Photosensitive composition, optical filter, image display device and solid-state imaging device

Abstract

To provide a photosensitive composition that excels in line width stability of a pattern and can be cured even at low temperatures to form a cured film having excellent hardness and high-temperature and high-humidity resistance (adhesion and stable thickness).SOLUTION: A photosensitive composition contains an alkali-soluble resin (A), a polymerizable compound (B), a photopolymerization initiator (C), a thermosetting compound (D) and an imidazole compound (E) containing a compound (E1) represented by general formula (1). (In general formula (1), X1-X3 independently represent a hydrogen atom, or a C1 to 20 alkyl group, a C6 to 30 aryl group, or a C7 to 30 arylalkyl group.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photosensitive composition and its use. [Background technology]

[0002] Organic EL (Electro-Luminescence) display devices using organic light-emitting diodes (OLEDs) and other devices do not require backlighting, and are therefore lighter, thinner, more energy-efficient, and more flexible than liquid crystal display devices. As a result, they are used in a variety of applications, including smartphones, tablet devices, and televisions.

[0003] Because the heat resistance of the organic light-emitting layer used in an organic EL display device is generally low, it is preferable to cure the photosensitive composition for forming the optical filter used in the organic EL display device at a low temperature, for example, 150° C. or less. However, when curing is performed at a low temperature, problems arise such that the curing does not proceed sufficiently, resulting in a decrease in hardness of the cured film, and in a decrease in adhesion and a change in film thickness under high temperature and high humidity.

[0004] In addition, organic EL display devices are equipped with a circular polarizer as an anti-reflection filter to prevent a decrease in visibility due to reflection of external light. However, circular polarizers are generally thick and have low flexibility, so photosensitive compositions that can form optical filters to replace circular polarizers have been investigated. However, such photosensitive compositions have a low colorant concentration, so when optical filters are formed using photolithography, they tend to transmit ultraviolet light, which creates a problem of increased line width in the pattern.

[0005] To solve the above problems, for example, Patent Document 1 discloses a coloring composition containing a colorant including a red colorant, a resin having a repeating unit including a blocked isocyanate group, a polymerizable compound, and a photopolymerization initiator, and in which the ratio of the maximum and minimum absorbance values at a specific wavelength is specified. Patent Document 2 also discloses a coloring composition containing a colorant, a polymer, and a polymerizable compound, in which at least one selected from the group consisting of the colorant, the polymer, and the polymerizable compound has a specific partial structure and a hydroxyl group. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2021 / 054248 [Patent Document 2] Patent Publication No. 2021-102759 Summary of the Invention [Problem to be solved by the invention]

[0007] However, the compositions described in Patent Documents 1 and 2 were unable to satisfy all of the requirements for pattern line width stability, hardness of the cured film when cured at low temperature, and high-temperature and high-humidity resistance (adhesion and film thickness stability) at a certain level or above.

[0008] An object of the present invention is to provide a photosensitive composition that can form a cured film having excellent pattern line width stability, and excellent hardness and high-temperature / high-humidity resistance (adhesion and film thickness stability) even when cured at low temperature. [Means for solving the problem]

[0009] The present invention provides a photosensitive composition comprising an alkali-soluble resin (A), a polymerizable compound (B), a photopolymerization initiator (C), a thermosetting compound (D), and an imidazole compound (E), The photosensitive composition according to the present invention relates to a photosensitive composition in which the imidazole compound (E) comprises a compound (E1) represented by the following general formula (1): General formula (1) [ka] (In general formula (1), X1 to X3 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms.) [Effects of the Invention]

[0010] According to the present invention, there is provided a photosensitive composition capable of forming a cured film having excellent pattern line width stability, and having excellent hardness and high-temperature and high-humidity resistance (adhesion and film thickness stability) even when cured at low temperature. The present invention also provides an optical filter, an image display device, and a solid-state imaging device. DETAILED DESCRIPTION OF THE INVENTION

[0011] Hereinafter, embodiments for carrying out the photosensitive composition of the present invention will be described in detail. Note that the present invention is not limited to the following embodiments, and can be modified and carried out within a range that can solve the problems.

[0012] In this specification, unless otherwise specified, "(meth)acryloyl," "(meth)acrylic," "(meth)acrylic acid," "(meth)acrylate," or "(meth)acrylamide" means "acryloyl and / or methacryloyl," "acrylic and / or methacrylic," "acrylic acid and / or methacrylic acid," "acrylate and / or methacrylate," or "acrylamide and / or methacrylamide," respectively. Furthermore, "CI" refers to the Color Index (CI; published by The Society of Dyers and Colourists). The polymerizable unsaturated group is an ethylenically unsaturated double bond. Regarding the molecular weight of a compound in the present invention, for a low-molecular-weight compound whose molecular weight can be specified, the molecular weight is a calculated value (formula weight) or a molecular weight measured by ESI-MS (electrospray ionization mass spectrometry), and for a compound having a molecular weight distribution, the molecular weight is a weight-average molecular weight in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran as a solvent. A monomer is a compound that polymerizes to form a resin. A monomer is in an unreacted state, and a monomer unit is a monomer that forms a resin after polymerization.

[0013] <Photosensitive composition> A photosensitive composition according to one embodiment of the present invention is a photosensitive composition comprising an alkali-soluble resin (A), a polymerizable compound (B), a photopolymerization initiator (C), a thermosetting compound (D), and an imidazole compound (E), The imidazole compound (E) contains a compound (E1) represented by the following general formula (1). General formula (1) [ka] (In general formula (1), X1 to X3 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms.)

[0014] The mechanism by which the photosensitive composition having the above-mentioned structure can solve the problems of the present invention is not clear, but is speculated as follows.

[0015] Imidazole compound (E) reacts with thermosetting compound (D) to promote the initiation of crosslinking reaction between thermosetting compounds (D). It is believed that compound (E1) represented by general formula (1), in which the nitrogen at position 1 is substituted with a benzyl group, reacts with thermosetting compound (D) at a lower temperature than imidazole compounds in which the nitrogen at position 1 is not substituted with a benzyl group, and then proceeds to crosslinking reaction between thermosetting compounds (D). Therefore, even at low temperatures, it is possible to form cured films with excellent hardness and high-temperature and high-humidity resistance. This mechanism is thought to be due to the fact that when the nitrogen at position 1 is not substituted with a benzyl group, the 1st position is a secondary amine and the 3rd position is a tertiary amine, but in reality the hydrogen bonded to the nitrogen at position 1 forms a resonance structure with the nitrogen at position 3, making them equivalent, inhibiting the reaction between the thermosetting compound (D) and the tertiary amine, making the reaction rate-limiting and requiring high temperatures for the reaction to occur.In contrast, when the 1st position is substituted with a benzyl group, the resonance disappears, resulting in a structure with two tertiary amines, which allows the thermosetting compound (D) to react with the tertiary amine even at lower temperatures, initiating the crosslinking reaction between the curable compounds (D).

[0016] Components that are or can be included in the photosensitive composition of one embodiment will be described in detail below.

[0017] [Alkali-soluble resin (A)] The photosensitive composition of the present invention contains an alkali-soluble resin (A).

[0018] The alkali-soluble resin (A) may be any resin that dissolves in an alkaline developer, and known resins can be used, such as (meth)acrylic resins, styrene resins, styrene-(meth)acrylic resins, urethane resins, polycarbonate resins, polyester resins, polyether resins, polyimide resins, polyamide-imide resins, and cyclic olefin resins.

[0019] From the viewpoint of developability, the weight average molecular weight (Mw) of the alkali-soluble resin (A) is preferably 4,000 to 40,000, more preferably 4,000 to 35,000. The Mw / Mn value is preferably not more than 10. An appropriate weight average molecular weight (Mw) improves adhesion to the substrate and solubility in development.

[0020] The acid value of the alkali-soluble resin (A) is preferably from 30 to 200 mgKOH / g, more preferably from 40 to 180 mgKOH / g. A suitable acid value improves adhesion to a substrate and solubility in development.

[0021] The content of the alkali-soluble resin (A) is preferably from 1 to 80 mass %, more preferably from 5 to 60 mass %, particularly preferably from 10 to 50 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0022] The alkali-soluble resin (A) can be used alone or in combination of two or more kinds.

[0023] (Alkali-soluble resin having blocked isocyanate group-containing monomer unit (a1) and hydroxyl group-containing monomer unit (a2)) From the viewpoint of low-temperature curing, the photosensitive composition of the present invention preferably contains an alkali-soluble resin (A) having a blocked isocyanate group-containing monomer unit (a1) and a hydroxyl group-containing monomer unit (a2), which crosslinks the alkali-soluble resin (A) between or within the resins upon heating, improving the durability of the cured film.

[0024] [Blocked isocyanate group-containing monomer unit (a1)] The blocked isocyanate group-containing monomer is a monomer in which the isocyanate group of an isocyanate group-containing monomer is protected with a compound that is thermally cleaved (hereinafter also referred to as a blocking agent). The cleavage temperature of the blocking agent is preferably 60 to 160°C, more preferably 80 to 140°C.

[0025] Examples of isocyanate group-containing monomers include 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, and methacryloyl isocyanate. Equimolar reaction products of 2-hydroxyalkyl (meth)acrylate and diisocyanate compounds can also be used. Among these, 2-isocyanatoethyl (meth)acrylate and 2-isocyanatopropyl (meth)acrylate are preferred.

[0026] Examples of the blocking agent include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, imide compounds, urea compounds, imine compounds, and bisulfite compounds.

[0027] Examples of the oxime compound include formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, cyclohexanone oxime, and benzophenone oxime, with methyl ethyl ketoxime being preferred. Examples of lactam compounds include ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam. Examples of phenolic compounds include phenol, cresol, 2,6-xylenol, 3,5-xylenol, ethylphenol, p-tert-butylphenol, nonylphenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, p-naphthol, and p-nitrophenol, with 3,5-xylenol, methyl 2-hydroxybenzoate, and methyl 4-hydroxybenzoate being preferred. Examples of the alcohol compound include methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, and furfuryl alcohol. Examples of the amine compound include diphenylamine, phenylnaphthylamine, aniline, and carbazole. Examples of the active methylene compound include dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone, with diethyl malonate being preferred. Examples of the pyrazole compound include pyrazole, methylpyrazole, and 3,5-dimethylpyrazole, with 3,5-dimethylpyrazole being preferred. Examples of the mercaptan compound include butyl mercaptan, thiophenol, and tert-dodecyl mercaptan. Examples of the imidazole compound include imidazole, 2-methylimidazole, 2-ethylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, and 1-benzyl-2-phenylimidazole. Examples of the imide compound include succinimide, maleimide, maleimide, and phthalimide. Examples of the urea compound include urea, thiourea, and ethylene urea. Examples of the imine compound include ethyleneimine and polyethyleneimine. Examples of bisulfite compounds include sodium bisulfite, potassium bisulfite, etc. These blocking agents can be used alone or in combination of two or more.

[0028] The blocking agent is preferably at least one selected from the group consisting of oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds, and from the viewpoint of the protection reaction and the deprotection reaction, more preferably at least one selected from the group consisting of oxime compounds, phenol compounds, active methylene compounds, and pyrazole compounds.

[0029] Examples of the blocked isocyanate group-containing monomer include the following compounds, but the present invention is not limited to these.

[0030] [ka]

[0031] Commercially available blocked isocyanate group-containing monomers include, for example, Karenz MOI-DEM (blocking agent desorption temperature: 85 to 95°C), MOI-BP (blocking agent desorption temperature: 105 to 115°C), and MOI-BM (blocking agent desorption temperature: 125 to 135°C) manufactured by Showa Denko K.K.

[0032] The content of the blocked isocyanate group-containing monomer unit (a1) is preferably from 1 to 50 mol %, more preferably from 5 to 40 mol %, of all the constituent units of the alkali-soluble resin, from the viewpoint of low-temperature curing.

[0033] [Hydroxyl group-containing monomer unit (a2)] Examples of hydroxyl group-containing monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-acryloyloxyethyl-2-hydroxyethyl phthalate.

[0034] From the viewpoint of low-temperature curing, the content of the hydroxyl group-containing monomer unit (a2) is preferably from 5 to 50 mol %, more preferably from 10 to 40 mol %, of all the constituent units of the alkali-soluble resin.

[0035] The molar ratio of the blocked isocyanate group-containing monomer unit (a1) to the hydroxyl group-containing monomer unit (a2) is preferably from 10:90 to 50:50, more preferably from 15:85 to 45:55, from the viewpoint of low-temperature curing.

[0036] The alkali-soluble resin having the blocked isocyanate group-containing monomer unit (a1) and the hydroxyl group-containing monomer unit (a2) may contain a monomer unit other than the blocked isocyanate group-containing monomer unit (a1) and the hydroxyl group-containing monomer unit (a2). Examples of such a monomer unit include an alicyclic hydrocarbon-containing monomer unit (a3), an acidic group-containing monomer unit (a4), an epoxy group-containing monomer unit (a5), a polymerizable unsaturated group-containing monomer unit (a6), and other monomer units (a7). Among these, the alicyclic hydrocarbon-containing monomer unit (a3) is preferred from the viewpoints of hardness of the cured film and resistance to high temperatures and high humidity.

[0037] [Alicyclic hydrocarbon-containing monomer unit (a3)] Examples of the alicyclic hydrocarbon-containing monomer include isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, adamantyl (meth)acrylate, etc. Among these, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentanyloxyethyl (meth)acrylate are preferred.

[0038] The content of the alicyclic hydrocarbon-containing monomer unit (a3) is preferably 1 to 40 mol %, more preferably 5 to 30 mol %, of all structural units of the alkali-soluble resin, from the viewpoints of hardness of the cured film and resistance to high temperatures and humidity.

[0039] [Acidic group-containing monomer unit (a4)] Examples of the acidic group-containing monomer include (meth)acrylic acid, crotonic acid, propiolic acid, cinnamic acid, itaconic acid, itaconic anhydride, maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, maleic anhydride, fumaric acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethylhexylhydrophthalic acid, p-styrenesulfonic acid, vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, and 2-(meth)acryloyloxyethyl acid phosphate.

[0040] From the viewpoint of developability, the content of the acidic group-containing monomer unit (a4) is preferably from 1 to 40 mol %, more preferably from 5 to 30 mol %, of all the constituent units of the alkali-soluble resin.

[0041] [Epoxy group-containing monomer unit (a5)] Examples of epoxy group-containing monomers include oxiranyl(meth)acrylate, glycidyl(meth)acrylate, 2-methylglycidyl(meth)acrylate, 2-ethylglycidyl(meth)acrylate, 2-oxiranylethyl(meth)acrylate, 2-glycidyloxyethyl(meth)acrylate, 3,4-epoxycyclohexyl(meth)acrylate, 3,4-epoxycyclohexylmethyl(meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl(meth)acrylate, 2-(3,4-epoxycyclohexylmethyloxy)ethyl(meth)acrylate, and 3-(3,4-epoxycyclohexylmethyloxy)propyl(meth)acrylate.

[0042] [Polymerizable unsaturated group-containing monomer unit (a6)] Examples of the polymerizable unsaturated group-containing monomer unit (a6) include units introduced by the following methods (i) to (iii).

[0043] <Method (i)> There is also a method (i) in which the above-mentioned epoxy group-containing monomer is added to the acidic group of a resin having an acidic group-containing monomer unit (a4).

[0044] <Method (ii)> There is also a method (ii) in which the above-mentioned acidic group-containing monomer is added to the epoxy group of a resin having an epoxy group-containing monomer unit (a5).

[0045] Furthermore, units obtained by further reacting an acid anhydride with the hydroxyl group generated by the reaction of the method (i) or (ii) are also preferred as the polymerizable unsaturated group-containing monomer unit (a6).

[0046] Examples of the acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride.

[0047] <Method (iii)> A method (iii) in which the hydroxyl group of a resin having the hydroxyl group-containing monomer unit (a2) is reacted with the isocyanate group of an isocyanate group-containing monomer is exemplified.

[0048] Examples of the isocyanate group-containing monomer include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate.

[0049] [Other monomer units (a7)] Examples of other monomers include acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of nonylphenol, EO- or PO-modified (meth)acrylate of paracumylphenol, dimethylaminoethyl (meth)acrylate, and diethylaminoethyl (meth)acrylate; Aromatic vinyl compounds such as styrene, α-methylstyrene, p-vinyltoluene, p-chlorostyrene, and vinylnaphthalene; (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or acryloylmorpholine; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether; vinyl fatty acid vinyl compounds such as vinyl acetate or vinyl propionate; Phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide N-substituted maleimides such as N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, and 9-maleimidoacridine; Examples include dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, diethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, di(n-propyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(isopropyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(2-ethylhexyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, etc. These monomers can be used alone or in combination of two or more.

[0050] The alkali-soluble resin having the blocked isocyanate group-containing monomer unit (a1) and the hydroxyl group-containing monomer unit (a2) can be used alone or in combination of two or more kinds.

[0051] The content of the alkali-soluble resin having the blocked isocyanate group-containing monomer unit (a1) and the hydroxyl group-containing monomer unit (a2) is preferably 30% by mass or more, and more preferably 50 to 100% by mass, based on 100% by mass of the alkali-soluble resin (A), from the viewpoint of low-temperature curing.

[0052] [Polymerizable compound (B)] The photosensitive composition of the present invention contains a polymerizable compound (B).

[0053] Examples of the polymerizable compound (B) include monomers and oligomers having a polymerizable unsaturated group. Examples of the polymerizable unsaturated group include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, and a (meth)acryloyloxy group. Examples of the polymerizable compound (B) include a lactone-modified polymerizable compound, a polymerizable compound having an acidic group, a polymerizable compound having a urethane bond, a polymerizable compound having a tertiary amine structure, a polymerizable compound having a dendrimer structure or a hyperbranched structure, and other polymerizable compounds. The polymerizable compound (B) is a compound that contributes to film formation. The number of polymerizable unsaturated groups in the polymerizable compound (B) is 1 or more, and preferably 2 or more.

[0054] (Lactone-modified polymerizable compound) The lactone-modified polymerizable compound is a compound having a lactone-modified structure in the molecule. The lactone-modified polymerizable compound can be obtained by esterifying a polyhydric alcohol such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaethylthritol, tripentaerythritol, glycerin, diglycerol, or trimetrolmelamine with (meth)acrylic acid and ε-caprolactone or another lactone compound.

[0055] Examples of commercially available lactone-modified polymerizable compounds include KAYARAD DPCA-20, DPCA-30, and DPCA-60 manufactured by Nippon Kayaku Co., Ltd.

[0056] (Polymerizable compound having an acidic group) Examples of the polymerizable compound having an acidic group include esters of free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohols and (meth)acrylic acid with dicarboxylic acids, esters of polycarboxylic acids with monohydroxyalkyl(meth)acrylates, etc. The polymerizable compound having an acidic group does not have a urethane bond.

[0057] Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.

[0058] Examples of the dicarboxylic acids include malonic acid, succinic acid, maleic acid, glutaric acid, phthalic acid, itaconic acid, and the like.

[0059] Examples of the polycarboxylic acid include trimellitic acid and pyromellitic acid. Examples of monohydroxyalkyl (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, pentaerythritol triacrylate, and 2-hydroxy-3-acryloyloxypropyl methacrylate.

[0060] Commercially available polymerizable compounds having an acidic group include Viscoat #2500P manufactured by Osaka Organic Chemical Industry Co., Ltd., Aronix M-5300, M-5400, M-5700, M-510, M-520, and M-521 manufactured by Toagosei Co., Ltd., and β-CEA manufactured by Daicel-Allnex Corporation.

[0061] (Polymerizable compound having a urethane bond) Examples of the polymerizable compound having a urethane bond include urethane (meth)acrylates obtained by reacting a hydroxyl group-containing (meth)acrylate with a polyfunctional isocyanate, and urethane (meth)acrylates obtained by reacting a polyhydric alcohol with a polyfunctional isocyanate and then reacting the resulting mixture with a hydroxyl group-containing (meth)acrylate.

[0062] Examples of the hydroxyl group-containing (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide (EO)-modified penta(meth)acrylate, dipentaerythritol propylene oxide (PO)-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy group-containing compound and a carboxy(meth)acrylate, and a hydroxyl group-containing polyol polyacrylate.

[0063] Examples of the polyfunctional isocyanate include aromatic diisocyanates such as tolylene diisocyanate, diphenylmethylene diisocyanate, and xylene diisocyanate; aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate; alicyclic diisocyanate such as isophorone diisocyanate; and biuret derivatives, isocyanate nurate derivatives, and trimethylolpropane adducts thereof.

[0064] From the viewpoint of developability, the polymerizable compound having a urethane bond may further have an acidic group. Examples of the acidic group include a sulfonic acid group, a carboxyl group, and a phosphate group. Among these, a carboxyl group is preferred.

[0065] The acidic group can be introduced into a polymerizable compound having a urethane bond by, for example, first reacting the hydroxyl group-containing (meth)acrylate with the polyfunctional isocyanate, and then adding a mercapto compound having a carboxyl group to the product.

[0066] Examples of the mercapto compound having a carboxyl group include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid, and mercaptosuccinic acid.

[0067] Examples of commercially available polymerizable compounds having a urethane bond include AH-600, UA-306H, UA-306T, UA-306I, UA-510H, and UF-8001G manufactured by Kyoeisha Chemical Co., Ltd., UA-1100H, U-6LPA, UA-33H, U-10HA, and U-15HA manufactured by Shin-Nakamura Chemical Co., Ltd., and EBECRYL1290 and KRM8452 manufactured by Daicel-Allnex Corporation.

[0068] (Polymerizable compound having a tertiary amine structure) Examples of the polymerizable compound having a tertiary amine structure include tris(acryloyloxyethyl)amine, tris(methacryloyloxyethyl)amine, tris(2-hydroxy-3-methacryloyloxypropyl)amine, and a Michael addition reaction product of a (meth)acrylate compound (X) and an amine compound (Y).

[0069] Examples of the (meth)acrylate compound (X) include glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and diglycerides thereof. Examples of the alkylene oxide-modified tri(meth)acrylate include lin tri(meth)acrylate, diglycerin tetra(meth)acrylate, trimethylolpropane alkylene oxide-modified tri- and tetra(meth)acrylate, ditrimethylolpropane alkylene oxide-modified tri- and tetra(meth)acrylate, pentaerythritol alkylene oxide-modified tri- and tetra(meth)acrylate, diglycerin alkylene oxide-modified tri- and tetra(meth)acrylate, and dipentaerythritol alkylene oxide-modified tetra-, penta-, and hexa(meth)acrylate. Examples of the alkylene oxide unit in the alkylene oxide modification include ethylene oxide, propylene oxide, and butylene oxide. The (meth)acrylate compound (X) also includes a (meth)acrylate compound having an acidic group.

[0070] The (meth)acrylate compound (X) can be used alone or in combination of two or more kinds.

[0071] Examples of the amine compound (Y) include primary amines such as n-propylamine, n-butylamine, n-hexylamine, benzylamine, aminocaproic acid, monoethanolamine, 2-(2-aminoethoxy)ethanol, o-aminophenol, m-aminophenol, and p-aminophenol; Examples of the secondary amines include dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, cyclohexylamine, morpholine, piperidine, 1-methylpiperazine, proline, N-merylethanolamine, N-acetylethanolamine, diethanolamine, 3-anilinephenol, and 4-anilinephenol.

[0072] The amine compound (Y) can be used alone or in combination of two or more kinds.

[0073] The method for producing the Michael addition reaction product of the (meth)acrylate compound (X) and the amine compound (Y) is not particularly limited, and known methods can be used, such as those described in International Publication No. 2006 / 075754, JP-A No. 2008-545859, and JP-A No. 2017-066347.

[0074] The polymerizable compound having a tertiary amine structure may have an acidic group and / or a hydroxyl group. Examples of methods for introducing the acidic group and / or the hydroxyl group include a method using a compound having an acidic group and / or a hydroxyl group in the (meth)acrylate compound (X) or the amine compound (Y), and a method of adding an acid anhydride after a Michael addition reaction.

[0075] Examples of commercially available polymerizable compounds having a tertiary amine structure include Aronix MT-3041 and 3042 manufactured by Toagosei Co., Ltd.

[0076] (Polymerizable compound having a dendrimer structure or a hyperbranched structure) A polymerizable compound with a dendrimer structure has a chemical structure in which branches are regularly repeated outward from a chemical structure constituting a core (hereinafter also referred to as the core portion), and polymerizable unsaturated groups are bonded to the ends of the branches, and has a spherical, highly controlled chemical structure and molecular weight. The hyperbranched structure has a chemical structure similar to that of a dendrimer structure.

[0077] Commercially available polymerizable compounds having a dendrimer structure or a hyperbranched structure include, for example, Viscoat #1000LT (dendrimer structure, average number of acryloyl groups: 14) manufactured by Osaka Organic Chemical Industry Co., Ltd., Miramer SP-1106 (dendrimer structure, average number of acryloyl groups: 18) and Miramer SP-1108 (dendrimer structure, average number of acryloyl groups: 13) manufactured by Miwon Specialty Chemical Co., Ltd., CN2301 (hyperbranched structure, average number of acryloyl groups: 9), CN2302 (hyperbranched structure, average number of acryloyl groups: 16), CN2303 (hyperbranched structure, average number of acryloyl groups: 6), and CN2304 (hyperbranched structure, average number of acryloyl groups: 18) manufactured by SARTOMER Co., Ltd., and Eternal Examples include Etercure 6361-100 (hyperbranched structure, average number of acryloyl groups: 8), Etercure 6362-100 (hyperbranched structure, average number of acryloyl groups: 12), Etercure 6363 (hyperbranched structure, average number of acryloyl groups: 16), and Etercure DR-E522 (hyperbranched structure, average number of acryloyl groups: 15), all manufactured by Materials Corporation.

[0078] (Other polymerizable compounds) Other polymerizable compounds include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, and ditrimethylolpropane tetra(meth)acrylate. , pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl (meth)acrylate, (meth)acrylic acid ester of methylolated melamine, various acrylic acid esters and methacrylic acid esters such as epoxy (meth)acrylate, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, acrylonitrile, and the like.

[0079] Other commercially available polymerizable compounds include, for example, KAYARAD R-128H, R526, PEG400DA, MAND, NPGDA, R-167, HX-220, R-551, R712, R-604, R-684, GPO-303, TMPTA, DPHA, DPEA-12, DPHA-2C, D-310, and D-330 manufactured by Nippon Kayaku Co., Ltd., and Aronix M-303, M-305, M-306, M-309, M-310, M-321, M-325, and M-330 manufactured by Toagosei Co., Ltd. -350, M-360, M-313, M-315, M-400, M-402, M-403, M-404, M-405, M-406, M-450, M-452, M-408, M-211B, M-101A, Viscoat #310HP, #335HP, #700, #295, #330, #360, #GPT, #400, #405 manufactured by Osaka Organic Chemical Industry Co., Ltd., and OGSOL manufactured by Osaka Gas Chemicals Co., Ltd. Examples of suitable acrylic acid esters include EA-0200, EA-0300, GA-5060P, and GA-2800, Miramer HR6060, 6100, and 6200 manufactured by Miwon Specialty Chemical Co., Ltd., NK Ester ABE-300, A-DOG, A-DCP, A-BPE-4, and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., and EBECRYL 40, 130, 140, and 145 manufactured by Daicel-Allnex Corporation.

[0080] The polymerizable compound (B) can be used alone or in combination of two or more kinds.

[0081] The content of the polymerizable compound (B) is preferably from 30 to 90 mass %, more preferably from 40 to 80 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0082] [Photopolymerization initiator (C)] The photosensitive composition of the present invention contains a photopolymerization initiator (C), which allows the photosensitive composition to be cured by irradiation with active energy rays.

[0083] Examples of the photopolymerization initiator (C) include acetophenone-based compounds such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; triazine-based compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; Oxime compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], or ethanol, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); acylphosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; Examples include quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; and carbazole compounds.

[0084] Commercially available products include acetophenone compounds such as Omnirad 907, 369E, 379EG, 184, and 2959 manufactured by IGM Resins, acylphosphine compounds such as Omnirad 819 and TPO manufactured by IGM Resins, oxime compounds such as IRGACURE OXE-01, 02, 03, and 04 manufactured by BASF Japan, N-1919, NCI-730, 831, and 930 manufactured by ADEKA, TRONLY TR-PBG-301, 304, 305, 309, 314, 345, 358, 380, 365, 610, 3054, and 3057 manufactured by Changzhou Strong New Materials Co., Ltd., and IGM Examples include Omnirad 1312, 1314, and 1316 manufactured by Resins Co., Ltd., SPI-02, 03, 04, 05, 06, and 07 manufactured by Samyang Corporation, and DFI-020, 306, and EOX-01 manufactured by Daito Chemiks Co., Ltd. Further examples include oxime compounds described in JP 2007-210991 A, JP 2009-179619 A, JP 2010-037223 A, JP 2010-215575 A, JP 2011-020998 A, WO 2015 / 036910, WO 2021 / 175855, etc.

[0085] The photopolymerization initiator (C) can be used alone or in combination of two or more kinds.

[0086] The content of the photopolymerization initiator (C) is preferably from 0.5 to 20 mass %, more preferably from 1 to 10 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0087] (Compound represented by general formula (2)) The photosensitive composition of the present invention preferably contains a compound represented by the following general formula (2) as the photopolymerization initiator (C) from the viewpoints of pattern line width stability, hardness at low temperature curing, and resistance to high temperature and humidity.

[0088] General formula (2) [ka] (In general formula (2), R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R3 represents a hydrogen atom or a monovalent substituent.)

[0089] R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. The alkyl group having 1 to 8 carbon atoms may be linear, branched, or cyclic, or may be a combination of these, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a cyclopentyl group, a cyclopentylmethyl group, a cyclohexyl group, a cyclohexylmethyl group, a cyclohexylmethyl group, etc. Of these, from the viewpoint of pattern shape, a linear alkyl group having 3 to 8 carbon atoms is preferred, and a linear alkyl group having 4 to 6 carbon atoms is more preferred.

[0090] R3 represents a hydrogen atom or any monovalent substituent. Examples of the monovalent substituent include alkyl groups having 1 to 20 carbon atoms, such as methyl and ethyl; alkoxy groups having 1 to 20 carbon atoms, such as methoxy and ethoxy; halogen atoms, such as F, Cl, Br, and I; acyl groups having 1 to 20 carbon atoms; alkyl ester groups having 1 to 20 carbon atoms; alkoxycarbonyl groups having 1 to 20 carbon atoms; halogenated alkyl groups having 1 to 20 carbon atoms, aromatic ring groups having 4 to 20 carbon atoms; amino groups; aminoalkyl groups having 1 to 20 carbon atoms; hydroxyl groups; nitro groups; cyano groups; optionally substituted benzoyl groups; and optionally substituted thenoyl groups. Examples of the substituents that the benzoyl or thenoyl groups may have include alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and alkoxycarbonyl groups having 1 to 10 carbon atoms. Among these, from the viewpoint of radical generation efficiency, a hydrogen atom and a nitro group are preferred, and a hydrogen atom is more preferred.

[0091] Examples of methods for producing the compound represented by general formula (2) include those described in JP-T-2019-507108 and JP-T-2019-528331.

[0092] Specific examples of the compound represented by formula (2) are shown below, but the present invention is not limited to these.

[0093] [ka] [ka]

[0094] Among the compounds of chemical formulas (4) to (7), the compound of chemical formula (4) is preferred from the viewpoints of pattern line width stability, hardness at low temperature curing, and resistance to high temperature and humidity.

[0095] The compounds represented by general formula (2) can be used alone or in combination of two or more.

[0096] The content of the compound represented by formula (2) is preferably from 90 to 100 mass %, more preferably from 95 to 100 mass %, in 100 mass % of the photopolymerization initiator (C).

[0097] [Thermosetting compound (D)] The photosensitive composition of the present invention contains a thermosetting compound (D), which crosslinks upon heating, improving the hardness and high-temperature, high-humidity resistance of the cured film.

[0098] The thermosetting compound (D) may be a low molecular weight compound or a high molecular weight compound such as a resin. Examples of the thermosetting compound (D) include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. Among these, from the viewpoint of low-temperature curing, epoxy compounds, oxetane compounds, and melamine compounds are preferred, and epoxy compounds are more preferred.

[0099] (epoxy compounds) The epoxy compound is preferably a compound having an aromatic ring and / or an aliphatic ring, and is more preferable than a compound having an aliphatic ring from the viewpoints of hardness at low temperature curing and resistance to high temperature and high humidity. The epoxy group is preferably bonded to the aromatic ring and / or the aliphatic ring via a single bond or a linking group. Examples of the linking group include an alkyl group, an arylene group, -O-, -NR- (wherein R represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent), -SO2-, -CO-, -O-, and -S-. In the case of a structure having an aliphatic ring, it is more preferable that the epoxy group be bonded to the aliphatic ring via a single bond.

[0100] From the viewpoints of hardness at low temperature curing and resistance to high temperature and high humidity, the epoxy compound is preferably a compound having two or more epoxy groups in the molecule, more preferably a compound having 5 to 50 epoxy groups, and particularly preferably a compound having 10 to 30 epoxy groups.

[0101] The epoxy equivalent of the epoxy compound is preferably 50 to 400 g / eg, more preferably 100 to 200 g / eg. The epoxy equivalent is defined as the mass of an epoxy compound containing one equivalent of epoxy groups.

[0102] Examples of epoxy compounds include polycondensates of bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), polycondensates of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, Examples of suitable epoxy resins include polymers of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), polycondensates of phenols and aromatic dimethanols (benzenedimethanol, α,α,α',α'-benzenedimethanol, biphenyldimethanol, α,α,α',α'-biphenyldimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes, glycidyl ether epoxy resins obtained by glycidylating alcohols, alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidylamine epoxy resins, and glycidyl ester epoxy resins.

[0103] Commercially available products include, for example, Epicoat 807, 815, 825, 827, 828, 190P, and 191P manufactured by Yuka Shell Epoxy Co., Ltd., and TECHMORE manufactured by Mitsui Chemicals, Inc. VG3101L, EPPN-201, 501H, 502H, EOCN-102S, 103S, 104S, 1020 manufactured by Nippon Kayaku Co., Ltd., Epicoat 1004, 1256, JER1032H60, 157S65, 157S70, 152, 154 manufactured by Japan Epoxy Resins Co., Ltd., Celoxide 2021, EHPE-3150, Epolead GT401 manufactured by Daicel Chemical Industries, Ltd., Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721 manufactured by Nagase ChemteX Corporation, TEPIC-L, H, S manufactured by Nissan Chemical Industries, Ltd., and EPICLON manufactured by DIC Corporation. Examples include 830, 840, 850, 860, 1050, 3050, 4050, N-660, N-670, N-740, N-770, N865, HP-7200, HP-4700, HP-4770, HP-5000, HP-6000, and HP-9500.

[0104] The content of the epoxy compound is preferably 1 to 20 mass %, more preferably 5 to 15 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition, from the viewpoint of hardness at low temperature curing and resistance to high temperature and humidity.

[0105] (Oxetane compounds) The oxetane compound is a known compound having an oxetane group, and examples of the oxetane compound include monofunctional oxetane compounds, bifunctional oxetane compounds, and trifunctional or higher functional oxetane compounds.

[0106] Examples of monofunctional oxetane compounds include (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, and 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane.

[0107] Examples of commercially available products include OXE-10,30 manufactured by Osaka Organic Chemical Industry Co., Ltd. and OXT-101,212 manufactured by Toagosei Co., Ltd.

[0108] Examples of the bifunctional oxetane compound include 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether, di[1-ethyl(3-oxetanyl)]methyl ether 3-ethyl-3-hydroxymethyloxetane, 3- Ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethyleneglycol bis(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenylbis(3-ethyl- 3-oxetanylmethyl) ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO)-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO)-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F(3-ethyl-3-oxetanylmethyl) ether, and the like.

[0109] Examples of commercially available products include OXBP and OXTP manufactured by Ube Industries, Ltd., and OXT-121 and 221 manufactured by Toagosei Co., Ltd.

[0110] Examples of trifunctional or higher oxetane compounds include pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, and caprolactone-modified dipentaerythritol. Examples of such polymers include erythritol hexa(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl) ether, resins containing an oxetane group (for example, the oxetane-modified phenol novolac resin described in Japanese Patent No. 3783462), and polymers obtained by radical polymerization of (meth)acrylic monomers such as the above-mentioned OXE-30.

[0111] The content of the oxetane compound is preferably 1 to 20 mass %, more preferably 5 to 15 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition, from the viewpoints of hardness at low temperature curing and resistance to high temperature and humidity.

[0112] (melamine compounds) The melamine compound is a compound having a melamine ring structure, and is preferably a compound having a methylol group.

[0113] Examples of commercially available products include Nikalac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS-001, MX-002, MX-730, MX-750, MX-708, MX-706, MX-042, MX-45, MX-500, MX-520, MX-43, MX-417, and MX-410 manufactured by Sanwa Chemical Co., Ltd., and Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, and 370 manufactured by Nippon Cytec Industries Co., Ltd.

[0114] The content of the melamine compound is preferably 0.01 to 10 mass %, more preferably 0.1 to 5 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition, from the viewpoints of hardness at low temperature curing and resistance to high temperature and humidity.

[0115] The thermosetting compound (D) can be used alone or in combination of two or more kinds.

[0116] [Imidazole compound (E)] (Compound (E1) represented by general formula (1)) The photosensitive composition of the present invention contains a compound (E1) represented by general formula (1) as the imidazole compound (E).

[0117] General formula (1) [ka] (In general formula (1), X1 to X3 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms.)

[0118] The alkyl group having 1 to 20 carbon atoms may be linear, branched, or cyclic, or may be a combination of any of these, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group, a 2-ethylhexyl group, a nonyl group, an isononyl group, a decyl group, an isodecyl group, an undecyl group, a dodecyl group, a hexadecyl group, a cyclopentyl group, a cyclopentylmethyl group, a cyclohexyl group, a cyclohexylmethyl group, and a cyclohexylmethyl group. Examples of the aryl group having 6 to 30 carbon atoms include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group, and an anthryl group. Examples of the arylalkyl group having 7 to 30 carbon atoms include a benzyl group, an α-methylbenzyl group, an α,α-dimethylbenzyl group, and a phenylethyl group.

[0119] From the viewpoint of hardness and resistance to high temperatures and humidity, X1 is preferably one selected from the group consisting of a methyl group, an ethyl group, and a phenyl group.

[0120] From the viewpoint of reactivity, X2 and X3 are preferably one selected from the group consisting of a hydrogen atom, a methyl group, and an ethyl group.

[0121] Examples of the compound (E1) represented by general formula (1) include 1-benzylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-4-methylimidazole, 1-benzyl-2-ethylimidazole, 1-benzyl-2-propylimidazole, 1-benzyl-2-isopropylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-phenyl-4-(4-methylphenyl)imidazole, etc. Among these, 1-benzyl-2-methylimidazole and 1-benzyl-2-phenylimidazole are preferred from the viewpoints of hardness in low-temperature curing and resistance to high temperatures and high humidity.

[0122] The compound (E1) represented by the general formula (1) can be used alone or in combination of two or more kinds.

[0123] The content of the compound (E1) represented by general formula (1) is preferably 50% by mass or more, and more preferably 70% by mass or more, based on 100% by mass of the imidazole compound (E).

[0124] (Compound (E2) represented by general formula (3)) From the viewpoints of hardness at low temperature curing and resistance to high temperatures and high humidity, the photosensitive composition of the present invention preferably further contains a compound (E2) represented by the following general formula (3) as the imidazole compound (E). The compound (E2) represented by general formula (3) initiates reaction with the thermosetting compound (D) at a higher temperature than the compound (E1) represented by general formula (1). However, the reaction mechanism is different, and once the reaction occurs, the subsequent reaction rate with the thermosetting compound (D) is presumably faster. Therefore, a cured film with high hardness and resistance to high temperatures and high humidity can be obtained.

[0125] General formula (3) [ka] (In general formula (3), X4 to X6 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms.)

[0126] The alkyl group having 1 to 20 carbon atoms may be linear, branched, or cyclic, or may be a combination of any of these, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group, a 2-ethylhexyl group, a nonyl group, an isononyl group, a decyl group, an isodecyl group, an undecyl group, a dodecyl group, a hexadecyl group, a cyclopentyl group, a cyclopentylmethyl group, a cyclohexyl group, a cyclohexylmethyl group, and a cyclohexylmethyl group. Examples of the aryl group having 6 to 30 carbon atoms include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group, and an anthryl group. Examples of the arylalkyl group having 7 to 30 carbon atoms include a benzyl group, an α-methylbenzyl group, an α,α-dimethylbenzyl group, and a phenylethyl group.

[0127] From the viewpoint of hardness and resistance to high temperatures and humidity, X4 is preferably one selected from the group consisting of a methyl group, an ethyl group, and a phenyl group.

[0128] From the viewpoint of reactivity, X5 and X6 are preferably one selected from the group consisting of a hydrogen atom, a methyl group, and an ethyl group.

[0129] Examples of the compound (E2) represented by general formula (3) include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-butylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2-phenylimidazole, 4-phenylimidazole, 4-methyl-2-phenylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2,4-diphenylimidazole, etc. Among these, 2-methylimidazole and 2-phenylimidazole are preferred.

[0130] The compound (E2) represented by the general formula (3) can be used alone or in combination of two or more kinds.

[0131] The total content of the compound (E1) represented by general formula (1) and the compound (E2) represented by general formula (3) is preferably 60% by mass or more, more preferably 80% by mass or more, based on 100% by mass of the imidazole compound (E). The content of the compound (E1) represented by general formula (1) is preferably 50% by mass or more, and more preferably 80% by mass or more, based on 100% by mass of the total content of the compound (E1) represented by general formula (1) and the compound (E2) represented by general formula (3).

[0132] (Other imidazole compounds (E3)) The photosensitive composition of the present invention may contain, as the imidazole compound (E), an imidazole compound other than the compound (E1) represented by general formula (1) and the compound (E2) represented by general formula (3) (hereinafter, also simply referred to as other imidazole compound (E3)).

[0133] Other examples of the imidazole compound (E3) include 1-methylimidazole, 1-ethylimidazole, 1-propylimidazole, 1-isopropylimidazole, 1-phenylimidazole, 1,2-dimethylimidazole, 1-cyanomethyl-2-methylimidazole, and 1-cyanoethyl-2-ethyl-4-methylimidazole.

[0134] The content of the imidazole compound (E) is preferably from 1 to 20 parts by mass, more preferably from 1.5 to 15 parts by mass, based on 100 parts by mass of the thermosetting compound (D).

[0135] Colorant (F) The photosensitive composition of the present invention may contain a colorant (F), which makes it possible to control the transmittance of each wavelength region of the optical filter and improves color separation.

[0136] The colorant (F) may be a pigment or a dye, and from the viewpoints of light resistance, heat resistance, and solvent resistance, a pigment is preferred.

[0137] (pigment) The pigment is preferably a compound classified as a pigment in the Color Index. Red pigments include, for example, CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179 ,181,184,185,187,188,190,193,194,200,202,206,207,208,209,210,214,216,220,221,224,230,231,232,233,235,236,237,238,239,242,243,245,247,249,250,251,253,254,255,256,257,258,259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 295, 296, JP 2014-134712 A, and the pigments described in Japanese Patent No. 6368844. Among these, from the viewpoints of heat resistance, light fastness, and transmittance, CI Pigment Red 48:1,122,177,224,242,269,254,291,295,296, the pigments described in JP-A-2014-134712, and the pigments described in Japanese Patent No. 6368844 are preferred, and CI Pigment Red 177,254,291,295,296, the pigments described in JP-A-2014-134712, and the pigments described in Japanese Patent No. 6368844 are more preferred.

[0138] Examples of orange pigments include CI Pigment Orange 36, 38, 43, 64, 71, and 73.

[0139] Yellow pigments include, for example, CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 178, 179, 180, 181, 182, 183, 184, 185, 186, 187, 188, 189, 190, 1,152, 153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,192,193,194,196,198,199,213,214,231,233, JP 2012-226110 A, JP 2017-171912 A, JP 2017-171913 A, JP 2017-171914 A, JP 2017-171915 A, and the like. Among these, CI Pigment Yellows 138, 139, 150, 185, 231, and 233, and the pigments described in JP-A-2012-226110 are preferred.

[0140] Examples of green pigments include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, and 63. Among these, CI Pigment Green 36, 58, 59, 62, and 63 are preferred.

[0141] Examples of blue pigments include CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79. Among these, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, and 15:6 are preferred.

[0142] Examples of purple pigments include CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50. Among these, CI Pigment Violet 19 and 23 are preferred.

[0143] Specific examples of black pigments include CI Pigment Black 1, 6, 7, 12, 20, 31, and 32. Other examples include compounds described in JP-A Nos. 2010-534726, 2012-515233, and 2012-515234, JP-A Nos. 1-170601, and 2-34664.

[0144] When the photosensitive composition of the present invention is used in an antireflection filter, it preferably contains, as a colorant (F), one or more pigments selected from the group consisting of red pigments, yellow pigments, blue pigments, green pigments, purple pigments and black pigments.

[0145] Suitable combinations for use in anti-reflection filters include, for example, the following embodiments. (1) Contains green and purple pigments. (2) Contains yellow pigment, blue pigment, and purple pigment. (3) Contains yellow pigment, green pigment, and purple pigment. (4) Contains red pigment, yellow pigment, and blue pigment. (5) Contains yellow pigment, green pigment, blue pigment and purple pigment. (6) Contains red pigment, yellow pigment, blue pigment and purple pigment. (7) Contains red pigment, green pigment, blue pigment, and purple pigment. (8) Contains yellow pigment, blue pigment, purple pigment and black pigment.

[0146] An example of the above embodiment (1) is an embodiment in which the green pigment contains at least one selected from CI Pigment Green 7, 36, 58, 59, and 63, and the purple pigment contains CI Pigment Violet 23. An example of the above embodiment (2) is an embodiment in which the yellow pigment contains at least one selected from CI Pigment Yellow 139, 185, 231, and 233, the blue pigment contains at least one selected from CI Pigment Blue 15:3, 15:4, and 15:6, and the purple pigment contains CI Pigment Violet 23. An example of the above embodiment (3) is an embodiment in which the yellow pigment contains at least one selected from CI Pigment Yellow 139, 185, 231, and 233, the green pigment contains at least one selected from CI Pigment Green 7, 36, 58, 59, and 63, and the purple pigment contains CI Pigment Violet 23. An example of the embodiment (4) above is an embodiment in which the red pigment contains at least one selected from CI Pigment Red 177, 254, 291, 295, and 296, the yellow pigment contains at least one selected from CI Pigment Yellow 139, 185, 231, and 233, and the blue pigment contains at least one selected from CI Pigment Blue 15:3, 15:4, and 15:6. An example of the embodiment (5) above is an embodiment in which the yellow pigment contains at least one selected from CI Pigment Yellow 139, 185, 231, and 233; the green pigment contains at least one selected from CI Pigment Green 7, 36, 58, 59, and 63; the blue pigment contains at least one selected from CI Pigment Blue 15:3, 15:4, and 15:6; and the purple pigment contains CI Pigment Violet 23. An example of the above embodiment (6) is an embodiment in which the red pigment contains at least one selected from CI Pigment Red 177, 254, 291, 295, and 296; the yellow pigment contains at least one selected from CI Pigment Yellow 139, 185, 231, and 233; the blue pigment contains at least one selected from CI Pigment Blue 15:3, 15:4, and 15:6; and the purple pigment contains CI Pigment Violet 23. An example of the above embodiment (7) is an embodiment in which the red pigment contains at least one selected from CI Pigment Red 177, 254, 291, 295, and 296; the green pigment contains at least one selected from CI Pigment Green 7, 36, 58, 59, and 63; the blue pigment contains at least one selected from CI Pigment Blue 15:3, 15:4, and 15:6; and the purple pigment contains CI Pigment Violet 23. An example of the above embodiment (8) is an embodiment in which the yellow pigment contains at least one selected from CI Pigment Yellow 139, 185, 231, and 233; the blue pigment contains at least one selected from CI Pigment Blue 15:3, 15:4, and 15:6; the purple pigment contains CI Pigment Violet 23; and the black pigment contains at least one selected from CI Pigment Black 7 and 32.

[0147] Table 1 shows the preferred mass ratio (mass %) of each pigment in each embodiment.

[0148] [Table 1]

[0149] In addition, inorganic pigments such as titanium oxide, barium sulfate, zinc oxide, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, umber, and synthetic iron black can also be used as the colorant (F).

[0150] (dye) Examples of dyes include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, etc. Also included are derivatives of these dyes and lake pigments obtained by converting dyes into lakes.

[0151] The acid dye preferably has an acidic group such as a sulfonic acid or carboxylic acid. Also preferred are salt-forming compounds that are salts of an acid dye with a nitrogen-containing compound such as a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound. Also preferred are salt-forming compounds that are salts of an acid dye with a resin component having these functional groups. Furthermore, the salt-forming compounds can be sulfonamidated to modify them into sulfonic acid amide compounds, which makes it easier to obtain photosensitive compositions with excellent resistance (light resistance, solvent resistance). In addition, a salt-forming compound of an acid dye and a compound having an onium salt group is also preferred because it has excellent resistance (light resistance, solvent resistance). The compound having an onium salt group is preferably a resin having a cationic group.

[0152] Although basic dyes can be used as they are, salt-forming compounds that form salts with organic acids, perchloric acid, or metal salts thereof are preferred. Salt-forming compounds of basic dyes are preferred because they have excellent resistance (lightfastness, solvent resistance) and affinity with pigments. Furthermore, in the salt-forming compounds of basic dyes, the anion component that acts as a counterion is preferably an organic sulfonic acid, organic sulfuric acid, a fluorine-containing phosphorus anion compound, a fluorine-containing boron anion compound, a cyano-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid with a halogenated hydrocarbon group, or a salt-forming compound formed with an acid dye. Furthermore, the resistance of salt-forming compounds is further improved when the salt-forming compound contains a polymerizable unsaturated group in the molecule.

[0153] The chemical structure of the dye may be, for example, azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azido dyes, ... Examples of the dye structure include dyes derived from dyes selected from the group consisting of quinone dyes, polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and metal complex dyes thereof.

[0154] Among these, from the viewpoint of color properties such as hue, color separation ability, and color unevenness, a dye structure derived from a dye selected from azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes is preferred, and a dye structure derived from a dye selected from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes is more preferred.

[0155] The colorant (F) can be used alone or in combination of two or more kinds.

[0156] When used in an anti-reflection filter, the content of the colorant (F) is preferably 5% by mass or less, more preferably 0.5 to 3% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0157] (Fine pigment particle size) The pigment is preferably micronized before use. The micronization method is not particularly limited, and for example, wet milling, dry milling, or solution precipitation can be used. Among these, salt milling treatment using a kneader method, which is a type of wet milling, is preferred. The average primary particle diameter of the micronized pigment determined by TEM (transmission electron microscope) is preferably 5 to 90 nm. From the viewpoints of dispersibility and contrast ratio, the average primary particle diameter is more preferably 10 to 70 nm.

[0158] Salt milling is a process in which a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is mechanically kneaded under heat using a kneader, two-roll mill, three-roll mill, ball mill, attritor, sand mill, or other kneading machine, and then the water-soluble inorganic salt and water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the high hardness of the inorganic salt is used to crush the pigment during salt milling. Optimizing the conditions for salt milling a pigment can produce a pigment with an extremely fine primary particle size, a narrow distribution, and a sharp particle size distribution.

[0159] Examples of water-soluble inorganic salts include sodium chloride, potassium chloride, and sodium sulfate, with sodium chloride (table salt) being preferred from the standpoint of cost. From the standpoint of both treatment efficiency and production efficiency, the amount of water-soluble inorganic salt used is preferably 50 to 2,000 parts by mass, and more preferably 300 to 1,000 parts by mass, per 100 parts by mass of the pigment.

[0160] The water-soluble organic solvent functions to moisten the pigment and water-soluble inorganic salt. It is not particularly limited as long as it is soluble (miscible) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent becomes prone to evaporation, a high-boiling solvent with a boiling point of 120°C or higher is preferred for safety reasons. Examples of water-soluble organic solvents that can be used include 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and liquid polypropylene glycol. The amount of water-soluble organic solvent used is preferably 5 to 1,000 parts by weight, more preferably 50 to 500 parts by weight, per 100 parts by weight of the pigment.

[0161] A resin may be added to the salt milling treatment as needed. The type of resin is not particularly limited, and examples include natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. Among these, resins that are solid at room temperature and insoluble in water are preferred, and those that are partially soluble in the organic solvents are preferred. The amount of resin added is preferably 2 to 200 parts by mass per 100 parts by mass of the pigment.

[0162] [Dispersion resin (G)] The photosensitive composition of the present invention may contain a dispersing resin (G). The dispersing resin (G) is used for the purpose of dispersing the colorant (F), which is a raw material of the photosensitive composition, when producing a dispersion of the colorant (F), and is distinguished from the alkali-soluble resin (A).

[0163] The dispersing resin (G) is preferably a resin having an adsorptive group that has a high affinity for the colorant (F). The adsorptive group preferably has at least one of a basic group and an acidic group.

[0164] Examples of the basic group include a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, and a group containing a nitrogen atom such as a nitrogen-containing heterocycle.

[0165] Examples of the acidic group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group.

[0166] Examples of resin types for the dispersing resin (G) include urethane resins, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, amides formed by the reaction of poly(lower alkylene imines) with polyesters having free carboxyl groups, and salts thereof, water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and polyvinylpyrrolidone, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and phosphate esters.

[0167] Examples of the structure of the dispersing resin (G) include a random structure, a block structure, a graft structure, a comb structure, and a star structure. Among these, the block structure and the comb structure are preferred from the viewpoint of dispersion stability.

[0168] Commercially available dispersion resins (G) include, for example, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, and 2095 manufactured by BYK Japan. , 2150, 2155, 2163, 2164, or Anti-Terra-U203, 204, or BYK-P104, P104S, 220S, or Lactimon, Lactimon-WS, or Bykumen, etc., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26 manufactured by Lubrizol Japan 000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, etc. manufactured by BASF Japan. 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., and Aji Super PA111, PB711, PB821, PB822, PB824 manufactured by Ajinomoto Fine-Techno Co., Ltd.

[0169] The dispersing resin (G) preferably has a polymerizable unsaturated group from the viewpoint of hardness at low temperature curing and resistance to high temperature and high humidity. Examples of dispersing resins having a polymerizable unsaturated group include those described in paragraphs 0317 to 0321 of JP 2019-78878 A, those described in paragraph 0083 of WO 2018 / 139534 A, those described in paragraphs 0167 to 0191 of WO 2019 / 163505 A, and those described in paragraphs 0299 to 0310 of WO 2021 / 131927 A.

[0170] The dispersing resin (G) can be used alone or in combination of two or more kinds.

[0171] From the viewpoint of dispersion stability, the content of the dispersing resin (G) is preferably from 3 to 200 parts by mass, more preferably from 5 to 100 parts by mass, relative to 100 parts by mass of the colorant (F).

[0172] [Thiol-based chain transfer agents (H)] The photosensitive composition of the present invention preferably contains a thiol-based chain transfer agent (H) from the viewpoints of hardness upon low-temperature curing and resistance to high temperatures and high humidity. When used in combination with a photopolymerization initiator (C), the thiol-based chain transfer agent (H) generates thiyl radicals that are resistant to polymerization inhibition by oxygen during radical polymerization after light irradiation, thereby improving the photosensitivity of the photosensitive composition. As a result, hardness and resistance to high temperatures and high humidity are improved.

[0173] The thiol chain transfer agent (H) is preferably a polyfunctional thiol having two or more thiol groups (SH groups), more preferably a polyfunctional thiol having four or more thiol groups. As the number of functional groups increases, photocuring becomes easier from the surface to the deepest part of the film.

[0174] Examples of polyfunctional thiols include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthioglycolate, Examples of the thiopropionate include erythritol tetrakisthiopropionate, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, and 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine. Preferred examples include ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

[0175] The thiol chain transfer agent (H) can be used alone or in combination of two or more kinds.

[0176] The content of the thiol chain transfer agent (H) is preferably 0.1 to 2.0 mass %, more preferably 0.2 to 1.5 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition, from the viewpoints of line width stability, hardness at low temperature curing, and resistance to high temperature and humidity.

[0177] [Leveling agent (I)] The photosensitive composition of the present invention may contain a leveling agent (I). This improves the wettability and drying properties of the composition to the substrate during application. Examples of the leveling agent (I) include silicone surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.

[0178] Examples of silicone surfactants include linear polymers formed from siloxane bonds and modified siloxane polymers in which organic groups have been introduced into the side chains or terminals.

[0179] Commercially available products include, for example, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, and 3570 manufactured by BYK-Chemie Co., Ltd., and FZ-7002 and 211 manufactured by Dow Corning Toray Co., Ltd. 0, 2122, 2123, 2191, 5609, and X-22-4952, X-22-4272, X-22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, and KP-341 manufactured by Shin-Etsu Chemical Co., Ltd.

[0180] Examples of the fluorine-based surfactant include a surfactant or leveling agent having a fluorocarbon chain.

[0181] Examples of commercially available products include Surflon S-242, 243, 420, 611, 651, and 386 manufactured by AGC Seimi Chemical Co., Ltd.; Megafac F-253, 477, 551, 552, 555, 558, 560, 570, 575, and 576, R-40-LM, R-41, RS-72-K, and DS-21 manufactured by DIC Corporation; FC-4430 and 4432 manufactured by Sumitomo 3M Limited; EF-PP31N09, EF-PP33G1, and EF-PP32C1 manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.; and Futergent 602A manufactured by Neos Corporation.

[0182] Examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myrister ether, polyoxyethylene octyldodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylenedistyrenated phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, and sorbitan tristearate. sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbitan tetraoleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkyl alkanolamide, alkyl imidazoline, and the like.

[0183] Commercially available products include, for example, Emulgen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430, 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS-106, and L manufactured by Kao Corporation. S-110, LS-114, MS-110, A-60, A-90, B-66, PP-290, Latemul PD-420, PD-430, PD-430S, PD-450, Leodor SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V, SP-O30V, Super SP-L10, AS-10V, AO-10V, AO-15V, TW-L120, TW- L106, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-IS399C, Super TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, Emanon 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-60(K), Amit 102, 105, 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, ADEKA Pluronic (registered trademark) L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R manufactured by ADEKA Corporation, and (meth)acrylic acid (co)polymer Polyflow No. 75, No. 90, No. 95 manufactured by Kyoeisha Chemical Co., Ltd.

[0184] Examples of cationic surfactants include alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, and ethylene oxide adducts thereof.

[0185] Examples of commercially available products include Acetamine 24, Cortamine 24P, 60W, and 86P Concentrate, manufactured by Kao Corporation.

[0186] Examples of anionic surfactants include polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine styrene-acrylic acid copolymers, and polyoxyethylene alkyl ether phosphates.

[0187] Examples of commercially available products include Futergent 100 and 150 manufactured by Neos Corporation, and Adeka Hope YES-25, Adekacol TS-230E, PS-440E, and EC-8600 manufactured by ADEKA Corporation.

[0188] Examples of amphoteric surfactants include alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, and alkyldimethylaminoacetic acid betaine; and alkylamine oxides such as lauryldimethylamine oxide.

[0189] Commercially available products include Anhithol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, and 20N manufactured by Kao Corporation.

[0190] The leveling agent (I) can be used alone or in combination of two or more kinds.

[0191] The content of the leveling agent (I) is preferably 0.001 to 2.0 mass %, more preferably 0.005 to 1.0 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition. When an appropriate amount is contained, the balance between the coatability and adhesion of the photosensitive composition is further improved.

[0192] [Organic solvent (J)] The photosensitive composition of the present invention may contain an organic solvent (J).

[0193] The organic solvent (J) is not particularly limited as long as it satisfies the solubility of each component of the photosensitive composition of the present invention and the coatability, and any known compound can be used.

[0194] Examples of the organic solvent (J) include 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy- 3-Methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, toluene, o-chlorotoluene, benzene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene , γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether,Examples of the alkyl esters include dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters. Among these, from the viewpoints of resin solubility and coatability, glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate, alcohols such as diacetone alcohol, and ketones such as cyclohexanone are preferred.

[0195] From an environmental viewpoint, the photosensitive composition of the present invention preferably does not substantially contain organic solvents that are aromatic hydrocarbons (toluene, xylene, benzene, chlorobenzene, etc.) "Substantially not containing" means that the content of such organic solvents in the photosensitive composition is 50 ppm by mass or less, preferably 30 ppm by mass or less, and more preferably 10 ppm by mass or less.

[0196] The organic solvent (J) can be used alone or in combination of two or more kinds.

[0197] The content of the organic solvent (J) is preferably an amount such that the nonvolatile content of the photosensitive composition is 5 to 50 mass %.

[0198] [Other ingredients] The photosensitive composition of the present invention may contain other components in addition to those described above. Examples of the other components include dye derivatives, sensitizers, polymerization inhibitors, ultraviolet absorbers, antioxidants, storage stabilizers, adhesion improvers, and near-infrared absorbers. The content of the other components can be appropriately set within a range that does not impair the effects of the present invention.

[0199] [Method for producing photosensitive composition] The photosensitive composition of the present invention can be produced by, for example, adding a colorant (F), a dispersing resin (G), an organic solvent (J), and the like and carrying out a dispersion treatment to produce a dispersion. The dispersion can then be blended and mixed with an alkali-soluble resin (A), a polymerizable compound (B), a photopolymerization initiator (C), a thermosetting compound (D), and a compound (E1) represented by general formula (1). The timing of blending each material is optional. The dispersion process can also be carried out multiple times.

[0200] Examples of dispersing machines for carrying out the dispersion treatment include a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, and an attritor.

[0201] The average dispersed particle size (secondary particle size) of the colorant (F) in the dispersion is preferably 30 to 200 nm, more preferably 40 to 200 nm. If the colorant (F) has an appropriate particle size, a photosensitive composition with high dispersion stability is easily obtained.

[0202] The average dispersed particle size (secondary particle size) is measured using, for example, Nikkiso's Microtrac UPA-EX150, which employs dynamic light scattering (FFT power spectrum method), with particle permeability set to absorption mode, particle shape set to non-spherical, and the D50 particle size set to the average size. The dilution solvent used for measurement is the same organic solvent used for dispersion, and it is preferable to measure samples treated with ultrasound immediately after sample preparation, as this tends to provide results with little variation.

[0203] The photosensitive composition is preferably subjected to removal of coarse particles of 5 μm or larger, preferably coarse particles of 1 μm or larger, and more preferably coarse particles of 0.5 μm or larger, as well as any dust particles that have been mixed in, by means of centrifugation, filtration through a sintered filter or membrane filter, etc. The photosensitive composition of the present invention preferably contains substantially no particles of 0.5 μm or larger, and more preferably contains no particles of 0.3 μm or smaller.

[0204] <Optical filters> The optical filter of the present invention comprises a substrate and a cured film of a photosensitive composition, the cured film being preferably a film patterned by photolithography.

[0205] [Optical filter manufacturing method] The method for producing an optical filter is not particularly limited, and can be, for example, produced by carrying out the following steps: (1) applying a photosensitive composition to a substrate to form a composition layer; (2) exposing the layer to light through a mask in a pattern; (3) developing the unexposed portions with an alkali to form a patterned cured film; and (4) heat-treating (post-baking) the pattern. In the present invention, the optical filter is produced at a temperature of 150°C or less throughout all steps, and more preferably at a temperature of 130°C or less.

[0206] The method for manufacturing the optical filter will now be described in detail.

[0207] (Process (1)) In the step (1) of forming a composition layer, the photosensitive composition is applied onto a substrate by a method such as spin coating, roll coating, slit coating, casting coating, or inkjet coating, and then dried (pre-baked) at a temperature of 50 to 100°C for 10 to 120 seconds using an oven, a hot plate, or the like, as needed. Examples of the substrate include a glass substrate, a resin substrate, and a silicon substrate. Examples of the resin substrate include a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamideimide substrate, and a polyimide substrate. An organic light-emitting layer may be formed on these substrates. For example, an imaging element such as a CCD or a CMOS may be formed on the surface of the silicon substrate. If necessary, an undercoat layer may be provided on the substrate to improve adhesion with upper layers, prevent diffusion of substances, and flatten the substrate surface. The coating is preferably carried out so that the layer has a thickness of 0.05 to 10.0 μm after drying, and more preferably 0.3 to 5.0 μm.

[0208] (Process (2)) In the exposure step, the layer obtained in step (1) is exposed to light in a specific pattern through a mask using an exposure device such as a stepper, thereby obtaining a cured film. Examples of radiation used for exposure include ultraviolet rays such as g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), and i-rays (wavelength 365 nm). Light with a wavelength of 300 nm or less can also be used. Examples of light with a wavelength of 300 nm or less include KrF rays (wavelength 248 nm) and ArF rays (wavelength 193 nm). Furthermore, the exposure may be performed by continuous irradiation with light, or by repeating irradiation and pauses of light in short cycles (for example, milliseconds or less) (pulse exposure).

[0209] (Step (3)) The cured film obtained in step (2) is subjected to an alkali development treatment, whereby the composition layer in the unexposed areas is dissolved in an alkaline aqueous solution, leaving only the cured areas, thereby obtaining a patterned cured film. Examples of the developer include alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene. The concentration of the alkaline developer is preferably from 0.001 to 10% by mass, more preferably from 0.01 to 1% by mass. The pH of the alkaline developer is preferably 11 to 13, more preferably 11.5 to 12.5. When used at an appropriate pH, it suppresses pattern roughening and peeling, and improves the remaining film rate after development.

[0210] Examples of the developing method include a dipping method, a spraying method, a puddling method, etc. The developing temperature is preferably 15 to 40° C. After the alkaline development, it is preferable to wash with pure water.

[0211] (Step (4)) In the heat treatment (post-baking), the patterned cured film obtained in step (3) is heated to sufficiently cure. The heating temperature for post-baking is preferably 150°C or lower, more preferably 130°C or lower. There is no particular lower limit to the heating temperature as long as it can promote curing, but a temperature of 50°C or higher is preferred. The heating time is preferably 5 minutes to 1 hour.

[0212] The optical filter of the present invention can be used for various purposes. For example, it can be used as an antireflection filter, a color filter, a black matrix, an infrared transmission filter, a light-shielding filter, a microlens, etc. Since it can be cured at low temperature, it is preferably used as an antireflection filter for an organic EL display device.

[0213] <Image display device> The image display device of the present invention includes the optical filter of the present invention. Examples of the image display device include a liquid crystal display and an organic EL display. The configuration used for the image display device is not particularly limited as long as it functions as an image display device. For example, the configuration described in "Next Generation Liquid Crystal Display Technology" (by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd. in 1994) can be mentioned. The definition of image display devices and details of each image display device are described, for example, in "Electronic Display Devices" (written by Sasaki Akio, published by Kogyo Chosakai Co., Ltd. in 1990) and "Display Devices" (written by Ibuki Nobuaki, published by Sangyo Tosho Co., Ltd. in 1989).

[0214] <Solid-state imaging element> The solid-state imaging device of the present invention includes the optical filter of the present invention. The solid-state imaging device may be formed in any suitable form. For example, the solid-state imaging device may include a substrate having a plurality of photodiodes and transfer electrodes made of polysilicon or the like that constitute the light-receiving area of the solid-state imaging device (e.g., CCD image sensor, CMOS image sensor, etc.), a light-shielding film formed on the photodiodes and transfer electrodes with only the light-receiving portions of the photodiodes exposed, a device protection film made of silicon nitride or the like that is formed on the light-shielding film to cover the entire light-shielding film and the light-receiving portions of the photodiodes, and a filter on the device protection film. Furthermore, the device protection film may include a light-focusing means (e.g., a microlens, etc.; the same applies below) below the filter (closer to the substrate) on the device protection film, or a light-focusing means on the filter. The filter may also have a structure in which a cured film forming each color pixel is embedded in spaces partitioned by partition walls, for example, in a grid pattern. In this case, the partition walls preferably have a low refractive index relative to the color pixels. An imaging device including the solid-state imaging element of the present invention can be used for various purposes, such as digital cameras, electronic devices with imaging functions (such as mobile phones and smartphones), vehicle-mounted cameras, surveillance cameras, and optical sensors. [Example]

[0215] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these examples. Note that "parts" means "parts by mass" and "%" means "% by mass." In the present invention, the nonvolatile content or nonvolatile content concentration refers to the mass remaining after leaving the sample to stand in an oven at 230°C for 30 minutes.

[0216] Before describing the examples, each measurement method will be explained.

[0217] The weight average molecular weight (Mw), number average molecular weight (Mn), acid value (mgKOH / g), and amine value (mgKOH / g) of the resin are measured as follows.

[0218] (average molecular weight of resin) The number-average molecular weight (Mn) and weight-average molecular weight (Mw) of the resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. The instrument used was an HLC-8220GPC (Tosoh Corporation). Two separation columns were connected in series, and both columns were packed with "TSK-GEL SUPER HZM-N" packing materials. Measurements were performed at an oven temperature of 40°C, a tetrahydrofuran (THF) solution as the eluent, and a flow rate of 0.35 ml / min. The sample was dissolved in a solvent consisting of 1% by mass of the above eluent, and 20 μl was injected. The molecular weight is a polystyrene equivalent value.

[0219] (resin acid value) 80 ml of acetone and 10 ml of water were added to 0.5 to 1 g of resin solution, and the mixture was stirred to dissolve uniformly. The solution was titrated using an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.) with a 0.1 mol / L KOH aqueous solution as the titrant to measure the acid value (mg KOH / g). The acid value per unit of nonvolatile content of the resin was calculated from the acid value of the resin solution and the concentration of nonvolatile content of the resin solution.

[0220] (Amine value of resin) The amine value of the resin is the total amine value (mgKOH / g) measured in accordance with the method of ASTM D 2074 and converted into nonvolatile content.

[0221] <Production of alkali-soluble resin (A)> (Alkali-soluble resin (A-1) solution) 100 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAc) was placed in a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, and the mixture was stirred while replacing the atmosphere with nitrogen and heated to 78°C. Next, a mixture of 25.2 parts of the blocked isocyanate group-containing monomer Karenz MOI-DEM (2-[[[[(2-methyl-1-oxo-2-propenyl)oxy]ethyl]amino]carbonyl]-1,3-diethyl ester malonate, manufactured by Showa Denko K.K.), 31.2 parts of the hydroxyl group-containing monomer 2-hydroxyethyl methacrylate, 37.5 parts of the alicyclic hydrocarbon-containing monomer dicyclopentanyl methacrylate, 20.7 parts of the acidic group-containing monomer methacrylic acid, and 27.0 parts of the other monomer unit methyl methacrylate, and a solution of 12.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) dissolved in 50 parts of PGMAc, was added dropwise from the dropping funnel to the flask. After the dropwise addition, the mixture was stirred at 78 ° C for 3 hours. Thereafter, PGMAc was added so that the nonvolatile content became 40% by mass, thereby preparing an alkali-soluble resin (A-1) solution. The alkali-soluble resin (A-1) had an acid value of 74 mg KOH / g and a weight-average molecular weight of 8,000.

[0222] (Alkali-soluble resin (A-2) solution) An alkali-soluble resin (A-2) was synthesized so as to have the molar ratios of the constituent components shown in Table 2, and PGMAc was added to adjust the nonvolatile content to 40 mass %.

[0223] [Table 2]

[0224] <Production of Colorant (F)> (Finely divided blue pigment (F-1)) 100 parts of CI Pigment Blue 15:6, 1,000 parts of sodium chloride, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 12 hours at 50° C. This kneaded mixture was added to 3,000 parts of warm water, and while heated to about 70° C., was stirred in a high-speed mixer for about 1 hour to form a slurry, which was then filtered and washed repeatedly with water to remove the sodium chloride and diethylene glycol.Then, the mixture was dried at 80° C. for 24 hours and pulverized to obtain a finely divided blue pigment (F-1).

[0225] (Finely divided purple pigment (F-2)) 100 parts of CI Pigment Violet 23, 1,000 parts of sodium chloride, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 12 hours at 70° C. This kneaded mixture was added to 3,000 parts of warm water, and while heated to about 70° C., was stirred in a high-speed mixer for about 1 hour to form a slurry, which was then filtered and washed repeatedly with water to remove the sodium chloride and diethylene glycol.The slurry was then dried at 80° C. for 24 hours and pulverized to obtain a finely divided purple pigment (F-2).

[0226] (Finely divided red pigment (F-3)) 100 parts of CI Pigment Red 177, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 6 hours at 60° C. Next, this kneaded mixture was added to 3,000 parts of warm water, and while heated to approximately 80° C., it was stirred for 1 hour using a high-speed mixer to form a slurry, which was then filtered and washed with water to remove the sodium chloride and diethylene glycol. After that, it was dried at 80° C. for 24 hours and pulverized to obtain a finely divided red pigment (F-3).

[0227] (Finely divided yellow pigment (F-4)) 100 parts of CI Pigment Yellow 139, 800 parts of sodium chloride, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 12 hours at 70° C. This kneaded mixture was added to 3,000 parts of warm water, and while heated to about 70° C., was stirred in a high-speed mixer for about 1 hour to form a slurry, which was then filtered and washed repeatedly with water to remove the sodium chloride and diethylene glycol.The slurry was then dried at 80° C. for 24 hours and pulverized to obtain a finely divided yellow pigment (F-4).

[0228] (Finely divided green pigment (F-5)) 100 parts of CI Pigment Green 58, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 6 hours at 70° C. This kneaded mixture was poured into 3,000 parts of warm water, and stirred for 1 hour with a high-speed mixer while heated to 70° C. to form a slurry. The slurry was filtered and washed with water repeatedly to remove the sodium chloride and diethylene glycol, then dried at 80° C. for 24 hours and pulverized to obtain a finely divided green pigment (F-5).

[0229] (Finely divided green pigment (F-6)) 100 parts of CI Pigment Green 36, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 6 hours at 70° C. This kneaded mixture was poured into 3,000 parts of warm water, and stirred for 1 hour with a high-speed mixer while heated to 70° C. to form a slurry. The slurry was filtered and washed with water repeatedly to remove the sodium chloride and diethylene glycol, then dried at 80° C. for 24 hours and pulverized to obtain a finely divided green pigment (F-6).

[0230] (Finely divided black pigment (F-7)) 100 parts of CI Pigment Black 1, 800 parts of sodium chloride, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 12 hours at 70° C. This kneaded mixture was added to 3,000 parts of warm water, and while heated to about 70° C., was stirred in a high-speed mixer for about 1 hour to form a slurry, which was then filtered and washed repeatedly with water to remove the sodium chloride and diethylene glycol, and then dried at 80° C. for 24 hours and pulverized to obtain a finely divided black pigment (F-7).

[0231] (Finely divided black pigment (F-8)) 100 parts of CI Pigment Black 32, 800 parts of sodium chloride, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 12 hours at 70° C. This kneaded mixture was added to 3,000 parts of warm water, and while heated to about 70° C., was stirred in a high-speed mixer for about 1 hour to form a slurry, which was then filtered and washed repeatedly with water to remove the sodium chloride and diethylene glycol, and then dried at 80° C. for 24 hours and pulverized to obtain a finely divided black pigment (F-8).

[0232] <Production of Dispersion Resin (G)> (Dispersion resin (G-1) solution) A reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer was charged with 108 parts of 1-thioglycerol, 174 parts of pyromellitic anhydride, 650 parts of PGMAc, and 0.2 parts of monobutyltin oxide as a catalyst. The atmosphere was purged with nitrogen gas, and the reaction was carried out at 120 °C for 5 hours (Step 1). Measurement of the acid value confirmed that more than 95% of the acid anhydride was half-esterified. Next, 160 parts (based on nonvolatile content) of the compound obtained in Step 1, 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of tert-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, 200 parts of methyl acrylate, 50 parts of methacrylic acid, and 663 parts of PGMAc were charged, and the reaction vessel was heated to 80 °C. 1.2 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, and the reaction was carried out for 12 hours (Step 2). It was confirmed by measuring the nonvolatile content that 95% had reacted. Finally, 500 parts of a 50% PGMAc solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate (MOI), and 0.1 parts of hydroquinone were added, and IR showed a 2270 cm peak due to the isocyanate group. -1 The reaction was continued until the disappearance of the peak was confirmed (third step). After the disappearance of the peak was confirmed, the reaction solution was cooled and the nonvolatile content was adjusted with PGMAc to obtain a dispersion resin (G-1) solution having a polymerizable unsaturated group with a nonvolatile content of 30% by mass. The dispersion resin (G-1) had an acid value of 68 mg KOH / g and a weight-average molecular weight of 13,000.

[0233] (Dispersion resin (G-2) solution) A reaction vessel equipped with a gas inlet tube, thermostat, condenser, and stirrer was charged with 10 parts methacrylic acid, 100 parts methyl methacrylate, 70 parts i-butyl methacrylate, 20 parts benzyl methacrylate, and 50 parts PGMAc, and the atmosphere was purged with nitrogen gas. The reaction vessel was heated to 50°C with stirring, and 12 parts 3-mercapto-1,2-propanediol was added. The temperature was raised to 90°C, and a solution of 0.1 parts 2,2'-azobisisobutyronitrile and 90 parts PGMAc was added while the reaction was continued for 7 hours. Measurement of the nonvolatile content confirmed that 95% reaction had occurred. 19 parts pyromellitic anhydride, 50 parts PGMAc, 50 parts cyclohexanone, and 0.4 parts 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was continued for 7 hours at 100°C. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value, and the mixture was diluted with PGMAc to a non-volatile content of 30% by mass to obtain a dispersion resin (G-2) solution. The dispersion resin (G-2) had an acid value of 70 mgKOH / g and a weight-average molecular weight of 8,500.

[0234] (Dispersion resin (G-3) solution) A reactor equipped with a gas inlet tube, condenser, stirring blade, and thermometer was charged with 30 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, 20 parts of hydroxyethyl methacrylate, and 13.2 parts of tetramethylethylenediamine. The mixture was stirred at 50°C for 1 hour while flowing nitrogen, and the system was purged with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and the temperature was raised to 110°C under a nitrogen stream to initiate polymerization of the first block (B block). After 4 hours of polymerization, a sample of the polymerization solution was taken and the nonvolatile content was measured. Based on the nonvolatile content, it was confirmed that the polymerization conversion was 98% or higher. Next, 61 parts of PGMAc and 20 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate (Hitachi Chemical Co., Ltd., Fancryl FA-711MM) as the second block (A block) monomer were added to the reactor, and the reaction was continued with stirring while maintaining the temperature at 110°C under a nitrogen atmosphere. Two hours after the addition of 1,2,2,6,6-pentamethylpiperidyl methacrylate, a sample of the polymerization solution was taken and the nonvolatile content was measured. Based on the nonvolatile content, it was confirmed that the polymerization conversion rate of the second block (A block) was 98% or higher. The reaction solution was then cooled to room temperature to terminate the polymerization. PGMAc was added to dilute the solution to a nonvolatile content of 30% by mass, yielding a dispersion resin (G-3) solution. The dispersion resin (G-3) had an amine value of 57 mgKOH / g and a number-average molecular weight of 4,500.

[0235] <Preparation of Dispersion> (Dispersion 1) The following raw materials were mixed and stirred until uniform, then dispersed in an Eiger mill (Eiger Japan, "Mini Model M-250 MKII") using zirconia beads with a diameter of 0.5 mm for 3 hours, and then filtered through a filter with a pore size of 1.0 μm to produce Dispersion 1. The organic solvent (J-1) was PGMAc. Finely divided blue pigment (F-1): 10.0 parts Dispersion resin (G-1) solution: 10.0 parts Dispersion resin (G-2) solution: 5.0 parts Organic solvent (J-1): 75.0 parts

[0236] (Dispersion 2~10) Dispersions 2 to 10 were prepared in the same manner as Dispersion 1, except that the raw materials and amounts shown in Table 3 were changed.

[0237] [Table 3]

[0238] <Production of Photosensitive Composition> [Example 1] (Photosensitive composition 1) The following raw materials were mixed and stirred, and then filtered through a filter with a pore size of 1.0 μm to obtain Photosensitive Composition 1. Dispersion 2: 1.6 parts Dispersion 5: 1.6 parts Alkali-soluble resin (A-1) solution: 10.0 parts Polymerizable compound (B-1): 12.5 parts Photopolymerization initiator (C-1): 1.0 part Thermosetting compound (D-1): 2.0 parts Compound (E1-1) represented by general formula (1): 0.6 parts Compound (E2-1) represented by general formula (3): 0.02 parts Thiol chain transfer agent (H-1): 0.2 parts Leveling agent (I): 1.0 part Organic solvent (J): 69.48 parts

[0239] [Examples 2 to 34, Comparative Examples 1 and 2] (Photosensitive composition 2-36) Photosensitive compositions 2 to 36 were prepared in the same manner as in Example 1, except that the raw materials and amounts of photosensitive composition 1 in Example 1 were changed to those shown in Tables 4-1 to 4-4.

[0240] [Table 4-1]

[0241] [Table 4-2]

[0242] [Table 4-3]

[0243] [Table 4-4]

[0244] The raw materials listed in Tables 4-1 to 4-4 are as follows:

[0245] [Polymerizable compound (B)] B-1: Aronix M-450 (manufactured by Toagosei Co., Ltd.)

[0246] [Photopolymerization initiator (C)] C-1: Compound of the above chemical formula (4) C-2: Omnirad907 (manufactured by IGM Resins) C-2: Irgacure OXE-02 (BASF)

[0247] [Thermosetting compound (D)] D-1: EHPE-3150 (manufactured by Daicel Corporation, a 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol with approximately 15 epoxy groups) D-2: Nikalac MX-706 (manufactured by Sanwa Chemical Co., Ltd., a methylated melamine compound having an imino group and a methylol group)

[0248] [Imidazole compound (E)] (Compound (E1) represented by general formula (1)) E1-1: 10% PGMAc solution of 1-benzyl-2-methylimidazole E1-2: 10% PGMAc solution of 1-benzyl-2-phenylimidazole E1-3: 1-benzylimidazole in 10% PGMAc

[0249] (Compound (E2) represented by general formula (3)) E2-1: 10% PGMAc solution of 2-methylimidazole E2-2: 10% PGMAc solution of 2-phenylimidazole E2-3: 10% PGMAc solution of imidazole

[0250] (Other imidazole compounds (E3)) E3-1: 10% PGMAc solution of 1,2-dimethylimidazole

[0251] [Thiol-based chain transfer agents (H)] H-1: Pentaerythritol tetrakis(3-mercaptopropionate) H-2: Pentaerythritol tetrakis(3-mercaptobutyrate)

[0252] [Leveling agent (I)] I-1: BYK-330 (BYK-Chemie) I-2: Megafac F-554 (DIC) One part each of (I-1) and (I-2) was mixed and dissolved in 98 parts of PGMAc to prepare a mixed solution, which was used as a leveling agent (I).

[0253] [Organic solvent (J)] J-1: 30 parts of propylene glycol monomethyl ether acetate J-2: 30 parts cyclohexanone J-3: 10 parts of ethyl 3-ethoxypropionate J-4: Propylene glycol monomethyl ether 10 parts J-5: Cyclohexanol acetate 10 parts J-6: Dipropylene glycol methyl ether acetate 10 parts The above (J-1) to (J-6) were mixed in the above-mentioned parts by mass to prepare an organic solvent (J).

[0254] <Evaluation of Photosensitive Composition> The obtained photosensitive compositions 1 to 36 (Examples 1 to 34 and Comparative Examples 1 and 2) were evaluated as follows. The evaluation results are shown in Table 5.

[0255] [Line width stability evaluation] The photosensitive composition thus obtained was applied by spin coating to a glass substrate (Corning Eagle 2000) measuring 100 mm in length, 100 mm in width, and 0.7 mm in thickness so that the dried film thickness would be 2.0 μm, and then dried on a hot plate at 70° C. for 1 minute. After cooling the substrate to room temperature, the substrate was irradiated with a high-pressure mercury lamp at an illuminance of 30 mW / cm.2 , exposure dose 50mJ / cm 2 and 100 mJ / cm 2 The substrate was exposed to light through a photomask with a 100 μm wide stripe pattern at two levels. The substrate was then spray-developed using an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23°C, then washed with ion-exchanged water, and air-dried. The resulting substrate was post-baked in a clean oven at 100°C for 60 minutes to obtain a substrate for evaluation. The obtained evaluation substrate was subjected to an exposure of 50 mJ / cm using a Nikon ECLIPSE LV100POL Model optical microscope. 2 Line width (CD 50 ) and 100mJ / cm 2 Line width (CD 100 The difference in line width (ΔCD) due to differences in exposure dose was calculated using the following formula. The evaluation criteria are as follows, with a score of 3 or higher being considered practical. Formula: ΔCD=CD 100 -CD 50 5: ΔCD is less than 2 μm 4: ΔCD is 2 μm or more and less than 3 μm 3: ΔCD is 3 μm or more and less than 5 μm 2: ΔCD is 5 μm or more and less than 6 μm 1: ΔCD is 6 μm or more

[0256] [Hardness evaluation] The photosensitive composition thus obtained was applied by spin coating to a glass substrate (Corning Eagle 2000) measuring 100 mm in length, 100 mm in width, and 0.7 mm in thickness so that the dried film thickness would be 2.0 μm, and then dried on a hot plate at 70° C. for 1 minute. After cooling the substrate to room temperature, the substrate was irradiated with a high-pressure mercury lamp at an illuminance of 30 mW / cm. 2 , 50 mJ / cm 2 After cooling the substrate to room temperature, it was spray-developed using an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23°C, washed with ion-exchanged water, and air-dried. The resulting substrate was then post-baked in a clean oven at 100°C for 60 minutes to obtain a substrate for evaluation. The pencil hardness of the obtained cured film was measured in accordance with JIS K5400-1999, using the following evaluation criteria, with a score of 3 or higher being considered practical. 5: Pencil hardness is 5H or higher 4: Pencil hardness is 4H 3: Pencil hardness is 3H 2: Pencil hardness is 2H 1: Pencil hardness is H or less

[0257] [High temperature and humidity resistance evaluation (1): Adhesion] The photosensitive composition thus obtained was applied by spin coating to a glass substrate (Corning Eagle 2000) measuring 100 mm in length, 100 mm in width, and 0.7 mm in thickness so that the dried film thickness would be 2.0 μm, and then dried on a hot plate at 70° C. for 1 minute. After cooling the substrate to room temperature, the substrate was irradiated with a high-pressure mercury lamp at an illuminance of 30 mW / cm. 2 , 50 mJ / cm 2 After cooling the substrate to room temperature, it was spray-developed using an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23°C, washed with ion-exchanged water, and air-dried. The resulting substrate was then post-baked in a clean oven at 100°C for 60 minutes to obtain a substrate for evaluation. The resulting cured film was cut with a utility knife to form a 1 mm square grid pattern (100 squares) and stored for 2 hours at a temperature of 120°C and humidity of 100%. After storage, a transparent adhesive tape (CT-24 manufactured by Nichiban Co., Ltd.) was firmly pressed onto the film and peeled off in a direction of approximately 180°C. The state of the grid patterns was observed, and the number of peeled grid patterns was counted. The evaluation criteria are as follows, with a score of 3 or higher being considered practical. 5: Less than 2 4: 2 or more, less than 5 3: 5 or more, less than 10 2: 10 or more, less than 15 1:15 pieces or more

[0258] [High temperature and humidity resistance evaluation (2): Film thickness stability] The obtained photosensitive composition was applied to a glass substrate (Corning Eagle 2000) measuring 100 mm in length, 100 mm in width, and 0.7 mm in thickness using a spin coater so that the dry film thickness was 2.0 μm, and then dried on a hot plate at 70° C. for 1 minute. Then, an ultra-high pressure mercury lamp was used to apply the coating with an illuminance of 30 mW / cm. 2 , 50 mJ / cm 2 The substrate was exposed to ultraviolet light through a photomask with a 100 μm wide stripe pattern. After cooling to room temperature, the substrate was spray-developed using an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23°C, washed with ion-exchanged water, and air-dried. The resulting substrate was post-baked in a clean oven at 100°C for 60 minutes, and the film thickness of the pattern was measured. This film thickness is the post-baking film thickness. The obtained substrate was stored for 200 hours under conditions of a temperature of 85°C and a humidity of 85%. After storage, the film thickness was measured at the same location where the film thickness was measured after post-baking. This film thickness was taken as the film thickness after storage. The film thickness change rate was calculated from the two film thicknesses using the following formula. The evaluation criteria are as follows, with a score of 3 or higher being practical. The film thickness was measured using a Dektak 3030 (manufactured by Japan Vacuum Engineering Co., Ltd.). Formula: Change rate (%) = |Film thickness after post-bake - Film thickness after storage| / Film thickness after post-bake x 100 5: The rate of change is less than 3% 4: The rate of change is 3% or more but less than 6% 3: The rate of change is 6% or more but less than 10% 2: The rate of change is 10% or more but less than 15% 1: The rate of change is 15% or more

[0259] [Table 5]

Claims

1. A photosensitive composition comprising an alkali-soluble resin (A), a polymerizable compound (B), a photopolymerization initiator (C), a thermosetting compound (D), and an imidazole compound (E), the alkali-soluble resin (A) contains an alkali-soluble resin having a blocked isocyanate group-containing monomer unit (a1) and a hydroxyl group-containing monomer unit (a2); The photosensitive composition, wherein the imidazole compound (E) comprises a compound (E1) represented by the following general formula (1): General formula (1) 【Chemical 1】 (In general formula (1), X １ ~X ３ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms.

2. The photosensitive composition according to claim 1 , wherein the photopolymerization initiator (C) comprises a compound represented by the following general formula (2): General formula (2) 【Chemistry 2】 (In general formula (2), R １ , R ２ R each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ３ represents a hydrogen atom or a monovalent substituent.

3. 3. The photosensitive composition according to claim 1, wherein the imidazole compound (E) further comprises a compound (E2) represented by the following general formula (3): General formula (3) 【Chemistry 3】 (In general formula (3), X ４ ~X ６ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms.

4. 4. The photosensitive composition according to claim 3, wherein the content of the compound (E1) represented by the general formula (1) is 50% by mass or more, based on a total of 100% by mass of the compound (E1) represented by the general formula (1) and the compound (E2) represented by the general formula (3).

5. The photosensitive composition according to any one of claims 1 to 4, further comprising a colorant (F), wherein the content of the colorant (F) is 5 mass% or less based on 100 mass% of the nonvolatile content of the photosensitive composition.

6. An optical filter comprising a substrate and a cured film of the photosensitive composition according to any one of claims 1 to 5.

7. An image display device comprising the optical filter according to claim 6.

8. A solid-state imaging device comprising the optical filter according to claim 6.

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