Photosensitive resin composition, cured article, method for manufacturing cured article, organic el display device, and display device

Abstract

The present invention relates to a photosensitive resin composition that has high sensitivity and can form a low-transmittance film after curing irrespective of the heating atmosphere during curing. This photosensitive resin composition contains an alkali-soluble resin (a), an aromatic hydrocarbon (b) having at least one aromatic C–H bond and at least three phenolic hydroxyl groups per aromatic ring, a thermal cross-linking agent (c) having a partial structure represented by formula (1), and a photosensitive compound (e). (In formula (1), R10 represents a hydrogen atom or an alkyl group. Each * represents a bond, but no carbonyl group is adjacent to the nitrogen atom.)

Description

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

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

[0002] Many products using organic electroluminescence (hereinafter, "organic EL") display devices have been developed for display devices with thin displays, such as smartphones, tablet PCs, and televisions. Generally, organic EL display devices have a driving circuit, a planarization layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode on a substrate, and can emit light by applying a voltage between the opposing first and second electrodes. Among these, photosensitive resin compositions that can be patterned by ultraviolet irradiation are commonly used as materials for the planarization layer and the insulating layer. In particular, photosensitive resin compositions using polyimide-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.

[0003] In recent years, with the application of driving thin film transistors (hereinafter referred to as TFTs) using oxide semiconductor layers to organic EL display devices, there has been a demand for lowering the ultraviolet light transmittance of insulating layers and planarizing layers in order to prevent malfunctions due to the intrusion of light into the TFTs. Furthermore, with the aim of improving the light extraction efficiency of organic EL display devices, display devices with thinner polarizing plates and polarizer-less displays have been developed, and there is also a demand for lowering the visible light transmittance of insulating layers and planarizing layers in order to improve contrast.

[0004] One technique for reducing the ultraviolet light transmittance of a cured product is to add dihydroxynaphthalene and a thermal crosslinker having a specific structure to an alkali-soluble resin made of polyimide and / or a polyimide precursor (see Patent Document 1). One technique for reducing the visible light transmittance of a cured product and increasing the blackness of the cured product is to add a colorant such as carbon black, organic or inorganic pigments, or dyes to a resin composition, as seen in black matrix materials for liquid crystal displays and RGB paste materials. Examples of such techniques include adding an esterified quinone diazide compound and at least one colorant selected from dyes, inorganic pigments, and organic pigments to an alkali-soluble heat-resistant resin (see Patent Document 2), and adding a photosensitizer and a yellow, red, or blue dye and / or pigment to an alkali-soluble resin made of polyimide and / or a polyimide precursor (see Patent Document 3).

[0005] However, the resin composition prepared by the method described in Patent Document 1 does not have sufficient ultraviolet light blocking properties, and the resin compositions prepared by the methods described in Patent Documents 2 and 3 contain a colorant that absorbs light in the exposure wavelength range of 350 nm to 450 nm of a mercury lamp that is generally used as an exposure light source, resulting in a problem of deteriorating exposure sensitivity.

[0006] In response to this, there is a method of adding a novolac resin, a photosensitizer, and a polymer other than the novolac resin as a technique for reducing the transmittance of ultraviolet light in a cured product (see Patent Document 4), and there is a method of adding, to an alkali-soluble resin, a quinone diazide compound and a thermochromic compound that develops color upon heating and has an absorption maximum in the range of 350 nm to 700 nm, or a compound that does not have an absorption maximum in the range of 350 nm to less than 500 nm but has an absorption maximum in the range of 500 nm to 750 nm (see Patent Document 5).

[0007] International Publication No. 2010 / 087238 Japanese Patent Application Laid-Open No. 2004-145320 Japanese Patent Application Laid-Open No. 2018-63433 International Publication No. 2015 / 129092 Japanese Patent Application Laid-Open No. 2004-326094

[0008] The applicant's investigations revealed that the heat-curable resin compositions described in Patent Documents 4 and 5 reduce transmittance by utilizing oxidation by oxygen in the atmosphere during heat curing, and therefore the transmittance does not decrease in an inert gas atmosphere, which places restrictions on the curing conditions.

[0009] In order to solve the above problems, the photosensitive resin composition of the present invention has the following constitution.

[0010] [1] A photosensitive resin composition comprising: (a) an alkali-soluble resin; (b) an aromatic hydrocarbon having at least one aromatic C-H bond and at least three phenolic hydroxyl groups in one aromatic ring; (c) a thermal crosslinking agent having a partial structure represented by formula (1); and (e) a photosensitive compound.

[0011]

[0012] (In formula (1), R １０ represents a hydrogen atom or an alkyl group. * represents a bond, but a carbonyl group is not adjacent to a nitrogen atom.) [2] The photosensitive resin composition according to [1], wherein the component (c) has two or more partial structures represented by the formula (1) in the molecule.

[0013] [3] The photosensitive resin composition according to [1] or [2], wherein the component (c) contains a triazine ring-containing compound (c1) represented by formula (2):

[0014]

[0015] (In formula (2), R １ ~R ６ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyl ether group having 2 to 10 carbon atoms, a methylol group, or an alkoxymethyl group. １ ~R ６ At least one of the groups is a methylol group or an alkoxymethyl group.) [4] Furthermore, the compound has a maximum absorption wavelength in the range of 490 nm or more and less than 800 nm in the range of 300 to 800 nm, and an absorbance Abs at the maximum absorption wavelength in the range of 490 nm or more and less than 800 nm in the range of 300 to 800 nm ｍａｘAbsorbance Abs at 365 nm ３６５ The photosensitive resin composition according to any one of [1] to [3], comprising a colorant (d) having a ratio of 0.1% or more to less than 60%.

[0016] [5] The photosensitive resin composition according to [4], wherein the component (d) includes a colorant (d-1) having a maximum absorption wavelength in the range of 490 nm or more and less than 580 nm in the range of 300 to 800 nm, and / or a colorant (d-2) having a maximum absorption wavelength in the range of 580 nm or more and less than 800 nm in the range of 300 to 800 nm.

[0017] [6] The photosensitive resin composition according to [4], wherein the component (d) contains a dye (d1-1) having a maximum absorption wavelength in the range of 490 nm or more and less than 580 nm in the range of 300 to 800 nm and / or a dye (d1-2) having a maximum absorption wavelength in the range of 580 nm or more and less than 800 nm in the range of 300 to 800 nm.

[0018] [7] The photosensitive resin composition according to [4] or [6], wherein the component (d) contains an ionic dye that forms an ion pair of an organic anion moiety and an organic cation moiety, and the organic anion moiety and the organic cation moiety are an organic anion moiety of an acid dye and an organic cation moiety of a basic dye, respectively.

[0019] [8] The photosensitive resin composition according to any one of [4] to [7], which contains, as the component (d), n types of ionic dyes that form an ion pair of an organic anion moiety and an organic cation moiety, and the number of organic ions contained in the photosensitive resin composition is (n+1). (n represents an integer from 2 to 10.) [9] The photosensitive resin composition according to any one of [1] to [8], wherein in the component (b), at least one substitution position of the other phenolic hydroxyl group relative to any one phenolic hydroxyl group is the ortho-position or the para-position.

[0020]

[10] The photosensitive resin composition according to any one of [1] to [9], wherein the content of the component (b) is 1 to 50 parts by mass per 100 parts by mass of the component (a).

[0021]

[11] The photosensitive resin composition according to any one of [1] to

[10] , wherein the content of the component (c) is 1 to 100 parts by mass per 100 parts by mass of the component (a).

[0022]

[12] The photosensitive resin composition according to any one of [1] to

[11] , wherein the component (a) includes one or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, polyamideimide precursor, and copolymers thereof.

[0023]

[13] The photosensitive resin composition according to any one of [1] to

[12] , wherein the total mass of all chlorine atoms and all bromine atoms contained in the photosensitive resin composition is 150 ppm or less relative to the total mass of solids excluding the solvent in the photosensitive resin composition.

[0024]

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

[13] .

[0025]

[15] A method for producing a cured product, comprising the steps of: forming a resin film made of the photosensitive resin composition according to any one of [1] to

[13] on a substrate; exposing the resin film; developing the exposed resin film; and heat-treating the developed resin film.

[0026]

[16] An organic EL display device having a driving circuit, a planarizing layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode on a substrate, wherein the planarizing layer and / or the insulating layer comprises the cured product according to

[14] .

[0027]

[17] The organic EL display device according to

[16] , wherein the planarizing layer and / or insulating layer has the cured product, and the planarizing layer and / or insulating layer has a transmittance of less than 30% at a wavelength of 450 nm.

[0028]

[18] The organic EL display device according to

[16] or

[17] , wherein the planarizing layer and / or insulating layer has the cured product, and the planarizing layer and / or insulating layer has an OD value of 0.5 to 1.5 in visible light per 1 μm of film thickness.

[0029]

[19] The organic EL display device according to any one of

[15] to

[18] , further comprising a color filter having a black matrix.

[0030]

[20] A display device having at least metal wiring, the cured product according to

[14] , and a plurality of light-emitting elements, wherein the light-emitting elements have a pair of electrode terminals on either side thereof, the pair of electrode terminals are connected to a plurality of the metal wirings extending in the cured product, and the plurality of the metal wirings maintain electrical insulation due to the cured product.

[0031]

[21] A cured product comprising a crosslinked product of 1,2,4-trihydroxybenzene or pyrogallol and a thermal crosslinking agent (c) having a partial structure represented by formula (1).

[0032]

[0033] (In formula (1), R １０ represents a hydrogen atom or an alkyl group. * represents a bond, but a carbonyl group is not adjacent to a nitrogen atom.)

[22] A cured product formed on a support, which is cut from the surface of the cured product toward the support by an Ar gas cluster ion beam method, and the primary ion species is Bi ３ ＋＋ The cured product was measured by time-of-flight secondary ion mass spectrometry under the measurement conditions of a primary ion current of 0.1 pA and a primary ion irradiation area of ​​an inner area of ​​a square with a side length of 200 μm. １３７ C ７ H ５ O ３ － The normalized secondary ion intensity is 1.0 × 10 －４ The hardened product is as described above.

[0034] The photosensitive resin composition of the present invention has high sensitivity and can form a film with low transmittance after curing, regardless of the heating atmosphere during curing.

[0035] 1 is a cross-sectional view of an example of an organic EL display device;

[0036] An embodiment of the present invention will now be described in detail.

[0037] The photosensitive resin composition of the present invention contains an alkali-soluble resin (a), an aromatic hydrocarbon (b) having at least one aromatic C—H bond and at least three phenolic hydroxyl groups in one aromatic ring, a thermal crosslinking agent (c) having a partial structure represented by formula (1), and a photosensitive compound (e).

[0038]

[0039] (In formula (1), R １０ represents a hydrogen atom or an alkyl group. * represents each bond, but a carbonyl group is not adjacent to a nitrogen atom.) <Alkali-Soluble Resin (a)> The photosensitive resin composition of the present invention contains an alkali-soluble resin (a) (hereinafter, may be referred to as component (a)). Alkali-soluble means that a dissolution rate of 50 nm / min or more is obtained by applying a solution of the resin dissolved in γ-butyrolactone to a silicon wafer and prebaking at 120°C for 4 minutes to form a prebaked film with a film thickness of 10 μm±0.5 μm, immersing the prebaked film in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide at 23±1°C for 1 minute, and then rinsing with pure water, as determined from the decrease in film thickness.

[0040] Component (a) is alkali-soluble and therefore has hydroxyl groups and / or acidic groups in the structural units of the resin and / or at the ends of its main chain. Examples of acidic groups include carboxyl groups, phenolic hydroxyl groups, and sulfonic acid groups.

[0041] Component (a) may include, but is not limited to, known resins such as polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, polyamideimide precursor, polyamide, polymer of radically polymerizable monomer having an acidic group, siloxane resin, cardo resin, and phenolic resin. The photosensitive resin composition of the present invention may contain two or more of these resins. Among these components (a), component (a) preferably includes one or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, polyamideimide precursor, and copolymers thereof, because of its high development adhesion, excellent heat resistance, and low outgassing at high temperatures, resulting in high long-term reliability when used in an organic EL display device. More preferably, component (a) includes polyimide, polyimide precursor, polybenzoxazole precursor, or copolymers thereof. Furthermore, from the viewpoint of further improving sensitivity, component (a) preferably includes a polyimide precursor or polybenzoxazole precursor. Here, the polyimide precursor refers to a resin that can be converted into a polyimide by heat treatment or chemical treatment, such as polyamic acid, polyamic acid ester, etc. The polybenzoxazole precursor refers to a resin that can be converted into a polybenzoxazole by heat treatment or chemical treatment, such as polyhydroxyamide, etc.

[0042] The polyimide precursor and polybenzoxazole precursor described above have a structural unit represented by the following formula (3), and the polyimide has a structural unit represented by the following formula (4). Two or more of these may be contained, or a resin in which the structural unit represented by formula (3) and the structural unit represented by formula (4) are copolymerized may be contained.

[0043]

[0044] In formula (3), X represents a divalent to octavalent organic group having 4 to 40 carbon atoms, and Y represents a divalent to elevenvalent organic group having 6 to 40 carbon atoms. １１ and R １３ R each independently represents a hydroxyl group or a sulfonic acid group. １２and R １４ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. t, u, and w represent integers of 0 to 3, and v represents an integer of 0 to 6. However, when the structural unit represented by formula (3) represents a structural unit of a polyimide precursor, u≧2; when the structural unit represented by formula (3) represents a structural unit of a polybenzoxazole precursor, v≧2; and when a plurality of R １３ At least two of these are hydroxyl groups.

[0045]

[0046] In formula (4), E represents a tetravalent to decavalent organic group having 4 to 40 carbon atoms, and G represents a divalent to octavalent organic group having 6 to 40 carbon atoms. １５ and R １６ each independently represents a carboxy group, a sulfonic acid group, or a hydroxyl group, and x and y each independently represent an integer of 0 to 6, provided that x+y>0.

[0047] The polyimide, polyimide precursor, polybenzoxazole precursor, or copolymer thereof preferably has 5 to 100,000 structural units represented by formula (3) or formula (4). In addition to the structural units represented by formula (3) or formula (4), other structural units may be contained. In this case, it is preferable that the structural units represented by formula (3) or formula (4) account for 50 mol % or more of 100 mol % of all structural units. In the above formula (3), X(R １１ ) ｔ (COOR １２ ) ｕ represents an acid residue. X is a divalent to octavalent organic group having 4 to 40 carbon atoms, and is preferably a divalent to octavalent organic group containing an aromatic ring or a cycloaliphatic group.

[0048] Examples of acid residues include residues of dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, and triphenyl dicarboxylic acid; residues of tricarboxylic acids such as trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, and biphenyl tricarboxylic acid; residues of pyromellitic acid, 3,3',4,4'-biphenyl tetracarboxylic acid, 2,3,3',4'-biphenyl tetracarboxylic acid, 2,2',3,3'-biphenyl tetracarboxylic acid, 3,3',4,4'-benzophenone tetracarboxylic acid, 2,2',3,3'-benzophenone tetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, and 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane. Examples of the X(R tetracarboxylic acid residue include tetracarboxylic acids such as 1,1-bis(3,4-dicarboxyphenyl)hexafluoropropane, 1,1-bis(3,4-dicarboxyphenyl)ethane, 1,1-bis(2,3-dicarboxyphenyl)ethane, bis(3,4-dicarboxyphenyl)methane, bis(2,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, and aromatic tetracarboxylic acids having the structures shown below, aliphatic tetracarboxylic acids such as butanetetracarboxylic acid, and aliphatic tetracarboxylic acids containing a cyclic aliphatic group such as 1,2,3,4-cyclopentanetetracarboxylic acid. １１ ) ｔ (COOR １２ ) ｕ may have two or more of these residues.

[0049]

[0050] R ２０ is an oxygen atom, C(CF ３ ) ２ or C(CH ３ ) ２ Represents R ２１ and R ２２each independently represents a hydrogen atom or a hydroxyl group. In the case of a tricarboxylic acid or tetracarboxylic acid residue among the above acid residues, one or two carboxy groups are (COOR １２ ) is equivalent to

[0051] In the above formula (4), E(R １５ ) ｘ represents a residue of an acid dianhydride. E is a tetravalent to decavalent organic group having 4 to 40 carbon atoms, and is preferably an organic group containing an aromatic ring or a cycloaliphatic group.

[0052] Specific examples of the acid dianhydride residue include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, and bis(3,4-dicarboxyphenyl). Examples of the E(R) include aromatic tetracarboxylic dianhydrides such as ether dianhydrides, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorene dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, and acid dianhydrides having the structures shown below; aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic dianhydride; and residues of aliphatic tetracarboxylic dianhydrides containing a cyclic aliphatic group such as 1,2,3,4-cyclopentanetetracarboxylic dianhydride. １５ ) ｘ may have two or more of these residues.

[0053]

[0054] R ２０ is an oxygen atom, C(CF ３ ) ２ or C(CH ３ ) ２ Represents R ２１ and R ２２ each independently represents a hydrogen atom or a hydroxyl group.

[0055] Y(R １３ ) ｖ (COOR １４ ) ｗ and G(R １６ ) ｙ represents a residue of a diamine. Y is a di- to eleven-valent organic group having 6 to 40 carbon atoms, and is preferably a di- to eleven-valent organic group containing an aromatic ring or a cycloaliphatic group. G is a di- to octa-valent organic group having 6 to 40 carbon atoms, and is preferably a di- to octa-valent organic group containing an aromatic ring or a cycloaliphatic group.

[0056] Specific examples of the diamine residue include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, and 3,3'-diethyl-4,4'-diaminobiphenyl. The amine compound may contain residues of aromatic diamines such as phenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-di(trifluoromethyl)-4,4'-diaminobiphenyl, 9,9-bis(4-aminophenyl)fluorene, 2,2'-bis(trifluoromethyl)-5,5'-dihydroxybenzidine, 3,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, and compounds in which at least a portion of the hydrogen atoms in the aromatic rings of these compounds are substituted with alkyl groups or halogen atoms; residues of aliphatic diamines containing cyclic aliphatic groups such as cyclohexyldiamine and methylenebiscyclohexylamine; and residues of diamines having the structures shown below. １３ )ｖ (COOR １４ ) ｗ and G(R １６ ) ｙ may have two or more of these residues.

[0057]

[0058] R ２０ is an oxygen atom, C(CF ３ ) ２ or C(CH ３ ) ２ Represents R ２１ ~R ２４ each independently represents a hydrogen atom or a hydroxyl group. The terminals of these resins may be blocked with a known monoamine, acid anhydride, acid chloride, monocarboxylic acid, or active ester compound having an acidic group.

[0059] Component (a) may be synthesized by a known method. Examples of methods for producing polyamic acid, which is a polyimide precursor, include reacting a tetracarboxylic dianhydride with a diamine compound in a solvent at low temperature. Examples of methods for producing polyamic acid esters, which are also polyimide precursors, include the aforementioned method of reacting a polyamic acid with an esterifying agent, as well as methods for obtaining a diester from a tetracarboxylic dianhydride with an alcohol, followed by reaction with an amine in a solvent in the presence of a condensing agent, and methods for obtaining a diester from a tetracarboxylic dianhydride with an alcohol, followed by conversion of the remaining dicarboxylic acid into an acid chloride, followed by reaction with an amine in a solvent. From the perspective of ease of synthesis, it is preferable to include a step of reacting a polyamic acid with an esterifying agent. The esterifying agent is not particularly limited, and known methods can be used, but N,N-dimethylformamide dialkyl acetal is preferred because it facilitates purification of the resulting resin.

[0060] Examples of methods for producing polyhydroxyamide, a polybenzoxazole precursor, include a method of condensing a bisaminophenol compound with a dicarboxylic acid in a solvent. Specifically, examples include a method of reacting a dehydration condensing agent such as dicyclohexylcarbodiimide (DCC) with an acid and then adding the bisaminophenol compound. Examples include a method of adding a dicarboxylic acid dichloride solution dropwise to a solution of the bisaminophenol compound to which a tertiary amine such as pyridine has been added.

[0061] Examples of methods for producing polyimides include a method in which the polyamic acid or polyamic acid ester obtained by the above-mentioned method is subjected to dehydration ring closure in a solvent, such as chemical treatment with an acid or base, or heat treatment.

[0062] Examples of methods for producing polybenzoxazole include a method in which polyhydroxyamide obtained by the above-mentioned method is dehydrated and cyclized in a solvent. Examples of methods for dehydration and cyclization include chemical treatment with an acid or a base, and heat treatment. Examples of polyamideimide precursors include polymers of tricarboxylic acids, corresponding tricarboxylic acid anhydrides, tricarboxylic acid anhydride halides, and diamine compounds, with polymers of trimellitic anhydride chloride and aromatic diamine compounds being preferred. Examples of methods for producing polyamideimide precursors include a method in which tricarboxylic acids, corresponding tricarboxylic acid anhydrides, tricarboxylic acid anhydride halides, etc. are reacted with diamine compounds in a solvent at low temperature.

[0063] Examples of methods for producing polyamideimide include a method of reacting trimellitic anhydride with an aromatic diisocyanate in a solvent, and a method of dehydrating and cyclizing the polyamideimide precursor obtained by the above method in a solvent. Examples of methods for dehydrating and cyclizing include chemical treatment with an acid or a base, and heat treatment.

[0064] Examples of polymers of radically polymerizable monomers having an acidic group include acrylic resins and polyhydroxystyrene resins. Known materials can be used as radically polymerizable monomers having an acidic group, including, for example, o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene, as well as alkyl- and alkoxy-substituted derivatives thereof, methacrylic acid and acrylic acid, and derivatives thereof substituted with haloalkyl, alkoxy, halogen, nitro, or cyano at the α-position. Of these, o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene, as well as alkyl- and alkoxy-substituted derivatives thereof, are particularly preferred in terms of sensitivity and resolution during patterning, film remaining rate after development, heat distortion resistance, solvent resistance, adhesion to the base, solution storage stability, and the like. These may be used alone or in combination of two or more.

[0065] Other radical polymerizable monomers having an acidic group may be any known material, such as styrene, alkyl, alkoxy, halogen, haloalkyl, nitro, cyano, amide, or ester substitutions at the α-, o-, m-, or p-position of styrene, diolefins such as butadiene and isoprene, esters of methacrylic acid or acrylic acid, etc. These may be used alone or in combination of two or more.

[0066] Cardo resins include resins having a cardo structure, i.e., a skeletal structure in which two cyclic structures are bonded to a quaternary carbon atom constituting a cyclic structure. A typical cardo structure is one in which a benzene ring is bonded to a fluorene ring. Specific examples of skeletal structures in which two cyclic structures are bonded to a quaternary carbon atom constituting a cyclic structure include a fluorene skeleton, a bisphenolfluorene skeleton, a bisaminophenylfluorene skeleton, a fluorene skeleton having an epoxy group, and a fluorene skeleton having an acrylic group.

[0067] Cardo resins are formed by polymerization of a cardo structure-containing backbone through reactions between the functional groups attached to it. Cardo resins have a structure (cardo structure) in which the main chain and bulky side chains are connected by a single element, forming a cyclic structure oriented approximately perpendicular to the main chain. Specific examples of monomers having a cardo structure include known compounds such as bis(glycidyloxyphenyl)fluorene epoxy resins, cardo structure-containing bisphenols such as 9,9-bis(4-hydroxyphenyl)fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(cyanoalkyl)fluorenes such as 9,9-bis(cyanomethyl)fluorene, and 9,9-bis(aminoalkyl)fluorenes such as 9,9-bis(3-aminopropyl)fluorene. Cardo resins are polymers obtained by polymerizing monomers having a cardo structure, but they may also be copolymers with other copolymerizable monomers.

[0068] The phenolic resins include well-known ones such as novolak phenolic resins and resol phenolic resins, which can be obtained by polycondensing various phenols alone or a mixture of several of them with aldehydes such as formalin.

[0069] 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.

[0070] In addition to formalin, examples of aldehydes include paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, and chloroacetaldehyde, which can be used alone or in combination.

[0071] Examples of polysiloxanes include known polysiloxanes obtained by hydrolyzing and dehydrating condensation of one or more organosilanes selected from tetrafunctional organosilanes, trifunctional organosilanes, difunctional organosilanes, and monofunctional organosilanes.

[0072] Specific examples of organosilanes include tetrafunctional silanes 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. (diphenyl)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 silanes 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 silanes 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 silanes 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.

[0073] Polysiloxanes are synthesized by hydrolysis and partial condensation of 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, a 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.

[0074] The catalyst is not particularly limited, but an acid catalyst or a base catalyst is preferably used. Specific examples of the acid catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acids or their anhydrides, and ion exchange resins. Specific examples of the base catalyst include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, sodium hydroxide, potassium hydroxide, alkoxysilanes having an amino group, and ion exchange resins.

[0075] The solvent used in the production of component (a) is not particularly limited, and examples thereof include alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether, alkyl acetates such as propyl acetate, butyl acetate and isobutyl acetate, ketones such as methyl isobutyl ketone and methyl propyl ketone, alcohols such as butyl alcohol and isobutyl alcohol, ethyl lactate, butyl lactate, dipropylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, 3-methoxybutyl acetate, ethylene glycol monoethyl ether acetate, gamma butyrolactone, N-methyl-2-pyrrolidone, diacetone alcohol, N-cyclohexyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetone, amide, dimethyl sulfoxide, propylene glycol monomethyl ether acetate, N,N-dimethylisobutyric acid amide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, 1,3-dimethyl-2-imidazolidinone, N,N-dimethylpropylene urea, delta valerolactone, 2-phenoxyethanol, 2-pyrrolidone, 2-methyl-1,3-propanediol, diethylene glycol butyl ether, triacetin, butyl benzoate, cyclohexylbenzene, bicyclohexyl, o-nitroanisole, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, N-(2-hydroxyethyl)-2-pyrrolidone, N,N-dimethylpropanamide ... N,N,N',N'-tetramethylurea, 3-methyl-2-oxazolidinone, and the like.

[0076] <Aromatic Hydrocarbon (b) Having at Least One Aromatic C-H Bond and at Least Three Phenolic Hydroxyl Groups in One Aromatic Ring> The photosensitive resin composition of the present invention further comprises an aromatic hydrocarbon (b) (hereinafter sometimes referred to as component (b)) having at least one aromatic C-H bond and at least three phenolic hydroxyl groups in one aromatic ring. When the photosensitive resin composition of the present invention contains component (b) and a thermal crosslinker (c) having a partial structure represented by formula (1) described below, the composition develops color upon heating, regardless of the curing atmosphere, and the transmittance in the 300 nm to 500 nm range can be reduced after curing. While the color-developing mechanism is unclear, it is believed that a crosslinking reaction between the aromatic C-H bond contained in component (b) and the thermal crosslinker (c) having the partial structure represented by formula (1) proceeds upon heating, and the resulting crosslinked product assumes a quinone structure, resulting in the generation of a color-developing product having absorption in the 300 nm to 500 nm range. Since the crosslinking reaction does not depend on the heating atmosphere during curing, the transmittance in the 300 nm to 500 nm range can be reduced after curing without being restricted by the curing conditions. Furthermore, before heating, neither component (b) nor the thermal crosslinking agent (c) having the partial structure represented by formula (1) has absorption in the 300 nm to 500 nm range. Therefore, before curing, the exposure wavelength range of 350 nm to 450 nm of a mercury lamp, which is generally used as an exposure light source, is blocked, allowing pattern formation with high sensitivity. Furthermore, within the 300 to 800 nm range described below, the maximum absorption wavelength is in the range of 490 nm to less than 800 nm, and the absorbance Abs at the maximum absorption wavelength is ｍａｘ Absorbance Abs at 365 nm ３６５ By containing the colorant (d) in which the ratio of is 0.1% or more and less than 60%, it is possible to obtain a film with high visible light blocking properties after curing.

[0077] The aromatic hydrocarbon structure of component (b) includes known monocyclic and fused polycyclic structures. Furthermore, the aromatic hydrocarbon has at least one aromatic C-H bond and at least three phenolic hydroxyl groups in one aromatic ring. An aromatic hydrocarbon having at least one aromatic C-H bond in one aromatic ring means that there is one or more unsubstituted aromatic C-H bonds in the aromatic ring. In the present invention, the state of having at least one aromatic C-H bond and at least three phenolic hydroxyl groups in one aromatic ring refers to the state of having at least one aromatic C-H bond and at least three phenolic hydroxyl groups in a single aromatic ring. For example, a compound having three aromatic rings, each with at least one aromatic C-H bond and one phenolic hydroxyl group, is not included in the scope of the present invention. Specific examples of component (b) include, but are not limited to, the structures shown below.

[0078]

[0079] R ７ are independently a monovalent organic group having 1 to 20 carbon atoms, k is an integer of 0 to 2, l is an integer of 0 to 6, and m is an integer of 3 to 9, provided that {(2k+6)-(l+m)}≧1.

[0080] When component (b) has at least one aromatic C—H bond in one aromatic ring, it can form a crosslinked body composed of a thermal crosslinking agent (c) having a partial structure represented by formula (1) described below, and can reduce the transmittance from 300 nm to 500 nm after curing. The aromatic C—H bonds in one aromatic ring contained in component (b) are one or more, preferably two or more, and more preferably three or more. The greater the number of aromatic C—H bonds in one aromatic ring, the more crosslinking points with the thermal crosslinking agent (c) having the partial structure represented by formula (1) can be increased, thereby further reducing the transmittance from 300 nm to 500 nm after curing, which is preferable.

[0081] Examples of aromatic hydrocarbons having at least one aromatic C—H bond and three phenolic hydroxyl groups in one aromatic ring include phloroglucinol, pyrogallol, 1,2,4-trihydroxybenzene, 2,4,5-trihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, gallacetophenone, 2,3,4-trihydroxybenzoic acid, gallic acid, methyl gallate, ethyl gallate, propyl gallate, octyl gallate, 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, and 4,4′-isopropylidenedipyrogallol. Examples of aromatic hydrocarbons having at least one aromatic C—H bond and four or more phenolic hydroxyl groups in one aromatic ring include 1,2,3,4-tetrahydroxybenzene, 1,2,3,5-tetrahydroxybenzene, 1,2,4,5-tetrahydroxybenzene, and leucoquinizarin.

[0082] From the viewpoint of further reducing the transmittance in the 300 nm to 500 nm range after curing, it is preferable that, in component (b), at least one substitution position of a phenolic hydroxyl group other than any of the phenolic hydroxyl groups in component (b) is the ortho or para position, and more preferably the para position. By having at least one substitution position of a phenolic hydroxyl group other than any of the phenolic hydroxyl groups be the ortho or para position, it is possible to further reduce the transmittance in the 300 nm to 500 nm range after curing. This is presumably because the crosslinked product after curing of component (b) and thermal crosslinker (c) having a partial structure represented by formula (1) has an orthoquinone or paraquinone structure, which further enhances color development.

[0083] Among the component (b), examples of the compound (b1) in which at least one substitution position of a phenolic hydroxyl group other than one of the phenolic hydroxyl groups is the ortho position include pyrogallol, 1,2.4-trihydroxybenzene, 2,4,5-trihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, gallacetophenone, 2,3,4-trihydroxybenzoic acid, gallic acid, methyl gallate, ethyl gallate, propyl gallate, octyl gallate, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 4,4'-isopropylidenedipyrogallol, 1,2,3,4-tetrahydroxybenzene, 1,2,3,5-tetrahydroxybenzene, and 1,2,4,5-tetrahydroxybenzene. Among the component (b), examples of the compound (b2) in which at least one substitution position of a phenolic hydroxyl group relative to any other phenolic hydroxyl group is para-position include 1,2,4-trihydroxybenzene, 2,4,5-trihydroxybenzaldehyde, 1,2,3,4-tetrahydroxybenzene, 1,2,3,5-tetrahydroxybenzene, 1,2,4,5-tetrahydroxybenzene, and leucoquinizarin.

[0084] The upper limit of the molecular weight of component (b) is not particularly limited, but is preferably 1000 or less, more preferably 800 or less, and even more preferably 600 or less. The lower limit of the molecular weight of component (b) is 126 or more.

[0085] In the present invention, the content of component (b) is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, per 100 parts by mass of component (a). By ensuring that the content of component (b) is 1 part by mass or more per 100 parts by mass of component (a), the transmittance from 300 nm to 500 nm after curing can be reduced in combination with a thermal crosslinking agent (c) having a partial structure represented by formula (1) described below. Furthermore, the content of component (b) is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, even more preferably 30 parts by mass or less, and particularly preferably 20 parts by mass or less, per 100 parts by mass of component (a). By ensuring that the content of component (b) is 50 parts by mass or less per 100 parts by mass of component (a), the chemical resistance of the cured product can be maintained.

[0086] <Thermal Crosslinking Agent (c) Having a Partial Structure Represented by Formula (1)> The photosensitive resin composition of the present invention further contains a thermal crosslinking agent (c) (hereinafter, may be referred to as component (c)) having a partial structure represented by formula (1).

[0087]

[0088] R １０ represents a hydrogen atom or an alkyl group. * represents a bond, but the nitrogen atom is not adjacent to a carbonyl group.

[0089] The photosensitive resin composition of the present invention contains components (c) and (b), which allows the composition to develop color upon heating regardless of the curing atmosphere and reduce the transmittance from 300 nm to 500 nm after curing. Component (c) has a partial structure represented by formula (1), i.e., a methylol group or an alkoxymethyl group directly substituted on a nitrogen atom, thereby enabling the composition to form a crosslinked product with component (b). Component (c) preferably has two or more partial structures represented by formula (1) in its molecule, more preferably three or more, even more preferably four or more, and most preferably six or more. The greater the number of partial structures represented by formula (1), the greater the crosslinking points with component (b), thereby further reducing the transmittance from 300 nm to 500 nm after curing, which is preferable. When two methylol groups or alkoxymethyl groups are bonded to the same nitrogen atom in the partial structure represented by formula (1), the molecule is considered to have two partial structures represented by formula (1) in its molecule. There is no particular upper limit to the number of partial structures represented by formula (1) contained in the molecule of component (c), but it is, for example, 20 or less. １０ represents a hydrogen atom or an alkyl group, and from the viewpoint of improving the storage stability of the photosensitive resin composition, R １０ is preferably an alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group.

[0090] In the partial structure represented by formula (1), no carbonyl group is adjacent to the nitrogen atom. When a methylol group or an alkoxymethyl group in formula (1) is directly bonded to a nitrogen atom that is not adjacent to a carbonyl group, the reactivity of the methylol group or the alkoxymethyl group increases, and the formation of a crosslinked product with component (b) is promoted, thereby reducing the transmittance in the 300 nm to 500 nm range after curing.

[0091] In the partial structure represented by formula (1), the substituent adjacent to the nitrogen atom is not particularly limited as long as it is other than a carbonyl group, and may be a hydrogen atom, a methylol group, an alkoxymethyl group, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkenyl ether group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent. From the viewpoint of increasing the reactivity of the methylol group or the alkoxymethyl group, it is preferable that the substituent adjacent to the nitrogen atom in formula (1) is at least one aryl group which may have a substituent or a heteroaryl group which may have a substituent, and examples thereof include, but are not limited to, compounds having the structure shown below.

[0092]

[0093] R １０ each independently represents a hydrogen atom or an alkyl group; L represents a single bond, an oxygen atom, or C(CF ３ ) ２ , C(CH ３ ) ２ , S.O. ２ or CO. M represents a nitrogen atom, CH or CCH ３ Represents R １ ~R ６ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyl ether group having 2 to 10 carbon atoms, a methylol group, or an alkoxymethyl group. １ ~R ６ At least one of these is a methylol group or an alkoxymethyl group.

[0094] From the viewpoint of further reducing the transmittance in the 300 nm to 500 nm wavelength range after curing, the component (c) of the present invention preferably contains a triazine ring-containing compound (c1) represented by formula (2) (hereinafter, may be referred to as component (c1)). That is, the photosensitive resin composition of the present invention is preferably a photosensitive resin composition containing an alkali-soluble resin (a), an aromatic hydrocarbon (b) having at least one aromatic C—H bond and at least three phenolic hydroxyl groups in one aromatic ring, a triazine ring-containing compound represented by formula (2), and a photosensitive compound (e).

[0095]

[0096] In formula (2), R １ ~R ６ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyl ether group having 2 to 10 carbon atoms, a methylol group, or an alkoxymethyl group. １ ~R ６ At least one of R is a methylol group or an alkoxymethyl group. １ ~R ６ At least one of the methylol groups or alkoxymethyl groups has a methylol group or an alkoxymethyl group, preferably two or more, more preferably three or more, even more preferably four or more, and most preferably all six are methylol groups or alkoxymethyl groups. The greater the number of methylol groups or alkoxymethyl groups, the more crosslinking points with component (b) there are, which makes it possible to further reduce the transmittance in the 300 nm to 500 nm range after curing, and this is therefore preferred. Examples of alkoxymethyl groups include methoxymethyl, ethoxymethyl, propoxymethyl, and butoxymethyl groups.

[0097] As the component (c), in addition to commercially available products, those synthesized by known methods can be used. For example, known methods include reacting a primary amino group- or secondary amino group-containing compound with formaldehyde under basic conditions to obtain a compound in which a methylol group is substituted on the nitrogen atom. Furthermore, by reacting the compound with an alcohol under acidic conditions, a compound in which an alkoxymethyl group is substituted on the nitrogen atom can be obtained.

[0098] The upper limit of the molecular weight of component (c) is not particularly limited, but is preferably not more than 1000, more preferably not more than 800, and even more preferably not more than 600. The lower limit of the molecular weight of component (c) is 47 or more.

[0099] In the present invention, the content of component (c) is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, per 100 parts by mass of alkali-soluble resin (a). By ensuring that the content of component (c) is 1 part by mass or more, it is possible to reduce the transmittance from 300 nm to 500 nm after curing in combination with component (b). Furthermore, the content of component (c) is preferably 100 parts by mass or less, more preferably 80 parts by mass or less, even more preferably 50 parts by mass or less, and particularly preferably 30 parts by mass or less, per 100 parts by mass of component (a). By ensuring that the content of component (c) is 100 parts by mass or less, it is possible to improve the sensitivity of the photosensitive resin composition.

[0100] <Photosensitive Compound (e)> The photosensitive resin composition of the present invention further contains a photosensitive compound (e) (hereinafter, sometimes referred to as component (e)). From the viewpoint of achieving high sensitivity, the content of component (e) is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 10 parts by mass or more, per 100 parts by mass of component (a). On the other hand, from the viewpoint of long-term reliability when the cured product of the present invention is used as a planarizing layer and / or insulating layer of an organic EL display device, the content of component (e) is preferably 100 parts by mass or less, per 100 parts by mass of component (a). The component (e) may contain a photoacid generator (e1) or a photopolymerization initiator (e2), for example. The photoacid generator (e1) is a compound that generates an acid upon irradiation with light, and the photopolymerization initiator (e2) is a compound that undergoes bond cleavage and / or reaction upon exposure to generate radicals.

[0101] By including a photoacid generator (e1), acid is generated in the light-irradiated areas, increasing the solubility of the light-irradiated areas in an alkaline aqueous solution, thereby obtaining a positive-tone relief pattern in which the light-irradiated areas are dissolved. Furthermore, by including a photoacid generator (e1) and an epoxy compound or a thermal crosslinking agent described below, the acid generated in the light-irradiated areas promotes the crosslinking reaction of the epoxy compound or the thermal crosslinking agent, thereby obtaining a negative-tone relief pattern in which the light-irradiated areas are insolubilized. On the other hand, by including a photopolymerization initiator (e2) and a radically polymerizable compound described below, radical polymerization proceeds in the light-irradiated areas, thereby obtaining a negative-tone relief pattern in which the light-irradiated areas are insolubilized. From the viewpoint of being able to form a fine pattern when the cured product of the present invention is used as a planarizing layer and / or insulating layer in an organic EL display device, it is preferable that the component (e) contains a photoacid generator (e1) capable of obtaining a positive-tone relief pattern.

[0102] The photoacid generator (e1) may include, for example, a quinone diazide compound. The photosensitive resin composition of the present invention preferably includes two or more types of photoacid generator (e1). When two or more types are included, a photosensitive resin composition with higher sensitivity can be obtained.

[0103] The quinone diazide compound may include a compound in which a sulfonic acid of quinone diazide is bonded to a polyhydroxy compound via an ester bond, a compound in which a sulfonic acid of quinone diazide is bonded to a polyamino compound via a sulfonamide bond, or a compound in which a sulfonic acid of quinone diazide is bonded to a polyhydroxypolyamino compound via an ester bond and / or a sulfonamide bond.

[0104] As the quinone diazide structure, either a 5-naphthoquinone diazide sulfonyl group or a 4-naphthoquinone diazide sulfonyl group is preferably used. A naphthoquinone diazide sulfonyl ester compound having a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule may be contained, or a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound may be contained. 4-naphthoquinone diazide sulfonyl ester compounds have absorption in the i-line region of a mercury lamp and are suitable for i-line exposure. 5-naphthoquinone diazide sulfonyl ester compounds have absorption extending to the g-line region of a mercury lamp and are suitable for g-line exposure.

[0105] It is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazide sulfonyl ester compound depending on the wavelength of exposure, but from the viewpoint of increasing sensitivity, it is preferable to include a 4-naphthoquinone diazide sulfonyl ester compound.

[0106] The quinone diazide compound can be synthesized by any esterification reaction of a compound having a phenolic hydroxyl group and a quinone diazide sulfonic acid compound. The use of such a quinone diazide compound further improves resolution, sensitivity, and film retention.

[0107] From the viewpoint of achieving high sensitivity, the content of the photoacid generator (e1) is preferably 0.1 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 25 parts by mass or more, per 100 parts by mass of the component (a). On the other hand, from the viewpoint of long-term reliability when the cured product of the present invention is used as a planarizing layer and / or insulating layer in an organic EL display device, the content of the photoacid generator (e1) is preferably 100 parts by mass or less, per 100 parts by mass of the component (a).

[0108] Examples of the photopolymerization initiator (e2) include a benzyl ketal-based photopolymerization initiator, an α-hydroxyketone-based photopolymerization initiator, an α-aminoketone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, an oxime ester-based photopolymerization initiator, an acridine-based photopolymerization initiator, a titanocene-based photopolymerization initiator, a benzophenone-based photopolymerization initiator, an acetophenone-based photopolymerization initiator, an aromatic ketoester-based photopolymerization initiator, and a benzoate ester-based photopolymerization initiator. The photosensitive resin composition of the present invention may contain two or more types of photopolymerization initiator (e2). From the viewpoint of further improving sensitivity, it is more preferable that the photopolymerization initiator (e2) contains an α-aminoketone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, or an oxime ester-based photopolymerization initiator.

[0109] Examples of the α-aminoketone photopolymerization initiator include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-butan-1-one, and 3,6-bis(2-methyl-2-morpholinopropionyl)-9-octyl-9H-carbazole.

[0110] Examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphine oxide.

[0111] Examples of the oxime ester photopolymerization initiator include 1-phenylpropane-1,2-dione-2-(O-ethoxycarbonyl)oxime, 1-phenylbutane-1,2-dione-2-(O-methoxycarbonyl)oxime, 1,3-diphenylpropane-1,2,3-trione-2-(O-ethoxycarbonyl)oxime, 1-[4-(phenylthio)phenyl]octane-1,2-dione-2-(O-benzoyl)oxime, 1-[4-[4-(carboxyphenyl)thio]phenyl]propane-1,2-dione-2-(O-acetyl)oxime, 1-[9- It may contain ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyl)oxime, 1-[9-ethyl-6-[2-methyl-4-[1-(2,2-dimethyl-1,3-dioxolan-4-yl)methyloxy]benzoyl]-9H-carbazol-3-yl]ethanone-1-(O-acetyl)oxime, or 1-(9-ethyl-6-nitro-9H-carbazol-3-yl)-1-[2-methyl-4-(1-methoxypropan-2-yloxy)phenyl]methanone-1-(O-acetyl)oxime.

[0112] From the viewpoint of increasing sensitivity, the content of the photopolymerization initiator (e2) is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 10 parts by mass or more, per 100 parts by mass of the total of the component (a) and the radical polymerizable compound described below. On the other hand, from the viewpoint of further improving resolution and reducing the taper angle, the content of the photopolymerization initiator (e2) is preferably 50 parts by mass or less, per 100 parts by mass of the total of the component (a) and the radical polymerizable compound described below.

[0113] <Having a maximum absorption wavelength in the range of 490 nm or more and less than 800 nm in the range of 300 to 800 nm, and an absorbance Abs at a maximum absorption wavelength in the range of 490 nm or more and less than 800 nm in the range of 300 to 800 nm ｍａｘ Absorbance Abs at 365 nm ３６５The photosensitive resin composition of the present invention further has a maximum absorption wavelength in the range of 490 nm or more and less than 800 nm, and an absorbance Abs at the maximum absorption wavelength in the range of 490 nm or more and less than 800 nm, ｍａｘ Absorbance Abs at 365 nm ３６５ It is preferable that the photosensitive resin composition of the present invention contains a colorant (d) (hereinafter, sometimes referred to as component (d)) in which the ratio of (b) to (c) is 0.1% or more and less than 60%. When the photosensitive resin composition of the present invention contains components (b), (c), and (d), a film with high visible light blocking properties can be obtained after curing. "At 300 to 800 nm" means that the maximum absorption wavelength is measured in the region of 300 to 800 nm.

[0114] Component (d) has a maximum absorption wavelength somewhere in the range of 490 nm or more and less than 800 nm in the 300 to 800 nm range. By containing components (b) and (c), it is possible to reduce the transmittance in the 300 to 500 nm range after curing, and therefore by combining it with component (d), it is possible to block all visible light after curing.

[0115] The component (d) has an absorbance Abs of a maximum absorption wavelength in the range of 490 nm or more and less than 800 nm in the range of 300 to 800 nm. ｍａｘ Absorbance Abs at 365 nm ３６５ (hereinafter referred to as absorbance Abs ｍａｘ Absorbance Abs ３６５ The absorbance (Abs) is 0.1% or more and less than 60%. ｍａｘ Absorbance Abs ３６５ The ratio of absorbance Abs ３６５ Absorbance Abs ｍａｘ The absorbance (Abs) is the percentage obtained by dividing the absorbance by 100. ｍａｘ Absorbance Abs ３６５ When the ratio is 0.1% or more and less than 60%, a pattern can be formed with high sensitivity. ｍａｘ Absorbance Abs ３６５The ratio is less than 60%, preferably less than 40%, more preferably less than 20%, even more preferably less than 15%, and most preferably less than 10%. ｍａｘ Absorbance Abs ３６５ The lower limit of the ratio is 0.1% or more. When two or more types of component (d) are used in combination, it is preferable that at least one type of component (d) falls within this range, and it is more preferable that all types of component (d) fall within this range.

[0116] The component (d) preferably contains a dye (d1) and / or a pigment (d2). The component (d) preferably contains at least one type, and for example, it is preferable to contain one type of dye (d1) or pigment (d2), or two or more types of dyes (d1) or pigments (d2), or to contain one or more types of dyes (d1) and one or more types of pigments (d2).

[0117] From the viewpoint of solvent solubility, it is preferable that the component (d) contains a dye (d1). Furthermore, from the viewpoint of increasing sensitivity and reducing residues, it is preferable that the dye (d1) is an ionic dye that forms an ion pair between organic ions. On the other hand, it is preferable that the component (d) contains a pigment (d2) from the viewpoint of suppressing fading of the colorant in the heat treatment step of the photosensitive resin composition described below.

[0118] In addition, from the viewpoint of increasing sensitivity and reducing residues, the component (d) preferably has a sulfonic acid group and / or a sulfonate group.

[0119] Component (d) preferably contains a colorant (d-1) (hereinafter sometimes referred to as component (d-1)) having a maximum absorption wavelength in the range of 490 nm or more and less than 580 nm in the range from 300 to 800 nm, and / or a colorant (d-2) (hereinafter sometimes referred to as component (d-2)) having a maximum absorption wavelength in the range of 580 nm or more and less than 800 nm in the range from 300 to 800 nm. Specifically, component (d-1) preferably contains a dye (d1-1) having a maximum absorption wavelength in the range of 490 nm or more and less than 580 nm in the range from 300 to 800 nm, and / or a pigment (d2-1) having a maximum absorption wavelength in the range of 490 nm or more and less than 580 nm in the range from 300 to 800 nm. Specifically, the component (d-2) preferably contains a dye (d1-2) having a maximum absorption wavelength in the range of 580 nm or more and less than 800 nm in the range of 300 to 800 nm, and / or a pigment (d2-2) having a maximum absorption wavelength in the range of 580 nm or more and less than 800 nm in the range of 300 to 800 nm.

[0120] The component (d) preferably contains a dye (d1-1) having a maximum absorption wavelength somewhere in the range of 490 nm or more and less than 580 nm in the range of 300 to 800 nm, and / or a dye (d1-2) having a maximum absorption wavelength somewhere in the range of 580 nm or more and less than 800 nm in the range of 300 to 800 nm. Hereinafter, these may be simply referred to as the component (d1-1), the component (d2-1), the component (d1-2), and the component (d2-2), respectively.

[0121] In the present invention, from the viewpoints of storage stability and fading during curing and light irradiation, the dye (d1) preferably contains a dye that is soluble in a solvent that dissolves the component (a) and is compatible with the resin, and a dye that has high heat resistance and light fastness. The component (d1-1) has a maximum absorption wavelength in the range of 490 nm or more and less than 580 nm in the 300 to 800 nm range, and therefore can contain, for example, a red dye or a violet dye. The component (d1-2) has a maximum absorption wavelength in the range of 580 nm or more and less than 800 nm in the 300 to 800 nm range, and therefore can contain, for example, a blue dye or a green dye. When the photosensitive resin composition of the present invention contains the component (d1-1) and the component (d1-2), from the viewpoints of improving heat resistance and maintaining visible light blocking properties after curing, it is preferable that either the component (d1-1) or the component (d1-2) has a xanthene structure, and it is more preferable that both the component (d1-1) and the component (d1-2) have a xanthene structure.

[0122] Examples of the skeletal structure of the dye (d1) include, but are not limited to, anthraquinone-based, azo-based, phthalocyanine-based, methine-based, oxazine-based, quinoline-based, triarylmethane-based, and xanthene-based dyes. Among these, anthraquinone-based, azo-based, methine-based, triarylmethane-based, and xanthene-based dyes are preferred from the viewpoints of solubility in solvents and heat resistance. Furthermore, xanthene-based dyes are more preferred from the viewpoint of improving heat resistance. Furthermore, each of these dyes may be used alone or as a metal-containing complex salt. Specifically, Sumilan and Lanyl dyes (manufactured by Sumitomo Chemical Co., Ltd.), Orasol, Oracet, Filamid, and Irgasperse dyes (manufactured by Ciba Specialty Chemicals Co., Ltd.), Zapon, Neozapon, Neptune, and Acidol dyes (manufactured by BASF Corporation), Kayaset and Kayakalan dyes (manufactured by Nippon Kayaku Co., Ltd.), Valifast Colors dyes (manufactured by Orient Chemical Industry Co., Ltd.), Savinyl, Sandoplast, Polysynthren, and Lanasyn dyes (manufactured by Clariant Japan Co., Ltd.), Aizen Spilon dyes (manufactured by Hodogaya Chemical Co., Ltd.), functional dyes (manufactured by Yamada Chemical Co., Ltd.), and Plast Color dyes, Oil Color dyes (manufactured by Arimoto Chemical Industry Co., Ltd.), etc. are available, but are not limited thereto. These dyes can be used alone or in combination.

[0123] In the present invention, the dye (d1) preferably contains an ionic dye (d1a) (hereinafter sometimes referred to as component (d1a)) that forms an ion pair between an organic anion moiety and an organic cation moiety. The component (d1a) refers to a salt-forming compound consisting of an organic anion moiety and a non-dye organic cation moiety, a salt-forming compound consisting of an organic cation moiety of a basic dye and a non-dye organic anion moiety, or a salt-forming compound consisting of an organic anion moiety of an acid dye and an organic cation moiety of a basic dye. From the viewpoint of improving sensitivity by increasing the proportion of coloring components per molecule and reducing the amount of ionic dye added, the ionic dye of the present invention preferably contains a salt-forming compound consisting of an organic anion moiety of an acid dye and an organic cation moiety of a basic dye. That is, the component (d) preferably contains an ionic dye that forms an ion pair between an organic anion moiety and an organic cation moiety, and the organic anion moiety and the organic cation moiety are each composed of the organic anion moiety of an acid dye and the organic cation moiety of a basic dye, respectively.

[0124] A salt-forming compound consisting of an organic anion moiety of an acid dye and an organic cation moiety of a non-dye can be produced by using an acid dye as a raw material and exchanging the counter cation with an organic cation of a non-dye by a known method. A salt-forming compound consisting of an organic cation moiety of a basic dye and an organic anion moiety of a non-dye can be produced by using a basic dye as a raw material and exchanging the counter anion with an organic anion of a non-dye by a known method. A salt-forming compound consisting of an organic anion moiety of an acid dye and an organic cation moiety of a basic dye can be produced by using an acid dye and a basic dye as raw materials and exchanging the counter ions of each dye by a known method.

[0125] The acid dyes used as raw materials for component (d1a) are compounds having an acidic substituent such as a sulfo group or a carboxy group in the dye molecule, or anionic water-soluble dyes that are salts thereof. Acid dyes include those that have an acidic substituent such as a sulfo group or a carboxy group and are classified as direct dyes.

[0126] Examples of acid dyes include C.I. Acid Yellow 1, 17, 18, 23, 25, 36, 38, 42, 44, 54, 59, 72, 78, 151; C.I. Acid Orange 7, 10, 12, 19, 20, 22, 28, 30, 52, 56, 74, 127; C.I. Acid Red 1, 3, 4, 6, 8, 11, 12, 14, 18, 26, 27, 33, 37, 53, 57, 88, 106, 108, 111, 114, 131, 137, 138, 151, 154, 158, 159, 173, 184, 186, 215, 257, 266, 296, 337; C.I. Acid Brown 2, 4, 13, 248; C.I. Acid Violet 11, 56, 58; C.I. Azo acid dyes such as Acid Blue 92, 102, 113, 117; C.I. Quinoline acid dyes such as Acid Yellow 2, 3, 5; C.I. Xanthene acid dyes such as Acid Red 50, 51, 52, 87, 91, 92, 93, 94, 289; C.I. Acid Red 82, 92; C.I. Acid Violet 41, 42, 43; C.I. Acid Blue 14, 23, 25, 27, 40, 45, 78, 80, 127:1, 129, 145, 167, 230; C.I. Anthraquinone acid dyes such as Acid Green 25, 27; C.I. Examples of suitable acid dyes include triarylmethane acid dyes such as C.I. Acid Violet 49; C.I. Acid Blue 7, 9, 22, 83, 90; C.I. Acid Green 9, 50; and C.I. Food Green 3; phthalocyanine acid dyes such as C.I. Acid Blue 249; and indigoid acid dyes such as C.I. Acid Blue 74. Among these, the acid dye preferably contains a xanthene acid dye in terms of high heat resistance. The xanthene acid dye more preferably contains a rhodamine acid dye such as C.I. Acid Red 50, 52, or 289.

[0127] The non-dye organic cation moiety that is the raw material for the component (d1a) is an ammonium ion [N(R) ４ ] ＋ , phosphonium ion [P(R) ４ ] ＋ , iminium ion [(R) ２ -N=C(R) ２ ] ＋, arsonium ion [As(R) ４ ] ＋ , stibonium ion [Sb(R) ４ ] ＋ , oxonium ion [O(R) ３ ] ＋ , sulfonium ion [S(R) ３ ] ＋ , selenonium ion [Se(R) ３ ] ＋ , stannonium ion [Sn(R) ３ ] ＋ , iodonium ion [I(R) ２ ] ＋ , diazonium ion [R-N ＋ From the viewpoint of insulating properties when a cured product made of the photosensitive resin composition of the present invention is used, an ammonium ion [N(R) ４ ] ＋ , phosphonium ion [P(R) ４ ] ＋ , iminium ion [(R) ２ -N=C(R) ２ ] ＋ In the ionic formula, R's are each independently a hydrocarbon group having 1 to 20 carbon atoms, which may have a substituent and which may have a heteroatom in the carbon chain. From the viewpoint of improving sensitivity by increasing the proportion of the coloring component per molecule and reducing the content of the ionic dye in the photosensitive resin composition, the molecular weight of the non-dye organic cation moiety is preferably 1,000 or less, more preferably 700 or less, and more preferably 400 or less. There is no particular restriction on the lower limit of the molecular weight of the non-dye organic cation moiety, but it is preferably 1 or more, and more preferably 100 or more.

[0128] The basic dye, which is the raw material for the component (d1a), is a compound having a basic group such as an amino group or an imino group in the molecule, or a salt thereof, and is a dye that becomes a cation in an aqueous solution.

[0129] Examples of basic dyes include C.I. Basic Red 17, 22, 23, 25, 29, 30, 38, 39, 46, 46:1, 82; C.I. Basic Orange 2, 24, 25; C.I. Basic Violet 18; C.I. Basic Yellow 15, 24, 25, 32, 36, 41, 73, 80; C.I. Basic Brown 1; C.I. Basic Blue 41, 54, 64, 66, 67, 129 and other azo-based basic dyes; C.I. Basic Red 1, 2; C.I. Basic Violet 10, 11 and other xanthene-based basic dyes; C.I. Basic Yellow 11, 13, 21, 23, 28; C.I. Basic Orange 21; C.I. Basic Red 13, 14; C.I. Examples of the basic dyes include methine-based basic dyes such as C.I. Basic Violet 16 and 39; anthraquinone-based basic dyes such as C.I. Basic Blue 22, 35, 45 and 47; C.I. Basic Violet 1, 2, 3, 4, 13, 14 and 23; C.I. Basic Blue 1, 5, 7, 8, 11, 15, 18, 21, 24 and 26; C.I. Basic Green 1 and 4; and xanthene-based basic dyes having the structures shown below.

[0130]

[0131] R ２５ ~R ３１ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms which may have a substituent. Among these, the basic dye preferably contains a xanthene-based basic dye or a triarylmethane-based basic dye in that it can increase the blackness of the cured product, and preferably contains a xanthene-based acid dye in that it has high heat resistance.

[0132] The non-dye organic anion moiety that serves as the raw material for the component (d1a) may include aliphatic or aromatic sulfonate ions, aliphatic or aromatic carboxylate ions, and sulfonimide anions [(RSO ２ ) ２ N] ― , borate anion (BR ４ ) ―Examples include: From the viewpoint of suppressing deterioration of electrodes and light-emitting layers of organic EL display devices when a cured product made from the photosensitive resin composition of the present invention is applied, the non-dye organic anion moiety is preferably an aliphatic or aromatic sulfonate ion or an aliphatic or aromatic carboxylate ion. Furthermore, from the viewpoint of increasing sensitivity and reducing residues, the non-dye organic anion moiety is preferably an aliphatic or aromatic sulfonate ion. Note that R in the ionic formula of the non-dye organic anion moiety is a hydrocarbon group having 1 to 20 carbon atoms, which may each independently have a substituent and which may have a heteroatom in the carbon chain. From the viewpoint of increasing the proportion of coloring components per molecule and reducing the content of ionic dye in the photosensitive resin composition to improve sensitivity, the molecular weight of the non-dye organic anion moiety is preferably 1,000 or less, more preferably 700 or less, and even more preferably 400 or less. The lower limit of the molecular weight of the non-dye anion moiety is not particularly limited, but is preferably 1 or more, and even more preferably 100 or more.

[0133] From the viewpoint of high heat resistance, it is preferable that the organic anion moiety and / or organic cation moiety of component (d1a) have a xanthene skeleton. Examples of organic anions having a xanthene skeleton include the above-mentioned xanthene acid dyes, and examples of organic cations having a xanthene skeleton include the above-mentioned xanthene basic dyes.

[0134] From the viewpoints of increasing alkali solubility during development and improving sensitivity, the component (d1a) preferably has an acidic group. Examples of the acidic group include a carboxy group, a phenolic hydroxyl group, a sulfonic acid group, and a sulfonate group, with the sulfonic acid group and sulfonate group being particularly preferred.

[0135] A salt-forming compound obtained by ion exchange of an acid dye or a basic dye can be produced by a known method. For example, an aqueous solution of an acid dye and an aqueous solution of a basic dye are separately prepared, and the two are slowly mixed with stirring to produce a salt-forming compound consisting of the organic anion moiety of the acid dye and the organic cation moiety of the basic dye as a precipitate. The salt-forming compound can be obtained by recovering the precipitate by filtration. The obtained salt-forming compound is preferably dried at about 60 to 70°C.

[0136] The photosensitive resin composition of the present invention may contain two or more types of component (d1a). However, when the photosensitive resin composition of the present invention contains n types of component (d1a), it is preferable that the photosensitive resin composition contain (n+1) types of organic ions. Here, n represents an integer from 2 to 10. The organic ions contained in the photosensitive resin composition refer not only to the organic ions constituting the ionic dye, but also to all organic ions contained in the photosensitive resin composition. For example, when a photosensitive resin composition contains n types of (d1a) components whose organic anion moieties and organic cation moieties are different, the photosensitive resin composition contains (n×2) types of organic ions. In this case, the presence of multiple types of organic anions and organic cations in the photosensitive resin composition can lead to an increase in foreign matter during frozen storage due to ion exchange between ionic dyes, resulting in a deterioration in storage stability. On the other hand, when the photosensitive resin composition contains n types of component (d1a) and contains (n+1) types of organic ions, storage stability during frozen storage is improved. This is presumably because the organic ion species for component (d1a) are limited, thereby suppressing ion exchange between ionic dyes in the photosensitive resin composition.

[0137] A first embodiment, in which n types of (d1a) components are contained and the photosensitive resin composition contains (n+1) types of organic ions, includes a case in which all of the n types of (d1a) components have the same organic anion moieties or organic cation moieties. For example, when n is 3, this represents a case in which all of the organic anion moieties or organic cation moieties in Ionic Dye 1, Ionic Dye 2, and Ionic Dye 3 are the same. Furthermore, when n is ≥ 3, a second embodiment includes a case in which two or more types of organic anion moieties and organic cation moieties in the n types of (d1a) components are the same. For example, when n is 3, this represents a case in which the organic anion moieties in Ionic Dye 1 and Ionic Dye 2 are the same, and the organic cation moieties in Ionic Dye 1 and Ionic Dye 3 are the same. The first embodiment is preferred from the viewpoint of suppressing ion exchange between ionic dyes and improving storage stability during frozen storage. From the viewpoint of improving storage stability, n is preferably 2 to 5, more preferably 2 to 3, and even more preferably 2.

[0138] In the present invention, the pigment (d2) is preferably a pigment having high heat resistance and light resistance from the viewpoint of preventing fading during curing and light irradiation. The component (d2-1) has a maximum absorption wavelength in the range of 490 nm or more and less than 580 nm in the range of 300 to 800 nm, and therefore can contain, for example, a red pigment or a violet pigment. The component (d2-2) has a maximum absorption wavelength in the range of 580 nm or more and less than 800 nm in the range of 300 to 800 nm, and therefore can contain, for example, a blue pigment or a green pigment.

[0139] Specific examples of organic pigments are represented by Color Index (C.I.) numbers. Examples of the (d2-1) component include red pigments such as Pigment Red 48:1, 122, 168, 177, 202, 206, 207, 209, 224, 242, and 254, and purple pigments such as Pigment Violet 19, 23, 29, 32, 33, 36, 37, and 38. Examples of the (d2-2) component include blue pigments such as Pigment Blue 15 (15:3, 15:4, 15:6, etc.), 21, 22, 60, and 64, and green pigments such as Pigment Green 7, 10, 36, 47, and 58. Pigments other than these may also be contained.

[0140] In the present invention, the organic pigment used as pigment (d2) may contain a pigment that has been subjected to a surface treatment such as rosin treatment, acidic group treatment, or basic group treatment, as necessary. Furthermore, a dispersant may be optionally contained. The dispersant may contain, for example, a cationic, anionic, nonionic, amphoteric, silicone, or fluorine-based surfactant.

[0141] The content of component (d) is preferably 0.1 to 300 parts by mass, more preferably 0.2 to 200 parts by mass, and particularly preferably 1 to 200 parts by mass, per 100 parts by mass of component (a). By making the content of component (d) 0.1 parts by mass or more per 100 parts by mass of component (a), light of the corresponding wavelength can be absorbed. Furthermore, by making the content 300 parts by mass or less, light of the corresponding wavelength can be absorbed while maintaining the adhesive strength between the photosensitive colored resin film and the substrate, the heat resistance of the film after heat treatment, and the mechanical properties.

[0142] The photosensitive resin composition of the present invention may also contain a colorant other than component (d). By adding another colorant in addition to component (d), it is possible to impart light-blocking properties, i.e., blocking light of wavelengths absorbed by the other colorant from light transmitted through or reflected from a film of the photosensitive resin composition. By imparting light-blocking properties, when the cured product of the present invention, described below, is used as a planarizing layer and / or insulating layer in an organic EL display device, deterioration, malfunction, leakage current, and the like due to light penetration into TFTs can be prevented. Furthermore, it is possible to suppress external light reflection from wiring and TFTs and improve the contrast between light-emitting and non-light-emitting areas.

[0143] <Radical Polymerizable Compound> The photosensitive resin composition of the present invention may contain a radical polymerizable compound. In particular, when the photosensitive resin composition contains a photopolymerization initiator (e2), it is essential that the composition contain a radical polymerizable compound. The radical polymerizable compound refers to a compound having multiple ethylenically unsaturated double bonds in its molecule. During exposure, radicals generated from the photopolymerization initiator (e2) cause radical polymerization of the radical polymerizable compound, insolubilizing the light-irradiated area and thereby obtaining a negative pattern. Furthermore, by containing a radical polymerizable compound, photocuring of the light-irradiated area is promoted, thereby further improving sensitivity. In addition, the crosslinking density after thermal curing is improved, thereby improving the hardness of the cured product.

[0144] The radical polymerizable compound is preferably a compound having a (meth)acrylic group, which facilitates radical polymerization. From the viewpoint of improving sensitivity during exposure and improving hardness of the cured product, a compound having two or more (meth)acrylic groups in the molecule is more preferred. From the viewpoint of improving sensitivity during exposure and improving hardness of the cured product, the double bond equivalent of the radical polymerizable compound is preferably 80 to 400 g / mol.

[0145] Examples of the radical polymerizable compound include trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, 2,2-bis[4-(

[0033] The acrylic acid copolymer may contain, for example, 1,3,5-tris((meth)acryloxyethyl)isocyanuric acid, 1,3-bis((meth)acryloxyethyl)isocyanuric acid, 9,9-bis[4-(2-(meth)acryloxyethoxy)phenyl]fluorene, 9,9-bis[4-(3-(meth)acryloxypropoxy)phenyl]fluorene, 9,9-bis(4-(meth)acryloxyphenyl)fluorene, or acid-modified, ethylene oxide-modified, or propylene oxide-modified products thereof.

[0146] The content of the radical polymerizable compound is preferably 15 parts by mass or more, and more preferably 30 parts by mass or more, per 100 parts by mass of the total of component (a) and the radical polymerizable compound, from the viewpoints of further improving the sensitivity and reducing the taper angle. On the other hand, from the viewpoints of further improving the heat resistance of the cured product and reducing the taper angle, the content is preferably 65 parts by mass or less, and more preferably 50 parts by mass or less, per 100 parts by mass of the total of component (a) and the radical polymerizable compound.

[0147] <Thermal Crosslinking Agent> The photosensitive resin composition of the present invention may contain a thermal crosslinking agent other than component (c). A thermal crosslinking agent refers to a compound having at least two thermally reactive functional groups in the molecule, such as an alkoxymethyl group, a methylol group, an epoxy group, or an oxetanyl group. The inclusion of a thermal crosslinking agent can crosslink between the thermal crosslinking agent and component (a) or between the thermal crosslinking agents themselves, improving the heat resistance, chemical resistance, and bending resistance of the cured product after thermal curing. From the viewpoint of reducing the transmittance in the 300-500 nm range after curing, a thermal crosslinking agent having low reactivity with phenolic hydroxyl groups is preferred, and an alkoxymethyl group is preferred. This is presumably because, in a crosslinked product consisting of components (b) and (c), when the phenolic hydroxyl group of component (b) reacts with the thermal crosslinking agent, the crosslinked product is less likely to form a quinone structure.

[0148] Preferred examples of the compound having at least two alkoxymethyl groups or methylol groups include DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, It may contain TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all of which are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), "NIKALAC" (registered trademark) MX-290, "NIKALAC" MX-280, "NIKALAC" MX-270, "NIKALAC" MX-279 (all of which are trade names, manufactured by Sanwa Chemical Co., Ltd.), and the like.

[0149] Preferred examples of compounds having at least two epoxy groups include "Epolite" (registered trademark) 40E, "Epolite" 100E, "Epolite" 200E, "Epolite" 400E, "Epolite" 70P, "Epolite" 200P, "Epolite" 400P, "Epolite" 1500NP, "Epolite" 80MF, "Epolite 4000," and "Epolite" 1500NP. "Denacol" (registered trademark) EX-3002 (all manufactured by Kyoeisha Chemical Co., Ltd.), "Denacol" (registered trademark) EX-212L, "Denacol" EX-214L, "Denacol" EX-216L, "Denacol" EX-850L (all manufactured by Nagase ChemteX Corporation), GAN, GOT (all manufactured by Nippon Kayaku Co., Ltd.), "Epicoat" (registered trademark) 828, "Epicoat" 1002, "Epicoat" 1750, "Epicoat" 1007, YX8100-BH30, E1256, E4250, E4275 (all manufactured by Japan Epoxy Resins Co., Ltd.), "Epiclon" (registered trademark) EXA-9583, HP4032 (all manufactured by DIC Corporation), VG3101 (manufactured by Mitsui Chemicals, Inc.), "Tepic" (registered trademark) S, "Tepic" G, "Tepic" P (all manufactured by Nissan Chemical Industries, Ltd.) The present invention may contain, for example, "Denacol" EX-321L (manufactured by Nagase ChemteX Corporation), "Denacol" EX-321L (manufactured by Nagase ChemteX Corporation), NC6000 (manufactured by Nippon Kayaku Co., Ltd.), "Epotohto" (registered trademark) YH-434L (manufactured by Tohto Kasei Co., Ltd.), EPPN502H, NC3000 (manufactured by Nippon Kayaku Co., Ltd.), "Epiclon" (registered trademark) N695, HP7200 (all manufactured by DIC Corporation), and the like.

[0150] Examples of compounds having at least two oxetanyl groups include Ethanacol EHO, Ethanacol OXBP, Ethanacol OXTP, and Ethanacol OXMA (all manufactured by Ube Industries, Ltd.), oxetanized phenol novolac, etc. Two or more types of thermal crosslinking agents may be used in combination.

[0151] The content of the thermal crosslinking agent is preferably 1 part by mass or more and 30 parts by mass or less in 100 parts by mass of the total amount of the photosensitive resin composition excluding the solvent. If the content of the thermal crosslinking agent is 1 part by mass or more in 100 parts by mass of the total amount of the photosensitive resin composition excluding the solvent, the chemical resistance of the cured product can be further improved. Furthermore, if the content of the thermal crosslinking agent is 30 parts by mass or less in 100 parts by mass of the total amount of the photosensitive resin composition excluding the solvent, the storage stability of the photosensitive resin composition is excellent.

[0152] <Solvent> The photosensitive resin composition of the present invention may contain a solvent. By containing a solvent, the composition can be made into a varnish state, and the coatability can be improved.

[0153] Examples of the solvent include polar aprotic solvents such as γ-butyrolactone, ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tetrahydrofuran, and dioxane, acetone, methyl Ketones such as ethyl ethyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, and diacetone alcohol; esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and ethyl lactate; ethyl 2-hydroxy-2-methylpropionate, 3- Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate,The solvent may contain other esters such as i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; amides such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N,N-dimethylpropanamide, and N,N-dimethylisobutyramide; and 3-methyl-2-oxazolidinone. The solvent may contain two or more of these.

[0154] The content of the solvent is not particularly limited, but is preferably 100 to 3,000 parts by mass, and more preferably 150 to 2,000 parts by mass, relative to 100 parts by mass of the total amount of the photosensitive resin composition excluding the solvent. Furthermore, the proportion of the solvent with a boiling point of 180°C or higher in 100 parts by mass of the total amount of solvent is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less. By keeping the proportion of the solvent with a boiling point of 180°C or higher to 20 parts by mass or less, the amount of outgassing after thermal curing can be further reduced, and the long-term reliability of the organic EL device can be further improved.

[0155] <Adhesion Improver> The photosensitive resin composition of the present invention may contain an adhesion improver. Examples of the adhesion improver 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 resin film, for example, it is possible to improve the adhesion of the photosensitive resin composition to silicon wafers, indium tin oxide (ITO), SiO ２The adhesion improver can improve the adhesion to the underlying substrate such as silicon nitride during development. It can also improve resistance to oxygen plasma and UV ozone treatments used for cleaning, etc. The content of the adhesion improver is preferably 0.01 to 10 parts by mass per 100 parts by mass of the total amount of the photosensitive resin composition excluding the solvent.

[0156] <Surfactant> The photosensitive resin composition of the present invention may contain an adhesion improver to improve wettability with the substrate. Examples of surfactants that can be used include fluorine-based surfactants such as the SH series, SD series, and ST series from Dow Corning Toray Co., Ltd., the BYK series from BYK Japan K.K., the KP series from Shin-Etsu Chemical Co., Ltd., the Disfoam series from NOF Corporation, the Megafac (registered trademark) series from DIC Corporation, the Fluorad series from Sumitomo 3M Limited, the Surflon (registered trademark) series and Asahi Guard (registered trademark) series from Asahi Glass Co., Ltd., and the Polyfox series from Omnova Solutions, as well as acrylic and / or methacrylic surfactants such as the Polyflow series from Kyoeisha Chemical Co., Ltd. and the Disparlon (registered trademark) series from Kusumoto Chemical Co., Ltd.

[0157] When a surfactant is contained, the content thereof is preferably 0.001 to 1 part by mass in 100 parts by mass of the total amount of the photosensitive resin composition excluding the solvent.

[0158] <Inorganic Particles> The photosensitive resin composition of the present invention may contain inorganic particles. Specific preferred examples of inorganic particles include silicon oxide, titanium oxide, barium titanate, alumina, and talc. The primary particle diameter of the inorganic particles is preferably 100 nm or less, and more preferably 60 nm or less.

[0159] The content of the inorganic particles is preferably 5 to 90 parts by mass in 100 parts by mass of the total amount of the photosensitive resin composition excluding the solvent.

[0160] <Total Chlorine Atoms, Total Bromine Atoms> In the photosensitive resin composition of the present invention, the total mass of all chlorine atoms and all bromine atoms contained in the photosensitive resin composition is preferably 150 ppm or less, more preferably 100 ppm or less, and even more preferably less than 2 ppm, which is the lower detection limit of combustion ion chromatography, relative to the total mass of the solids in the photosensitive resin composition excluding the solvent.

[0161] By controlling the total amount of all chlorine atoms and all bromine atoms contained in the photosensitive resin composition to 150 ppm or less relative to the solid content of the photosensitive resin composition, it is possible to suppress deterioration of the electrodes and light-emitting layers of an organic EL display device having a cured product obtained by curing the photosensitive resin composition, and to improve long-term reliability.

[0162] Furthermore, by setting the total amount of all chlorine atoms and all bromine atoms contained in the photosensitive resin composition to 150 ppm or less based on the solid content excluding the solvent in the photosensitive resin composition, the storage stability of the photosensitive resin composition of the present invention during frozen storage can be improved.

[0163] The total mass of all chlorine atoms and all bromine atoms contained in the photosensitive resin composition can be measured by, for example, combustion ion chromatography, in which the photosensitive resin composition is burned at 900 to 1000°C in a combustion tube of an analyzer, the generated gas is absorbed into a solution, and then a portion of the absorbed solution is analyzed by ion chromatography.

[0164] <Method for producing photosensitive resin composition> Next, a method for producing the photosensitive resin composition of the present invention will be described. For example, the photosensitive resin composition of the present invention can be obtained by dissolving the components (a), (b), (c), and (e), and, if necessary, the component (d), a radical polymerizable compound, a thermal crosslinking agent, a solvent, an adhesion improver, a surfactant, inorganic particles, etc.

[0165] Examples of dissolution methods include stirring and heating. When heating, the heating temperature is preferably set within a range that does not impair the performance of the photosensitive resin composition, and is typically room temperature to 80°C. The order in which the components are dissolved is not particularly limited, and examples include a method in which compounds with low solubility are dissolved in order. For components that tend to generate bubbles when dissolved by stirring, such as surfactants and some adhesion improvers, adding them last after dissolving the other components can prevent poor dissolution of the other components due to the generation of bubbles.

[0166] The obtained photosensitive resin composition is preferably filtered using a filter to remove dust and particles. Examples of filter pore sizes include, but are not limited to, 0.5 μm, 0.2 μm, 0.1 μm, 0.07 μm, 0.05 μm, and 0.02 μm. Examples of filter materials include polypropylene (PP), polyethylene (PE), nylon (NY), and polytetrafluoroethylene (PTFE). Among these, polyethylene and nylon are preferred.

[0167] <Method for Producing a Cured Product> The method for producing a cured product of the present invention includes the steps of forming a resin film made of the photosensitive resin composition of the present invention on a substrate, exposing the resin film to light, developing the exposed resin film, and heat-treating the developed resin film.

[0168] The process of forming a resin film made of the photosensitive resin composition of the present invention on a substrate will now be described. In the present invention, the resin film can be obtained by applying the photosensitive resin composition of the present invention to obtain a coating film of the photosensitive resin composition, and then drying the coating film. The substrate can be a known substrate such as a glass substrate.

[0169] Examples of methods for applying the photosensitive resin composition of the present invention include spin coating, slit coating, dip coating, spray coating, and printing. Among these, slit coating is preferred because it allows application with a small amount of coating liquid, which is advantageous in reducing costs. The amount of coating liquid required for slit coating is, for example, approximately 1 / 5 to 1 / 10 of that required for spin coating. Slit nozzles used for application can be selected from those commercially available from multiple manufacturers, including, for example, the "Linear Coater" manufactured by Dainippon Screen Mfg. Co., Ltd., the "Spinless" manufactured by Tokyo Ohka Kogyo Co., Ltd., the "TS Coater" manufactured by Toray Engineering Co., Ltd., the "Table Coater" manufactured by Chugai Ro Kogyo Co., Ltd., the "CS Series" and "CL Series" manufactured by Tokyo Electron Limited, the "Inline Slit Coater" manufactured by Cermatronics Trading Co., Ltd., and the "Head Coater HC Series" manufactured by Hirata Corporation. The coating speed is generally in the range of 10 mm / s to 400 mm / s. The thickness of the coating film varies depending on the solid content and viscosity of the photosensitive resin composition, but is usually applied so that the thickness after drying is 0.1 to 10 μm, preferably 0.3 to 5 μm.

[0170] Prior to coating, the substrate to which the photosensitive resin composition is to be applied may be pretreated with the adhesion improver described above. Examples of pretreatment methods include treating the substrate surface with a solution prepared by dissolving 0.5 to 20% by mass of an adhesion improver in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, or diethyl adipate. Examples of methods for treating the substrate surface include spin coating, slit die coating, bar coating, dip coating, spray coating, and steam treatment.

[0171] After coating, a reduced-pressure drying treatment is performed as needed. The reduced-pressure drying speed depends on the vacuum chamber volume, the vacuum pump capacity, the piping diameter between the chamber and the pump, etc., but is preferably set, for example, under conditions such that the pressure inside the vacuum chamber is reduced to 40 Pa after 60 seconds without a coated substrate. The typical reduced-pressure drying time is often about 30 to 100 seconds, and the ultimate pressure inside the vacuum chamber at the end of the reduced-pressure drying is usually 100 Pa or less with a coated substrate present. By setting the ultimate pressure to 100 Pa or less, the coating film surface can be dried with reduced stickiness, thereby suppressing surface contamination and particle generation during subsequent substrate transportation.

[0172] After coating or drying under reduced pressure, the coating film is generally heated and dried. This process is also called pre-baking. Drying is performed using a hot plate, oven, infrared rays, or the like. When using a hot plate, the coating film is heated directly on the plate or held on a jig such as a proxy pin placed on the plate. The heating time is preferably from one minute to several hours. The heating temperature varies depending on the type and purpose of the coating film, but from the viewpoint of accelerating solvent drying during pre-baking, it is preferably 80°C or higher, and more preferably 90°C or higher. On the other hand, from the viewpoint of reducing the progress of curing during pre-baking, it is preferably 150°C or lower, and more preferably 140°C or lower.

[0173] Next, the step of exposing the resin film will be described. The resin film of the present invention can be patterned. For example, the resin film can be exposed to actinic radiation through a photomask having a desired pattern, and then developed to form a desired pattern.

[0174] In the step of exposing the resin film, the photomask used during exposure is preferably a halftone photomask having a light-transmitting portion, a light-shielding portion, and a semi-transmitting portion. By exposing using a halftone photomask, a pattern having a stepped shape can be formed after development. When a positive resin film is used, in the pattern having a stepped shape, the portion formed from the light-shielding portion corresponds to a thick film portion, and the portion formed from the half-tone exposed portion irradiated with activated actinic rays through the semi-transmitting portion corresponds to a thin film portion. When the transmittance of the light-transmitting portion of the halftone photomask is taken as 100%, the transmittance of the semi-transmitting portion is preferably 5% or more, more preferably 10% or more. When the transmittance of the semi-transmitting portion is within the above-mentioned range, a clear step between the thick film portion and the thin film portion can be formed. On the other hand, the transmittance of the semi-transmitting portion is preferably 30% or less, more preferably 25% or less, more preferably 20% or less, and most preferably 15% or less. When the transmittance of the semi-transparent portion is within the above-mentioned range, the film thickness of the thin film portion can be made thicker, and even when forming a black cured product with a low OD value in visible light per μm of film thickness, the OD value of the entire film can be increased.

[0175] Examples of actinic radiation used for exposure include ultraviolet light, visible light, electron beams, and X-rays. In the present invention, it is preferable to use i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) from a mercury lamp. When the film has positive photosensitivity, the exposed area dissolves in a developer. When the film has negative photosensitivity, the exposed area hardens and becomes insoluble in a developer.

[0176] Next, the process of developing the exposed resin film will be described. After exposure, the desired pattern is formed by removing the exposed areas in the case of a positive-tone film or the unexposed areas in the case of a negative-tone film using a developer. Examples of the developer include aqueous solutions of alkaline compounds such as tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine. These alkaline aqueous solutions may contain one or more polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone, and dimethylacrylamide; alcohols such as methanol, ethanol, and isopropanol; esters such as ethyl lactate and propylene glycol monomethyl ether acetate; and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone. Examples of the developing method include spray, puddle, immersion, and ultrasonic methods.

[0177] Next, the pattern formed by development is preferably rinsed with distilled water. Alternatively, alcohols such as ethanol and isopropyl alcohol, or esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to the distilled water for rinsing.

[0178] Next, the step of heat-treating the developed resin film will be described. After development, the developed resin film is heat-treated to obtain a cured product. The heat treatment temperature is preferably 180°C or higher, more preferably 200°C or higher, even more preferably 230°C or higher, and particularly preferably 250°C or higher, from the viewpoint of further reducing the amount of outgassing from the cured product. On the other hand, from the viewpoint of improving the film toughness of the cured product, it is preferably 500°C or lower, more preferably 450°C or lower. Within this temperature range, the temperature may be increased stepwise or continuously. The heat treatment time is preferably 30 minutes or longer, from the viewpoint of further reducing the amount of outgassing. Furthermore, from the viewpoint of improving the film toughness of the cured product, it is preferably 3 hours or shorter. For example, a method of heat-treating at 150°C and 250°C for 30 minutes each, or a method of heat-treating while linearly increasing the temperature from room temperature to 300°C over 2 hours, can be used.

[0179] <Cured Product> A first embodiment of the cured product of the present invention is a cured product obtained by curing the photosensitive resin composition of the present invention (hereinafter, sometimes referred to as the cured product of the first embodiment). By heat-treating the photosensitive resin composition of the present invention, components with low heat resistance can be removed, thereby further improving the heat resistance and chemical resistance. In particular, when the photosensitive resin composition of the present invention contains a polyimide precursor, a polybenzoxazole precursor, a copolymer thereof, or a copolymer thereof with a polyimide, imide rings and oxazole rings are formed by heat treatment, thereby further improving the heat resistance and chemical resistance.

[0180] In addition, in the present invention, the combined use of components (b) and (c) can reduce the ultraviolet light transmittance of the cured product. Furthermore, in the present invention, the combined use of components (b), (c), and (d) can reduce the visible light transmittance of the cured product, resulting in a black cured product. The heat treatment temperature is preferably 180°C or higher, more preferably 200°C or higher, even more preferably 230°C or higher, and particularly preferably 250°C or higher, from the viewpoint of further reducing the amount of outgassing from the cured product. On the other hand, from the viewpoint of improving the film toughness of the cured product, it is preferably 500°C or lower, more preferably 450°C or lower. Within this temperature range, the temperature may be increased stepwise or continuously. The heat treatment time is preferably 30 minutes or longer, from the viewpoint of further reducing the amount of outgassing. Furthermore, it is preferably 3 hours or shorter, from the viewpoint of improving the film toughness of the cured product. For example, a method of heat treatment at 150°C and 250°C for 30 minutes each, or a method of heat treatment while linearly increasing the temperature from room temperature to 300°C over 2 hours, can be used.

[0181] A second embodiment of the cured product of the present invention is a cured product comprising a crosslinked product of 1,2,4-trihydroxybenzene or pyrogallol and a thermal crosslinking agent (c) having a partial structure represented by formula (1) (hereinafter, this may be referred to as the cured product of the second embodiment).

[0182]

[0183] In formula (1), R １０ represents a hydrogen atom or an alkyl group. * represents a bond, but the nitrogen atom is not adjacent to a carbonyl group.

[0184] The transmittance of the cured product in the range of 300 nm to 500 nm can be reduced by including a crosslinked product of 1,2,4-trihydroxybenzene or pyrogallol and a thermal crosslinking agent (c) having a partial structure represented by formula (1). From the viewpoint of further reducing the transmittance in the range of 300 nm to 500 nm after curing, it is more preferable that the cured product include a crosslinked product of 1,2,4-trihydroxybenzene and a thermal crosslinking agent (c) having a partial structure represented by formula (1).

[0185] Specifically, the crosslinked product of 1,2,4-trihydroxybenzene or pyrogallol and a thermal crosslinking agent (c) having a partial structure represented by formula (1) is a crosslinked product of OR in the thermal crosslinking agent (c) having a partial structure represented by formula (1). １０ is eliminated by heat and crosslinked with the aromatic C-H bond in 1,2,4-trihydroxybenzene or pyrogallol via a methylene bond. Examples of such compounds include the partial structures shown below and partial structures that have become quinone structures by dehydrogenation of the partial structures shown below.

[0186]

[0187] Each * represents a bond, but the nitrogen atom is not adjacent to a carbonyl group.

[0188] When the thermal crosslinking agent (c) having the partial structure represented by formula (1) has two or more partial structures represented by formula (1) in the molecule, it is sufficient that a crosslinked compound with 1,2,4-trihydroxybenzene or pyrogallol is formed in the molecule at at least one crosslinking point, and a crosslinked compound with another compound may be formed at other crosslinking points.

[0189] Other suitable aspects of the thermal crosslinking agent (c) having a partial structure represented by formula (1) in the cured product of the second aspect are the same as those of the thermal crosslinking agent (c) having a partial structure represented by formula (1) described above.

[0190] Methods for measuring whether a cured product contains a crosslinked product of 1,2,4-trihydroxybenzene or pyrogallol and a thermal crosslinking agent (c) having a partial structure represented by formula (1) include, for example, a method of extracting the components in the cured product with an organic solvent and measuring the extract by liquid ion chromatography, as well as a method of measuring the components in the cured product using time-of-flight secondary ion mass spectrometry.

[0191] A third embodiment of the cured product of the present invention is a cured product formed on a support, which is cut from the surface of the cured product toward the support by an Ar gas cluster ion beam method, and the primary ion species is Bi ３ ＋＋The cured product was measured by time-of-flight secondary ion mass spectrometry under the measurement conditions of a primary ion current of 0.1 pA and a primary ion irradiation area of ​​an inner area of ​​a square with a side length of 200 μm. １３７ C ７ H ５ O ３ － The normalized secondary ion intensity is 1.0 × 10 －４ The cured product described above (hereinafter may be referred to as the cured product of the third embodiment) is as follows.

[0192] The normalized secondary ion intensity in the present invention is １３７ C ７ H ５ O ３ － This is the secondary ion intensity obtained by normalizing the integrated ion intensity by the total number of primary ion irradiations. The total number of primary ion irradiations can be calculated by multiplying the number of primary ion irradiations per one time by the cumulative number of times per depth point and the number of depth points from the surface of the cured product to the support.

[0193] When the cured product of the third aspect is contained in a planarizing layer and / or pixel dividing layer of an organic EL display element described below, it is preferable to perform time-of-flight secondary ion mass spectrometry on the surface of the cured product in a region 2 μm or more away from the edge of a contact hole or the edge of a pixel opening in the planar direction. The region 2 μm or less away from the edge of the contact hole or the edge of the pixel opening in the planar direction overlaps with the bottom of the cured product, making the film thickness from the surface of the cured product to the support non-uniform within the analysis area, and the number of depth points within the measurement area may not be stable.

[0194] For example, when performing time-of-flight secondary ion mass spectrometry on a cured product provided in an organic EL display device, it is necessary to expose the surface of the cured product. An example of a method for exposing the surface of the cured product is described below, but the exposure method is not limited to the following. Furthermore, when supports exist above and below the cured product, time-of-flight secondary ion mass spectrometry can be performed with the interface between the cured product and either of the supports exposed.

[0195] As a method for exposing the surface of the cured product, for example, a sputtering gun using argon, cesium, oxygen, gallium, or the like can be used to remove the upper surface of the target cured product, thereby exposing the cured product surface. Alternatively, as an exposure method using chemical etching, both or one of the electrodes sandwiched above and below the pixel dividing layer can be dissolved with an acid or alkali to create gaps above and below the cured product, and the laminate can be peeled off, thereby exposing the cured product surface. Furthermore, as an exposure method using oblique cutting, the cover glass of the organic EL display device can be removed, and the exposed laminate including the organic EL layer, pixel dividing layer, etc. can be cut obliquely with respect to the light extraction direction, thereby exposing the surface of the cured product.

[0196] Cutting is performed from the surface of the cured product toward the support by the Ar gas cluster ion beam method, and the primary ion species is Bi ３ ＋＋ The cured product was measured by time-of-flight secondary ion mass spectrometry under the measurement conditions of a primary ion current of 0.1 pA and a primary ion irradiation area of ​​an inner area of ​​a square with a side length of 200 μm. １３７ C ７ H ５ O ３ － The normalized secondary ion intensity is 1.0 × 10 －４ By doing so, the transmittance of the cured product in the range of 300 nm to 500 nm can be reduced.

[0197] The cured product of the third embodiment can be obtained by, for example, heat-treating a resin film on a support, which is made of a composition containing component (a), trihydroxybenzene, and a thermal crosslinking agent (c) having a partial structure represented by formula (1). This is because the crosslinked product of trihydroxybenzene and the thermal crosslinking agent (c) having a partial structure represented by formula (1) is dehydrogenated to form a quinone structure, and fragment ions, １３７ C ７ H ５ O ３ － This is presumably because the concentration of becomes higher in the cured product.

[0198] In the cured product of the third embodiment１３７ C ７ H ５ O ３ － The normalized secondary ion intensity is 1.0 × 10 －４ From the viewpoint of further reducing the transmittance of the cured product in the range of 300 nm to 500 nm, 2.0 × 10 －４ More preferably, 3.0 × 10 －４ The above is more preferable. １３７ C ７ H ５ O ３ － The upper limit of the normalized secondary ion intensity is not particularly limited, but is preferably 1.0 × 10 －２ The following is preferred:

[0199] Examples of trihydroxybenzenes include 1,2,4-trihydroxybenzene, pyrogallol, and phloroglucinol, and from the viewpoint of further reducing the transmittance of the cured product in the range of 300 nm to 500 nm, 1,2,4-trihydroxybenzene and pyrogallol are preferred, and 1,2,4-trihydroxybenzene is more preferred. Other suitable aspects of the thermal crosslinking agent (c) having a partial structure represented by formula (1) in the cured product of the third aspect are the same as those of the thermal crosslinking agent (c) having a partial structure represented by formula (1) described above.

[0200] <Application Examples of Photosensitive Resin Composition and Cured Product> The photosensitive resin composition and cured product of the present invention are suitable for use as a surface protection layer or interlayer insulating layer for semiconductor elements, an insulating layer for organic electroluminescence (EL) elements, a planarization layer for thin film transistor (TFT) substrates for driving display devices using organic EL elements, a wiring protection insulating layer for circuit boards, an on-chip microlens for solid-state imaging elements, and a planarization layer for various display devices and solid-state imaging elements. For example, they are suitable as a surface protection layer or interlayer insulating layer for MRAM with low heat resistance, polymer memory (Polymer Ferroelectric RAM: PFRAM) and phase change memory (Phase Change RAM: PCRAM, Ovonics Unified Memory: OUM), which are promising next-generation memories. The insulating layer can also be used in a display device including a first electrode formed on a substrate and a second electrode provided opposite the first electrode, such as an LCD, an ECD, an ELD, or a display device using an organic electroluminescent element (organic electroluminescent device). Hereinafter, an organic EL display device, a semiconductor device, and a semiconductor electronic component will be described as examples.

[0201] <Organic EL Display Device> The organic EL display device of the present invention is an organic EL display device having, on a substrate, a driving circuit, a planarizing layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode, and the planarizing layer and / or the insulating layer has the cured product of the present invention.

[0202] When the planarization layer and / or insulating layer contains the cured product of the present invention, the planarization layer and / or insulating layer preferably has a transmittance of less than 30% at a wavelength of 450 nm. When the transmittance at a wavelength of 450 nm is less than 30%, malfunctions due to the penetration of ultraviolet light into the TFT can be prevented in organic EL display devices using oxide semiconductor layer TFTs. To prevent ultraviolet light from penetrating the TFT, the transmittance at a wavelength of 450 nm is preferably less than 30%, more preferably less than 20%, and even more preferably less than 10%. The lower limit of the transmittance at a wavelength of 450 nm is not particularly limited, but is preferably 0.01% or more.

[0203] Furthermore, when the planarizing layer and / or insulating layer comprises the cured product of the present invention, the planarizing layer and / or insulating layer preferably has an OD value (optical density) of 0.5 to 1.5 in visible light per 1 μm of film thickness. An OD value of 0.5 or more can improve the light-blocking properties of the cured product, thereby further reducing external light reflection in displays such as organic EL displays or liquid crystal displays, thereby improving the contrast of image display. From the viewpoint of reducing reflection, the OD value is preferably 0.5 or more, more preferably 0.6 or more, even more preferably 0.7 or more, and particularly preferably 0.8 or more. Furthermore, an OD value of 1.5 or less can improve the sensitivity upon exposure when used as a photosensitive resin composition containing a photosensitive compound. From the viewpoint of increasing sensitivity, the OD value is 1.5 or less, more preferably 1.0 or less.

[0204] When the insulating layer is a black film, the thickness of the insulating layer is preferably 1.0 to 5.0 μm, more preferably 1.5 μm or more, and even more preferably 2.0 μm or more. By making the thickness of the black insulating layer within the above range, even if the black film has a low OD value in visible light per μm of film thickness, the OD value of the entire film can be increased, and the effect of reducing external light reflection can be improved.

[0205] Taking an active matrix display device as an example, a display device has a TFT and wiring located on the sides of the TFT and connected to the TFT on a substrate such as glass or various plastics, a planarizing layer covering the unevenness thereon, and a display element on the planarizing layer. The display element and wiring are connected via contact holes formed in the planarizing layer. In particular, since flexible organic EL display devices have become mainstream in recent years, it is preferable that the substrate having the aforementioned drive circuit be an organic EL display device containing a resin film. When a cured product obtained by curing the photosensitive resin composition of the present invention is used as an insulating layer or planarizing layer of such a flexible display device, it is particularly preferred because it has excellent bending resistance. From the viewpoint of improving adhesion to the cured product obtained by curing the photosensitive resin composition of the present invention, polyimide is particularly preferred as the resin film.

[0206] In order to enhance the effect of reducing external light reflection, the organic EL display device preferably further includes a color filter having a black matrix. The black matrix preferably contains a resin such as an epoxy resin, an acrylic resin, a urethane resin, a polyester resin, a polyimide resin, a polyolefin resin, or a siloxane resin.

[0207] The black matrix contains a colorant. Examples of colorants that can be used include black organic pigments, mixed-color organic pigments, and inorganic pigments. Examples of black organic pigments include carbon black, perylene black, aniline black, and benzofuranone-based pigments. Examples of mixed-color organic pigments include pseudo-black pigments obtained by mixing two or more pigments, such as red, blue, green, purple, yellow, magenta, and / or cyan. Examples of black inorganic pigments include graphite; fine particles of metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver; metal oxides; metal composite oxides; metal sulfides; metal nitrides; metal oxynitrides; and metal carbides. Among these, carbon black, titanium nitride, titanium carbide, and composite particles of these with metals such as silver, which have high light-shielding properties, are preferred.

[0208] The OD value of the black matrix is ​​preferably 1.5 or more, more preferably 2.5 or more, and even more preferably 4.5 or more.

[0209] FIG. 1 shows a cross-sectional view of an example of an organic EL display device. Bottom-gate or top-gate thin film transistors (TFTs) 1 are arranged in a matrix on a substrate 6. A TFT insulating layer 3 is formed to cover the TFTs 1. Wiring 2 connected to the TFTs 1 is also provided on the TFT insulating layer 3. A planarization layer 4 is further formed on the TFT insulating layer 3, burying the wiring 2. Contact holes 7 are formed in the planarization layer 4, reaching the wiring 2. An ITO (transparent electrode) 5 is formed on the planarization layer 4 and connected to the wiring 2 via the contact holes 7. The ITO 5 serves as an electrode for a display element (e.g., an organic EL element). An insulating layer 8 is formed to cover the periphery of the ITO 5. The organic EL elements may be top-emission types that emit light from the side opposite the substrate 6, or bottom-emission types that extract light from the substrate 6 side. In this manner, an active matrix organic EL display device is obtained, in which TFTs 1 for driving each organic EL element are connected to the corresponding TFTs 1.

[0210] The TFT insulating layer 3, the planarizing layer 4, and / or the insulating layer 8 can be formed by the steps of forming a resin film made of the photosensitive resin composition of the present invention, exposing the resin film to light, developing the exposed resin film, and heat-treating the developed resin film, as described above. An organic EL display device can be obtained by a manufacturing method including these steps.

[0211] <Display Device Other Than Organic EL Display Device> A display device other than an organic EL display device of the present invention is a display device having at least metal wiring, the cured product of the present invention, and a plurality of light-emitting elements, wherein the light-emitting elements are provided with a pair of electrode terminals on either side thereof, the pair of electrode terminals are connected to a plurality of the metal wirings extending in the cured product, and the plurality of the metal wirings maintain electrical insulation due to the cured product.

[0212] The display device will be described with reference to FIG. 2 as an example. In FIG. 2, the display device 11 has a plurality of light-emitting elements 12 arranged on a counter substrate 15, and a cured product 13 arranged on the light-emitting elements 12. "On the light-emitting elements" does not necessarily mean the surface of the light-emitting elements, but may also mean the upper side of a supporting substrate or the light-emitting elements. The embodiment shown in FIG. 2 illustrates a configuration in which a total of three layers are stacked on top of a cured product 13 arranged so as to contact at least a portion of the light-emitting elements 12, but the cured product 13 may also be a single layer. The light-emitting element 12 has a pair of electrode terminals 16 on the surface opposite to the surface contacting the counter substrate 15, and each electrode terminal 16 is connected to a metal wiring 14 extending into the cured product 13. If the plurality of metal wirings 14 extending into the cured product 13 are covered with the cured product 13, the cured product 13 also functions as an insulating layer, thereby maintaining electrical insulation. The phrase "the metal wiring has a structure that maintains electrical insulation" means that the part of the metal wiring that requires electrical insulation is covered with a cured product obtained by curing a photosensitive resin composition containing an alkali-soluble resin (a). In addition, in the present invention, the phrase "the insulating layer has electrical insulation" means that the insulating layer has a volume resistivity of 10 １２ This means a state in which the electrical resistance is Ω cm or more. Furthermore, the light emitting element 12 is electrically connected to a driving element 18 attached to a light emitting element driving substrate 17 provided at a position opposite to the counter substrate 15 via metal wiring 14 or 14c, thereby controlling the light emission of the light emitting element 12. Furthermore, the light emitting element driving substrate 17 is electrically connected to the metal wiring 14 via, for example, solder bumps 20. Furthermore, a barrier metal 19 may be provided to prevent diffusion of metal such as the metal wiring 14.

[0213] The cured product 13 is preferably black and has an OD value of 0.5 to 1.5 in visible light per 1 μm of insulating layer thickness. An OD value of 0.5 or more can improve the light-blocking properties of the cured product, thereby making it possible to visualize electrode wiring and further reduce external light reflection in displays such as organic electroluminescence (EL) displays or liquid crystal display devices, thereby improving the contrast of image displays. Furthermore, an OD value of 1.5 or less can improve the sensitivity upon exposure when the photosensitive compound is used as a photosensitive resin composition.

[0214] The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Evaluations in the examples were carried out by the following methods.

[0215] (1) Evaluation of Sensitivity The varnishes obtained in each of the Examples and Comparative Examples were applied to an 8-inch silicon wafer by spin coating using a coating and developing apparatus ACT-8 (manufactured by Tokyo Electron Limited), and baked at 120°C for 2 minutes to produce a pre-baked film with a thickness of 4.0 μm. The film thickness was measured using a stylus profiler (P-15; manufactured by KLA Tencor Corporation). Thereafter, using an exposure machine i-line stepper NSR-2005i9C (manufactured by Nikon Corporation), the varnishes were exposed to light at an exposure dose of 50 to 500 mJ / cm through a mask having a pattern of 10 μm holes. ２ in the range of 5 mJ / cm ２ After the exposure, the film was developed using the ACT-8 developing device with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as TMAH, manufactured by Tama Chemicals Co., Ltd.) as a developer until the film thickness was reduced to 0.5 μm, and then rinsed with distilled water and spun off to dry, thereby obtaining a pattern.

[0216] The obtained pattern was observed at a magnification of 20 times using an FPD microscope MX61 (manufactured by Olympus Corporation), and the opening diameter of the hole was measured. The minimum exposure dose at which the opening diameter of the contact hole reached 10 μm was determined, and this was taken as the sensitivity. ２ If it was less than 90 mJ / cm, it was rated "A" ２ 120mJ / cm or more ２ If it was less than 120 mJ / cm, it was rated "B"; ２ If the result was above this, it was judged as "C".

[0217] (2) Evaluation of UV Light Shielding Properties (Transmittance at 450 nm) The varnishes obtained in each Example and Comparative Example were spin-coated onto a 5 cm square glass substrate so that the film thickness after heat treatment (curing) would be 2.0 μm, and the substrate was pre-baked at 120°C for 120 seconds to produce a pre-baked film. The film was then cured for 60 minutes at 250°C under a nitrogen atmosphere or air atmosphere using a high-temperature clean oven INH-9CD-S manufactured by Koyo Thermo Systems Co., Ltd. The film thickness of the cured film was measured using a stylus profiler (P-15; manufactured by KLA-Tencor Corporation). The transmission spectrum of the thus obtained cured film from wavelengths of 300 nm to 800 nm was measured using a UV-visible spectrophotometer MultiSpec-1500 (manufactured by Shimadzu Corporation), and the transmittance at a wavelength of 450 nm at a film thickness of 2.0 μm after curing was determined. If the transmittance at a wavelength of 450 nm at a film thickness of 2.0 μm after curing was less than 10%, it was rated as "S", if it was 10% or more but less than 20%, it was rated as "A", if it was 20% or more but less than 30%, it was rated as "B", and if it was 30% or more, it was rated as "C".

[0218] (3) Evaluation of visible light blocking properties (OD value per 1 μm, transmittance at 450 nm) For cured films obtained in the same manner as in (2), the OD value was measured using an optical densitometer (361T; manufactured by X-Rite Corporation), and the transmission spectrum at wavelengths of 300 nm to 800 nm was measured using a UV-visible spectrophotometer MultiSpec-1500 (manufactured by Shimadzu Corporation), and the transmittance at a wavelength of 450 nm at a film thickness of 2.0 μm after curing was determined. The obtained OD value was divided by the film thickness of the cured film to obtain the OD value per 1 μm (OD value per 1 μm = OD value / film thickness of cured film). "S" if the OD value per μm was 0.70 or more and the transmittance at a wavelength of 450 nm was less than 10%, "A" if the OD value per μm was 0.70 or more and the transmittance at a wavelength of 450 nm was 10% or more and less than 20%, "B" if the OD value per μm was 0.70 or more and the transmittance at a wavelength of 450 nm was 20% or more and less than 30%, "C" if the OD value per μm was 0.70 or more and the transmittance at a wavelength of 450 nm was 30% or more, "A" if the OD value per μm was less than 0.70 and 0.50 or more and the transmittance at a wavelength of 450 nm was less than 10%, "B" if the OD value per μm was less than 0.70 and 0.50 or more and the transmittance at a wavelength of 450 nm was 10% or more and less than 20%, If the OD value per μm was less than 0.70 but 0.50 or more and the transmittance at a wavelength of 450 nm was 20% or more, it was rated as "C." If the OD value per μm was less than 0.50 regardless of the transmittance at a wavelength of 450 nm, it was rated as "C."

[0219] (4) Chemical Resistance After measuring the thickness of the cured film obtained in the same manner as in (2), the cured film was immersed in a mixed solution of N-methylformamide / ethylene glycol = 55 / 45 (weight ratio) at 60 °C for 3 minutes. The cured film was removed from the mixed solution, washed with pure water, and then baked at 100 °C for 1 minute to dehydrate. The film thickness was measured again, and the absolute value of the change in film thickness before and after immersion in the solution was calculated. When the absolute value of the change in film thickness was less than 0.3 μm, it was judged as "A", when it was 0.3 μm or more but less than 0.8 μm, it was judged as "B", and when it was 0.8 μm or more, it was judged as "C".

[0220] (5) Evaluation of change in OD value due to repeated curing For the cured film obtained in the same manner as in (2), the OD value was measured using an optical densitometer (361T; manufactured by X-Rite Corporation), and the obtained OD value was divided by the film thickness of the cured film to determine the OD value per 1 μm after one cure (OD value per 1 μm = OD value / film thickness of cured film). Subsequently, the same cured film was cured again at 250°C for 60 minutes in a nitrogen atmosphere using a high-temperature clean oven INH-9CD-S manufactured by Koyo Thermo Systems Co., Ltd. to produce a cured film after two cures. The film thickness and OD value of the cured film were measured in the same manner, and the obtained OD value was divided by the film thickness of the cured film to calculate the OD value per 1 μm after two cures. The absolute value of the difference between the OD value per 1 μm after one cure and the OD value per 1 μm after two cures was calculated as the amount of change in OD value due to repeated curing. If the amount of change in OD value due to repeated curing was less than 0.05, it was judged as "A." If it was less than 0.15 but 0.05 or more, it was judged as "B." If it was 0.15 or more, it was judged as "C."

[0221] (6) Evaluation of frozen storage stability Using a Tokyo Electron Ltd. coating and developing apparatus "CLEAN TRACK ACT-12," each varnish that had been filtered and then stored in a freezer at -18°C for 60 days was applied to a 12-inch Si wafer and dried on a hot plate at 100°C for 3 minutes to obtain a photosensitive resin film with a film thickness of 1000 nm. The number of foreign particles with a size of 0.27 μm or more was counted for the obtained photosensitive resin film using a Topcon Corporation wafer surface inspection apparatus "WM-10." The measurement area was approximately 201 cm2 within a circle with a radius of 8 cm from the center of the wafer. ２ and the coating thickness is 1 cm ２ The number of foreign particles per substrate (defect density) was calculated. ２ If it is less than 1.00 pieces / cm, it is rated as "A"; ２ More than 3.00 pieces / cm ２ If it was less than 3.00 pieces / cm, it was rated "B"; ２ If the result was above this, it was judged as "C".

[0222] Synthesis Example 1 Synthesis of Hydroxyl Group-Containing Diamine Compound (α) 18.3 g (0.05 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter referred to as BAHF) was dissolved in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide, and the solution was cooled to −15°C. To this solution, a solution of 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride dissolved in 100 mL of acetone was added dropwise. After completion of the dropwise addition, the mixture was reacted at −15°C for 4 hours and then returned to room temperature. The precipitated white solid was filtered and dried in vacuo at 50°C.

[0223] 30 g of the solid was placed in a 300 mL stainless steel autoclave and dispersed in 250 mL of methyl cellosolve, followed by the addition of 2 g of 5 mass % palladium on carbon. Hydrogen was introduced into the autoclave using a balloon, and the reduction reaction was carried out at room temperature. After approximately 2 hours, the reaction was terminated after confirming that the balloon no longer deflated. After the reaction was completed, the palladium compound catalyst was removed by filtration, and the mixture was concentrated using a rotary evaporator to obtain a hydroxyl group-containing diamine compound (α) represented by the following formula:

[0224]

[0225] Synthesis Example 2 Synthesis of Quinone Diazide Compound (e-1) Under a dry nitrogen stream, 21.22 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 26.87 g (0.10 mol) of 5-naphthoquinone diazide sulfonyl chloride were dissolved in 450 g of 1,4-dioxane at room temperature. To this solution, 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature in the system did not exceed 35°C. After the 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 (e-1) represented by the following formula:

[0226]

[0227] Synthesis Example 3: Synthesis of Alkali-Soluble Resin (a-1) Under a dry nitrogen stream, 31.0 g (0.10 mol) of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (hereinafter referred to as ODPA) was dissolved in 500 g of N-methylpyrrolidone (hereinafter referred to as NMP). To this solution, 45.35 g (0.075 mol) of the hydroxyl group-containing diamine compound (α) obtained in Synthesis Example 1 and 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane (hereinafter referred to as SiDA) were added along with 50 g of NMP, and the mixture was allowed to react at 40°C for 2 hours. Next, 4.36 g (0.04 mol) of 3-aminophenol (hereinafter referred to as MAP) was added as an end-capping agent along with 5 g of NMP, and the mixture was allowed to react at 50°C for 2 hours. Thereafter, a solution prepared by diluting 32.39 g (0.22 mol) of N,N-dimethylformamide diethyl acetal with 50 g of NMP was added. After addition, the mixture was stirred at 50°C for 3 hours. After stirring was completed, the solution was cooled to room temperature and then added to 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 24 hours to obtain a polyimide precursor (a-1), which is an alkali-soluble resin.

[0228] Synthesis Example 4: Preparation of Ionic Dye d1-2-2 A mixture of 18.46 g (0.05 mol) of the compound represented by (β-1) in the following reaction formula, 120 g of sulfolane, 13.63 g of zinc chloride, and 20.58 g (0.15 mol) of 4-ethoxyaniline was heated and stirred at 170°C for 8 hours. After completion of the reaction, the reaction solution was allowed to cool to room temperature, and then added dropwise to 450 g of 17.5% by mass hydrochloric acid at 0 to 10°C and stirred for 1 hour. Subsequently, the precipitate was collected by filtration, added to 500 g of a 5% by mass aqueous sodium carbonate solution, stirred for 1 hour, collected by filtration, washed with pure water, and dried at 60°C for 24 hours to obtain a xanthene compound (β-2) in which two of the nitrogen atoms were substituted with aryl groups.

[0229] Next, a mixture of 22.83 g (0.04 mol) of the obtained compound (β-2), 150 g of 1-methyl-2-pyrrolidone, 1.3 g of copper powder, 8.3 g of potassium carbonate, and 19.84 g (0.08 mol) of 4-iodophenetole was heated and stirred at 150°C for 12 hours. After completion of the reaction, the reaction solution was filtered to remove insoluble matter, and the reaction solution was added dropwise to 450 g of 17.5% by mass hydrochloric acid at 0 to 10°C and stirred for 1 hour. Thereafter, the precipitate was collected by filtration and dried at 60°C for 24 hours to obtain a xanthene compound (β-3) in which four nitrogen atoms were substituted with aryl groups.

[0230] Next, 1.69 g (0.011 mol) of phosphorus oxychloride was added dropwise to a mixture of 8.10 g (0.01 mol) of the obtained compound (β-3), 2.54 g (0.015 mol) of diphenylamine, 10.11 g (0.1 mol) of triethylamine, and 150 g of 1,2-dichloroethane at room temperature, and the mixture was heated and stirred at 85°C for 3 hours. After completion of the reaction, the reaction solution was allowed to cool to room temperature, then added to 300 g of pure water, and extracted with 100 g of chloroform. The organic layer was washed with 150 g of 4 mol / L hydrochloric acid and 150 g of pure water, and the solvent was then distilled off to obtain xanthene compound (β-4) in which xanthene compound (β-3) was amidated.

[0231] Next, 9.98 g (0.01 mol) of the obtained compound (β-4) was dissolved in 150 g of N,N-dimethylformamide (DMF), 2.91 g (0.015 mol) of sodium paratoluenesulfonate was added, and the mixture was heated and stirred at 40 ° C. for 3 hours. After the reaction solution was allowed to cool to room temperature, the reaction solution was poured into 1000 g of pure water, and the precipitated crystals were collected by filtration, washed with water, and then dried at 60 ° C. for 24 hours to obtain an ionic dye (d1-2-2) in which the counter ion of (β-4) was exchanged. The obtained compound was subjected to LC-MS analysis using a liquid chromatograph mass spectrometer (Shimadzu Corporation LC-MS2020) and confirmed to be the target compound. LC-MS (ESI, posi): m / z 963 [M+H] ＋ LC-MS (ESI, nega): m / z 171 [M] － .

[0232]

[0233] The names of the compounds used in each example and comparative example are shown below. Note that the ionic dyes and component (c) other than commercially available products were synthesized using known methods. The maximum absorption wavelength and absorbance Abs of each colorant are also shown below. ｍａｘ Absorbance Abs ３６５ The ratio (Abs ３６５ / Abs ｍａｘ × 100) was calculated by measuring the transmission spectrum at wavelengths of 300 nm to 800 nm in a DMSO solution whose concentration was adjusted so that the maximum absorbance value was 1 or less, using a UV-visible spectrophotometer MultiSpec-1500 (manufactured by Shimadzu Corporation). The results are shown in Table 1. GBL: γ-butyrolactone EL: ethyl lactate PGME: propylene glycol monomethyl ether b-1: phloroglucinol b1-1: pyrogallol (an aromatic hydrocarbon (b) that satisfies the condition that at least one substitution position of a phenolic hydroxyl group other than any one of the phenolic hydroxyl groups is the ortho position) b12-1: 1,2,4-trihydroxybenzene (an aromatic hydrocarbon (b) that satisfies the condition that at least one substitution position of a phenolic hydroxyl group other than any one of the phenolic hydroxyl groups is the ortho position and the para position) b'-1: 1,6-dihydroxynaphthalene b'-2: 4,4',4''-methylidynetrisphenol b'-3: hexahydroxybenzene d1-1-1: C.I. Solvent Red 18 d1-2-1: C.I. Solvent Blue 45 d'-1: VALIFAST (registered trademark) BLACK 3830 (a black dye specified in C.I. Solvent Black 34 (manufactured by Orient Chemical Industry Co., Ltd.))

[0234]

[0235]

[0236]

[0237] Example 1 10.0 g of polyimide precursor (a-1), 2.0 g of aromatic compound (b-1), 2.0 g of triazine ring-containing compound (c-1), and 2.0 g of photosensitive compound (e-1) were dissolved in a mixed solution of 10 g of GBL, 20 g of EL, and 70 g of PGME, and then filtered through a 0.2 μm polytetrafluoroethylene filter to obtain a positive photosensitive resin composition, varnish AA. The obtained varnish was used to evaluate the sensitivity, ultraviolet light shielding property, and chemical resistance as described above. However, for the evaluation of ultraviolet light shielding property and chemical resistance, a cured film cured under a nitrogen atmosphere was used.

[0238] Examples 2 to 3, 5 to 12, Comparative Examples 1 to 7 Varnishes of photosensitive resin compositions were obtained in the same manner as in Example 1, except that component (a), component (b), component (c), component (e), other components, and solvents were changed as shown in Tables 2 and 3. The sensitivity, ultraviolet light-shielding ability, and chemical resistance of the obtained varnishes were evaluated as described above. However, for the evaluation of ultraviolet light-shielding ability and chemical resistance, cured films cured under a nitrogen atmosphere were used.

[0239] Example 4 The sensitivity, ultraviolet light-shielding ability, and chemical resistance were evaluated as described above using the varnish AC obtained in Example 3. However, for the evaluation of ultraviolet light-shielding ability and chemical resistance, a cured film cured in the air was used.

[0240] Example 13 10.0 g of polyimide precursor (a-1), 2.0 g of aromatic compound (b-1), 2.0 g of thermal crosslinking agent (c-1), 1.0 g of colorant (d1a-1-1), 0.8 g of colorant (d1a-2-1), 2.0 g of photosensitive compound (e-1), 10 g of GBL, 20 g of EL, and 70 g of PGME were dissolved in a mixed solution, and then filtered through a 0.2 μm polytetrafluoroethylene filter to obtain a positive photosensitive resin composition varnish BA. The obtained varnish was used to evaluate the sensitivity, visible light shading, and chemical resistance as described above. However, the evaluation of visible light shading and chemical resistance was performed using a cured film cured under a nitrogen atmosphere.

[0241] Examples 14 to 25, Comparative Examples 8 to 12 Varnishes of photosensitive resin compositions were obtained in the same manner as in Example 12, except that the components (a), (b), (c), (d), (e), thermal crosslinking agent, other components, and solvent were changed as shown in Tables 4 and 5. The sensitivity, visible light-shielding ability, and chemical resistance of the obtained varnishes were evaluated as described above. However, for the evaluation of visible light-shielding ability and chemical resistance, cured films cured under a nitrogen atmosphere were used.

[0242] Example 26: The change in OD value due to repeated curing and frozen storage stability were evaluated as described above using the varnish BC obtained in Example 15. However, the change in OD value due to repeated curing was evaluated using a cured film cured under a nitrogen atmosphere.

[0243] Example 27 The change in OD value due to repeated curing and frozen storage stability were evaluated in the same manner as in Example 26, except that the varnish BM obtained in Example 25 was used instead of the varnish BC obtained in Example 15. However, the change in OD value due to repeated curing was evaluated using a cured film cured under a nitrogen atmosphere.

[0244] Example 28 A cured film formed on a 5 cm square glass substrate made of varnish AI obtained in Example 10 was extracted with 10 ml of tetrahydrofuran heated to 40°C, and the obtained extract was used to perform LC-MS analysis under the following conditions.

[0245] LC system: UltiMate 3000 (Thermo Fisher) MS system: Orbitrap Fusion (Thermo Fisher) Mobile phase: A 10 mmol / L ammonium acetate aqueous solution B Methanol / THF = 1 / 1 Time program: 0 → 3 min 3 → 15 min 15 → 30 min 15 → 30 min Flow rate: 0.5 ml / min Ionization: atmospheric pressure chemical ionization (APCI) method MS detection: scan (m / z 100-1500) Column temperature: 45°C As a result of the analysis, m / z 304.0968 (C １９ H １４ O ３ N) and m / z 302.0828 (C１９ H １２ O ３ The negative molecular ions of N) were confirmed. This is because the crosslinked product of the aromatic compound (b-1) and the thermal crosslinking agent (c-4) used in Example 10 was dehydrogenated into the molecule (C １９ H １３ O ３ It was confirmed that the cured film contained a crosslinked product of 1,2,4-trihydroxybenzene and component (c).

[0246] Example 29 Using a cured film of Varnish AC obtained in Example 3 on a 5 cm square glass substrate, the cured product was analyzed by TOF-SIMS under the following conditions. １３７ C ７ H ５ O ３ － The normalized secondary ion intensity was measured. １３７ C ７ H ５ O ３ － The normalized secondary ion intensity of １３７ C ７ H ５ O ３ － The ion intensity was calculated by dividing the total number of primary ion irradiations, which is the number of primary ion irradiations per time multiplied by the cumulative number of times per depth point and the number of depth points from the surface of the cured product to the glass substrate.

[0247] Apparatus: ION-TOF "TOF.SIMS5" Ar cluster size (median): 1600 Primary ion: Bi ３ ＋＋ Acceleration voltage of primary ions: 30 kV Primary ion current: 0.1 pA Measurement cycle time: 140 μs Number of scans: 1 scan / cycle Measurement range: 200 μm × 200 μm Number of integrations per depth point: 256 × 256 times / point Number of primary ions irradiated per time: 43.7 / time As a result of the analysis, the number of points from the surface of the cured product to the glass substrate was 89, １３７ C ７ H ５ O ３－ The integrated intensity of the ion is 69327.09, and the １３７ C ７ H ５ O ３ － The normalized secondary ion intensity of －４ It was.

[0248] Comparative Example 13 The same procedure as in Example 29 was repeated except that a cured film of varnish XA obtained in Comparative Example 1 on a 5 cm square glass substrate was used instead of varnish AC obtained in Example 3, and the thickness of the cured product was measured by TOF-SIMS. １３７ C ７ H ５ O ３ － The normalized secondary ion intensity was measured. As a result of the analysis, the number of points from the surface of the cured product to the glass substrate was 110, １３７ C ７ H ５ O ３ － The integrated intensity of the ion was 15821.09, and the １３７ C ７ H ５ O ３ － The normalized secondary ion intensity of －５ It was.

[0249] The compositions and evaluation results of each of the Examples and Comparative Examples are shown in Tables 2 to 6.

[0250]

[0251]

[0252]

[0253]

[0254]

[0255] 1: TFT (thin film transistor) 2: Wiring 3: TFT insulating layer 4: Planarizing layer 5: ITO (transparent electrode) 6: Substrate 7: Contact hole 8: Insulating layer 11: Display device 12: Light-emitting element 13: Cured product 14, 14c: Metal wiring 15: Counter substrate 16: Electrode terminal 17: Light-emitting element driving substrate 18: Driving element 19: Barrier metal 20: Solder bump

Claims

1. A photosensitive resin composition comprising: (a) an alkali-soluble resin; (b) an aromatic hydrocarbon having three or more aromatic C-H bonds and at least three phenolic hydroxyl groups in one aromatic ring; (c) a thermal crosslinking agent having a partial structure represented by formula (1); and (e) a photosensitive compound. 【Chemistry 1】 (In formula (1), R １０ represents a hydrogen atom or an alkyl group. * represents a bond, but the carbonyl group is not adjacent to the nitrogen atom.)

2. A photosensitive resin composition as described in Claim 1, wherein in component (b), at least one substitution position of a phenolic hydroxyl group other than any of the phenolic hydroxyl groups is the ortho position or the para position.

3. The photosensitive resin composition according to claim 1, wherein the component (b) comprises 1,2,4-trihydroxybenzene.

4. A photosensitive resin composition according to claim 1, wherein the content of the component (b) is 1 to 50 parts by mass per 100 parts by mass of the component (a).

5. The photosensitive resin composition according to claim 1 or 2, wherein the component (c) contains a triazine ring-containing compound (c1) represented by formula (2): 【Chemistry 2】 (In formula (2), R １ ~R ６ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyl ether group having 2 to 10 carbon atoms, a methylol group, or an alkoxymethyl group. １ ~R ６ At least one of these is a methylol group or an alkoxymethyl group.

6. Furthermore, the maximum absorption wavelength is in the range of 490 nm or more and less than 800 nm in the range of 300 to 800 nm, and the absorbance Abs at the maximum absorption wavelength is in the range of 490 nm or more and less than 800 nm in the range of 300 to 800 nm ｍａｘ Absorbance Abs at 365 nm ３６５ 3. The photosensitive resin composition according to claim 1, further comprising a colorant (d) having a ratio of from 0.1% to less than 60%.

7. 7. The photosensitive resin composition according to claim 6, wherein the component (d) comprises a dye (d1-1) having a maximum absorption wavelength in the range of 490 nm or more and less than 580 nm in the range of 300 to 800 nm and / or a dye (d1-2) having a maximum absorption wavelength in the range of 580 nm or more and less than 800 nm in the range of 300 to 800 nm.

8. 7. The photosensitive resin composition according to claim 6, wherein the component (d) contains an ionic dye that forms an ion pair of an organic anion moiety and an organic cation moiety, and the organic anion moiety and the organic cation moiety are an organic anion moiety of an acidic dye and an organic cation moiety of a basic dye, respectively.

9. 7. The photosensitive resin composition according to claim 6, wherein the component (d) is a photosensitive resin composition containing n types of ionic dyes that form an ion pair of an organic anion moiety and an organic cation moiety, and the number of organic ions contained in the photosensitive resin composition is (n+1). (n represents an integer of 2 to 10.)

10. 3. The photosensitive resin composition according to claim 1, wherein the content of the component (c) is 1 to 100 parts by mass per 100 parts by mass of the component (a).

11. 3. The photosensitive resin composition according to claim 1, wherein the component (a) comprises one or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, polyamideimide precursor, and copolymers thereof.

12. 3. The photosensitive resin composition according to claim 1, wherein the total mass of all chlorine atoms and all bromine atoms contained in the photosensitive resin composition is 150 ppm or less based on the total mass of solids excluding the solvent in the photosensitive resin composition.

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

14. An organic EL display device having, on a substrate, a driving circuit, a planarizing layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode, wherein the planarizing layer and / or the insulating layer comprises the cured product according to claim 13.

15. The organic electroluminescence display device according to claim 14 , wherein the planarizing layer and / or the insulating layer comprises the cured product, and the planarizing layer and / or the insulating layer has a transmittance of less than 30% at a wavelength of 450 nm.

16. The organic EL display device according to claim 14, wherein the planarizing layer and / or insulating layer has the cured product, and the planarizing layer and / or insulating layer has an OD value of 0.5 to 1.5 in visible light per 1 μm of film thickness.

17. 15. The organic electroluminescence display device according to claim 14, further comprising a color filter having a black matrix.

18. A display device having at least metal wiring, the cured product according to claim 13, and a plurality of light-emitting elements, wherein the light-emitting elements have a pair of electrode terminals on either side thereof, the pair of electrode terminals are connected to a plurality of the metal wirings extending in the cured product, and the plurality of the metal wirings maintain electrical insulation due to the cured product.

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