chemicals, Inc.), and "Epolite" (registered trademark) 40E, 100E, 200E, 400E, 70P, 200P, 400P, 1500NP, 80MF, and 4000 , 3002, 1708A, 1608F (all trade names, manufactured by Kyoeisha Chemical Co., Ltd.), "Denacol" (registered trademark) EX-212L, EX-214L, EX-216L, EX-252, EX-850L, EX-201-IM, EX-321L, EX-614B, EX-313, EX-512, EX-321L, EX-810, EX-861, EX-211 (all trade names, manufactured by Nagase ChemteX Corporation), GAN, GOT (all trade names, manufactured by Nippon Kayaku Co., Ltd.), "Celloxide" (registered trademark) 2021P (trade name, manufactured by Daicel Corporation), "Rika" (registered trademark) Resin" (registered trademark) DME-100, BEO-60E (all trade names, manufactured by New Japan Chemical Co., Ltd.), "TBIS" (registered trademark) -GG, -RXG, -BNEG (all trade names, manufactured by Taoka Chemical Co., Ltd.), VG3101L (trade name, manufactured by Printec Co., Ltd.), "TEPIC" (registered trademark) -S, -L, -VL, -FL, -UC (all trade names, manufactured by Nissan Chemical Industries, Ltd.), "Epiclon" N660, N695, HP7200 (all trade names, manufactured by Dainippon Ink and Chemicals, Inc.), NC6000, EPPN502H, NC3000 (all trade names, manufactured by Nippon Printec Co., Ltd.), Examples of such an acrylic acid ester include "Epotohto" (registered trademark) YH-434L (trade name, manufactured by Tohto Kasei Co., Ltd.), EHPE-3150 (trade name, manufactured by Daicel Corporation), MA-DGIC (trade name, manufactured by Shikoku Kasei Co., Ltd.), "Epocalic" (registered trademark) THI-DE, DE-102, DE-103 (all trade names, manufactured by ENEOS Corporation), "Shofree" (registered trademark) CDMDG (trade name, manufactured by Showa Denko K.K.), and "Epogose" (registered trademark) BD, NPG, HD (all trade names, manufactured by Yokkaichi Chemical Co., Ltd.), and each of these is available from the respective companies.

[0077] Examples of compounds having an oxetanyl group include OXT-121, OXT-221, OX-SQ-H, OXT-191, PNOX-1009, and RSOX (all trade names, manufactured by Toagosei Co., Ltd.), and "Ethanacol" (registered trademark) OXBP and OXTP (all trade names, manufactured by Ube Industries, Ltd.), each of which is available from the respective companies.

[0078] Examples of compounds having a bismaleimide structure include 1,2-bis(maleimide)ethane, 1,3-bis(maleimide)propane, 1,4-bis(maleimide)butane, 1,5-bis(maleimide)pentane, 1,6-bis(maleimide)hexane, 2,2,4-trimethyl-1,6-bis(maleimide)hexane, N,N'-1,3-phenylenebis(maleimide), 4-methyl-N,N'-1 , 3-phenylenebis(maleimide), N,N'-1,4-phenylenebis(maleimide), 3-methyl-N,N'-1,4-phenylenebis(maleimide), 4,4'-bis(maleimide)diphenylmethane, 3,3'-diethyl-5,5'-dimethyl-4,4'-bis(maleimide)diphenylmethane, or 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane.

[0079] Examples of compounds having an isocyanate structure include aromatic polyisocyanates such as 4,4'-methylenebis(phenylene isocyanate) (MDI) and tolylene diisocyanate (TDI); aliphatic polyisocyanates such as hexamethylene diisocyanate (HDI), trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, pentamethylene diisocyanate and lysine diisocyanate; and alicyclic polyisocyanates such as isophorone diisocyanate (IPDI) and 4,4'-methylenebis(cyclohexyl isocyanate) (H12MDI). Examples of blocked isocyanate compounds include compounds in which the above-mentioned isocyanate compounds are blocked with a blocking agent such as oxime, lactam or pyrazole, and the crosslinking temperature can be easily adjusted.

[0080] Examples of compounds having an oxazine structure include P-d, Fa, and ALP-d (all trade names, manufactured by Shikoku Chemical Industry Co., Ltd.), JBZ series (trade names, manufactured by JFE Chemical Corporation), and BTBz (trade name, manufactured by Japan Materials Technology Co., Ltd.).

[0081] The content of the crosslinking agent (C) is preferably 1 to 40 parts by mass per 100 parts by mass of the alkali-soluble resin (A), from the viewpoint of easily increasing the bending resistance of the cured product.

[0082] In the present invention, from the viewpoint of easily increasing the exposure sensitivity of the photosensitive resin composition and easily increasing the bending resistance of the cured product, the component (C) preferably contains a compound having a methylol group and / or an alkoxymethyl group.

[0083] <Thermal Acid Generator> The photosensitive resin composition of the present invention contains a thermal acid generator (D) (hereinafter, sometimes referred to as component (D)). A thermal acid generator is a compound that generates an acid upon heating. The thermal decomposition onset temperature of the thermal acid generator (D) is preferably 120°C or higher, more preferably 130°C or higher, and even more preferably 140°C or higher. By setting the thermal decomposition temperature to 120°C or higher, it is possible to prevent the generation of acid during the process of drying a photosensitive resin film obtained by applying the photosensitive resin composition to a substrate by heating (sometimes referred to as a pre-baking process) during pattern processing. Furthermore, the thermal decomposition onset temperature of the thermal acid generator (D) is preferably 250°C or lower, more preferably 240°C or lower, and even more preferably 230°C or lower. Setting the thermal decomposition temperature to 250°C or lower allows sufficient acid to be generated during the heating process. In the present invention, the generation of acid during the heating process can promote the crosslinking reaction of component (C), thereby improving the bending resistance of the cured product.

[0084] The thermal acid generator (D) used in the present invention is preferably a compound that generates a strong acid, such as an arylsulfonic acid (e.g., p-toluenesulfonic acid, benzenesulfonic acid), an alkylsulfonic acid (e.g., methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid), or camphorsulfonic acid, upon heating.

[0085] The thermal acid generator (D) used in the present invention is preferably an ester compound of a sulfonic acid with a compound containing an alcoholic hydroxyl group or a compound containing a phenolic hydroxyl group. Specific examples include compounds obtained by sulfonating a compound containing an alcoholic hydroxyl group or a compound containing a phenolic hydroxyl group with methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, octanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, camphorsulfonic acid, or the like. Examples of compounds containing a monohydric alcoholic hydroxyl group include methanol, ethanol, propanol, and butanol. Examples of compounds containing a monohydric phenolic hydroxyl group include phenol, cresol, and naphthol. Examples of compounds containing a dihydric alcoholic hydroxyl group include methanediol, ethanediol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, and decanediol. Specific examples of the compound containing a trihydric or higher alcoholic hydroxyl group include propanetriol, butanetriol, pentanetriol, hexanetriol, heptanetriol, octanetriol, nonanetriol, decanetriol, pentaerythritol, etc. Specific examples of the compound containing a polyhydric phenolic hydroxyl group include dihydroxybenzene, trihydroxybenzene, tetrahydroxybenzene, etc.

[0086] Among the thermal acid generators (D), from the viewpoint of easily increasing the bending resistance and heat resistance of the cured product, it is preferable that the thermal acid generator (D) contains a compound represented by the following formula (4):

[0087]

[0088] In formula (4), R ３ is a monovalent to tetravalent group having 1 to 10 carbon atoms. ４ each independently represents an alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent. f represents an integer of 1 to 4.

[0089] The R ３If the number of carbon atoms in R exceeds 10, residual components tend to remain in the cured product after the sulfonic acid is generated, which may increase outgassing. ３ is preferably a monovalent to tetravalent group having 1 to 10 carbon atoms. ３ is a monovalent to tetravalent group having 1 to 9 carbon atoms. From the viewpoint of easily increasing bending resistance and easily reducing outgassing components, f is more preferably an integer of 2 to 4.

[0090] The content of the thermal acid generator (D) is preferably 0.1 to 10 parts by mass per 100 parts by mass of the alkali-soluble resin (A), from the viewpoint of easily improving the bending resistance of the cured product.

[0091] <Compound Represented by Formula (1)> The photosensitive resin composition of the present invention contains (E) an alicyclic bisphenol represented by formula (1) (hereinafter, sometimes referred to as component (E)). Note that (E) an alicyclic bisphenol represented by formula (1) is referred to as a compound represented by formula (1).

[0092]

[0093] In formula (1), T represents a divalent to tetravalent group containing an alicyclic structure having 7 to 20 carbon atoms. １ each independently represents a monovalent group having 1 to 10 carbon atoms. a and b each independently represent an integer of 1 to 3, and c and d each independently represent an integer of 0 to 2. 1≦(a+c)≦4, and 1≦(b+d)≦4.

[0094] T in the component (E) is a group containing an alicyclic structure having 7 to 20 carbon atoms. If the carbon number is less than 7, it is difficult to obtain the effects described below, and outgassing cannot be sufficiently reduced. On the other hand, if the carbon number exceeds 20, the bending resistance of the cured product tends to decrease.

[0095] T is a divalent to tetravalent group containing an alicyclic structure having 7 to 20 carbon atoms. The alicyclic structure in the present invention refers to a polycyclic alicyclic structure in which a single cycloalkane-type monocyclic structure, such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, or cyclododecane, or a single cycloalkene-type monocyclic structure, such as cyclopropene, cyclobutene, cyclopropene, cyclohexene, cycloheptene, or cyclooctene, is connected, and the alicyclic structure may be saturated or may contain an unsaturated structure. Examples of polycyclic alicyclic structures include dicyclopentadiene, spirocyclic compounds, bicycloundecane, decahydronaphthalene (decalin), adamantane, norbornene, norbornadiene, cubane, basketane, and housane.

[0096] Preferably, T in the component (E) contains a polycyclic alicyclic structure. By containing a polycyclic alicyclic structure, the acid resistance of the crosslinked structures of the components (C) and (E) described below can be further improved, and outgassing can be more easily reduced. From the viewpoint of easily reducing outgassing, it is more preferable that T in the component (E) contains, among polycyclic alicyclic structures, a structure represented by formula (2) or formula (3).

[0097]

[0098] In formula (2), each e independently represents an integer of 0 to 5. In formula (3), R ２ each independently represents a hydrogen atom or a group having 1 to 10 carbon atoms. * indicates the bonding position.

[0099] Among polycyclic alicyclic structures, T in the component (E) particularly preferably contains a structure represented by formula (10) or formula (11).

[0100]

[0101] In formula (4), R ２５ ~R ２８ indicates a hydrogen atom or a group having 1 to 10 carbon atoms. * indicates a bonding position.

[0102] Specific examples of compounds having a monocyclic structure include BisP-CDE and BisP-HTG (trade names, manufactured by Honshu Chemical Industry Co., Ltd.).

[0103]

[0104] Examples of compounds having a polycyclic structure include RF-Z (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), SPI (trade name, manufactured by JFE Chemical Corporation), a compound represented by the following formula (7), and a compound represented by the following formula (8).

[0105] The compound represented by formula (8) is synthesized by reacting phenol with dicyclopentadiene in the presence of an acid catalyst. Furthermore, by modifying the structure of phenol, a bisphenol compound represented by the following formula (9) composed of a phenol compound and cyclopentadiene can be synthesized. This compound corresponds to the component (E) of the present invention and is an example of a compound having a polycyclic structure. Examples of phenol compounds include monohydric and dihydric phenols. Specific examples include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, p-ethylphenol, o-isopropylphenol, p-n-propylphenol, p-sec-butylphenol, p-cyclohexylphenol, p-chlorophenol, o-bromophenol, p-bromophenol, resorcinol, catechol, and hydroquinone, but are not limited to these.

[0106] When reacting a phenol compound with dicyclopentadiene, the molecular weight can be adjusted by adjusting the charge ratio. Increasing the charge ratio of the phenol compound decreases the molecular weight, while decreasing the charge ratio of phenol increases the molecular weight. From the viewpoint of easily achieving the effects of the present invention, the charge molar ratio of the phenol compound to dicyclopentadiene is preferably phenol compound / dicyclopentadiene = 10 / 1 to 40 / 1 (molar ratio).

[0107]

[0108] Although details will be described later, in the present invention, the highly acid-resistant crosslinked structure formed by the components (C) and (E) makes it easier to achieve the effects of the present invention. The component (E) used in the present invention preferably has a low molecular weight, from the viewpoint of increasing conformational diversity during curing treatment and facilitating the formation of a crosslinked structure with the component (C). Specifically, the molecular weight is preferably 1,500 g / mol or less, more preferably 1,200 g / mol or less, even more preferably 1,000 g / mol or less, and particularly preferably 800 g / mol or less.

[0109] <Component Ratio> In the present invention, by including the aforementioned components (C), (D), and (E), a cured product with high bending resistance and low outgassing is obtained. The reason for this effect is unclear, but is presumed to be as follows. Generally, when a thermal acid generator is used, the strong acid generated during thermal curing decomposes a portion of the cured product, leading to increased outgassing of the cured product. In the present invention, components (C) and (E) are included, which form a crosslinked structure during thermal curing. The formed crosslinked structure is highly acid-resistant due to the highly acid-resistant group T in component (E) containing an alicyclic structure having 7 to 20 carbon atoms. As a result, it is believed that the cured product is less susceptible to decomposition by the strong acid generated by component (D), resulting in reduced outgassing. The strong acid generated by component (D) during thermal curing promotes the crosslinking reaction of components (C) and (E), forming a stronger crosslinked structure, which ultimately improves the bending resistance of the cured product.

[0110] In the present invention, when the contents (mass) of the components (C), (E), and (D) are γ1, γ2, and γ3, respectively, it is preferable that the mass ratio γ2 / γ1 is in the range of 0.50≦γ2 / γ1≦3.00 and the mass ratio γ3 / (γ1+γ2) is in the range of 0.05≦γ3 / (γ1+γ2)≦0.20. When γ1, γ2, and γ3 are in the above ranges, outgassing can be easily reduced, making it easier to achieve the effects of the present invention.

[0111] The ratio γ2 / γ1 is more preferably 1.00 or more, even more preferably 1.50 or more, and particularly preferably 1.90 or more. The ratio γ2 / γ1 is more preferably 2.70 or less, even more preferably 2.40 or less, and particularly preferably 2.10 or less.

[0112] γ3 / (γ1+γ2) is more preferably 0.06 or more, even more preferably 0.07 or more, and particularly preferably 0.08 or more. γ3 / (γ1+γ2) is more preferably 0.17 or less, even more preferably 0.14 or less, and particularly preferably 0.11 or less.

[0113] <Adhesion Improver> The photosensitive resin composition of the present invention may contain an adhesion improver. Examples of adhesion improvers include silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane; titanium chelating agents; aluminum chelating agents; and compounds obtained by reacting an aromatic amine compound with an alkoxy group-containing silicon compound. Two or more of these may be contained. By containing these adhesion improvers, when developing a photosensitive resin film, for example, it becomes easier to adhere the photosensitive resin film to silicon wafers, ITO, SiO ２ The adhesion improver can improve adhesion to the underlying substrate such as silicon nitride. It can also improve resistance to oxygen plasma and UV ozone treatments used for cleaning, etc. The content of the adhesion improver is preferably 0.1 to 10 mass % based on the total amount of the photosensitive resin composition excluding organic solvents and water.

[0114] <Surfactant> The photosensitive resin composition of the present invention may contain a surfactant, if necessary, for the purpose of improving wettability with a substrate. The surfactant may be a commercially available compound. Specific examples of silicone surfactants include the SH series, SD series, and ST series from Dow-Toray Industries, Inc., the BYK series from BYK Japan K.K., the KP series from Shin-Etsu Chemical Co., Ltd., the Disfoam series from NOF Corporation, and the TSF series from Momentive Performance Materials Japan LLC. Specific examples of fluorine-based surfactants include the Megafac (registered trademark) series from DIC Corporation, the Fluorad series from 3M Japan Limited, the Surflon (registered trademark) series and Asahiguard (registered trademark) series from AGC Inc., the EF series from Mitsubishi Materials Electronic Chemicals Co., Ltd., and the Polyfox series from Omnova Solutions. Specific examples of surfactants made from acrylic and / or methacrylic polymers include the Polyflow series from Kyoeisha Chemical Co., Ltd., and the Disparlon (registered trademark) series from Kusumoto Chemicals Co., Ltd., but are not limited to these.

[0115] The content of the surfactant is preferably 0.001 to 1% by mass based on the total amount of the photosensitive resin composition excluding the organic solvent and water.

[0116] <Compound Having a Phenolic Hydroxyl Group> The photosensitive resin composition of the present invention may contain a compound having a phenolic hydroxyl group, as needed, for the purpose of supplementing the alkaline developability of the photosensitive resin composition. However, this compound having a phenolic hydroxyl group does not fall under the category of component (E) of the present invention, and may be contained within a range that does not impair the effects of the present invention. Examples of such compounds having a phenolic hydroxyl group include Bis-C, BisOPP-A, BisOCHP-A, Bis26X-A, BisOTBP-A, BisOFP-A, BisP-AP, BisP-MIBK, BisP-B, Bis-Z, BisOC-Z, BisOC-FL, BisP-CP, BisOC-CP, BisOCHP-Z, TM-BPF, BisOC-F, Bis -E, BisP-IOTD, BisP-IBTD, BisP-DED, Bis3M6B-IBTD, BisP-BA, BisOC-IST, BisP-IST, BisP-PR, BisOC-PR , BisP-PRM, BisP-LV, TrisP-PA, TrisP-PHBA, TrisP-236S, TrisP-HAP, TrisP-RK, TrisOC-RK, Methylene TrisP-CR , MTPC, TekP-4HBPA (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-BI25X-FN, BIP-BZ, BIP-PHBZ, TEP-BOCP, BIR-PTBP, BIR-PC , 3PC, BIP-R, BI4MC-34DHBZ, BI4MC-BZ (all trade names, manufactured by Asahi Yokuzai Kogyo Co., Ltd.), 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, Examples of suitable compounds include hydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,4-dihydroxyquinoline, 2,6-dihydroxyquinoline, 2,3-dihydroxyquinoxaline, anthracene-1,2,10-triol, anthracene-1,8,9-triol, and 8-quinolinol. By incorporating these compounds having a phenolic hydroxyl group, the resulting photosensitive resin composition is almost insoluble in an alkaline developer before exposure, but readily dissolves in an alkaline developer after exposure, resulting in less film loss due to development and facilitating development in a short time. This tends to improve sensitivity.

[0117] The content of such a compound having a phenolic hydroxyl group is preferably 1 to 40 parts by mass relative to 100 parts by mass of the alkali-soluble resin (A).

[0118] <Organic Solvent> The photosensitive resin composition of the present invention preferably contains an organic solvent, which allows the composition to be in a varnish state and improves the coatability.

[0119] Examples of the organic solvent include polar aprotic organic solvents such as γ-butyrolactone, ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tetrahydrofuran, and dioxane, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, and diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tetrahydrofuran, and dioxane, and ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, and diacetone alcohol. Examples of organic solvents that can be used alone or in combination include esters such as ethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, 3-methoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, methyl acetoacetate, and ethyl acetoacetate; aromatic hydrocarbons such as toluene and xylene; and amides such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0120] The amount of the organic solvent used is not particularly limited, but is preferably 100 to 3,000 parts by mass, and more preferably 150 to 2,000 parts by mass, relative to 100 parts by mass of the total amount of the photosensitive resin composition excluding the organic solvent and water. Furthermore, the proportion of organic solvents with a boiling point of 180°C or higher relative to the total amount of organic solvents is preferably 20% by mass or less, and more preferably 10% by mass or less. By keeping the proportion of organic solvents with a boiling point of 180°C or higher to 20% by mass or less, the amount of outgassing from the cured product can be kept low, and as a result, the reliability of the organic EL display device can be improved.

[0121] <Colorant> The photosensitive resin composition of the present invention may contain a colorant. The colorant refers to an organic pigment, an inorganic pigment, or a dye. The colorant is preferably an organic pigment and / or an inorganic pigment.

[0122] Examples of organic pigments include diketopyrrolopyrrole pigments, azo pigments such as azo, disazo, or polyazo, phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine, or metal-free phthalocyanine, anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavanthrone, anthanthrone, indanthrone, pyranthrone, or violanthrone, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, threne pigments, benzofuranone pigments, or organometallic complex pigments.

[0123] Examples of inorganic pigments include titanium oxide, zinc white, zinc sulfide, white lead, calcium carbonate, precipitated barium sulfate, white carbon, alumina white, kaolin clay, talc, bentonite, black iron oxide, cadmium red, red iron oxide, molybdenum red, molybdate orange, chrome vermilion, yellow lead, cadmium yellow, yellow iron oxide, titanium yellow, chromium oxide, viridian, titanium cobalt green, cobalt green, cobalt chrome green, Victoria green, ultramarine, Prussian blue, cobalt blue, cerulean blue, cobalt silica blue, cobalt zinc silica blue, manganese violet, and cobalt violet.

[0124] Examples of dyes include azo dyes, anthraquinone dyes, condensed polycyclic aromatic carbonyl dyes, indigoid dyes, carbonium dyes, phthalocyanine dyes, methine or polymethine dyes.

[0125] For the purpose of improving the contrast of an organic EL display device, the colorant is preferably black, which can block visible light across the entire wavelength range. It is preferable to incorporate at least one colorant selected from organic pigments, inorganic pigments, and dyes into the photosensitive resin composition, which will exhibit a black color when cured. To achieve this, the photosensitive resin composition may contain the above-mentioned black organic pigments and black inorganic pigments, or two or more organic pigments and dyes may be mixed to produce a pseudo-black color. A pseudo-black color can be obtained by mixing two or more organic pigments and dyes, such as those described above, such as red, orange, yellow, purple, blue, and green. The photosensitive resin composition of the present invention does not necessarily have to be black; a colorant that changes color upon heat curing to produce a black cured product may also be used.

[0126] Among these, from the viewpoint of ensuring high heat resistance, it is preferable to contain an organic pigment and / or an inorganic pigment and a colorant that will exhibit a black color when cured. Also, from the viewpoint of ensuring high insulating properties, it is preferable to contain an organic pigment and / or a dye and a colorant that will exhibit a black color when cured. In other words, from the viewpoint of achieving both high heat resistance and insulating properties, it is preferable to contain an organic pigment and a colorant that will exhibit a black color when cured.

[0127] The content of the colorant is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, based on the total amount of the photosensitive resin composition excluding the organic solvent and water, from the viewpoint of obtaining the necessary colorability in the cured product. Also, from the viewpoint of obtaining good storage stability, the content is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less, based on the total amount of the photosensitive resin composition excluding the organic solvent and water.

[0128] When the photosensitive resin composition contains a pigment, it preferably contains a dispersant. The inclusion of a dispersant allows the colorant to be uniformly and stably dispersed in the photosensitive resin composition. The dispersant is not particularly limited, but a polymeric dispersant is preferred. Examples of polymeric dispersants include polyester-based polymeric dispersants, acrylic-based polymeric dispersants, polyurethane-based polymeric dispersants, polyallylamine-based polymeric dispersants, and carbodiimide-based dispersants. More specifically, a polymeric dispersant refers to a polymeric compound whose main chain is made of polyamino, polyether, polyester, polyurethane, polyacrylate, or the like, and which has polar groups such as amine, carboxylic acid, phosphoric acid, amine salt, carboxylate salt, and phosphate salt on the side chain or main chain end. The polar groups adsorb to the pigment, and the steric hindrance of the main chain polymer stabilizes the pigment dispersion. Dispersants are classified into (polymeric) dispersants having only an amine value, (polymeric) dispersants having only an acid value, (polymeric) dispersants having both an amine value and an acid value, and (polymeric) dispersants having neither an amine value nor an acid value. Of these, (polymeric) dispersants having both an amine value and an acid value and (polymeric) dispersants having only an amine value are preferred, and (polymeric) dispersants having only an amine value are more preferred.

[0129] The content of the dispersant is preferably 1 part by mass or more, more preferably 3 parts by mass or more, per 100 parts by mass of the pigment from the viewpoint of obtaining good dispersion stability, and is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, per 100 parts by mass of the pigment from the viewpoint of maintaining the heat resistance of the cured product.

[0130] <Inorganic Particles> The photosensitive resin composition of the present invention may also contain inorganic particles. Preferred examples include, but are not limited to, silicon oxide, titanium oxide, barium titanate, alumina, and talc. The primary particle diameter of these inorganic particles is preferably 100 nm or less, more preferably 60 nm or less. The content of the inorganic particles is preferably 5 to 90 mass% based on the total amount of the photosensitive resin composition excluding the organic solvent and water.

[0131] <Method for Producing Photosensitive Resin Composition> Next, a method for producing the photosensitive resin composition of the present invention will be described. For example, a photosensitive resin composition can be obtained by dissolving (A) an alkali-soluble resin, (B) a quinone diazide compound, (C) a crosslinking agent, (D) a thermal acid generator, (E) a compound represented by formula (1), and, if necessary, an organic solvent, an adhesion improver, a surfactant, a compound having a phenolic hydroxyl group, a colorant, inorganic particles, and the like. Examples of dissolution methods include stirring and heating. When heating, the heating temperature is preferably set within a range that does not impair the performance of the photosensitive resin composition, typically room temperature to 80°C. The order in which the components are dissolved is not particularly limited. For example, compounds with low solubility may be dissolved sequentially. For components that tend to generate bubbles during stirring and dissolution, such as surfactants and some adhesion improvers, adding them last after dissolving the other components can prevent incomplete dissolution of the other components due to bubble formation. The resulting photosensitive resin composition is preferably filtered through a filter to remove dust and particles. The pore size of the filter may be, but is not limited to, 0.5 μm, 0.2 μm, 0.1 μm, 0.07 μm, 0.05 μm, 0.02 μm, etc. The material of the filter may be polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), etc., with polyethylene and nylon being preferred.

[0132] <Cured Product> 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-treating the photosensitive resin composition. The heat treatment can be performed using a known method such as a hot plate, an oven, or infrared rays. Preferred heat treatment conditions will be described later in the section on the method for producing a cured product (5) "heat-treating the developed photosensitive resin film."

[0133] Next, an example of a method for producing a cured product using the photosensitive resin composition of the present invention will be described in detail. The method for producing a cured product can include, for example, the following steps in this order: (1) applying the photosensitive resin composition of the present invention to a substrate to form a photosensitive resin film, (2) drying the photosensitive resin film, (3) exposing the dried photosensitive resin film through a photomask, (4) developing the exposed photosensitive resin film, and (5) heat-treating the developed photosensitive resin film.

[0134] (1) In the step of applying the photosensitive resin composition of the present invention to a substrate to form a photosensitive resin film, the photosensitive resin composition of the present invention is applied by a method such as spin coating, slit coating, dip coating, spray coating, or printing to obtain a photosensitive resin film of the photosensitive resin composition. Prior to application, the substrate to which the photosensitive resin composition is to be applied may be pretreated with the adhesion promoter described above. For example, the substrate surface may be treated with a solution in which 0.5 to 20% by mass of the adhesion promoter is dissolved in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, or diethyl adipate. Examples of methods for treating the substrate surface include spin coating, slit die coating, bar coating, dip coating, spray coating, and steam treatment.

[0135] (2) In the step of drying the photosensitive resin film, the applied photosensitive resin film is subjected to a reduced pressure drying treatment as necessary, and then subjected to a heat treatment at a temperature in the range of 50°C to 180°C for 1 minute to several hours using a hot plate, an oven, infrared rays, or the like, to obtain a dried photosensitive resin film.

[0136] Next, we will explain the step (3) of exposing the dried photosensitive resin film through a photomask. The dried photosensitive resin film is irradiated with actinic radiation through a photomask having a desired pattern. Actinic radiation used for exposure includes ultraviolet light, visible light, electron beams, and X-rays. In the present invention, however, it is preferable to use i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) from a mercury lamp. After exposure to actinic radiation, post-exposure baking may be performed. Post-exposure baking can be expected to improve the resolution after development or increase the tolerance for development conditions. Post-exposure baking can be performed using an oven, hot plate, infrared light, a flash annealing device, or a laser annealing device. The post-exposure baking temperature is preferably 50 to 180°C, more preferably 60 to 150°C. The post-exposure baking time is preferably 10 seconds to several hours. When the post-exposure baking time is within the above range, the reaction proceeds smoothly, and the development time may be shortened.

[0137] (4) In the step of developing the exposed photosensitive resin film, the exposed photosensitive resin film is developed using a developer to remove areas other than the exposed area. Preferred developers include aqueous solutions of alkaline compounds such as tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine. In some cases, these alkaline aqueous solutions may contain polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, and dimethylacrylamide; alcohols such as methanol, ethanol, and isopropanol; esters such as ethyl lactate and propylene glycol monomethyl ether acetate; and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone, either singly or in combination. The development method may be spray, puddle, immersion, ultrasonic, or the like.

[0138] Next, the pattern formed by development is preferably rinsed with distilled water. Here, too, alcohols such as ethanol and isopropyl alcohol, or esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to the distilled water for rinsing.

[0139] Next, (5) a step of heat-treating the developed photosensitive resin film is performed. Heat treatment can remove residual organic solvents and components with low heat resistance, thereby improving heat resistance and chemical resistance. When the photosensitive resin composition of the present invention contains a polyimide precursor, a polybenzoxazole precursor, and / or a copolymer thereof, heat treatment can form imide rings and oxazole rings, thereby improving heat resistance and chemical resistance. Furthermore, since the photosensitive resin composition of the present invention contains a thermal crosslinking agent, heat treatment can promote a thermal crosslinking reaction, thereby 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. On the other hand, from the viewpoint of avoiding the effects of thermal degradation of TFT elements, the heat treatment temperature is preferably 400°C or lower, more preferably 350°C or lower, and even more preferably 320°C or lower. Within this temperature range, the temperature may be increased stepwise or continuously. The heat treatment time is preferably 30 minutes or more, more preferably 45 minutes or more, from the viewpoint of improving the heat resistance of the cured product. From the viewpoint of productivity, the heat treatment time is preferably 180 minutes or less, more preferably 120 minutes or less. Examples of the heat treatment time include a method of heat treating at 150°C and 250°C for 60 minutes each, and a method of heat treating while linearly increasing the temperature from room temperature to 250°C over 2 hours.

[0140] <Display Device> The display device of the present invention is a display device including the cured product. The cured product formed from the photosensitive resin composition of the present invention can be used in a display device including a first electrode formed on a substrate and a second electrode disposed opposite the first electrode, specifically, for example, a planarizing layer of a liquid crystal display device, a planarizing layer and / or pixel dividing layer of an organic EL display device, etc. Furthermore, the cured product formed from the photosensitive resin composition of the present invention can also be used in a panel equipped with a micro LED element including a micro LED chip, a drive circuit, and contact electrodes. More specifically, it can be used as a rewiring material for forming a planarizing layer of a drive circuit and contact electrodes on the drive circuit, etc. The following description will be given using an organic EL display device as an example.

[0141] The organic EL display device containing the cured product of the present invention preferably has a substrate on which a driving circuit, a planarization layer, a first electrode, a pixel division layer, an organic EL layer (light-emitting layer), and a second electrode are disposed, and the planarization layer and / or the pixel division layer contains the cured product. Taking an active matrix display device as an example, a substrate such as glass or a resin film has a thin film transistor (hereinafter sometimes referred to as TFT) as a driving circuit and wiring located on the sides of the TFT and connected to the TFT, a planarization layer is disposed thereon to cover the irregularities, and an organic EL layer is further disposed on the planarization layer. The organic EL layer and the wiring are connected via contact holes and the first electrode formed in the planarization layer. In particular, flexible organic EL display devices have become mainstream in recent years, and it is preferable that the substrate having the driving circuit be made of a resin film.

[0142] Preferably, the organic EL display device has at least a portion of the cured product that can be bent and / or a portion that is fixed in a bent state. By using a cured product obtained by curing the photosensitive resin composition of the present invention, an organic EL display device with excellent bending resistance can be obtained. The radius of curvature of the bendable portion and / or the portion that is fixed in a bent state is preferably 0.1 mm or more and preferably 5 mm or less. A radius of curvature of 0.1 mm or more ensures bending resistance at the bent portion, while a radius of curvature of 5 mm or less ensures design features such as a narrow frame. The organic EL display device can be bent at any appropriate portion. For example, the organic EL display device may be bent at the center, like a foldable display device, or at the end to maximize design and display screen. Furthermore, the organic EL display device may be bent along its longitudinal direction or along its lateral direction. Depending on the application, it is sufficient for a specific portion of the organic EL display device to be bendable (for example, some or all of the four corners can be bent diagonally).

[0143] FIG. 1 shows a cross-sectional view of an example of a TFT substrate on which a planarization layer and a pixel division layer are formed. Bottom-gate or top-gate TFTs 2 are arranged in a matrix on a substrate 1, and a TFT insulating layer 3 is formed to cover the TFTs 2. Wiring 4 connected to the TFTs 2 is provided on the TFT insulating layer 3. A planarization layer 5 is formed on the TFT insulating layer 3, burying the wiring 4. Contact holes 6 are formed in the planarization layer 5, reaching the wiring 4. An ITO (transparent electrode) is formed on the planarization layer 5 as a first electrode 7, connected to the wiring 4 through the contact holes 6. The first electrode 7 serves as an electrode for a display element (e.g., an organic EL element). A pixel division layer 8 is formed to cover the periphery of the first electrode 7. The organic EL element may be a top-emission type that emits light from the side opposite the substrate 1, or a bottom-emission type that extracts light from the substrate 1 side. In this manner, an active matrix organic EL display device is obtained, in which TFTs 2 for driving each organic EL element are connected to the corresponding TFTs 2.

[0144] As described above, the TFT insulating layer 3, the planarizing layer 5, and / or the pixel dividing layer 8 can be formed by the steps of (1) applying the photosensitive resin composition of the present invention to a substrate to form a photosensitive resin film, (2) drying the photosensitive resin film, (3) exposing the dried photosensitive resin film through a photomask, (4) developing the exposed photosensitive resin film, and (5) heat-treating the developed photosensitive resin film. An organic EL display device can be obtained by a manufacturing method including these steps.

[0145] <Semiconductor Device> The photosensitive resin composition of the present invention can also be suitably used in semiconductor devices. Cured products of the photosensitive resin composition of the present invention are preferably used in semiconductor devices due to their low outgassing and high bending resistance, which prevents defects such as cracks. The cured products can be used as insulating films or protective films constituting semiconductor devices (electronic components). Examples of semiconductor devices (electronic components) include active components such as transistors, diodes, integrated circuits (hereinafter referred to as ICs), and memories, and passive components such as resistors, capacitors, and inductors. Electronic components using semiconductors are also referred to as semiconductor devices. Specific examples of cured products suitable for electronic components include passivation films for semiconductors, surface protective films for semiconductor elements and TFTs, interlayer insulating films in multilayer wiring for high-density packaging of 2 to 10 layers, and insulating films and protective films for touch panel displays. However, the present invention is not limited to these and can have a variety of structures. The surface of the substrate on which the cured product is formed can be appropriately selected depending on the application and process. Examples include silicon, ceramics, metals, glass, and epoxy resins, and multiple of these may be arranged on the same surface. Examples of electronic devices having a surface protection film or interlayer insulating film, etc., in which the cured product of the present invention is disposed include magnetoresistive memories (hereinafter, MRAMs) with low heat resistance. That is, the cured product of the present invention is suitable for use as a surface protection film for MRAMs. In addition to MRAMs, polymer memories (Polymer Ferroelectric RAM: PFRAM), phase change memories (Phase Change RAM: PCRAM, or Ovonics Unified Memory: OUM), which are promising next-generation memories, are also likely to use new materials with lower heat resistance than conventional memories. Therefore, the cured product of the present invention is also suitable for use as a surface protection film for these memories. It is also suitable for use in fan-out wafer-level packages (hereinafter, fan-out WLPs). Fan-out WLPs are semiconductor packages in which an extension portion is provided around a semiconductor chip using an encapsulating resin such as an epoxy resin, rewiring is performed from the electrodes on the semiconductor chip to the extension portion, and solder balls are also mounted on the extension portion to ensure the required number of terminals.In fan-out WLP, wiring is installed so as to straddle the boundary formed between the main surface of the semiconductor chip and the main surface of the encapsulating resin. That is, an interlayer insulating film is formed on a substrate composed of two or more materials, namely, a semiconductor chip with metal wiring and an encapsulating resin, and wiring is then formed on the interlayer insulating film. In addition, in a semiconductor package in which a semiconductor chip is embedded in a recess formed in a glass epoxy resin substrate, wiring is installed so as to straddle the boundary between the main surface of the semiconductor chip and the main surface of the printed circuit board. In this embodiment, an interlayer insulating film is also formed on a substrate composed of two or more materials, and wiring is then formed on the interlayer insulating film. The cured product obtained by curing the photosensitive resin composition of the present invention has high adhesion to a semiconductor chip with metal wiring and also to encapsulating resins such as epoxy resins, making it suitable for use as an interlayer insulating film on a substrate composed of two or more materials.

[0146] The present invention will be described below with reference to examples, but the present invention is not limited to these examples. The photosensitive resin compositions in the examples were evaluated by the following methods.

[0147] (1) Evaluation of Sensitivity of Photosensitive Resin Composition The photosensitive resin compositions obtained in each of the Examples and Comparative Examples described below were applied to an 8-inch silicon wafer by spin coating using a coating and developing apparatus ACT-8 (manufactured by Tokyo Electron Limited) to obtain a photosensitive resin film, which was then prebaked on a hot plate at 120°C for 2 minutes to produce a prebaked film with a thickness of 3.0 μm. The film thickness was measured using a Lambda Ace STM-602 (manufactured by SCREEN Holdings Co., Ltd.) under the condition of a refractive index of 1.63. Thereafter, using an exposure machine i-line stepper NSR-2005i9C (manufactured by Nikon Corporation), the film was exposed to 50 to 300 mJ / cm through a mask having a pattern of contact holes with a diameter of 10 μm. ２ at an exposure dose of 10 mJ / cm ２The film was exposed in steps. After exposure, the film was developed using the ACT-8 developing device with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (manufactured by Tama Chemicals Co., Ltd.) for a time period until the film thickness was reduced to 0.5 μm during development, and then rinsed with distilled water and spun dry to obtain a pattern. The developed photosensitive resin film pattern was observed at 20x magnification using an FDP microscope MX61 (manufactured by Olympus Corporation), and the minimum required exposure dose at which the contact hole opening diameter reached 10 μm was determined, and this was taken as the exposure sensitivity.

[0148] (2) Evaluation of bending resistance of cured product The photosensitive resin compositions obtained in each of the examples and comparative examples described below were applied to a polyimide film substrate by spin coating at an arbitrary rotation speed to obtain a photosensitive resin film, which was then pre-baked for 2 minutes on a hot plate at 120 °C as a drying step to obtain a dried photosensitive resin film. No exposure step was performed, and the film was then shower-developed for 90 seconds with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide using an automatic developing apparatus AD-2000 (manufactured by Takizawa Sangyo Co., Ltd.), followed by rinsing with pure water for 30 seconds. The substrate with the developed photosensitive resin film attached to the entire surface was cured (heat-treated) for 60 minutes in a nitrogen atmosphere at 250 °C using an inert oven CLH-21CD-S (manufactured by JTEKT Corporation, hereinafter referred to as the inert oven) to obtain a polyimide film substrate having a cured product with a film thickness of 2.0 μm.

[0149] Next, the polyimide film substrate having the cured product was cut into 10 pieces measuring 50 mm long x 10 mm wide. The cut polyimide film substrate having the cured product was then stored in an air atmosphere at 100°C for 500 hours. Thereafter, the polyimide film substrate having the cured product was bent 180° along a 25 mm vertical line with the side having the cured product facing outward, and held in this state for 30 seconds. After 30 seconds had elapsed, the bent polyimide film substrate was unfolded, and the bent portion along the 25 mm vertical line on the surface of the cured product on the polyimide film substrate was observed using an FPD inspection microscope MX-61L (manufactured by Olympus Corporation), and changes in the appearance of the surface of the cured product were evaluated. The bending test was carried out at radii of curvature of 0.05 mm, 0.10 mm, 0.20 mm, 0.30 mm, 0.40 mm, 0.50 mm, 0.60 mm, 0.70 mm, 0.80 mm, 0.90 mm, and 1.00 mm, and the smallest radius of curvature at which the cured product did not peel off from the polyimide film substrate or cracks occurred on the surface of the cured product was recorded.

[0150] (3) Outgassing Amount Evaluation The photosensitive resin compositions obtained in each of the Examples and Comparative Examples described below were applied to an 8-inch silicon wafer substrate by spin coating at an arbitrary rotation speed to obtain a photosensitive resin film, which was then pre-baked for 2 minutes on a hot plate at 120°C as a drying step to obtain a dried photosensitive resin film. No exposure step was performed, and the film was then shower-developed for 90 seconds with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide using an automatic developing apparatus AD-2000 (manufactured by Takizawa Sangyo Co., Ltd.), and then rinsed with pure water for 30 seconds. The substrate with the developed photosensitive resin film attached to the entire surface was cured (heat-treated) for 60 minutes in an inert oven at 250°C under a nitrogen atmosphere to obtain a silicon wafer substrate having a cured product with a film thickness of 2.0 μm.

[0151] Next, the silicon wafer substrate bearing the cured product was scraped off using a scraper to obtain a powdered sample. The sample was measured under a nitrogen atmosphere (nitrogen flow rate: 300 mL / min) using a differential thermal and thermogravimetric simultaneous analyzer DTG-60A (manufactured by Shimadzu Corporation). The temperature profile was increased to 100°C at a rate of 10°C / min and held for 30 minutes. Subsequently, the temperature was increased to 250°C at a rate of 10°C / min and held at 250°C for 60 minutes to obtain thermal weight loss data. The weight loss rate after 60 minutes of holding relative to the weight loss before 60 minutes of holding was evaluated as the amount of outgassing, using the point at which 250°C was reached as the reference.

[0152] (4) Reliability Evaluation of Organic EL Display Device <Fabrication of Organic EL Display Device> Figure 2 shows a schematic diagram of the substrate used. First, a 100 nm ITO transparent conductive film was formed on the entire surface of a 38 mm x 46 mm alkali-free glass substrate 11 by sputtering, and unnecessary portions were removed by etching to simultaneously form a first electrode 12 and an auxiliary electrode 13 for connecting the second electrode (Figure 2(a)). The resulting substrate was ultrasonically cleaned for 10 minutes using a cleaning solution "Semicoclean" (registered trademark) 56 (manufactured by Furuuchi Chemical Co., Ltd.) and then washed with ultrapure water.

[0153] Next, the photosensitive resin composition obtained in each of the Examples and Comparative Examples described below was applied to the entire surface of the substrate on which the above-mentioned electrodes were formed by spin coating at an arbitrary rotation speed to obtain a photosensitive resin film, and as a step of drying the photosensitive resin film, the film was pre-baked on a hot plate at 120°C for 2 minutes to obtain a dried photosensitive resin film.

[0154] The dried photosensitive resin film thus obtained was exposed to UV light using a Parallel Light Mask Aligner PLA-501F (Canon Inc.) as a photomask and an ultra-high pressure mercury lamp as a light source (a mixture of g-line, h-line, and i-line), and then developed with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide using an automatic developing apparatus AD-2000 (Takizawa Sangyo Co., Ltd.) to dissolve only the exposed areas, followed by rinsing with pure water. The resulting patterned substrate was cured (heat treated) for 60 minutes in an inert oven at 250°C under a nitrogen atmosphere.

[0155] In this way, pixel division layer 14 was formed in the limited area of ​​the substrate, with openings 50 μm wide and 260 μm long arranged at a pitch of 155 μm in the width direction and a pitch of 465 μm in the length direction, and each opening exposing the first electrode ( FIG. 2( b)). In this way, a pixel division layer with an aperture ratio of 18% was provided in the effective area of ​​the substrate, which was a rectangle with one side measuring 16 mm, and the thickness of this pixel division layer was approximately 2.0 μm.

[0156] Next, after nitrogen plasma treatment as a pretreatment, the organic EL layer 15 was formed by vacuum deposition (FIG. 2(c)). Note that the degree of vacuum during deposition was 1×10 －３ The pressure was 0.05 Pa or less, and the substrate was rotated relative to the evaporation source during evaporation. First, compound (HT-1) was evaporated to a thickness of 10 nm as a hole injection layer, and compound (HT-2) was evaporated to a thickness of 50 nm as a hole transport layer. Next, compound (GT-1) as a host material and compound (GD-1) as a dopant material were evaporated to a thickness of 40 nm in the light-emitting layer so that the doping concentration was 10%. Next, compound (ET-1) and compound (LiQ) were laminated to a thickness of 40 nm at a volume ratio of 1:1 as electron transport materials. The structures of the compounds used in the organic EL layer are shown below.

[0157]

[0158] Next, a compound (LiQ) was vapor-deposited to a thickness of 2 nm, followed by vapor-depositing 60 nm of Mg and Ag at a volume ratio of 1:10 to form the second electrode 16 (FIG. 2(d)). Finally, a cap-shaped glass plate was attached using an epoxy resin adhesive in a low-humidity nitrogen atmosphere to seal the substrate, and four 5 mm square organic EL display devices were fabricated on one substrate. Note that the film thickness here is the value displayed on a quartz crystal oscillator film thickness monitor.

[0159] <Reliability Evaluation> The fabricated organic EL display device was stored in an air atmosphere at 100°C, and the organic EL display device was taken out every 50 hours, and a current of 10 mA / cm ２ The organic EL display device was driven to emit light by DC current at 100 V, and the light-emitting area of ​​the light-emitting pixel was measured. The minimum time required for the light-emitting area after long-term storage to become 50 or less, assuming that the initial light-emitting area before reliability evaluation was 100, was defined as the reliability (unit: hours), and a reliability of 400 hours or more was considered to be acceptable.

[0160] (5) Compounds used in Examples and Comparative Examples <(A) Alkali-Soluble Resin> Synthesis of Diamine A (Synthesis Example 1) 18.3 g (0.05 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was dissolved in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide (manufactured by Tokyo Chemical Industry Co., Ltd.), and the solution was cooled to −15°C. To this solution, a solution prepared by dissolving 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 100 mL of acetone was added dropwise. After completion of the dropwise addition, the mixture was stirred at −15°C for 4 hours and then returned to room temperature. The precipitated white solid was filtered and dried in vacuo at 50°C.

[0161] 30 g of the obtained solid was placed in a 300 mL stainless steel autoclave and dispersed in 250 mL of methyl cellosolve, and 2.0 g of 5% palladium-carbon (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 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 terminated when it was confirmed that the balloon no longer deflated. After the reaction was completed, the palladium compound catalyst was removed by filtration, and the mixture was concentrated using a rotary evaporator to obtain diamine A represented by the following formula:

[0162]

[0163] Synthesis of Diamine B (Synthesis Example 2) A 500 mL four-neck flask equipped with a stirrer, a thermocouple, and a dropping funnel was charged with 26.70 g (0.086 mol) of BisP-HTG (4,4'-(3,3,5-trimethylcyclohexylidene)bisphenol; manufactured by Honshu Chemical Industry Co., Ltd.) and 100 mL of glacial acetic acid, and the mixture was stirred. The internal temperature was raised to 50°C in a hot water bath. To this was added dropwise 2 mL (0.026 mol) of concentrated nitric acid over 1 hour, and the mixture was then ice-cooled to lower the internal temperature to 13°C. 13.3 mL (0.149 mol) of concentrated nitric acid was then added dropwise over 1 hour. Stirring was then continued for 3 hours, and the precipitated yellow crystals were filtered, washed successively with 40 mL of glacial acetic acid and 80 mL of deionized water, and dried under reduced pressure to obtain a dinitro form.

[0164] Next, 54.06 g (0.135 mol) of the dinitro compound, 180 mL (3.71 mol) of hydrazine monohydrate, and 900 mL of ethanol were placed in a 2 L four-neck flask equipped with a stirrer, thermocouple, Dimroth condenser, and dropping funnel, and the mixture was stirred under ice cooling. 0.9 g of 5% palladium-carbon (Fujifilm Wako Pure Chemical Industries, Ltd.) suspended in 30 mL of ethanol was added dropwise over 1 hour. The solution was then refluxed for 2 hours, and the palladium-carbon was removed by filtration while washing with 300 mL of ethanol. All solvents were removed by heating under reduced pressure, and the residue was washed with 75 mL of ice-cold ethanol, filtered, and then washed with 75 mL of deionized water and 150 mL of diethyl ether, followed by drying under reduced pressure, to obtain diamine B represented by the following formula:

[0165]

[0166] Synthesis of Diamine C (Synthesis Example 3) 17.0 g (0.05 mol) of the diamine B was dissolved in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide (manufactured by Tokyo Chemical Industry Co., Ltd.), and the solution was cooled to −15° C. To this solution, a solution prepared by dissolving 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 100 mL of acetone was added dropwise. After completion of the dropwise addition, the mixture was stirred at −15° C. for 4 hours and then returned to room temperature. The precipitated white solid was filtered and dried in vacuo at 50° C.

[0167] 30 g of the obtained solid was placed in a 300 mL stainless steel autoclave and dispersed in 250 mL of methyl cellosolve, and 2.0 g of 5% palladium-carbon (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 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 terminated when it was confirmed that the balloon no longer deflated. After the reaction was completed, the palladium compound catalyst was removed by filtration, and the mixture was concentrated using a rotary evaporator to obtain diamine C represented by the following formula:

[0168]

[0169] Synthesis of Alkali-Soluble Resin (A1) (Synthesis Example 4) Under a dry nitrogen stream, 62.0 g (0.20 mol) of 3,3',4,4'-diphenylethertetracarboxylic dianhydride (hereinafter referred to as ODPA) was dissolved in 500 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP). 96.7 g (0.16 mol) of diamine A obtained in Synthesis Example 1 was added together with 100 g of NMP, and the mixture was allowed to react at 20°C for 1 hour, followed by a reaction at 50°C for 2 hours. Next, 8.7 g (0.08 mol) of 3-aminophenol as an end-capping agent was added together with 50 g of NMP, and the mixture was allowed to react at 50°C for 2 hours. Thereafter, a solution prepared by diluting 47.7 g (0.40 mol) of N,N-dimethylformamide dimethyl acetal with 100 g of NMP was added dropwise over 10 minutes. After the dropwise addition, the mixture was stirred at 50°C for 3 hours. After stirring, the solution was cooled to room temperature and then poured into 5 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 24 hours to obtain the target polyimide precursor (A1).

[0170] Synthesis of Alkali-Soluble Resin (A2) (Synthesis Example 5) Under a dry nitrogen stream, 62.0 g (0.20 mol) of ODPA was dissolved in 500 g of NMP. To this was added 92.6 g (0.16 mol) of diamine C obtained in Synthesis Example 3 together with 100 g of NMP, and the mixture was allowed to react at 20°C for 1 hour, followed by a reaction at 50°C for 2 hours. Next, 8.7 g (0.08 mol) of 3-aminophenol as an end-capping agent was added together with 50 g of NMP, and the mixture was allowed to react at 50°C for 2 hours. Thereafter, a solution prepared by diluting 47.7 g (0.40 mol) of N,N-dimethylformamide dimethyl acetal with 100 g of NMP was added dropwise over 10 minutes. After the dropwise addition, the mixture was stirred at 50°C for 3 hours. After stirring was completed, the solution was cooled to room temperature and then poured into 5 L of water, yielding a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80° C. for 24 hours to obtain the desired polyimide precursor (A2).

[0171] Synthesis of Alkali-Soluble Resin (A3) (Synthesis Example 6) Under a dry nitrogen stream, 54.5 g (0.16 mol) of diamine B obtained in Synthesis Example 2 and 8.7 g (0.08 mol) of 3-aminophenol as an end-capping agent were dissolved in 300 g of N-methyl-2-pyrrolidone (NMP). 62.0 g (0.20 mol) of ODPA was added to the solution along with 100 g of NMP, and the mixture was stirred at 20°C for 1 hour, followed by stirring at 50°C for 4 hours. 15 g of xylene was then added, and the mixture was stirred at 150°C for 5 hours while azeotropically distilling water with the xylene. After stirring, the solution was poured into 5 L of water, and a white precipitate was collected. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 24 hours to obtain the target polyimide (A3).

[0172] Synthesis of Alkali-Soluble Resin (A4) (Synthesis Example 7) 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 68.1 g (0.20 mol) of diamine B obtained in Synthesis Example 2 were dissolved in 570 g of NMP and then reacted at 75°C for 12 hours. Next, 13.1 g (0.08 mol) of 5-norbornene-2,3-dicarboxylic anhydride dissolved in 70 g of NMP was added, and the mixture was stirred for an additional 12 hours to complete the reaction. The reaction mixture was filtered and then poured into a solution of water / methanol = 3 / 1 (volume ratio), yielding a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80° C. for 24 hours to obtain the desired polybenzoxazole precursor (A4).

[0173] Synthesis of Alkali-Soluble Resin (A5) (Synthesis Example 8) A methyl methacrylate / methacrylic acid / styrene copolymer (mass ratio 30 / 40 / 30) was synthesized by the method described in Example 1 of Japanese Patent No. 3120476. 40 parts by mass of glycidyl methacrylate was added to 100 parts by mass of the copolymer, and the mixture was reprecipitated in purified water, filtered, and dried to obtain an acrylic resin (A5), which is a polymer obtained by polymerizing a radically polymerizable monomer.

[0174] Synthesis of Alkali-Soluble Resin (A6) (Synthesis Example 9) Under a dry nitrogen stream, 68.1 g (0.20 mol) of diamine B obtained in Synthesis Example 2 was dissolved in 370 g of NMP, and the reaction vessel was cooled to -10°C. 47.2 g (0.16 mol) of 4,4'-oxydibenzoyl chloride dissolved in 200 g of NMP was added dropwise. Next, 7.2 g (0.08 mol) of acryloyl chloride dissolved in 70 g of NMP was added dropwise, and the mixture was stirred for an additional 12 hours to terminate the reaction. The reaction mixture was filtered, and then poured into a solution of water / methanol = 3 / 1 (volume ratio), to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 24 hours to obtain the desired polybenzoxazole precursor (A6).

[0175] Synthesis of Alkali-Soluble Resin (A7) (Synthesis Example 10) Under a dry nitrogen stream, 49.6 g (0.16 mol) of ODPA was dissolved in 500 g of NMP. To this was added 115.7 g (0.20 mol) of diamine C obtained in Synthesis Example 3 together with 100 g of NMP, and the mixture was allowed to react at 20°C for 1 hour, followed by a reaction at 50°C for 2 hours. Next, 10.1 g (0.08 mol) of acrylic anhydride as an end-capping agent was added together with 50 g of NMP, and the mixture was allowed to react at 50°C for 2 hours. Thereafter, a solution prepared by diluting 47.7 g (0.40 mol) of N,N-dimethylformamide dimethyl acetal with 100 g of NMP was added dropwise over 10 minutes. After the dropwise addition, the mixture was stirred at 50°C for 3 hours. After stirring was completed, the solution was cooled to room temperature and then poured into 5 L of water, yielding a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80° C. for 24 hours to obtain the desired polyimide precursor (A7).

[0176] <(B) Quinonediazide Compound> Synthesis of Quinonediazide Compound 1 (Synthesis Example 11) Under a dry nitrogen stream, 21.22 g (0.05 mol) of TrisP-PA (trade name; manufactured by Honshu Chemical Industry Co., Ltd.) and 36.27 g (0.135 mol) of 5-naphthoquinone diazide sulfonyl chloride were dissolved in 450 g of 1,4-dioxane and the solution was allowed to reach room temperature. To this solution, 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature in the system did not exceed 35°C. After the dropwise addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into water. The precipitate was then collected by filtration. This precipitate was dried in a vacuum dryer to obtain quinone diazide compound (B1) represented by the following formula:

[0177]

[0178] <(C) Crosslinking Agent> HMOM-TPHAP (compound represented by the following chemical formula; manufactured by Honshu Chemical Industry Co., Ltd.)

[0179]

[0180] TEPIC-VL: "TEPIC" (registered trademark)-VL (compound represented by the following chemical formula; manufactured by Nissan Chemical Industries, Ltd.)

[0181]

[0182] OXBP: "Ethanacol" (registered trademark) OXBP (compound represented by the following chemical formula; manufactured by Ube Industries, Ltd.)

[0183]

[0184] (n represents an integer of 1 to 3.) <(D) Thermal Acid Generator> D1: methyl p-toluenesulfonate (compound represented by the chemical formula below; manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) D2: 1,3-propanediol di-p-toluenesulfonate (compound represented by the chemical formula below; manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) D3: 1,2,4-tris(methanesulfonyloxy)butane (compound represented by the chemical formula below; manufactured by Tokyo Chemical Industry Co., Ltd.)

[0185]

[0186] <Compound Represented by Formula (1) (E)> Synthesis of Compound E1 Represented by Formula (1) (E) (Synthesis Example 12) Under a dry nitrogen stream, 282.3 g (3.00 mol) of phenol was added to a separable flask equipped with a reflux device and heated to 80°C. Then, 16 g of a fluorine-based ion exchange membrane "Nafion" (registered trademark) 117 (manufactured by DuPont) was cut into 2 cm squares and added. The temperature was raised to 105°C, and 13.2 g (0.10 mol) of dicyclopentadiene was added dropwise over 30 minutes. At this time, the dropping speed was adjusted so that the temperature did not exceed 110°C. The temperature was then raised to 120°C, and the reaction was carried out for 6 hours. Thereafter, the reaction solution was filtered while hot, and unreacted phenol was distilled from the filtrate at 210°C under reduced pressure. After allowing to cool, a brownish-red target product (E1) represented by the following formula (9) was obtained.

[0187]

[0188] BisP-CDE (compound shown in the chemical formula below; manufactured by Honshu Chemical Industry Co., Ltd.) BisP-HTG (compound shown in the chemical formula below; manufactured by Honshu Chemical Industry Co., Ltd.) RF-Z (compound shown in the chemical formula below; manufactured by Honshu Chemical Industry Co., Ltd.) SPI (compound shown in the chemical formula below; manufactured by JFE Chemical Corporation) SBITL (compound shown in formula (7) below: 3,3,3',3'-tetramethyl-1,1'-spirobiindan-5,5',6,6'-tetraol; manufactured by Fujifilm Wako Chemical Co., Ltd.)

[0189]

[0190] <Phenol compounds not corresponding to component (E)> Phenol compound 1: Bisphenol A (manufactured by Tokyo Chemical Industry Co., Ltd.) Phenol compound 2: 1,1,1-tris(4-hydroxyphenyl)ethane (manufactured by Tokyo Chemical Industry Co., Ltd.) Phenol compound 3: 1,1-bis(4-hydroxyphenyl)cyclohexane (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0191]

[0192] Synthesis of Phenolic Compound 4 (Synthesis Example 13) Referring to a known synthesis, 31.9 g (0.29 mol) of resorcinol as a phenolic compound, 28.3 g (0.17 mol) of 4,4'-bis(methoxymethyl)biphenyl as an addition condensation agent, 1.3 g (0.007 mol) of p-toluenesulfonic acid as a catalyst, and 50 g of propylene glycol monomethyl ether (PGME) as a solvent were mixed and stirred at 50°C under a dry nitrogen stream to dissolve the solids and obtain a solution. The obtained solution was stirred at 120°C for 3 hours. After stirring, the solution was cooled to room temperature, and then 100 g of PGME was added and stirred to obtain a diluted solution. The diluted solution was poured into 2 L of water to obtain a precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 24 hours to obtain the target phenolic compound 4.

[0193] <Organic Solvent> PGME: Propylene glycol monomethyl ether GBL: γ-butyrolactone Example 1 Under yellow light, 10.0 g of (A) alkali-soluble resin A5 obtained in Synthesis Example 8, 3.0 g of (B) quinone diazide compound B1 obtained in Synthesis Example 9 (30 parts by mass per 100 parts by mass of the component (A)) as a (C) crosslinking agent TEPIC-VL (15 parts by mass per 100 parts by mass of the component (A)), 0.4 g of (D) thermal acid generator D1 (4 parts by mass per 100 parts by mass of the component (A)), and 0.7 g of (E) component BisP-CDE (7 parts by mass per 100 parts by mass of the component (A)) were weighed out and dissolved in 40.0 g of PGME and 10.0 g of GBL. The resulting solution was then filtered through a filter with a pore size of 1 μm to obtain photosensitive resin composition AA. The photosensitive resin composition thus obtained was used to carry out the evaluations (1) to (4) described above.

[0194] Examples 2 to 32 and Comparative Examples 1 to 8 Photosensitive resin compositions AB to AZ, BA to BE, and a to h were obtained in the same manner as in Example 1, with the types and amounts of compounds being as shown in Tables 1-1, 1-2, 1-3, and 2. The obtained photosensitive resin compositions were used to carry out the evaluations (1) to (4) described above.

[0195] The compositions and evaluation results of the examples and comparative examples are shown in Tables 1 and 2.

[0196]

[0197]

[0198]

[0199]

[0200] In all of Examples 1 to 32, good results were obtained in terms of bending resistance, outgassing amount, and reliability of the organic EL display device. In contrast, Comparative Example 1, which did not contain the components (E) and (D), showed poor results in exposure sensitivity, bending resistance, outgassing amount, and reliability of the organic EL display device. Comparative Examples 2, 3, and 5 to 8, which did not contain the component (E), showed poor results in bending resistance, outgassing amount, and reliability of the organic EL display device. Comparative Example 4, which did not contain the component (D), showed particularly poor results in bending resistance.

[0201] 1: Substrate 2: TFT 3: TFT insulating layer 4: Wiring 5: Planarization layer 6: Contact hole 7: First electrode 8: Pixel dividing layer 9: Organic EL layer 10: Second electrode 11: Alkali-free glass substrate 12: First electrode 13: Auxiliary electrode 14: Pixel dividing layer 15: Organic EL layer 16: Second electrode

Claims

1. A photosensitive resin composition comprising (A) an alkali-soluble resin, (B) a quinone diazide compound, (C) a crosslinking agent, (D) a thermal acid generator, and (E) a compound represented by formula (1). (In formula (1), T represents a divalent to tetravalent group containing an alicyclic structure having 7 to 20 carbon atoms. R １ each independently represents a monovalent group having 1 to 10 carbon atoms. a and b each independently represent an integer of 1 to 3, and c and d each independently represent an integer of 0 to 2. 1≦(a+c)≦4, and 1≦(b+d)≦4.

2. The photosensitive resin composition according to claim 1, wherein T in the compound represented by formula (1) (E) contains a polycyclic alicyclic structure.

3. The photosensitive resin composition according to claim 1, wherein T in the compound represented by formula (1) (E) contains a structure represented by formula (2) or formula (3). (In formula (2), each e independently represents an integer of 0 to 5. In formula (3), R ２ each independently represents a hydrogen atom or a group having 1 to 10 carbon atoms. * indicates the bonding position.

4. The photosensitive resin composition according to claim 1, wherein the contents (mass) of the (C) crosslinking agent, (E) compound represented by formula (1), and (D) thermal acid generator are γ1, γ2, and γ3, respectively, and the mass ratio γ2 / γ1 is in the range of 0.50≦γ2 / γ1≦3.00, and the mass ratio γ3 / (γ1+γ2) is in the range of 0.05≦γ3 / (γ1+γ2)≦0.

20.

5. The photosensitive resin composition according to claim 1, wherein the crosslinking agent (C) comprises a compound having a methylol group and / or an alkoxymethyl group.

6. The photosensitive resin composition according to claim 1, wherein the thermal acid generator (D) comprises a compound represented by formula (4). (In formula (4), R ３ is a monovalent to tetravalent group having 1 to 10 carbon atoms. ４ each independently represents an alkyl group having 1 to 10 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms which may have a substituent; and f represents an integer of 1 to 4.

7. The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (A) comprises one or more selected from the group consisting of polyimide precursors, polyimides, polybenzoxazole precursors, polybenzoxazoles, and copolymers thereof.

8. The photosensitive resin composition according to claim 7, wherein the alkali-soluble resin (A) has a terminal structure represented by formula (5). (In formula (5), R ５ are each independently a hydrogen atom or a monovalent group having 1 to 10 carbon atoms. * indicates the bonding position.

9. The photosensitive resin composition according to claim 7, wherein the alkali-soluble resin (A) has a structure represented by formula (6). (In formula (6), U is a divalent hydrocarbon group having 4 to 20 carbon atoms, R ６ are each independently a hydrocarbon group having 1 to 4 carbon atoms or a hydroxyl group, and each g is independently an integer of 0 to 4. * indicates a bonding position.

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

11. A display device comprising the cured product according to claim 10.

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