Photosensitive composition, film, optical filter, image display device, solid-state imaging element, and infrared sensor

Abstract

To provide a photosensitive composition that is less likely to undergo heat shock, less likely to cause dry deposits during coating, excellent in solvent resistance after a low-temperature curing process, and capable of forming a film that generates little outgas.SOLUTION: A photosensitive composition comprises a binder resin, a polymerizable compound (B), and a photopolymerization initiator (C), where the photopolymerization initiator (C) includes a photopolymerization initiator (C1) represented by formula (1) in the figure, where Ar1 and Ar2 are each independently a substituted group containing an aromatic ring or a heteroaromatic ring.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photosensitive composition that can be used to form optical filters such as color filters. [Background technology]

[0002] 2. Description of the Related Art Optical filters such as color filters are used in devices such as image display devices, smartphones, and infrared sensors.

[0003] Among image display devices, the organic light-emitting layers used in organic EL (electroluminescence) display devices using OLEDs (organic light-emitting diodes) and the like have low heat resistance. Therefore, photosensitive compositions used to form optical filters must be post-baked at lower temperatures than conventional methods, for example, at 150°C or below. However, low temperatures can result in insufficient film curing and reduced solvent resistance. Furthermore, because post-baking is not performed at high temperatures, low-boiling-point volatile components (hereinafter referred to as outgassing) can remain inside the coating film of the photosensitive composition, potentially shortening the product life of the display device. Furthermore, when the photosensitive composition contains materials with low compatibility, problems arise, such as heat shock due to fluctuations in storage temperature and the formation of dried precipitates during coating.

[0004] In an effort to produce optical filters at low temperatures, Patent Document 1 discloses a photosensitive composition containing an alkali-soluble resin having a blocked isocyanato group and a reactive diluent. Patent Document 2 also discloses a colored photosensitive resin composition containing a photosensitive polymer having a repeating unit with a specific structure, in an effort to improve outgassing. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2019 / 026547 [Patent Document 2] International Publication No. 2016 / 194619 Summary of the Invention [Problem to be solved by the invention]

[0006] However, conventional compositions have not been able to simultaneously satisfy the problems of solvent resistance after low-temperature curing, heat shock, dry deposits, and outgassing.

[0007] An object of the present invention is to provide a photosensitive composition that is resistant to heat shock, resistant to drying deposits during coating, has excellent solvent resistance after a low-temperature curing step, and can form a film that is resistant to outgassing.

[0008] <1> The photosensitive composition of the present invention is a photosensitive composition comprising a binder resin, a polymerizable compound (B), and a photopolymerization initiator (C), The photopolymerization initiator (C) includes a photopolymerization initiator (C1) represented by the following general formula (1). General formula (1) [ka] <2> The photopolymerization initiator (C) includes a photopolymerization initiator (C2) (excluding the photopolymerization initiator C1 represented by the general formula (1)). <1> The photosensitive composition according to claim 1. <3> the mass ratio of the photopolymerization initiator (C1) represented by the general formula (1) to the photopolymerization initiator (C2) is 95:5 to 5:95; <2> The photosensitive composition according to claim 1. <4> the binder resin contains an alkali-soluble resin (A1) having a monomer unit (a1) whose homopolymer has a glass transition temperature of 0°C or lower; <1> ~ <3> 1. The photosensitive composition according to any one of claims 1 to 9. <5> Further, the composition contains a thermally crosslinkable compound (E), <1> ~ <4> 1. The photosensitive composition according to any one of claims 1 to 9. <6> Further, a silane coupling agent (F) is contained. <1> ~ <5> 10. The photosensitive composition for color filters according to claim 9, wherein the photosensitive composition for color filters is a photosensitive composition for color filters. <7> The polymerizable compound (B) contains an amine-containing polymerizable compound (B1). <1> ~ <6> 1. The photosensitive composition according to any one of claims 1 to 9. <8> Further, the composition contains an ultraviolet absorber (G) or a polymerization inhibitor (H), <1> ~ <7> 1. The photosensitive composition according to any one of claims 1 to 9. <9> <1> ~ <7> 1. A film formed from the photosensitive composition according to any one of claims 1 to 9. <10> <9> An optical filter having the film according to claim 1. <11> <10> A solid-state imaging device having the optical filter according to claim 1. <12> <10> An image display device comprising the optical filter according to claim 1. <13> <10> An infrared sensor having the optical filter according to claim 1. [Effects of the Invention]

[0009] The present invention provides a photosensitive composition that can form a film that is less susceptible to heat shock, less likely to produce drying precipitates during coating, has excellent solvent resistance after a low-temperature curing step, and is less likely to outgas.The present invention also provides a film, an optical filter, an image display device, a solid-state imaging device, and an infrared sensor. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 is a schematic cross-sectional view of an infrared sensor. DETAILED DESCRIPTION OF THE INVENTION

[0011] The terms used in this specification are defined below. Unless otherwise specified, the terms "(meth)acryloyl," "(meth)acrylic," "(meth)acrylic acid," "(meth)acrylate," "(meth)allyl," and "(meth)acrylamide" respectively mean "acryloyl and / or methacryloyl," "acrylic and / or methacrylic," "acrylic acid and / or methacrylic acid," "acrylate and / or methacrylate," "allyl and / or methallyl," and "acrylamide and / or methacrylamide." "CI" means Color Index (CI). The polymerizable unsaturated group is an ethylenically unsaturated group such as a vinyl group, a (meth)acryloyl group, or a (meth)allyl group. The monomer refers to the state before polymerization. The monomer unit refers to the state constituting the resin after polymerization of the monomer. "C1" means that the number of carbon atoms is 1. For example, when written as a C1-C20 alkyl group, it means that the alkyl group has 1 to 20 carbon atoms. For example, 1 to 10% indicates 1% or more and 10% or less.

[0012] The photosensitive composition of the present invention is a photosensitive composition containing a binder resin, a polymerizable compound (B), and a photopolymerization initiator (C), and the photopolymerization initiator (C) contains a photopolymerization initiator (C1) represented by general formula (1).

[0013] The photosensitive composition of the present invention contains a photopolymerization initiator (C1) represented by general formula (1), which exhibits high photocurability, resulting in improved crosslink density and suppressed solvent infiltration, thereby improving solvent resistance after low-temperature heating. Furthermore, the amount of unreacted polymerizable compound remaining after the photocuring process can be reduced, thereby suppressing outgassing during the heating process. Furthermore, the photopolymerization initiator (C1) represented by general formula (1) exhibits superior compatibility with binder resins and polymerizable compounds (B) compared to conventional photopolymerization initiators that do not have the skeleton represented by general formula (1), thereby improving heat shock and drying precipitation. It is believed that the photopolymerization initiator (C1) represented by general formula (1) exhibits a longer wavelength shift in absorption wavelength due to the influence of the conjugated aromatic or heteroaromatic ring, thereby increasing absorbance and improving the curability of the composition. This characteristic improves the deep curability of films when the photosensitive composition is used for color filters, for example.

[0014] In this specification, the curing temperature of the photosensitive composition is preferably 150° C. or lower, more preferably 110° C. or lower, and even more preferably 95° C. or lower. The curing temperature is preferably 60° C. or higher.

[0015] [Binder resin] The photosensitive composition of the present specification contains a binder resin. The binder resin is a resin that has a transmittance of 80% or more over the entire wavelength range of 400 to 700 nm when a film having a thickness of 2 μm is formed. Examples of the binder resin include thermoplastic resins, thermosetting resins, and active energy ray-curable resins. Furthermore, when the binder resin is used for applications requiring developability, an alkali-soluble resin (A) is preferred.

[0016] [Alkali-soluble resin (A)] The alkali-soluble resin (A) is a resin that can be dissolved in an alkaline developer used in photolithography.

[0017] The alkali-soluble resin (A) is not particularly limited, and known resins can be used, such as (meth)acrylic resins, styrene resins, styrene / (meth)acrylic resins, epoxy resins, urethane resins, polycarbonate resins, polyester resins, polyether resins, polyimide resins, polyamideimide resins, and cyclic olefin resins.

[0018] The weight average molecular weight (MW) of the alkali-soluble resin (A) is preferably from 3,000 to 50,000, more preferably from 4,000 to 40,000.

[0019] 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.

[0020] The alkali-soluble resin (A) can be used alone or in combination of two or more kinds.

[0021] The alkali-soluble resin (A) preferably accounts for 1 to 95 mass %, more preferably 5 to 80 mass %, of 100 mass % of the nonvolatile content of the photosensitive composition.

[0022] (Alkali-soluble resin (A1) having a monomer unit (a1) whose homopolymer has a glass transition temperature of 0°C or lower) From the viewpoints of outgassing and solvent resistance at low temperatures, the alkali-soluble resin (A) can contain an alkali-soluble resin (A1) having a monomer unit (a1) whose homopolymer glass transition temperature is 0° C. or lower (hereinafter simply referred to as alkali-soluble resin (A1)). The photocured film contains rigid portions where the polymerizable compound (B) is polymerized and flexible portions derived from the monomer unit (a1) of the alkali-soluble resin (A1). This improves the reaction rate of double bonds and allows the formation of a film with a higher crosslink density. This is thought to result in a film that is less likely to outgas and has excellent solvent resistance at low temperatures.

[0023] The alkali-soluble resin (A1) is preferably a resin containing a monomer unit (a1) (hereinafter referred to as monomer unit (a1)) whose homopolymer has a glass transition temperature of 0° C. or lower, and other monomer units.

[0024] The glass transition temperature (hereinafter also referred to as TG) can be a measured TG obtained by actual measurement. Specifically, the measured TG can be a value measured by differential scanning calorimetry (DSC). However, if measurement is difficult due to decomposition of the resin, etc., the calculated TG obtained by the following formula is applied. 1 / TG=W1 / TG1+W2 / TG2+······+W N / TG N Here, the resins to be calculated are W1 to W N N kinds of monomer components up to W are copolymerized. N is the weight fraction of the Nth monomer, TG N is the glass transition temperature (absolute temperature) of the homopolymer of the Nth monomer. The glass transition temperature of the homopolymer of each monomer (hereinafter also referred to as homopolymer) is the value shown in "POLYMER HANDBOOK, THIRD EDITION, JOHN WILEY & SONS, 1989" edited by Brandrup, J. Immergut, EH.

[0025] [Monomer unit (a1) having a homopolymer glass transition temperature of 0°C or lower] Examples of monomers having a homopolymer glass transition temperature of 0°C or lower include phenoxyethyl acrylate (-22°C), lauryl acrylate (-3°C), 2-ethylhexyl acrylate (-50°C), butoxytriethylene glycol methacrylate (-72°C), 2-(2-ethoxyethoxy)ethyl acrylate (-67°C), N-hexyl acrylate (-57°C), N-butyl acrylate (-48°C), isobutyl acrylate (-40°C), and ethyl acrylate. (-24°C), lauryl methacrylate (-65°C), N-hexyl methacrylate (-5°C), 2-ethylhexyl methacrylate (-10°C), 2-methoxyethyl acrylate (-50°C), tetrahydrofurfuryl acrylate (-12°C), 2-hydroxyethyl acrylate (-15°C), 4-hydroxybutyl acrylate (-60°C), 2-hydroxypropyl acrylate (-7°C), 2-acryloyloxyethyl succinate (-40°C), etc. Among these, from the viewpoints of heat shock, drying precipitates, and solvent resistance at low temperature heating, monomers whose homopolymer glass transition temperature is -60 to -10°C are preferred.

[0026] The content of the monomer units (a1) is preferably 1 to 50 mol %, more preferably 5 to 40 mol %, of all the monomer units in the alkali-soluble resin (A1), from the viewpoints of heat shock, drying precipitates, and solvent resistance at low temperatures.

[0027] Examples of the other monomer units include polymerizable unsaturated group-containing monomer units (a2), acidic group-containing monomer units (a3), aliphatic condensed ring-containing monomer units (a4), hydroxyl group-containing monomer units (a5), epoxy group-containing monomer units (a6), blocked isocyanate group-containing monomer units (a7), and vinyl monomer units (a8). Among these, it is preferable to have polymerizable unsaturated group-containing monomer units (a2) from the viewpoints of heat shock, drying precipitates, and solvent resistance at low temperatures.

[0028] [Polymerizable unsaturated group-containing monomer unit (a2)] The alkali-soluble resin (A1) can be made to contain the polymerizable unsaturated group-containing monomer unit (a2) by, for example, the following methods (I) to (III).

[0029] <Method (I)> In the method (I), for example, a polymer (precursor) of an epoxy group-containing monomer and other monomers is first synthesized, and then a carboxyl group-containing monomer (modifying compound) is added to the epoxy group of the precursor.

[0030] Examples of the epoxy group-containing monomer include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity.

[0031] Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, etc. Among these, acrylic acid and methacrylic acid are preferred.

[0032] From the viewpoint of pattern shape, a polymerizable unsaturated group and a carboxyl group can be made to coexist by reacting an acid anhydride with the site formed by adding a carboxyl group of a carboxyl group-containing monomer to an epoxy group of an epoxy group-containing monomer unit.

[0033] Examples of the acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride.

[0034] <Method (II)> In the method (II), for example, a polymer (precursor) of a carboxyl group-containing monomer and other monomers is first synthesized, and then an epoxy group-containing monomer (modifying compound) is added to the carboxyl group of the precursor.

[0035] <Method (III)> In the method (III), for example, a polymer (precursor) of a hydroxyl group-containing monomer and other monomers is first synthesized, and then the hydroxyl group of the precursor is reacted with the isocyanate group of an isocyanate group-containing monomer (modifying compound).

[0036] Examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3-, or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, and cyclohexanedimethanol mono(meth)acrylate.

[0037] Examples of the isocyanate group-containing monomer include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate.

[0038] The content of the polymerizable unsaturated group-containing monomer unit (a2) is preferably 5 to 80 mol %, more preferably 30 to 80 mol %, of the total monomer units of the alkali-soluble resin (A1), from the viewpoints of outgassing and solvent resistance at low temperature heating.

[0039] [Acidic group-containing monomer unit (a3)] 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-acryloyloxyethyl hexylhydrophthalic acid, p-styrenesulfonic acid, vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, 2-(meth)acryloyloxyethyl acid phosphate, etc. The acidic group includes an acid anhydride group.

[0040] [Aliphatic fused ring-containing monomer unit (a4)] From the viewpoints of outgassing and solvent resistance at low temperature heating, the alkali-soluble resin (A1) more preferably contains an aliphatic fused ring-containing monomer unit (a4).

[0041] Examples of the aliphatic fused ring-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.

[0042] The content of the aliphatic fused ring-containing monomer unit (a4) is preferably 1 to 40 mol % of all monomer units in the alkali-soluble resin (A1) from the viewpoints of outgassing and solvent resistance at low temperature heating.

[0043] [Hydroxyl group-containing monomer unit (a5)] Examples of hydroxyl group-containing monomers include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-acryloyloxyethyl-2-hydroxyethyl phthalate.

[0044] [Epoxy group-containing monomer unit (a6)] 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.

[0045] [Blocked isocyanate group-containing monomer unit (a7)] The blocked isocyanate group-containing monomer is a compound in which the isocyanate group in the 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.

[0046] 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.

[0047] 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.

[0048] Examples of the oxime compound include formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, cyclohexanone oxime, benzophenone oxime, etc. Among these, methyl ethyl ketoxime is 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, p-nitrophenol, etc. Among these, 3,5-xylenol, methyl 2-hydroxybenzoate, and methyl 4-hydroxybenzoate are 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 the bisulfite compound include sodium bisulfite and potassium bisulfite.

[0049] The blocking agents can be used alone or in combination of two or more.

[0050] 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 protection reactions and deprotection reactions, more preferably at least one selected from the group consisting of oxime compounds, phenol compounds, active methylene compounds, and pyrazole compounds.

[0051] Examples of the blocked isocyanate group-containing monomer include the following compounds, but the present invention is not limited to these.

[0052] [ka] JPEG2025163947000003.jpg37151JPEG2025163947000004.jpg39150JPEG2025163947000005.jpg32150JPEG2025163947 000006.jpg33150JPEG2025163947000007.jpg43150JPEG2025163947000008.jpg30151JPEG2025163947000009.jpg3270

[0053] Commercially available blocked isocyanate group-containing monomers include Karenz MOI-DEM (blocking agent desorption temperature: 85 to 95°C), MOI-BP (blocking agent desorption temperature: 105 to 115°C), and MOI-BM (125 to 135°C) manufactured by Resonac Corporation.

[0054] [Vinyl monomer unit (a8)] Examples of the vinyl monomer include acrylic acid esters such as methyl (meth)acrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxydiethylene glycol methacrylate, and EO- or PO-modified (meth)acrylate of paracumylphenol; 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, 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- N-substituted maleimides such as (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.

[0055] The alkali-soluble resin (A1) can be used alone or in combination of two or more kinds.

[0056] The content of the alkali-soluble resin (A1) is preferably 10 to 100 mass %, more preferably 15 to 100 mass %, based on 100 mass % of the alkali-soluble resin (A) from the viewpoints of outgassing and solvent resistance at low temperature heating.

[0057] (Alkali-soluble resin (A2) having blocked isocyanate group-containing monomer unit (a7)) From the viewpoint of outgassing and solvent resistance at low temperatures, the photosensitive composition of the present invention preferably contains, as the alkali-soluble resin (A), an alkali-soluble resin (A2) having a blocked isocyanate group-containing monomer unit (a7) (hereinafter, also referred to simply as alkali-soluble resin (A2)). It is presumed that post-baking improves outgassing and solvent resistance at low temperatures by regenerating the isocyanate group through elimination of the blocking agent or by reacting with other components contained in the photosensitive composition through an ester exchange reaction. The alkali-soluble resin (A2) does not contain a monomer unit (a1) whose homopolymer glass transition temperature is 0°C or lower.

[0058] The alkali-soluble resin (A2) can contain, as a monomer unit other than the blocked isocyanate group-containing monomer unit (a7), a monomer unit other than the above-mentioned monomer unit (a1).

[0059] The content of the blocked isocyanate group-containing monomer unit (a7) is preferably from 1 to 50 mol %, more preferably from 3 to 40 mol %, of all the monomer units in the alkali-soluble resin (A2).

[0060] The alkali-soluble resin (A2) preferably contains a hydroxyl group-containing monomer unit (a5) in addition to the blocked isocyanate group-containing monomer unit (a7). It is presumed that hydrogen bonding of the hydroxyl groups makes it easier for the resins to come into close proximity with each other, facilitating reaction between the isocyanate groups and the hydroxyl groups, thereby further improving solvent resistance even when heated at low temperatures.

[0061] The total content of the blocked isocyanate group-containing monomer unit (a7) and the hydroxyl group-containing monomer unit (a5) is preferably from 10 to 60 mol %, more preferably from 20 to 50 mol %, of all the monomer units in the alkali-soluble resin (A2).

[0062] The molar ratio of the blocked isocyanate group-containing monomer unit (a7) to the hydroxyl group-containing monomer unit (a5) is preferably from 10:90 to 50:50, more preferably from 15:85 to 45:55.

[0063] The alkali-soluble resin (A2) can be used alone or in combination of two or more kinds.

[0064] The alkali-soluble resin (A2) is preferably used in combination with the alkali-soluble resin (A1) from the viewpoint of solvent resistance after low-temperature heating.

[0065] The content of the alkali-soluble resin (A2) is preferably 5% by mass or more, more preferably 10 to 85% by mass, based on 100% by mass of the alkali-soluble resin (A).

[0066] (Alkali-soluble resin (A3)) The photosensitive composition of the present invention may contain, as the alkali-soluble resin (A), an alkali-soluble resin (A3) other than the alkali-soluble resin (A1) and the alkali-soluble resin (A2) (hereinafter, also simply referred to as the alkali-soluble resin (A3)).

[0067] [Polymerizable compound (B)] The polymerizable compound (B) is a monomer or oligomer having a polymerizable unsaturated group, such as a vinyl group, a (meth)allyl group, or a (meth)acryloyl group.

[0068] Examples of the polymerizable compound (B) include an amine-containing polymerizable compound (B1), a hydroxyl group-containing polymerizable compound (B2), an acidic group-containing polymerizable compound (B3), a lactone-modified polymerizable compound (B4), a polymerizable compound having a urethane bond (B5), a polymerizable compound having a dendrimer structure or a hyperbranched structure (B6), and other polymerizable compounds (B7). Among these, it is preferable to contain at least one selected from the group consisting of an amine-containing polymerizable compound (B1), a hydroxyl group-containing polymerizable compound (B2), and an acidic group-containing polymerizable compound (B3).

[0069] (Amine-containing polymerizable compound (B1)) The amine contained in the amine-containing polymerizable compound (B1) may be a primary amine, a secondary amine, or a tertiary amine. Among these, from the viewpoint of viscosity stability, secondary amines and tertiary amines are preferred, and tertiary amines are more preferred. In this specification, the term "amine" does not include amides, imides, and urethanes in which a carbonyl group is directly bonded to a nitrogen atom.

[0070] Examples of the amine-containing polymerizable compound (B1) include tris(acryloyloxyethyl)amine, tris(methacryloyloxyethyl)amine, tris(2-hydroxy-3-methacryloyloxypropyl)amine, and Michael addition reaction products of (meth)acrylate compounds and amine compounds.

[0071] Examples of the (meth)acrylate compound 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, diglycerin tri(meth)acrylate, diglycerin tetra(meth)acrylate, trimethylolpropane alkylene oxide-modified tri(meth)acrylate, and the like. Examples of the alkylene oxide-modified tetra(meth)acrylate include diglycerol alkylene oxide-modified tri(meth)acrylate, ditrimethylolpropane alkylene oxide-modified (meth)acrylate, ditrimethylolpropane alkylene oxide-modified tri(meth)acrylate, pentaerythritol alkylene oxide-modified tetra(meth)acrylate, diglycerol alkylene oxide-modified tri(meth)acrylate, diglycerol alkylene oxide-modified tetra(meth)acrylate, dipenerythritol alkylene oxide-modified penta(meth)acrylate, and dipenerythritol alkylene oxide-modified hexa(meth)acrylate. Examples of the alkylene oxide-modified copolymer include ethylene oxide, propylene oxide, and butylene oxide. The (meth)acrylate compound may be an acidic group-containing (meth)acrylate compound.

[0072] The (meth)acrylate compounds can be used alone or in combination of two or more.

[0073] Examples of the amine compound 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.

[0074] The amine compounds can be used alone or in combination of two or more.

[0075] The method for producing the Michael addition reaction product of a (meth)acrylate compound and an amine compound 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.

[0076] The amine-containing polymerizable compound (B1) 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 of using an acidic group and / or a hydroxyl group-containing compound in a (meth)acrylate compound or an amine compound, and a method of adding an acid anhydride after a Michael addition reaction.

[0077] Commercially available products of the amine-containing polymerizable compound (B1) include, for example, Aronix MT-3041 manufactured by Toagosei Co., Ltd., EBECRYL80 and 7100 manufactured by Daicel-Allnex Co., Ltd., and CN371NS, 372, 374, 383, and 386 manufactured by Arkema.

[0078] (Multifunctional urethane (meth)acrylate (B1-1) having a secondary amino group or a tertiary amino group) The amine-containing polymerizable compound (B1) preferably contains a multifunctional urethane (meth)acrylate (B1-1) having a secondary amino group or a tertiary amino group. This forms a chemical crosslinked structure due to polymerization of the polymerizable unsaturated groups, as well as a physical crosslinked structure due to intermolecular hydrogen bonds between urethane bonds and between urethane bonds and functional groups of the substrate. The molecular cohesive energy of the intermolecular hydrogen bonds at the urethane bonds is greater than the cohesive energy of other organic structures such as ether bonds. Therefore, we believe that the interaction between the urethane bonds makes the film flexible and strong, improving its solvent resistance after low-temperature heating.

[0079] The urethane bond can be introduced, for example, by synthesizing the compound by a urethane reaction between a polyisocyanate compound and a Michael addition reaction product (precursor) of the (meth)acrylate compound and the hydroxyl group-containing amine compound.

[0080] Examples of the polyisocyanate compound include aliphatic ring-containing polyisocyanate compounds such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate; alicyclic polyisocyanate compounds such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dimethylcyclohexyl diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, and bis(isocyanatemethyl)cyclohexane; Examples of the aromatic ring-containing polyisocyanate compound include 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylylene diisocyanate, M-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, bischloromethyldiphenylmethane diisocyanate, 2,6-diisocyanate-benzyl chloride, and bis(isocyanatomethyl)benzene. Further, biuret, isocyanurate, adduct, allophanate and the like of these compounds may also be used.

[0081] The polyisocyanate compounds can be used alone or in combination of two or more kinds.

[0082] The method for the urethane reaction between the precursor and the polyisocyanate compound is not particularly limited, and known methods can be used, such as those described in JP-A-2018-517797.

[0083] An example of a commercially available product of the polyfunctional urethane (meth)acrylate (B1-1) having a secondary amino group or a tertiary amino group is CN9906NS manufactured by Arkema.

[0084] The amine-containing polymerizable compound (B1) can be used alone or in combination of two or more kinds.

[0085] The content of the amine-containing polymerizable compound (B1) is preferably 1 to 80 mass %, more preferably 5 to 60 mass %, in 100 mass % of the polymerizable compound (B) from the viewpoints of outgassing and solvent resistance after low-temperature heating.

[0086] From the viewpoints of outgassing and solvent resistance after low-temperature heating, the amine-containing polymerizable compound (B1) is preferably used in combination with a hydroxyl group-containing polymerizable compound (B2) or an acidic group-containing polymerizable compound (B3), which will be described later. The mass ratio of the polymerizable compound (B1) having an amine structure to the polymerizable compound (B2) having a hydroxyl group is preferably 5:95 to 95:5, more preferably 10:90 to 50:50. The mass ratio of the polymerizable compound (B1) having an amine structure to the polymerizable compound (B3) having an acidic group is preferably 5:95 to 95:5, more preferably 10:90 to 50:50.

[0087] (Hydroxy group-containing polymerizable compound (B2)) Examples of the hydroxyl group-containing polymerizable compound (B2) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2,3-hydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, glycerol di(meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, isocyanuric acid EO or P Examples of the acrylic acid ester include O-modified (meth)acrylate, isocyanuric acid EO- or PO-modified di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, polypentaerythritol penta(meth)acrylate, dipentaerythritol EO- or PO-modified penta(meth)acrylate, and dipentaerythritol caprolactone-modified penta(meth)acrylate; and epoxy (meth)acrylates obtained by reacting the epoxy group of an epoxy compound with the carboxyl group of (meth)acrylic acid. Among these, glycerol di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate are preferred.

[0088] Examples of commercially available hydroxyl group-containing polymerizable compounds (B2) include KAYARAD R-128H and R-167 manufactured by Nippon Kayaku Co., Ltd., Aronix M-5700 and M-920 manufactured by Toagosei Co., Ltd., NK Ester 701A manufactured by Shin-Nakamura Chemical Co., Ltd., Light Ester HOP(N), HOA(N), HOP-A(N), HOB(N), and G-201P, and Epoxy Ester M-600A, 40EM, 70PA, 200PA, 80MFA, 3002M(N), 3002A(N), and 3000A manufactured by Kyoeisha Chemical Co., Ltd., and OGSOL GA-5060P and GA-2800 manufactured by Osaka Gas Chemical Co., Ltd.

[0089] The hydroxyl group-containing polymerizable compound (B2) can be used alone or in combination of two or more kinds.

[0090] The content of the hydroxyl group-containing polymerizable compound (B2) is preferably 10 to 99 mass %, more preferably 20 to 90 mass %, based on 100 mass % of the polymerizable compound (B) from the viewpoints of outgassing and solvent resistance after low-temperature heating.

[0091] (Acidic group-containing polymerizable compound (B3)) Examples of the acidic group-containing polymerizable compound (B3) include esters of dicarboxylic acids with free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohols and (meth)acrylic acid; and esters of polycarboxylic acids with monohydroxyalkyl (meth)acrylates.

[0092] Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.

[0093] Examples of the dicarboxylic acid include malonic acid, succinic acid, maleic acid, glutaric acid, phthalic acid, and itaconic acid.

[0094] 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.

[0095] Commercially available products of the acidic group-containing polymerizable compound (B3) include Aronix M-5300, M-5400, M-510, M-520, and M-521 manufactured by Toagosei Co., Ltd., and B-CEA manufactured by Daicel Allnex Corporation.

[0096] The acidic group-containing polymerizable compound (B3) can be used alone or in combination of two or more kinds.

[0097] The content of the acidic group-containing polymerizable compound (B3) is preferably 1 to 90 mass %, more preferably 1 to 50 mass %, in 100 mass % of the polymerizable compound (B) from the viewpoints of outgassing and solvent resistance after low-temperature heating.

[0098] (Lactone-modified polymerizable compound (B4)) The lactone-modified polymerizable compound (B4) is a compound having a lactone-modified structure in the molecule. The lactone-modified polymerizable compound (B6) can be synthesized by an esterification reaction of 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.

[0099] Commercially available lactone-modified polymerizable compounds (B4) include, for example, KAYARAD DPCA-20, DPCA-30, DPCA-60, and DPCA-120 manufactured by Nippon Kayaku Co., Ltd.

[0100] (Polymerizable compound (B5) having a urethane bond) Examples of the polymerizable compound (B5) having a urethane bond include a urethane (meth)acrylate obtained by reacting a hydroxyl group-containing (meth)acrylate with a polyfunctional isocyanate, and a urethane (meth)acrylate obtained by reacting a polyhydric alcohol with a polyfunctional isocyanate and then reacting the resulting mixture with a hydroxyl group-containing (meth)acrylate. The polymerizable compound (B5) having a urethane bond does not include an amine-containing compound.

[0101] 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 mono(meth)acrylate, glycerol di(meth)acrylate, 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.

[0102] 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; and alicyclic diisocyanate such as isophorone diisocyanate; as well as biuret derivatives, isocyanurates, and trimethylolpropane adducts thereof.

[0103] The polymerizable compound (B5) having a urethane bond may 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. The polymerizable compound (B5) having a urethane bond does not have an amine structure.

[0104] The acidic group can be introduced into the polymerizable compound (B5) 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 reaction product.

[0105] 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.

[0106] Examples of commercially available polymerizable compounds (B5) 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.

[0107] (Polymerizable compound (B6) having a dendrimer structure or a hyperbranched structure) A 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 part), 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.

[0108] Commercially available polymerizable compounds (B6) having a dendrimer structure or a hyperbranched structure include, for example, Viscoat #1000LT (dendrimer structure, average number of acryloyl groups: 14) and SIRUS-501 (dendrimer structure, average number of acryloyl groups: 18) manufactured by Osaka Organic Chemical Industry Co., Ltd.; MIRAMER SP-1106 (dendrimer structure, average number of acryloyl groups: 18) and SP-1108 (dendrimer structure, average number of acryloyl groups: 13) manufactured by MIWON SPECIALTY CHEMICAL; 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; Examples include ETERCURE 6361-100 (hyperbranched structure, average number of acryloyl groups: 8), 6362-100 (hyperbranched structure, average number of acryloyl groups: 12), 6363 (hyperbranched structure, average number of acryloyl groups: 16), and DR-E522 (hyperbranched structure, average number of acryloyl groups: 15), all manufactured by MATERIALS Co., Ltd.

[0109] The polymerizable compound (B6) having a dendrimer structure or a hyperbranched structure can be used alone or in combination of two or more kinds.

[0110] The polymerizable compound (B6) having a dendrimer structure or a hyperbranched structure is preferably contained in an amount of 1 to 90 mass %, more preferably 1 to 50 mass %, based on 100 mass % of the polymerizable compound (B), from the viewpoint of solvent resistance after low-temperature heating.

[0111] (Other polymerizable compounds (B7)) Examples of other polymerizable compounds (B7) include methyl (meth)acrylate, ethyl (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 EO or PO modified tri(meth)acrylate, isocyanuric acid Examples of the methacrylic acid ester include EO- or PO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol EO- or PO-modified hexa(meth)acrylate, tricyclodecanyl (meth)acrylate, and (meth)acrylic acid ester of methylolated melamine; styrene, vinyl acetate, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-vinylformamide, and acrylonitrile.

[0112] Other commercially available products of the polymerizable compound (B7) include, for example, KAYARAD NPGDA, PEG400DA, FM-400, HX-200, HX-620, R-551, R-712, R-604, R-684, GPOD-303, TMPTA, T-1420(T), RP-1040, DPEA-12, and D-310 manufactured by Nippon Kayaku Co., Ltd., and Aronix M-101A, M-102, M-111, M-113, M-120, M-140, M-208, and M-21 manufactured by Toagosei Co., Ltd. 1B, M-220, M-225, M-270, M-240, M-309, M-310, M-321, M-350, M-360, M-408, M-460, Viscoat #150, #155, #160, #192, #MTG, #200, #196, #195, #230, #260, #310, #700HV, #295 manufactured by Osaka Organic Chemical Industry Co., Ltd., and OGSOL manufactured by Osaka Gas Chemicals Co., Ltd. Examples of such esters include EA-0200, EA-0300, MIRAMER HR6060, 6100, and 6200 manufactured by MIWON SPECIALTY CHEMICAL CO., LTD., and NK Ester A-HD-N, A-NPG, A-200, A-400, APG-200, APG-400, A-DCP, ABE-300, A-BPE-4, A-BPE-10, A-TMPT, A-TMPT-9EO, A-GLY-3E, A-GLY-9E, A-TMMT, ATM-35E, and AD-TMP manufactured by Shin-Nakamura Chemical Co., Ltd.

[0113] The other polymerizable compounds (B7) can be used alone or in combination of two or more.

[0114] The content of the polymerizable compound (B) is preferably from 1 to 50 mass %, more preferably from 5 to 30 mass %, of the nonvolatile content of the photosensitive composition.

[0115] [Photopolymerization initiator (C)] The photopolymerization initiator (C) contains a photopolymerization initiator (C1) represented by general formula (1).

[0116] (Photopolymerization initiator (C1) represented by general formula (1)) The photosensitive composition of the present invention contains a photopolymerization initiator (C1) represented by general formula (1) (hereinafter also referred to as photopolymerization initiator (C1)), which efficiently generates radicals upon exposure to ultraviolet light, resulting in a cured film with high crosslink density. This improves outgassing and solvent resistance, particularly after low-temperature curing. Furthermore, the photopolymerization initiator (C1) has excellent compatibility, improving heat shock resistance and reducing the formation of drying precipitates.

[0117] General formula (1) [ka]

[0118] In general formula (1), Ar1 and Ar2 each independently represent a substituent containing an aromatic ring or a heteroaromatic ring, and R1 represents a C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C1-C10 alkyl group substituted with a C3-C8 cycloalkyl group, a C3-C8 cycloalkyl group substituted with a C1-C20 alkyl group, a C6-C20 aryl group, a C6-C20 aryl group substituted with a C1-C5 alkyl group, a C4-C20 heteroaryl group, or a C6-C20 heteroaryl group substituted with a C1-C5 alkyl group.

[0119] Examples of the aromatic ring or heteroaromatic ring are shown below as (ar1) to (ar10), where * indicates a bond.

[0120] [ka] JPEG2025163947000012.jpg35121JPEG2025163947000013.jpg37120JPEG2025163947000014.jpg49121JPEG2025163947000015.jpg4950

[0121] Among the above structures, (ar2), (ar4) and (ar8) are preferred, and (ar4) and (ar8) are more preferred, from the viewpoint of solvent resistance after low-temperature curing.

[0122] In the above structure, -CH2- may be replaced with -O- or -S-. R3 is a hydrogen atom, a nitro group, a hydroxy group, a C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C4-C20 alkylcycloalkyl group, a C4-C20 cycloalkylalkyl group, a C2-C20 chain alkenyl group, a C5-C10 cyclic alkenyl group, a C5-C10 heterocyclic alkenyl group, a C6-C12 aryl group, a C6-C12 heteroaryl group, a C1-C4 alkyl group substituted with a C6-C12 aryl group, or a C1-C4 alkyl group substituted with a C6-C12 heteroaryl group, and optionally, -CH2- in these substituents may be replaced with -O- or -C(=O)-. R4 represents a hydrogen atom, a C1 to C6 alkyl group, a C1 to C6 chain alkenyl group, a phenyl group or a substituted phenyl group.

[0123] More preferred structures of the above Ar1 and Ar2 are as follows: * indicates a bond.

[0124] [ka] JPEG2025163947000017.jpg26146JPEG2025163947000018.jpg24145JPEG2025163947000019.jpg25147JPEG2025163947000020. jpg20146JPEG2025163947000021.jpg18147JPEG2025163947000022.jpg20150JPEG2025163947000023.jpg19147JPEG2025163947 000024.jpg20146JPEG2025163947000025.jpg23147JPEG2025163947000026.jpg27149JPEG2025163947000027.jpg21145JPEG20 25163947000028.jpg25146JPEG2025163947000029.jpg21146JPEG2025163947000030.jpg26145JPEG2025163947000031.jpg1642

[0125] When the above structures are selected for Ar1 and Ar2, outgassing, solvent resistance after low-temperature curing, heat shock resistance, and dried deposits are further improved.

[0126] Examples of the photopolymerization initiator (C1) include compounds represented by the following chemical formulas (C1) to (C62), but the present invention is not limited thereto.

[0127] [ka] JPEG2025163947000033.jpg30118JPEG2025163947000034.jpg36118JPEG2025163947000035.jpg30117JPEG20251639470 00036.jpg30115JPEG2025163947000037.jpg29118JPEG2025163947000038.jpg35119JPEG2025163947000039.jpg37116J PEG2025163947000040.jpg31118JPEG2025163947000041.jpg29117JPEG2025163947000042.jpg29116JPEG202516394700 0043.jpg29119JPEG2025163947000044.jpg29120JPEG2025163947000045.jpg29118JPEG2025163947000046.jpg29118JP EG2025163947000047.jpg29117JPEG2025163947000048.jpg29115JPEG2025163947000049.jpg29117JPEG2025163947000 050.jpg29117JPEG2025163947000051.jpg30116JPEG2025163947000052.jpg36119JPEG2025163947000053.jpg29116JPE G2025163947000054.jpg29117JPEG2025163947000055.jpg35120JPEG2025163947000056.jpg36118JPEG20251639470000 57.jpg30119JPEG2025163947000058.jpg29116JPEG2025163947000059.jpg30116JPEG2025163947000060.jpg24117(C57) (C58) JPEG2025163947000061.jpg36119JPEG2025163947000062.jpg31112

[0128] Among the above compounds, the compounds represented by the chemical formulae (C29) to (C44) are preferred from the viewpoint of solvent resistance when heated at low temperatures.

[0129] The above compound can be synthesized, for example, by the method described in WO 2022 / 237644.

[0130] From the viewpoints of heat shock, drying precipitates, outgassing, and solvent resistance at low temperatures, the content of the photopolymerization initiator (C1) is preferably 0.5 to 20 mass%, more preferably 1 to 15 mass%, and particularly preferably 3 to 10 mass%, based on 100 mass% of the nonvolatile content of the photosensitive composition.

[0131] The photopolymerization initiator (C1) can be used alone or in combination of two or more kinds.

[0132] The photopolymerization initiator (C1) is preferably one of the chemical formulae (C29) to (C44) from the viewpoints of heat shock, dry precipitates, outgassing, and solvent resistance at low temperature heating.

[0133] (Photopolymerization initiator (C2)) The photopolymerization initiator (C) may contain a photopolymerization initiator (C2) other than the photopolymerization initiator (C1). Examples of the photopolymerization initiator (C2) include an oxime ester photopolymerization initiator (C2a) and other photopolymerization initiators (C2b).

[0134] (Oxime ester photoinitiator (C2a)) When the composition contains an oxime ester photopolymerization initiator (C2a) (hereinafter also referred to as photopolymerization initiator (C2a)), it is possible to form a coating film that is more excellent in outgassing and solvent resistance when heated at low temperatures.

[0135] Examples of the photopolymerization initiator (C2a) include a carbazole compound, a diphenyl sulfide compound, a phenothiazine compound, a fluorene compound, and an indole compound.

[0136] Examples of the carbazole compound include those represented by the following chemical formulas (C2a-1) to (C2a-9), but the present invention is not limited thereto.

[0137] [ka] JPEG2025163947000064.jpg3591JPEG2025163947000065.jpg48141JPEG2025163947 000066.jpg4396JPEG2025163947000067.jpg3891JPEG2025163947000068.jpg54144

[0138] Examples of diphenyl sulfide compounds include those represented by the following chemical formulas (C2a-10) to (C2a-13), although the present invention is not limited thereto.

[0139] [ka] JPEG2025163947000070.jpg42140

[0140] Examples of phenothiazine compounds include those represented by the following chemical formula (C2a-14): However, the present invention is not limited thereto.

[0141] [ka]

[0142] Examples of the fluorene compound include those represented by the following chemical formulas (C2a-15) to (C2a-16), but the present invention is not limited thereto.

[0143] [ka]

[0144] Examples of indole compounds include those represented by the following chemical formula (C2a-17): However, the present invention is not limited thereto.

[0145] [ka]

[0146] Among the photopolymerization initiators (C2a), from the viewpoints of heat shock, drying precipitates, outgassing, and solvent resistance at low temperatures, we selected a photopolymerization initiator with an absorption coefficient of 5.0 × 10 at a wavelength of 365 nm in propylene glycol monomethyl ether acetate. 3 L / mol cm or more is preferred, and 7.0 × 10 3 L / mol cm or more is more preferable, and the 4 L / mol·cm or more are particularly preferred.

[0147] The content of the photopolymerization initiator (C2a) is preferably 1 to 5 mass %, more preferably 1 to 3 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition, from the viewpoints of heat shock, drying precipitates, outgassing, and solvent resistance at low temperature heating.

[0148] (Other photopolymerization initiators (C2b)) When the photopolymerization initiator (C2b) is contained, a coating film having good outgassing and solvent resistance after low-temperature heating can be obtained.

[0149] Examples of the photopolymerization initiator (C2b) include acetophenone-based compounds such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl 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, and 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; acylphosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and diphenyl-2,4,6-trimethylbenzoylphosphine oxide; Quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds; Compounds having a fluorene skeleton, etc. Among these, compounds having a fluorene skeleton (C2b-1) are preferred.

[0150] (Compound (C2b-1) having a fluorene skeleton) The compound (C2b-1) having a fluorene skeleton more preferably includes a compound represented by the following general formula (100).

[0151] General formula (100) [ka]

[0152] In general formula (100), R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R3 represents a hydrogen atom or a monovalent substituent.

[0153] The alkyl group having 1 to 8 carbon atoms includes linear, branched, and cyclic groups, as well as groups formed by combining these groups. Examples 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, and a cyclohexylmethyl group. Of these, 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.

[0154] 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. Substituents that the benzoyl and 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.

[0155] The compound represented by general formula (100) can be synthesized by the method described in, for example, JP-T-2019-507108, JP-T-2019-528331, or the like.

[0156] Specific examples of the compound represented by formula (100) are shown below, but the present invention is not limited to these.

[0157] [ka] JPEG2025163947000076.jpg42141

[0158] The photopolymerization initiator (C1) and the compound (C2b-1) having a fluorene skeleton are preferably used in combination from the viewpoints of heat shock and drying precipitation.

[0159] The mass ratio of the photopolymerization initiator multimer (C1) to the compound having a fluorene skeleton (C2b-1) is preferably from 90:10 to 10:90, more preferably from 90:10 to 70:30, from the viewpoint of solvent resistance after low-temperature heating.

[0160] Commercially available photopolymerization initiators (C2) include acetophenone-based compounds such as Omnirad 907, 369E, 379EG, 127, 184, 1173, and 2959 manufactured by IGM Resins, and acylphosphine-based compounds such as Omnirad 819 and TPO manufactured by IGM Resins. Further examples include 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, JP 2019-507108 A, JP 2019-528331 A, WO 2021 / 175855, etc.

[0161] The photopolymerization initiator (C) can be used alone or in combination of two or more kinds.

[0162] The content of the photopolymerization initiator (C) is preferably from 1 to 25 mass %, more preferably from 2 to 15 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0163] The mass ratio of the photopolymerization initiator (C1) to the photopolymerization initiator (C2) is preferably from 95:5 to 5:95, more preferably from 95:5 to 33:67, from the viewpoints of outgassing, dry precipitates, and solvent resistance at low temperature heating.

[0164] [Thermal polymerization initiator (D)] The photosensitive composition of the present invention may contain a thermal polymerization initiator (D). The thermal polymerization initiator (D) is preferably used in combination with a photopolymerization initiator (C). This allows radical polymerization reactions to occur in both the film exposure step and the post-bake step, further improving resistance. Examples of the thermal polymerization initiator (D) include peroxides and azo compounds. The photosensitive composition of the present invention, by containing a peroxide (D1), can form a coating film that has good outgassing and solvent resistance after low-temperature heating.

[0165] [Peroxide (D1)] When the oxide (D1) is contained, a film having excellent solvent resistance can be formed after low-temperature heating.

[0166] Examples of the peroxide (D1) include methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,2-bis(tert-butylperoxy)butane, succinic peroxide, and benzoyl peroxide.

[0167] [Other thermal polymerization initiators (D2)] The photosensitive composition of the present invention may contain a thermal polymerization initiator (D2) other than the peroxide (D1).

[0168] Examples of the thermal polymerization initiator (D2) include benzopinacol, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-diphenoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetra(4-methylphenyl)ethane, 1,2-diphenoxy-1,1,2,2-tetra(4-methoxyphenyl)ethane, and 1,2-bis(trimethylsiloxy)-1,1,2,2-tetraphenyl. Pinacol compounds such as ethane, 1,2-bis(triethylsiloxy)-1,1,2,2-tetraphenylethane, 1,2-bis(TERT-butyldimethylsiloxy)-1,1,2,2-tetraphenylethane, 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-triethylsiloxy-1,1,2,2-tetraphenylethane, and 1-hydroxy-2-TERT-butyldimethylsiloxy-1,1,2,2-tetraphenylethane; Examples of azo compounds include 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis[N-(2-propenyl)2-methylpropionamide], 1-[(1-cyano-1-methylethyl)azo]formamide, 2,2'-azobis(N-butyl-2-methylpropionamide), and 2,2'-azobis(N-cyclohexyl-2-methylpropionamide).

[0169] The thermal polymerization initiator (D) can be used alone or in combination of two or more kinds.

[0170] The content of the thermal polymerization initiator (D) is preferably from 0.1 to 15 mass %, more preferably from 1 to 5 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0171] When the photopolymerization initiator (C) and the thermal polymerization initiator (D) are used in combination, the mass ratio is preferably 91:9 to 11:89, more preferably 91:9 to 33:67, from the viewpoints of outgassing, dried precipitates, and solvent resistance at low temperatures.

[0172] [Thermal crosslinkable compound (E)] The photosensitive composition of the present invention may contain a thermally crosslinkable compound (E). The thermally crosslinkable compound (E) crosslinks with other components upon heating, further improving solvent resistance during low-temperature curing. The thermally crosslinkable compound (E) does not have a polymerizable unsaturated group and is not alkali-soluble. Therefore, it is a different compound from alkali-soluble resins and polymerizable compounds.

[0173] The thermally crosslinkable compound (E) is not particularly limited as long as it is a compound having a thermally crosslinkable group, and known compounds can be used, such as oxetanyl group-containing compounds, methylol group-containing compounds, phenol group-containing compounds, alkoxyalkyl group-containing compounds, blocked isocyanate group-containing compounds (E1) and epoxy compounds (E2), which will be described later. Among these, it is preferable to contain one or more compounds selected from the group consisting of blocked isocyanate group-containing compounds (E1) and epoxy compounds (E2), and it is more preferable to contain a blocked isocyanate group-containing compound.

[0174] [Blocked isocyanate group-containing compound (E1)] The blocked isocyanate group-containing compound (E1) is a compound in which the isocyanate group of an isocyanate group-containing compound is blocked with a blocking agent. The desorption temperature of the blocking agent is preferably 60 to 160°C, more preferably 70 to 130°C, and even more preferably 80 to 110°C, from the viewpoints of storage stability and solvent resistance after low-temperature heating.

[0175] The blocked isocyanate group-containing compound (E1) is synthesized by reacting an isocyanate group-containing compound with a blocking agent by a known method, such as those described in JP-A-52-116420, JP-A-60-149572, JP-A-7-31953, JP-A-10-306136, and JP-A-2012-012567.

[0176] The blocking agent is preferably one or more 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, more preferably oxime compounds, phenol compounds, active methylene compounds, and pyrazole compounds, and from the viewpoint of solvent resistance after low-temperature heating, active methylene compounds are particularly preferred. The elimination temperature or transesterification temperature of the active methylene compounds is low, at 80 to 110°C, and they react sufficiently even at low temperatures, improving resistance.

[0177] Examples of the isocyanate group-containing compound include aliphatic ring-containing compounds such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate; Alicyclic ring-containing compounds such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dimethylcyclohexyl diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, and bis(isocyanatomethyl)cyclohexane; Examples of aromatic ring-containing compounds include 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylylene diisocyanate, M-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, bischloromethyldiphenylmethane diisocyanate, 2,6-diisocyanate-benzyl chloride, and bis(isocyanatomethyl)benzene. Further examples include biuret, isocyanurate, adduct and allophanate forms of these compounds, and reaction products of these compounds with polyols.

[0178] The isocyanate group-containing compound is preferably a biuret, isocyanurate, adduct or allophanate of an aliphatic ring-containing compound or an alicyclic ring-containing compound, more preferably a biuret or isocyanurate of a compound having an aliphatic structure.

[0179] Examples of the blocked isocyanate group-containing compound (E1) include the following compounds: In the following structural formulas (N-1) to (N-7), X represents a blocked isocyanate group, although the present invention is not limited thereto.

[0180] [ka]

[0181] Among these, from the viewpoints of stability over time and solvent resistance after low-temperature heating, compounds represented by (N-1), (N-2), (N-4), and (N-7) are preferred, compounds represented by (N-1) and (N-2) are more preferred, and compound represented by (N-1) is even more preferred.

[0182] Examples of X (blocked isocyanate group) in the above compound include the structures shown in (X-1) to (X-8) below. In the following structures, * represents a bond. However, the present invention is not limited to these.

[0183] [ka]

[0184] Among the above structures, from the viewpoints of storage stability and solvent resistance after low-temperature heating, (X-1), (X-4), (X-6), (X-7), and (X-8) are preferred, (X-1) and (X-8) are more preferred, and (X-1) is even more preferred.

[0185] Among the blocked isocyanate group-containing compounds (E1), from the viewpoints of storage stability and solvent resistance after low-temperature heating, structures of (N-1) or (N-2) and (X-1), (X-4) or (X-8) are preferred.

[0186] By using (X-1) and (X-8) in combination, it is possible to achieve high levels of both storage stability and solvent resistance after low-temperature heating. The molar ratio of (X-1) to (X-8) is preferably 90:10 to 10:90, more preferably 90:10 to 30:70, and even more preferably 90:10 to 70:30.

[0187] Commercially available aliphatic ring-containing compounds that are the blocked isocyanate group-containing compound (E1) include, for example, Duranate SBN-70D, SBB-70P, SBF-70E, TPA-B80E, 17B-60P, E402-B80B, and WM44-L70G manufactured by Asahi Kasei Corporation, Takenate B-882 manufactured by Mitsui Chemicals, Inc., and BI7960, BI7961, BI7982, BI7991, and BI7992 manufactured by Baxenden Chemical Co., Ltd.; Examples of the alicyclic compound include Takenate B-846N manufactured by Mitsui Chemicals, Inc., Coronate BI-301, 2507, and 2554 manufactured by Tosoh Corporation, and BI7950, BI7951, and BI7990 manufactured by Baxenden Chemical Co., Ltd.; Examples of aromatic ring-containing compounds include Takenate B-830 and B-815N manufactured by Mitsui Chemicals.

[0188] The blocked isocyanate group-containing compound (E1) preferably has 1 to 20 blocked isocyanate groups, more preferably 2 to 15 blocked isocyanate groups.

[0189] The weight average molecular weight of the blocked isocyanate group-containing compound (E1) is preferably from 300 to 5,000, more preferably from 500 to 3,000.

[0190] The acid value of the blocked isocyanate group-containing compound (E1) is preferably less than 10 mgKOH / g.

[0191] The blocked isocyanate group-containing compound (E1) can be used alone or in combination of two or more kinds.

[0192] From the viewpoints of storage stability, outgassing, and solvent resistance after low-temperature heating, the content of the blocked isocyanate group-containing compound (E1) is preferably 1 to 20 mass%, more preferably 3 to 15 mass%, and particularly preferably 5 to 10 mass%, based on 100 mass% of the nonvolatile content of the photosensitive composition.

[0193] [Epoxy compound (E2)] The epoxy compound (E2) is a compound having an epoxy group. The epoxy group is a group having a three-membered cyclic ether, including an alicyclic epoxy group. The epoxy compound (E2) does not have an alkoxysilyl group or a polymerizable unsaturated group.

[0194] Examples of the epoxy compound (E2) include polyglycidyl ether compounds of bisphenols such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and hydrogenated bisphenol F diglycidyl ether; Polyglycidyl ether compounds of polyhydric alcohols such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether; Polyglycidyl ether compounds of polyether polyols obtained by adding alkylene oxides to polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin; 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl) compounds having two or more 3,4-epoxycyclohexyl groups in the molecule, such as bis(3,4-epoxycyclohexylmethyl)-5,5-spiro-3,4-epoxy)cyclohexane-metadioxane, bis(3,4-epoxycyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, methylenebis(3,4-epoxycyclohexane), ethylenebis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl)-modified e-caprolactone; Examples include 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol.

[0195] Commercially available epoxy compounds (E2) include, for example, JER807, 815, 825, 827, 828, 190P, 191P, 1004, 1256, 1032H60, 157S65, 157S70, 152, and 154 manufactured by Mitsubishi Chemical Corporation; TECHMORE VG3101L, EPPN-201, 501H, 502H, EOCN-102S, 103S, 104S, 1020 manufactured by Nippon Kayaku Co., Ltd., Celoxide 2021, EHPE-3150, Epolead GT401 manufactured by Daicel Corporation, 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., 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.

[0196] The epoxy compound (E2) is preferably a compound having 2 to 50 epoxy groups in the molecule.

[0197] The epoxy equivalent of the epoxy compound (E2) is preferably 50 to 400 g / eq, more preferably 90 to 220 g / eq, from the viewpoints of heat shock, outgassing, dried precipitates, and solvent resistance after low-temperature heating. The epoxy equivalent is defined as the mass of an epoxy compound containing one equivalent of epoxy groups.

[0198] From the viewpoints of heat shock, outgassing, dried precipitates, and solvent resistance after low-temperature heating, the epoxy compound (E2) more preferably contains a compound represented by the following general formula (50).

[0199] General formula (50) [ka]

[0200] In the general formula (50), R represents a group obtained by removing n hydroxyl groups from an m-hydric alcohol, m represents an integer of 1 to 6, and n represents an integer of 1 to 30.

[0201] R is preferably an alkyl group having 2 to 20 carbon atoms, and may be linear, branched, or cyclic, or a group formed by combining these. Examples of the alkyl group having 2 to 20 carbon atoms include ethyl, methyl, propyl, isopropyl, 2,2-dimethylpropyl, butyl, isobutyl, tert-butyl, 3,3-dimethylbutyl, pentyl, isopentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, hexadecyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, cyclohexylmethyl, and cyclohexylmethyl. Among these, branched alkyl groups having 3 to 12 carbon atoms are more preferred. When m is 2 or more, n in each of the groups in parentheses in general formula (50) may be the same or different.

[0202] An example of the compound represented by general formula (50) is a 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol. Commercially available products include EHPE-3150 and EHPE-3150CE manufactured by Daicel Corporation.

[0203] The acid value of the epoxy compound (E2) is preferably 10 mgKOH / g or less.

[0204] The epoxy compound (E2) can be used alone or in combination of two or more kinds.

[0205] The content of the epoxy compound (E2) is preferably 0.5 to 20 mass%, more preferably 2 to 7 mass%, and particularly preferably 3 to 5 mass%, based on 100 mass% of the nonvolatile content of the photosensitive composition, from the viewpoints of heat shock, dried precipitates, and dry precipitates.

[0206] From the viewpoints of heat shock, drying precipitates, outgassing, and solvent resistance after low-temperature curing, it is preferable to use the thermally crosslinkable compound (E) in combination with a blocked isocyanate group-containing compound (E1) and an epoxy compound (E2).

[0207] The mass ratio of the blocked isocyanate group-containing compound (E1) to the epoxy compound (E2) is preferably from 5:95 to 95:5, more preferably from 37:63 to 91:9, and particularly preferably from 55:45 to 77:23, from the viewpoints of heat shock, outgassing, and dry deposits.

[0208] The thermally crosslinkable compound (E) can be used alone or in combination of two or more kinds.

[0209] From the viewpoints of heat shock, outgassing, and drying precipitates, the content of the thermally crosslinkable compound (E) is preferably 0.5 to 40 mass%, more preferably 1 to 30 mass%, and particularly preferably 5 to 20 mass%, based on 100 mass% of the nonvolatile content of the photosensitive composition.

[0210] [Silane coupling agent (F)] The photosensitive composition of the present invention may contain a silane coupling agent (F).

[0211] The silane coupling agent (F) is a compound having an alkoxysilyl group and other reactive functional groups. The alkoxysilyl group is a group in which an alkoxy group is bonded to a silicon atom, and is a group that generates a silanol group upon hydrolysis. Examples of the alkoxy group include a methoxy group, an ethoxy group, and a butoxy group. Examples of the other functional group include an epoxy group, an amino group, a vinyl group, a (meth)acryloyl group, an isocyanate group, an isocyanurate group, a mercapto group, an oxetanyl group, a styryl group, and a ureido group.

[0212] (Compound (F1) Having an Alkoxysilyl Group, a (Meth)acryloyl Group, and a Urethane Bond) The silane coupling agent (F) preferably contains a compound (F1) having an alkoxysilyl group, a (meth)acryloyl group, and a urethane bond (hereinafter, also simply referred to as compound (F1)).

[0213] The compound (F1) can be produced, for example, by a urethane reaction between an alkoxysilyl group- and isocyanate group-containing compound and a hydroxyl group-containing (meth)acrylate.

[0214] Examples of the alkoxysilyl group- and isocyanate group-containing compound include isocyanate propyl triethoxysilane, isocyanate propyl methyl diethoxysilane, isocyanate propyl dimethyl ethoxysilane, isocyanate propyl trimethoxysilane, isocyanate propyl methyl dimethoxysilane, isocyanate propyl dimethyl methoxysilane, isocyanate propyl tripropoxysilane, isocyanate propyl methyl dipropoxysilane, isocyanate propyl dimethyl propoxysilane, isocyanate propyl tributoxysilane, isocyanate propyl methyl dibutoxysilane, and isocyanate propyl dimethyl butoxysilane.

[0215] Examples of the hydroxyl group-containing (meth)acrylate 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, 4-hydroxyphenyl (meth)acrylate, isocyanuric acid EO or PO modified (meth)acrylate, isocyanuric acid EO or PO modified di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, polypentaerythritol penta(meth)acrylate, dipentaerythritol EO or PO modified penta(meth)acrylate, dipentaerythritol caprolactone modified penta(meth)acrylate, etc.

[0216] The urethane reaction can use a solvent and a reaction catalyst as needed. Examples of the solvent include hydrocarbon solvents. Among these, chain hydrocarbons, cyclic hydrocarbons, and aromatic hydrocarbons are preferred. Examples of the reaction catalyst include urethane catalysts such as tertiary amines and tin compounds.

[0217] From the viewpoint of solvent resistance after low-temperature heating, the compound (F1) preferably contains 1 to 5 (meth)acryloyl groups, and more preferably 1 to 3 (meth)acryloyl groups, per 1 silicon atom in the alkoxysilyl group.

[0218] In terms of solvent resistance after low-temperature heating, the alkoxysilyl group in the compound (F1) is preferably a methoxysilyl group or an ethoxysilyl group.

[0219] The compound (F1) is preferably a compound represented by the following general formula (56).

[0220] General formula (56) [ka]

[0221] In general formula (56), three R1s each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R2 represents an alkylene group having 1 to 8 carbon atoms, X represents a group represented by the following general formulas (X-1) to (X-4), and n represents an integer of 1 to 10.

[0222] [ka]

[0223] In the general formula (X-1), R3 represents an alkylene group having 1 to 8 carbon atoms. In the general formulae (X-1) to (X-4), R4 represents a hydrogen atom or a methyl group. * represents a bond to an oxygen atom.

[0224] In the general formula (56), the three R1s are preferably methyl groups from the viewpoints of heat shock, dry precipitates, and solvent resistance after low-temperature heating.

[0225] In the general formula (56), X is preferably any of the general formulae (X-1) to (X-3) from the viewpoints of heat shock, dry precipitates, and solvent resistance after low-temperature heating.

[0226] The compound (F1) can be used alone or in combination of two or more kinds.

[0227] The content of compound (F1) is preferably 0.1 to 15 mass %, more preferably 0.5 to 10 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition, from the viewpoints of heat shock, drying precipitates, and solvent resistance after low-temperature heating.

[0228] (Compound (F2)) The silane coupling agent (F) can contain a compound (F2) other than the compound (F1) (hereinafter also simply referred to as the compound (F2)).

[0229] Examples of the compound (F2) include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride. salts, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, p-styryltrimethoxysilane, 3-ureidopropyltrialkoxysilane, and the like.

[0230] Commercially available products of compound (F2) include, for example, KBM-302, KBM-402, KBM-403, KBE-402, KBE-403, KBM-4803, KBM-602, KBM-603, KBM-903, KBE-9103P, KBM-573, KBM-6803, KBM-1003, KBE-1003, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5803, X-12-1048, X-12-1050, KBE-9007N, KBM-9659, KBM-802, KBM-803, KBM-1043, and KBE-585A, all manufactured by Shin-Etsu Silicones Co., Ltd.

[0231] The compound (F2) may also be a polymer type, such as a polysiloxane type or an organic polymer type.

[0232] The polysiloxane type is a silane coupling agent in which the alkoxysilyl group and other functional groups are bonded to a polymer having a polysiloxane skeleton in the main chain. Commercially available polysiloxane type products include KR-513, KR-516, KR-517, X-41-1805, and X-41-1810 manufactured by Shin-Etsu Silicones Co., Ltd.

[0233] The organic polymer type is a silane coupling agent in which the alkoxysilyl group and other functional groups are bonded to an organic polymer whose main chain has an organic structure. Commercially available organic polymer type products include X-12-9815, X-12-9845, X-12-1154, X-12-972F, and X-12-1159L manufactured by Shin-Etsu Silicones Co., Ltd.

[0234] The compound (F2) can be used alone or in combination of two or more kinds.

[0235] The content of the compound (F2) is preferably from 0.1 to 15 mass %, more preferably from 0.5 to 10 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0236] [Ultraviolet absorber (G)] The photosensitive composition of the present invention may contain an ultraviolet absorber (G).

[0237] The ultraviolet absorber (G) is a compound having an ultraviolet absorbing function, and examples thereof include benzotriazole compounds, triazine compounds, benzophenone compounds, salicylic acid ester compounds, cyanoacrylate compounds, and salicylate compounds.

[0238] Examples of the benzotriazole compound include 2-(5-tert-butyl-2-hydroxyphenyl)benzotriazole, ester compounds of benzenepropanoic acid and 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy(C7-9 branched and linear alkyl), 2-[5-chloro-(2H)-benzotriazol-2-yl]-4-methyl-6-(tert-butyl)phenol, and 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol. , 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, etc. Commercially available products include Tinuvin PS, 99-2, 326, 384-2, 900, 928, 970, 1130, and UVA-903KT manufactured by BASF Japan, and Adeka STAB LA-31RG and LA-31G manufactured by ADEKA Corporation.

[0239] Examples of benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid trihydrate, 2-hydroxy-4-octyloxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, diethylaminohydroxybenzoylhexyl benzoate, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 2-aminobenzophenone, etc. Commercially available products include Uvinal A, 3049, 3050, UVA-935LH manufactured by BASF Japan, Adeka STAB 1413 manufactured by ADEKA, and Omnirad EMK manufactured by IGM Resins.

[0240] The ultraviolet absorbers (G) can be used alone or in combination of two or more kinds.

[0241] From the viewpoint of solvent resistance after low-temperature heating, the content of the ultraviolet absorber (G) is preferably 0.1 to 5 mass %, more preferably 0.5 to 2 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0242] The ultraviolet absorber (G) is preferably a benzotriazole compound.

[0243] [Polymerization inhibitor (H)] The photosensitive composition of the present invention may contain a polymerization inhibitor (H).

[0244] Examples of the polymerization inhibitor (H) include alkyl catechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methyl catechol, 3-methyl catechol, 4-methyl catechol, 2-ethyl catechol, 3-ethyl catechol, 4-ethyl catechol, 2-propyl catechol, 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-tert-butyl catechol, 3-tert-butyl catechol, 4-tert-butyl catechol, and 3,5-di-tert-butyl catechol; 2-methyl resorcinol, 4-methyl resorcinol, 2-ethyl resorcinol, 4-ethyl resorcinol, 2-propyl resorcinol, 4-propyl resorcinol; alkylresorcinol compounds such as 1-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, and 4-tert-butylresorcinol; alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, and 2,5-di-tert-butylhydroquinone; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, and tribenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite; pyrogallol; and phloroglucinol.

[0245] The polymerization inhibitor (H) can be used alone or in combination of two or more kinds.

[0246] From the viewpoint of storage stability, the content of the polymerization inhibitor (H) is preferably 0.005 to 0.4% by mass relative to 100% by mass of the nonvolatile content of the photosensitive composition.

[0247] [Dye (I)] The photosensitive composition of the present invention can contain a dye (I). The coloring matter (I) may be a pigment, a dye, or a near-infrared absorbing coloring matter, and the pigment may be an inorganic pigment or an organic pigment. 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, 174,175,176,177,178,179,181,184,185,187,188,190,193,194,200,202,206,207,208,209,210,214,216,220,221,224,230,231,232,233,235,236,237,238,239,242,243,245,247,249,25 0, 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, etc.

[0248] Examples of orange pigments include CI Pigment Orange 36, 38, 43, 64, 71, and 73.

[0249] 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, and 118. , 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 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, etc. Among these, CI Pigment Yellow 138, 139, 150, 185, 231, 233 are preferred.

[0250] 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 7, 36, 58, 59, 62, and 63 are preferred.

[0251] 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, 15:6, and 16 are preferred.

[0252] 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.

[0253] Examples of black pigments include CI Pigment Black 1, 6, 7, 12, 20, and 31.

[0254] Further examples include 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, iron blue, chromium oxide green, cobalt green, umber, and synthetic iron black.

[0255] The near-infrared absorbing dye is a compound having a maximum absorption in the wavelength range of 700 to 2,000 nm. Examples of the near-infrared absorbing dye include pigments (also called near-infrared absorbing pigments) and dyes (also called near-infrared absorbing dyes). The near-infrared absorbing pigment and the near-infrared absorbing dye may be used in combination. From the viewpoint of heat resistance, the near-infrared absorbing dye is preferably a near-infrared absorbing pigment. The solubility of the near-infrared absorbing pigment in 100 g of propylene glycol monomethyl ether acetate at 25° C. is preferably less than 2 g, more preferably less than 1 g, and even more preferably 0.5 g or less.

[0256] Examples of near-infrared absorbing dyes include cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, indigo compounds, immonium compounds, anthraquinone compounds, pyrrolopyrrole compounds, squarylium compounds, croconium compounds, etc. Among these, from the viewpoint of heat resistance, naphthalocyanine compounds, pyrrolopyrrole compounds, and squarylium compounds are preferred, and naphthalocyanine compounds and squarylium compounds are more preferred.

[0257] (Squarylium compounds)

[0258] Specific examples of squarylium compounds are shown below, but the present invention is not limited to these. [ka]

[0259] [ka]

[0260] (Pyrrolopyrrole compounds) The pyrrolopyrrole compound is preferably a compound represented by the following general formula (15).

[0261] General formula (15) [ka]

[0262] (In general formula (15), R 1X and R 1Y each independently represents an alkyl group, an aryl group, or a heteroaryl group; R 2 and R 3 each independently represents a hydrogen atom or a substituent, R 2 and R 3 may be bonded to each other to form a ring, R 4 represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BR 4X R 4Y or a metal atom, and R 4 is R 1X , R 1Y and R 3 R may be covalently or coordinately bonded to at least one selected from the group consisting of 4X R 4Y each independently represents a substituent. Compounds represented by general formula (15) are described in JP-A-2009-263614, JP-A-2011-68731, and WO 2015 / 166873.

[0263] Specific examples of pyrrolopyrrole compounds are shown below. In the following structural formulas, Me represents a methyl group and Ph represents a phenyl group. However, the present invention is not limited to these.

[0264] [ka]

[0265] (Naphthalocyanine compounds) The naphthalocyanine compound is preferably a compound represented by the following general formula (16).

[0266] General formula (16) [ka]

[0267] In general formula (16), R 1 ~R 24 each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 4 to 20 carbon atoms, -OR 25 or -SR 26 represents R 25 and R 26 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. R in general formula (16) 1 ~R 24 Examples of the halogen atom represented by include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0268] In general formula (16), M represents two hydrogen atoms, a metal atom, a metal oxide, or a metal halide. When M represents two hydrogen atoms, a structure is formed in which the NMN portion in general formula (16) is represented by two NH atoms. Examples of metal atoms represented by M in general formula (16) include iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium, and tin. Examples of metal oxides represented by M in general formula (16) include titanyl and vanadyl. Examples of metal halides represented by M in general formula (16) include aluminum chloride, indium chloride, germanium chloride, tin(II) chloride, tin(IV) chloride, and silicon chloride. In general formula (16), M is preferably copper, zinc, cobalt, nickel, iron, vanadyl, titanyl, indium chloride, or tin(II) chloride, more preferably copper, zinc, vanadyl, or titanyl, and particularly preferably vanadyl.

[0269] Specific examples of the compound represented by formula (16) are shown below, but the present invention is not limited to these. [ka] JPEG2025163947000088.jpg43101JPEG2025163947000089.jpg50102JPEG2025163947000090.jpg51103

[0270] The naphthalocyanine compounds represented by the general formula (16) can be used alone or in combination.

[0271] The naphthalocyanine compound represented by the general formula (16) is preferably a compound having a maximum absorption wavelength in the wavelength region of 750 to 1500 nm, more preferably a compound having a maximum absorption wavelength in the wavelength region of 780 to 1000 nm.

[0272] The naphthalocyanine compound is preferably a compound represented by the following general formula (17).

[0273] General formula (17) [ka]

[0274] In general formula (17), R 1 ~R 24 each independently represents a halogen atom, a nitro group, a nitrile group, a carboxyl group, a sulfone group, an alkyl group which may have a substituent, an aryl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, an arylthio group which may have a substituent, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, or a sulfamoyl group which may have a substituent. Z is a polymer moiety containing a monomer unit represented by general formula (18) or a phosphorus compound moiety represented by general formula (19).

[0275] [ka]

[0276] In the general formula (18), X is -CONH-R 25 -,-COO-R 26 -, -CONH-R 27 -O-, -COO-R 28 -O-, R 25 ~R 28 represents an alkylene group or an arylene group in which carbon atoms may be linked by -O-, -CO-, -COO-, -OCO-, -CONH-, or -NHCO-. 31 represents hydrogen or a methyl group. N is 0 or an integer of 1 to 10. * represents a bond to AL. In general formula (19), R 29 and R 30 each independently represents a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryloxy group which may have a substituent; R 29 and R30 may be bonded to each other to form a ring. * is a bond to AL.

[0277] Specific examples of the compound represented by formula (17) are shown below, but the present invention is not limited to these.

[0278] [ka] [ka]

[0279] The near-infrared absorbing dyes can be used alone or in combination of two or more. When using two or more dyes in combination, it is preferable to use compounds with different maximum absorption wavelengths. This broadens the absorption spectrum waveform compared to when a single near-infrared absorbing dye is used, allowing near-infrared rays to be absorbed over a wide wavelength range.

[0280] (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. Furthermore, as the dye, derivatives of these dyes or lake pigments obtained by lake-forming dyes can also be used.

[0281] The acid dye preferably contains an acidic group such as a sulfonic acid or carboxylic acid. The direct dye preferably forms an inorganic salt of the acid dye, or a salt-forming compound formed between the acid dye and 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 the acid dye and a resin component having these functional groups. Furthermore, the salt-forming compound can be sulfonamidated to modify it into a sulfonic acid amide compound, which makes it easy to obtain a photosensitive composition 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.

[0282] 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 counter ion 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.

[0283] From the viewpoint of color properties such as hue, color separation, and color unevenness, the chemical structure of the dye is preferably 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, and more preferably a dye structure derived from a dye selected from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes.

[0284] The dye (I) can be used alone or in combination of two or more kinds.

[0285] The content of the dye (I) is preferably from 0.5 to 80% by mass, more preferably from 1 to 60% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0286] (Micronization of organic pigments) It is preferable to use an organic pigment after it has been micronized. The micronization method is not particularly limited, and for example, any of wet milling, dry milling, and 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 as 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.

[0287] A resin may be added to the salt milling treatment as needed. By adding a resin, the pigment is coated with the resin, improving stability, light resistance, and the like. 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, insoluble in water, and 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.

[0288] [Pigment Derivatives (J)] The photosensitive composition of the present invention can contain a pigment derivative (J).

[0289] The pigment derivative (J) is not particularly limited, and known compounds can be used. For example, compounds having a structure in which a portion of the pigment is substituted with an acidic group, a basic group, a neutral group, or the like can be used. Specific examples include compounds having an acidic substituent such as a sulfo group, a carboxy group, or a phosphate group, and their amine salts; compounds having a basic substituent such as a sulfonamide group or a terminal tertiary amino group; and compounds having a neutral substituent such as a phenyl group or a phthalimidoalkyl group. Examples of pigments include diketopyrrolopyrrole compounds, phthalocyanine compounds, anthraquinone compounds, quinacridone compounds, dioxazine compounds, perinone compounds, perylene compounds, thiazine indigo compounds, triazine compounds, benzimidazolone compounds, benzoisoindole compounds, isoindoline compounds, isoindolinone compounds, quinophthalone compounds, naphthol compounds, squarylium compounds, threne compounds, and naphthalocyanine compounds.

[0290] The pigment derivative (J) is preferably added during the micronization of the coloring matter (I) or during the dispersion treatment of the coloring matter (I).The average primary particle size of the pigment derivative (J) is preferably 5 to 200 nm.

[0291] The pigment derivative (J) can be used alone or in combination of two or more kinds.

[0292] The content of the pigment derivative (J) is preferably from 1 to 50 parts by mass, more preferably from 2 to 40 parts by mass, relative to 100 parts by mass of the coloring matter (I).

[0293] [Dispersion resin (K)] The photosensitive composition of the present invention may contain a dispersing resin (K), which is a resin other than the alkali-soluble resin (A).

[0294] The dispersing resin (K) is preferably a resin having an adsorptive group that has a high affinity for the dye (I). The adsorptive group contains at least one of a basic group and an acidic group.

[0295] 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.

[0296] Examples of the acidic group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group.

[0297] Examples of resin types for the dispersion resin (K) 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.

[0298] Examples of the structure of the dispersing resin (K) include a random structure, a block structure, a graft structure, a comb structure, and a star structure. Among these, from the viewpoint of dispersion stability, the block structure, the graft structure, and the comb structure are preferred.

[0299] Commercially available dispersion resins (K) 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 209 manufactured by BYK Japan. 5, 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, 25000, 26000, 27000, 28000, 29000, 30000, 31000, 32000, 33000, 34000, 35000, 36000, 37000, 38000, 39000, 40000, 41000, 42000, 43000, 44000, 45000, 46000, 47000, 48000, 49000, 50000, 51000, 52000, 53000, 54000, 55000, 56000, 57000, 58000, 59000, 60000, 61000, 62000, 63000, 64000, 65000, 66000, 67000, 68000, 69000, 70000, 71000, 72000, 7 6000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc., and BASF Japan's EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400 , 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 Ajisper PA111, PB711, PB821, PB822, PB824 manufactured by Ajinomoto Fine-Techno Co., Ltd. Further, the resins described in JP 2008-029901 A, JP 2009-155406 A, JP 2010-185934 A, JP 2011-157416 A, and WO 2013175978 A, paragraphs 0122 to 0155, the resins described in JP 2019-78878 A, paragraphs 0317 to 0321, and the resins described in WO 2018 / 139534 A, paragraph 00 83, the resins described in paragraphs 0167 to 0191 of WO 2019 / 163505, the resins described in paragraphs 0299 ​​to 0310 of WO 2021 / 131927, the resins described in paragraphs 0080 to 0085 of WO 2022 / 102367, and the resins described in paragraphs 0099 to 0109 of WO 2022 / 172607.

[0300] The dispersing resin (K) can be used alone or in combination of two or more kinds.

[0301] The dispersing resin (K) is preferably a dispersing resin having basicity from the viewpoints of heat shock and drying precipitates.

[0302] The content of the dispersing resin (K) 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 dye (I).

[0303] [Organic solvent (L)] The photosensitive composition of the present invention may contain an organic solvent (L).

[0304] The organic solvent (L) is not particularly limited, and known compounds can be used, such as 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-methyl Butyl acetate, 3-methoxy-1-butanol, 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-butyl benzene, 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,Examples of the esters include dipropylene glycol dimethyl ether, 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.

[0305] 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.

[0306] The organic solvent (L) can be used alone or in combination of two or more kinds.

[0307] The content of the organic solvent (L) is preferably an amount such that the nonvolatile content of the photosensitive composition is 5 to 60% by mass.

[0308] [Leveling agent (M)] The photosensitive composition of the present invention may contain a leveling agent (M).

[0309] The leveling agent (M) is not particularly limited and known compounds can be used, such as silicone-based leveling agents, fluorine-based leveling agents, acrylic-based leveling agents, and acetylene diol-based leveling agents.

[0310] Commercially available silicone leveling agents 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, 2110, 2122, 2123, 2191, and 5609 manufactured by Toray Dow Corning Co., Ltd. Examples include 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 Silicones Co., Ltd., and TegoGlide 432, 440, and 450, and TegoWet 250, 260, 265, 270, and 280 manufactured by Evonik.

[0311] Commercially available fluorine-based leveling agents include, for example, 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.

[0312] Examples of commercially available acrylic leveling agents include BYK-350, 352, 354, 355, 358, 380, 381, 392, and 394 manufactured by BYK-Chemie, and Polyflow 57, 77, and 95 manufactured by Kyoeisha Chemical.

[0313] Commercially available acetylene diol leveling agents include, for example, Surfynol 420, 440, 465, 485, SE, DF110D, DE85, and Olfine E1004 and 1010 manufactured by Nissin Chemical Industry Co., Ltd.

[0314] The leveling agent (M) can be used alone or in combination of two or more kinds.

[0315] The content of the leveling agent (M) is preferably from 0.001 to 2.0 mass %, more preferably from 0.005 to 1.0 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0316] [Thiol-based chain transfer agents (N)] The photosensitive composition of the present invention may contain a thiol chain transfer agent (N).

[0317] Examples of the thiol chain transfer agent (N) include monofunctional thiol compounds such as thiophenol, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-benzimidazole, butanethiol, octanethiol, 1-dodecanethiol, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate, and 2-ethylhexyl 3-mercaptopropionate; hydroxyl group- or acidic group-containing monofunctional thiol compounds, such as 2-mercaptoethanol, 1-thioglycerol, thioglycolic acid, 2-mercaptobenzoic acid, 3-mercaptobenzoic acid, 4-mercaptonicotinic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 4-mercaptobutanoic acid, octyl thioglycolate, mercaptosuccinic acid, 11-mercaptoundecanoic acid, and 2-mercaptoethanesulfonic acid; Examples of polyfunctional thiol compounds 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 tetrakis thioglycolate, pentaerythritol tetrakis(3-mercaptopropionate), 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.

[0318] The thiol chain transfer agent (N) can be used alone or in combination of two or more kinds.

[0319] The content of the thiol chain transfer agent (N) is preferably 1 to 10% by mass based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0320] [Storage stabilizer (O)] The photosensitive composition of the present invention may contain a storage stabilizer (O).

[0321] The storage stabilizer (O) is not particularly limited and may be a known compound, for example, quaternary ammonium chlorides such as benzyl trimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as tert-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine, and phosphites.

[0322] The content of the storage stabilizer (O) is preferably 0.05 to 5% by mass relative to 100% by mass of the nonvolatile content of the photosensitive composition.

[0323] [Antioxidant (P)] The photosensitive composition of the present invention may contain an antioxidant (P).

[0324] Examples of commercially available hindered phenol antioxidants include ADK STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, and AO-330 manufactured by ADEKA Corporation; KEMINOX 101, 179, 76, and 9425 manufactured by Chemipro Corporation; IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, and 565 manufactured by BASF Japan Ltd.; and Cyanox CY-1790 and CY-2777 manufactured by Sun Chemical Company.

[0325] Examples of commercially available hindered amine antioxidants include ADK STAB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402F, and LA-502XP manufactured by ADEKA CORPORATION; KAMISTAB 29, 62, 77, and 94 manufactured by Chemipro Chemicals; Tinuvin 111FDL, 123, 144, 249, 292, and 5100 manufactured by BASF Japan Ltd.; and Cyasorb UV-3346, UV-3529, and UV-3853 manufactured by Sun Chemical Company.

[0326] Commercially available phosphorus-based antioxidants include, for example, Adeka STAB PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, and TPP manufactured by ADEKA CORPORATION, IRGAFOS168 manufactured by BASF Japan Ltd., and HostanoxP-EPQ manufactured by Clariant Chemicals.

[0327] Examples of commercially available sulfur-based antioxidants include Adekastab AO-412S and AO-503 manufactured by ADEKA Corporation, and KEMINOXPLS manufactured by Chemipro Chemicals.

[0328] The antioxidant (P) can be used alone or in combination of two or more kinds.

[0329] The content of the antioxidant (P) is preferably 0.5 to 5.0% by mass relative to 100% by mass of the nonvolatile content of the photosensitive composition.

[0330] [Sensitizer (Q)] The photosensitive composition of the present invention may contain a sensitizer (Q).

[0331] Examples of the sensitizer (Q) include unsaturated ketones typified by dibenzalacetone, 1,2-diketone compounds typified by benzil and camphorquinone, benzoin compounds, fluorene compounds, naphthoquinone compounds, anthraquinone compounds, anthracene compounds, xanthene compounds, thioxanthene compounds, xanthone compounds, thioxanthone compounds, coumarin compounds, ketocoumarin compounds, cyanine compounds, merocyanine compounds, and polymethine dyes such as oxonol compounds, acridine compounds, azine compounds, thiazine compounds, oxazine compounds, indoline compounds, azulene compounds, and azides. Examples thereof include rhenium-based compounds, squarylium-based compounds, porphyrin-based compounds, tetraphenylporphyrin-based compounds, triarylmethane-based compounds, tetrabenzoporphyrin-based compounds, tetrapyrazinoporphyrazine-based compounds, phthalocyanine-based compounds, tetraazaporphyrazine-based compounds, tetraquinoxalylporphyrazine-based compounds, naphthalocyanine-based compounds, subphthalocyanine-based compounds, pyrylium-based compounds, thiopyrylium-based compounds, tetraphyrin-based compounds, annulene-based compounds, spiropyran-based compounds, spirooxazine-based compounds, thiospiropyran-based compounds, metal arene complexes, and organic ruthenium complexes. Among these, thioxanthone compounds are preferred.

[0332] Examples of thioxanthone compounds include 2-isopropylthioxanthone and 2,4-diethylthioxanthone. Commercially available products include Kayacure DETX-S manufactured by Nippon Kayaku Co., Ltd., Omnirad ITX manufactured by IGM Resins, and SpeedCure 7010 manufactured by Arkema. Examples of anthracene compounds include UVS-1331 manufactured by Kawasaki Kasei Chemicals, Ltd.

[0333] The sensitizer (Q) can be used alone or in combination of two or more kinds.

[0334] As the sensitizer (Q), from the viewpoints of outgassing and solvent resistance at low temperature heating, thioxanthone compounds and anthracene compounds are preferred, and thioxanthone compounds are more preferred.

[0335] The mass ratio of the photopolymerization initiator (C1) to the sensitizer (Q) is preferably from 95:5 to 5:95, more preferably from 95:5 to 50:50, and even more preferably from 95:5 to 75:25, from the viewpoints of outgassing and solvent resistance at low temperature heating.

[0336] The photosensitive composition of the present invention may contain components other than those described above. Examples of other components include an acid generator, a salt generator, and a curing catalyst. The content of the other components can be appropriately set within a range that does not impair the effects of the present invention.

[0337] [Specific metal element content] The photosensitive composition of the present invention preferably contains 500 mass ppm or less of Li, Na, K, Mg, Ca, Fe, and Cr (hereinafter also referred to as specific metal elements) in total.

[0338] A photosensitive composition in which the total amount of the specific metal elements is within the above range has excellent dispersion stability and sensitivity even after storage over time. The content of the specific metal elements can be measured by inductively coupled plasma atomic emission spectrometry (ICP).

[0339] [Water content] The photosensitive composition of the present invention preferably has a water content of 2.0% by mass or less. Photosensitive compositions with a water content within the above range have excellent dispersion stability and sensitivity even after storage over time. The water content can be measured by a known method such as the Karl Fischer method.

[0340] [Method for producing photosensitive composition] The photosensitive composition of the present invention can be produced by mixing the above-mentioned components. During production, the components may be mixed together, or the components may be dissolved or dispersed in the polymerizable compound (B) or the organic solvent (L) and then mixed sequentially. When a pigment is used as the coloring matter (I), it is preferable to disperse the pigment. For example, a dispersion is produced by adding a dye (I), a dispersing resin (K), an organic solvent (L), and the like and performing a dispersion process. The dispersion is then blended with an alkali-soluble resin (A), a polymerizable compound (B), a photopolymerization initiator (C), a thermal polymerization initiator (D), a thermally crosslinkable compound (E), and the like, and mixed to produce the dispersion. The timing of blending each material is optional. The dispersion process can also be performed multiple times.

[0341] 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.

[0342] The average dispersed particle size (secondary particle size) of the pigment particles in the dispersion is preferably 30 to 200 nm, more preferably 40 to 200 nm. If the particle size is appropriate, a photosensitive composition with high dispersion stability is easily obtained.

[0343] 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). The conditions are particle permeability in absorption mode, particle shape aspherical, and the D50 particle size as the average diameter. The organic solvent used for dispersion is used as the dilution solvent for measurement, and measurements are taken on ultrasonically treated samples immediately after sample preparation to obtain results with little variation.

[0344] 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 contaminated dust, 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.

[0345] The photosensitive composition of the present invention is preferably used for pattern formation by photolithography, although the present invention is not limited thereto.

[0346] <Membrane> The film of the present invention is a film formed from the above-mentioned photosensitive composition. The film is preferably a patterned film, but can also be used as a flat film without forming a pattern.

[0347] [Membrane manufacturing method] The method for producing the film is not particularly limited, and any known method can be used. For example, the film can be produced by applying the colored composition of the present invention onto a substrate and drying the applied composition.

[0348] [Coating process] Examples of the substrate include substrates made of materials such as glass, resin, and silicone. The glass may be colorless and transparent, or colored glass such as blue glass may be used depending on the application. Examples of the resin include polyester-based resins such as polyester terephthalate, polyolefin-based resins such as polypropylene and polyethylene, polycarbonate resins, and epoxy resins. The thickness of the substrate is preferably 0.01 to 10 mm. An organic light-emitting layer may be formed on these substrates. Furthermore, an imaging device such as a CCD or CMOS may be formed on the substrate. Furthermore, an undercoat layer may be provided on the substrate, if necessary, to improve adhesion with the upper layer, prevent diffusion of substances, and flatten the surface.

[0349] Any known coating method can be used, such as a dropping method, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, an inkjet method, flexographic printing, screen printing, gravure printing, or offset printing.

[0350] The thickness of the film can be adjusted appropriately depending on the purpose, and is preferably 0.05 to 20.0 μm, more preferably 0.3 to 10.0 μm.

[0351] [Drying process] The method for drying the film coated on the substrate is not particularly limited, and known methods can be used, such as reduced pressure drying using a vacuum drying device, heat drying using a hot plate, an IR oven, a convection oven, or the like, and a combination of these methods.

[0352] The drying temperature and time can be adjusted as appropriate. The drying temperature is preferably about 50 to 130°C, and the drying time is preferably about 5 seconds to 5 minutes.

[0353] Next, a pattern is formed. Examples of a method for forming a pattern include photolithography and dry etching. Among these, photolithography is preferred. When the film is used as a flat film, the step of forming a pattern is not carried out, and after coating, the film is dried or the entire surface is exposed to light as necessary.

[0354] The method of forming a pattern by photolithography will be described in detail below. In the photolithography method, the photosensitive composition of the present invention is applied to a substrate, the layer formed by drying is exposed to light in a pattern through a mask (exposure step), the unexposed portions are removed by alkaline development (development step), and the pattern is then heat-treated (post-bake step).

[0355] [Exposure process] In the exposure process, the layer formed by coating and drying is exposed to a specific pattern through a mask using an exposure device such as a stepper. This allows the exposed area to harden. Examples of active energy rays 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). When using light with a specific wavelength, an optical filter can also be used. The exposure may be performed by continuous irradiation with light, or by repeated irradiation and pause in a short cycle (for example, milliseconds or less) (pulse exposure). Furthermore, a plurality of active energy rays may be used in combination, or exposure may be performed in multiple steps.

[0356] [Development process] Next, an alkaline development treatment is carried out, whereby the unexposed portions of the layer are dissolved in the alkaline developer, leaving only the hardened portions, thereby obtaining a patterned film. Examples of alkaline developers include aqueous solutions containing 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. Two or more of these alkaline compounds can be used in combination. The alkaline developer may contain a surfactant and an organic solvent in addition to the alkaline compound and water. The concentration of the alkaline developer is preferably 0.001 to 10% by mass, more preferably 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, pattern roughening and peeling are suppressed, and the remaining film rate after development is improved. 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.

[0357] [Post-baking process] After development, a heat treatment (post-baking) is performed, which improves the film's resistance. The temperature is preferably 80 to 300°C, more preferably 100 to 260°C. The time is preferably about 2 minutes to 2 hours. When a material with low heat resistance is used for the substrate, when a substrate having an organic electroluminescence element as the light-emitting layer is used, or from an environmental viewpoint, the temperature is preferably 180°C or less.

[0358] <Optical filters> The optical filter of the present invention has the above-mentioned film. The optical filter is used, for example, as a clear filter, a color filter, a black matrix, a light-shielding filter, an anti-reflection filter, an infrared cut filter, an infrared transmission filter, etc. The optical filter of the present invention can be produced by the same method as the above-mentioned film.

[0359] <Solid-state imaging element> The solid-state imaging device of the present invention has the above optical filter. The solid-state imaging device is not particularly limited as long as it has the optical filter of the present invention and functions as a solid-state imaging device, and examples thereof include the following configurations.

[0360] The present invention is configured to include a substrate having a plurality of photodiodes constituting the light-receiving area of ​​a solid-state imaging device (e.g., a CCD image sensor, a CMOS image sensor, etc.) and transfer electrodes made of polysilicon or the like; a light-shielding film, which is open only to the light-receiving portions of the photodiodes, on the photodiodes and transfer electrodes; a device protection film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire light-shielding film and the light-receiving portions of the photodiodes; and an optical filter (color filter) of the present invention on the device protection film. Furthermore, the present invention may also be configured to include a light-focusing means (e.g., a microlens, etc.; the same applies hereinafter) on the device protection film below the optical filter (closer to the substrate), or to include a light-focusing means on the optical 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 lattice pattern. In this case, the partition walls preferably have a low refractive index relative to each color pixel. 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, and surveillance cameras.

[0361] <Image display device> The image display device of the present invention includes the optical filter. Examples of the image display device include a liquid crystal display and an organic EL display. The form of the image display device is not particularly limited as long as it functions as an image display device. For example, the following liquid crystal display configurations can be mentioned.

[0362] A liquid crystal display includes a color filter, a counter substrate having a TFT array substrate or the like, and a liquid crystal layer formed between the color filter and the counter substrate. Examples of driving methods for liquid crystal displays include TN, IPS, OCB, and MVA. The counter substrate can be appropriately selected depending on the driving method. The liquid crystal layer can use various liquid crystals with different dielectric anisotropies, or mixtures thereof, depending on the driving method.

[0363] Specifically, it is described in "Next Generation Liquid Crystal Display Technology" (by Uchida Tatsuo, published by Kogyo Chosakai Co., Ltd. in 1994), "Electronic Display Devices" (by Sasaki Akio, published by Kogyo Chosakai Co., Ltd. in 1990), and "Display Devices" (by Ibuki Nobuaki, published by Sangyo Tosho Co., Ltd. in 1989).

[0364] <Infrared sensor> The infrared sensor of the present invention has the above optical filter. The form of the infrared sensor is not particularly limited as long as it has the optical filter of the present invention and functions as an infrared sensor, and examples thereof include the following configurations.

[0365] A substrate has a plurality of photodiodes constituting the light receiving area of ​​a solid-state imaging device (such as a CCD image sensor or a CMOS image sensor) and transfer electrodes made of polysilicon or the like. A light-shielding film, which is open only in the light receiving portions of the photodiodes, is placed on the photodiodes and transfer electrodes. A device protective film is placed on this light-shielding film, and the optical filter of the present invention is placed on this device protective film. Furthermore, the device protective film may have a light-collecting means (e.g., a microlens, etc.; the same applies below) on the device protective film and below the optical filter (on the side closer to the substrate), or the light-collecting means may be placed on the optical filter.

[0366] 1 is a schematic cross-sectional view showing an example of the configuration of an infrared sensor equipped with an optical filter of the present invention, which includes an infrared sensor 100 shown in FIG.

[0367] The imaging area provided on the solid-state imaging element 110 is configured by combining an infrared cut filter 111 and a color filter 112 .

[0368] The infrared cut filter 111 transmits light in the visible light range (for example, light with a wavelength of 400 to 700 nm) and blocks light in the infrared range (for example, light with a wavelength of 800 to 1,300 nm).

[0369] The color filter 112 is a color filter formed with pixels that transmit and absorb light of specific wavelengths in the visible light range. For example, a color filter formed with red (R), green (G), and blue (B) pixels is used.

[0370] Between the infrared transmission filter 113 and the solid-state imaging element 110, a resin film 114 that is capable of transmitting light of a wavelength that has passed through the infrared transmission filter 113 is disposed.

[0371] The infrared transmission filter 113 is a filter that has a visible light blocking property and transmits infrared rays of a specific wavelength. The infrared transmission filter 113 preferably blocks light with a wavelength of 400 to 830 nm and transmits light with a wavelength of 900 to 1,300 nm, for example.

[0372] A microlens 115 is disposed on the incident light h side of the color filter 112 and the infrared transmission filter 113. A planarization film 116 is formed to cover the microlens 115.

[0373] In the embodiment shown in FIG. 1, the resin film 114 is disposed, but instead of the resin film 114, an infrared transmission filter 113 may be formed.

[0374] This infrared sensor can simultaneously capture image information, enabling motion sensing that recognizes the movement of an object. It can also acquire distance information, enabling it to capture images that include 3D information. Furthermore, this infrared sensor can also be used as a biometric authentication sensor. [Example]

[0375] 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." Furthermore, in the present invention, the nonvolatile content or nonvolatile content concentration refers to the mass residue after leaving the composition in an oven at 120°C for 60 minutes.

[0376] <Production of alkali-soluble resin (A)> (Solution of alkali-soluble resin (A1-1) having monomer unit (a1) whose homopolymer has a glass transition temperature of 0°C or lower) 262.0 parts of propylene glycol monomethyl ether acetate (hereinafter, PGMAc) was placed in a reaction vessel equipped with a separable four-neck flask thermometer, a condenser, a nitrogen gas inlet tube, and a stirrer, and the vessel was heated to 120°C while nitrogen gas was injected into the vessel. At the same temperature, a mixture of 49.7 parts of 2-ethylhexyl acrylate (hereinafter, 2-EHA), 99.4 parts of glycidyl methacrylate (hereinafter, GMA), 6.6 parts of dicyclopentanyl methacrylate, 19.0 parts of t-butylperoxy-2-ethylhexanoate as a polymerization initiator, and PGMAc was added dropwise from the dropping tube over 2.5 hours to carry out a reaction. After the dropwise addition was completed, the mixture was stirred for another 2 hours at 120°C to carry out the reaction, yielding a precursor. The atmosphere in the flask was then replaced with air, and 50.4 parts of acrylic acid (hereinafter referred to as AA) as a modifying compound, 0.6 parts of triphenylphosphine as catalysts, and 0.2 parts of methylhydroquinone were added, followed by a reaction at 110°C for 10 hours. This yielded a monomer unit (hereinafter referred to as GMA+AA) in which the epoxy group of GMA reacted with the carboxyl group of AA, and introduced the polymerizable unsaturated group-containing monomer unit (a2). Next, 21.3 parts of tetrahydrophthalic anhydride (hereinafter referred to as THPA) was added as a modifying compound, and the mixture was allowed to react at 110°C for 4 hours. This allowed some of the hydroxyl groups of GMA+AA to react with THPA. PGMAc was then added so that the nonvolatile content was 30% by mass, to prepare an alkali-soluble resin (A1-1) solution containing a monomer unit (a1) whose homopolymer glass transition temperature was 0°C or lower. The alkali-soluble resin (A1-1) had an acid value of 38 mgKOH / g and a weight-average molecular weight of 12,000. The blending amounts in Table 1 are expressed in mol%.

[0377] (Alkali-soluble resin (A1-2) to (A1-7) solutions) As with the alkali-soluble resin (A1-1), alkali-soluble resins (A1-2) to (A1-7) were synthesized by varying the type and amount of monomer and the amount of polymerization initiator so as to achieve the composition ratio and weight-average molecular weight shown in Table 1, and PGMAc was added to adjust the non-volatile content to 30 mass%.

[0378] [Table 1]

[0379] GMA+AA+SHA in Table 1 represents a polymerizable unsaturated group-containing monomer unit (a2) obtained by reacting some of the hydroxyl groups of GMA+AA with succinic anhydride (hereinafter, SHA).

[0380] (Solution of alkali-soluble resin (A2-1) having blocked isocyanate group-containing monomer unit (a7)) A flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube was charged with 100 parts of PGMAc, and the mixture was stirred while purging with nitrogen and heated to 78 ° C. Next, a mixture of 25.2 parts of Karenz MOI-DEM (2-[[[[(2-methyl-1-oxo-2-propenyl)oxy]ethyl]amino]carbonyl]-1,3-diethyl ester of malonic acid, manufactured by Resonac Corporation), 31.2 parts of 2-hydroxyethyl methacrylate, 37.5 parts of dicyclopentanyl methacrylate, 20.7 parts of methacrylic acid, and 27.0 parts of methyl methacrylate, and a mixture of 12.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) dissolved in 50 parts of PGMAc were added dropwise from the dropping funnel to the flask, and the reaction was carried out. After the dropwise addition was completed, the reaction was continued with stirring at 78 ° C for 3 hours. Then, PGMAc was added so that the nonvolatile content was 30% by mass, to prepare an alkali-soluble resin (A2-1) solution having a blocked isocyanate group-containing monomer unit (a7). The alkali-soluble resin (A2-1) had an acid value of 74 mg KOH / g and a weight-average molecular weight of 8,000. The blending amounts in Table 2 are expressed in mol%.

[0381] (Alkali-soluble resin (A2-2) to (A2-6) solutions) As with the alkali-soluble resin (A2-1), alkali-soluble resins (A2-2) to (A2-6) were synthesized by varying the type and amount of monomer and the amount of polymerization initiator used so as to achieve the composition ratio and weight-average molecular weight shown in Table 2, and PGMAc was added to adjust the non-volatile content to 30 mass%.

[0382] [Table 2]

[0383] Karenz MOI-BP listed in Table 2 is 2-(3,5-diethylpyrazol-1-yl)carbonylaminoethyl methacrylate manufactured by Resonac, and Karenz MOI-BM is 2-[O-(1'-methylpropylideneamino)carboxyamino]ethyl methacrylate manufactured by Resonac.

[0384] (Alkali-soluble resin (A3-1) solution) A separable four-neck flask equipped with a thermometer, condenser, nitrogen gas inlet, dropping tube, and stirrer was charged with 196 parts of cyclohexanone and heated to 80°C while stirring. The atmosphere inside the reaction vessel was then replaced with nitrogen. A mixture of 20.2 parts of methacrylic acid, 21.8 parts of 2-hydroxyethyl methacrylate, 38.9 parts of Aronix M-110 (a paracumylphenol EO-modified acrylate manufactured by Toagosei Co., Ltd.), 35.8 parts of n-butyl methacrylate, 39.0 parts of benzyl methacrylate, and 1.0 part of 2,2'-azobisisobutyronitrile (polymerization initiator) was added dropwise over two hours via the dropping tube to allow the reaction to proceed. After the addition was complete, the reaction was continued for an additional three hours. PGMAc was then added to achieve a nonvolatile content of 30% by mass. The alkali-soluble resin (A3-1) had an acid value of 81 mgKOH / g and a weight-average molecular weight of 28,000. In Table 3, the blending amounts are expressed in mol %.

[0385] (Alkali-soluble resin (A3-2) and (A3-3) solutions) As with the alkali-soluble resin (A3-1), alkali-soluble resins (A3-2) and (A3-3) were synthesized by varying the type and amount of monomer and the amount of polymerization initiator used so as to achieve the composition ratio and weight-average molecular weight shown in Table 3, and PGMAc was added to adjust the non-volatile content to 30 mass%.

[0386] [Table 3]

[0387] <(Production of Blocked Isocyanate Group-Containing Compound (E1)> (Production of Blocked Isocyanate Group-Containing Compound E1-1) A four-neck flask equipped with a thermometer, stirring blade, and reflux condenser was charged with 100 parts by mass of hexamethylene diisocyanate (hereinafter referred to as HDI) under a nitrogen stream. The temperature inside the reactor was maintained at 60°C with stirring, and 0.095 parts by mass of trimethylbenzylammonium hydroxide was added to carry out the reaction. After 4.5 hours, when the conversion rate reached 40% by mass, 0.02 parts by mass of phosphoric acid was added to terminate the reaction. The reaction solution was filtered, and unreacted HDI was removed using a thin-film evaporator to obtain an isocyanurate-type polyisocyanate (hereinafter referred to as "E1 precursor"). The NCO content of the obtained E1-1 precursor was 22.0% by mass, the number-average molecular weight was 655, and the average number of isocyanate groups was 3.43. Furthermore, the obtained E1 precursor 1 H-NMR analysis confirmed the presence of isocyanurate groups. A four-neck flask equipped with a thermometer, a stirring blade, and a reflux condenser was charged with 100 parts by mass of the E1 precursor and diethyl malonate (100 mol% relative to 100 mol% of NCO groups) under a nitrogen stream, and butyl acetate was added to adjust the nonvolatile content to 60% by mass. Next, 1.0 part by mass of a methanol solution containing sodium methylate (28% by mass relative to the total mass of the solution) was added dropwise with stirring, and the external bath was adjusted so that the solution temperature was 55°C. A blocking reaction was carried out at 55°C for 5 hours to obtain a blocked isocyanate group-containing compound E1-1 with a nonvolatile content of 60% by mass and containing the blocked isocyanate group (X-1).

[0388] (Production of Blocked Isocyanate Group-Containing Compound E1-2) A four-neck flask equipped with a thermometer, a stirring blade, and a reflux condenser was charged with 100 parts by mass of the E1 precursor, diethyl malonate (70 mol% relative to 100 mol% of NCO groups), and dibutyl malonate (30 mol% relative to 100 mol% of NCO groups) under a nitrogen stream. Butyl acetate was then added to adjust the nonvolatile content to 60% by mass. Next, 1.0 part by mass of a methanol solution containing sodium methylate (28% by mass relative to the total mass of the solution) was added dropwise with stirring. The external bath was then adjusted to a solution temperature of 55°C, and the blocking reaction was carried out at 55°C for 5 hours to obtain a blocked isocyanate group-containing compound E1-2 containing the above (X-1) and (X-8) in a molar ratio of 70:30 as blocked isocyanate groups with a nonvolatile content of 60% by mass.

[0389] (Production of Blocked Isocyanate Group-Containing Compound E1-3) A four-neck flask equipped with a thermometer, a stirring blade, and a reflux condenser was charged with 100 parts by mass of the E1 precursor, diethyl malonate (30 mol% relative to 100 mol% of NCO groups), and dibutyl malonate (70 mol% relative to 100 mol% of NCO groups) under a nitrogen stream. Butyl acetate was then added to adjust the nonvolatile content to 60% by mass. Next, 1.0 part by mass of a methanol solution containing sodium methylate (28% by mass relative to the total mass of the solution) was added dropwise with stirring. The external bath was then adjusted to a solution temperature of 55°C, and the blocking reaction was carried out at 55°C for 5 hours to obtain a blocked isocyanate group-containing compound E1-3 with a nonvolatile content of 60% by mass and containing the blocked isocyanate groups (X-1) and (X-8) in a molar ratio of 30:70.

[0390] (Production of Blocked Isocyanate Group-Containing Compound E1-4) A four-necked flask equipped with a thermometer, a stirring blade, and a reflux condenser was charged with 100 parts by weight of E1 precursor, diisopropyl malonate (70 mol% relative to 100 mol% of NCO groups), and di-tert-butyl malonate (30 mol% relative to 100 mol% of NCO groups) under a nitrogen stream. Butyl acetate was added to adjust the nonvolatile content to 60% by weight. Next, 1.0 part by weight of a methanol solution containing sodium methylate (28% by weight relative to the total weight of the solution) was added dropwise with stirring. The external bath was then adjusted to a solution temperature of 55°C. The blocking reaction was carried out at 55°C for 5 hours to obtain a blocked isocyanate group-containing compound E1-4 with a nonvolatile content of 60% by weight and containing the blocked isocyanate groups (X-4) and (X-7) in a molar ratio of 70:30.

[0391] <Production of Silane Coupling Agent (F)> (Compound (F1-1)) A 1-L separable flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer was charged with 116 parts of hydroxyethyl acrylate and heated to 80°C while stirring. 205 parts of 3-isocyanatopropyltrimethoxysilane was added dropwise thereto, and the mixture was allowed to react at 80°C for 4 hours. Subsequently, IR measurement confirmed that the absorption peaks derived from the isocyanate groups of the raw material had completely disappeared, and instead, absorption peaks derived from urethane bonds had appeared, yielding compound (F1-1) whose main component is represented by the following chemical formula (13). Note that the compound also contained a dimer to decamer (a compound in which n is 2 to 10 in general formula (56)), which is a condensation product of chemical formula (13), as a minor component.

[0392] Chemical formula (13) [ka]

[0393] (Compound (F1-2)) A 1-L separable flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer was charged with 524 parts of dipentaerythritol pentaacrylate and heated to 80°C with stirring. 205 parts of 3-isocyanatopropyltrimethoxysilane was added dropwise, and the mixture was allowed to react at 80°C for 4 hours. Subsequently, IR measurement confirmed that the absorption peaks derived from the isocyanate groups of the raw material had completely disappeared, and instead, absorption peaks derived from urethane bonds had appeared, yielding compound (F1-2) whose main component is represented by the following chemical formula (14). Note that a dimer to decamer (a compound in which n is 2 to 10 in general formula (56)), which is a condensation product of chemical formula (14), was included as a minor component.

[0394] Chemical formula (14) [ka]

[0395] (Compound (F1-3)) A 1-L separable flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer was charged with 298 parts of pentaerythritol triacrylate and heated to 80°C with stirring. 205 parts of 3-isocyanatopropyltrimethoxysilane was added dropwise thereto, and the mixture was allowed to react at 80°C for 4 hours. Subsequently, IR measurement confirmed that the absorption peaks derived from the isocyanate groups of the raw material had completely disappeared, and instead, absorption peaks derived from urethane bonds had appeared, yielding compound (F1-3) whose main component is represented by the following chemical formula (15). Note that the compound also contained a dimer to decamer (a compound in which n is 2 to 10 in general formula (56)), a condensate of chemical formula (15), as a minor component.

[0396] Chemical formula (15) [ka]

[0397] (Compound (F1-4)) A 1-L separable flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer was charged with 116 parts of hydroxyethyl acrylate and heated to 80°C while stirring. 247 parts of 3-isocyanatopropyltriethoxysilane was added dropwise, and the mixture was allowed to react at 80°C for 4 hours. Subsequently, IR measurement confirmed that the absorption peaks derived from the isocyanate groups of the raw material had completely disappeared, and instead, absorption peaks derived from urethane bonds had appeared, yielding compound (F1-4) whose main component is represented by the following chemical formula (16). Note that the compound contains, as a minor component, a dimer to decamer (a compound in which n is 2 to 10 in general formula (56)), which is a condensation product of chemical formula (16).

[0398] Chemical formula (16) [ka]

[0399] The compounds (F1-1) to (F1-4) are compounds (F1) having an alkoxysilyl group, a (meth)acryloyl group, and a urethane bond.

[0400] <Production of dye (I)> (yellow pigment (y)) In a reaction vessel, 46.2 parts of diazobarbituric acid and 38.4 parts of barbituric acid were added to 1,100 parts of distilled water at 85° C. Next, an aqueous potassium hydroxide solution was added to adjust the pH to about 5, and the mixture was stirred for 90 minutes to synthesize an azobarbituric acid precursor. 0.3 mol of the resulting azobarbituric acid precursor was mixed with 1,500 parts of distilled water at 82°C, and 10 parts of 30% hydrochloric acid was added dropwise, followed by the addition of 0.6 mol of melamine. Next, 0.195 mol of nickel chloride solution, 0.09 mol of zinc chloride solution, and 0.015 mol of copper chloride solution were mixed and added dropwise, and the mixture was stirred at 82°C for 3 hours to carry out the reaction. Potassium hydroxide was then added to adjust the pH to approximately 5.2, and 100 parts of distilled water was added and the mixture was heated to 90°C. Next, 21 parts of 30% hydrochloric acid were added dropwise, and the mixture was stirred for 12 hours to carry out the reaction. Potassium hydroxide was then added to adjust the pH to approximately 5, and the product was then filtered to remove the product. The product was washed with ion-exchanged water and filtered. After drying at 80°C, it was pulverized to obtain a yellow pigment (y) having a Ni, Zn, and Cu molar ratio of 65:30:5.

[0401] <Production of near-infrared absorbing dye> (Production of near-infrared absorbing dye (1)) A near-infrared absorbing dye (1) represented by the following chemical formula (400) was obtained by the method described in JP-A-2022-96687.

[0402] Chemical formula (400) [ka]

[0403] (Production of near-infrared absorbing dye (2)) A near-infrared absorbing dye (2) represented by the following chemical formula (401) was obtained by the method described in JP-A-2022-96687.

[0404] Chemical formula (401) [ka]

[0405] (Production of near-infrared absorbing dyes (31), (32), and (33)) By the method described in JP 2022-72558 A, a micronized near-infrared absorbing dye (31) represented by the following chemical formula (403), a near-infrared absorbing dye (32) represented by the following chemical formula (404), and a near-infrared absorbing dye (33) represented by the following chemical formula (405) were obtained.

[0406] [ka]

[0407] Near-infrared absorbing dyes (31) to (33) were mixed in a ratio of 1:1:1 to obtain near-infrared absorbing dye (3).

[0408] (Production of near-infrared absorbing dye (4)) According to the description in WO 2019 / 058882, a near-infrared absorbing dye (4) represented by chemical formula (406) was obtained.

[0409] Chemical formula (406) [ka]

[0410] <Production of Dispersion Resin (K)> (Acidic group-containing dispersion resin (K-1) solution) A reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer was charged with 10 parts methacrylic acid, 100 parts methyl methacrylate, 70 parts iso-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 more than 95% had reacted. 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. After cooling, PGMAc was added so that the nonvolatile content was 30% by mass, and an acidic group-containing dispersion resin (K-1) solution was obtained. The acid value was 70 mg KOH / g and the weight-average molecular weight was 8,500.

[0411] (Dispersion resin (K-2) solution having basic groups) A reactor equipped with a gas inlet tube, condenser, stirring blade, and thermometer was charged with 40 parts of methyl methacrylate, 10 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine as a catalyst. The mixture was stirred at 50 °C for 1 hour under a nitrogen stream, and the system was then purged with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate as an initiator, 5.6 parts of cuprous chloride as a catalyst, and 100 parts of PGMAc were added. 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 was taken of the polymerization solution and the nonvolatile content was measured. Based on the nonvolatile content, the polymerization conversion was confirmed to be 98% or higher. Next, 50 parts of PGMAc, 40 parts of dimethylaminoethyl methacrylate as a second block (A block) monomer, and 10 parts of methacryloyloxyethyl benzyl dimethyl ammonium chloride were added to the reactor. The reaction was continued at 110 °C under a nitrogen atmosphere with stirring. Two hours after addition, the polymerization solution was sampled 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. After cooling, PGMAc was added to the solution so that the nonvolatile content reached 30% by mass, yielding a dispersion resin (K-2) solution with basic groups. The amine value was 169.8 mg KOH / g. <Preparation of Dispersion> (Dispersion 1) The following raw materials were mixed and stirred until uniform, and then dispersed in an Eiger mill (Eiger Japan Co., Ltd., "Mini Model M-250 MKII") using zirconia beads with a diameter of 0.5 mm for 3 hours, followed by filtration through a filter with a pore size of 1.0 μm to produce Dispersion 1. The nonvolatile content was 20% by mass. Red pigment (I-1): 14.0 parts Dispersion resin (K-1) solution: 16.7 parts Pigment derivative (J-4): 1.0 part Organic solvent (propylene glycol monomethyl ether acetate): 68.3 parts

[0412] (Dispersion 2~19) Dispersions 2 to 19 were produced in the same manner as Dispersion 1, except that the raw materials and amounts were changed as shown in Tables 4 to 6. The values ​​in the tables indicate the non-volatile content ratio. The solvent was PGMAc in all cases, and the non-volatile content of Dispersions 2 to 19 was 20%.

[0413] [Table 4]

[0414] [Table 5]

[0415] [Table 6]

[0416] The components listed in Tables 4 to 6 are as follows.

[0417] [Dye (I)] (red pigment) I-1: CI Pigment Red 177 (Shinic, "Shinilex Red SR3C") I-2: CI Pigment Red 254 (BASF Japan, "Irgajin Red L 3630") I-3: CI Pigment Red 264 (BASF Japan, "Irgazin Rubin L4025") (green pigment) I-4: CI Pigment Green 36 (Toyo Color Co., Ltd., "Lionol Green 6YK") I-5: CI Pigment Green 58 (DIC, FASTOGEN Green A110) I-6: CI Pigment Green 59 (DIC) I-7: CI Pigment Green 62 (Toyo Color Co., Ltd.) I-8: CI Pigment Green 63 (manufactured by Toyo Color Co., Ltd.) (blue pigment) I-9: CI Pigment Blue 15:3 (Toyo Color Co., Ltd., "Lionor Blue FG7351") I-10: CI Pigment Blue 15:6 (manufactured by Toyo Color Co., Ltd., "Lionol Blue ES") (purple pigment) I-11: CI Pigment Violet 23 (manufactured by Toyo Color Co., Ltd., "Lionogen Violet FG6140") (yellow pigment) I-12: CI Pigment Yellow 138 (BASF Japan, "Paliothol Yellow K0960-HD") I-13: CI Pigment Yellow 139 (BASF Japan, "Paliotol Yellow D1819") I-14: CI Pigment Yellow 150 (LANXESS, "Yellow Pigment E4GN") I-15: CI Pigment Yellow 231 (Toyo Color Co., Ltd.) I-16: The yellow pigment (y) (near infrared absorbing dye) I-17: The near-infrared absorbing dye (1) I-18: Near-infrared absorbing dye (2) I-19: Near-infrared absorbing dye (3) I-20: The near-infrared absorbing dye (4)

[0418] The dyes (I-1) to (I-20) were all pulverized by salt milling, thoroughly washed, and dried before use.

[0419] [Pigment Derivatives (J)] [ka]

[0420] <Production of Photosensitive Composition> [Example 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 having a nonvolatile content of 15%. Dispersion 1: 0.32 parts Dispersion 6: 18.96 parts Dispersion 11: 6.43 parts Dispersion 12: 6.43 parts Alkali-soluble resin (A1-1) solution: 8.01 parts Polymerizable compound (B-1): 1.50 parts Polymerizable compound (B-2): 1.50 parts Photopolymerization initiator (C1-1): 0.30 parts Thermal polymerization initiator (D1-1): 0.45 parts Blocked isocyanate group-containing compound (E1-1): 2.50 parts Epoxy compound (E2-1): 0.75 parts Silane coupling agent (F1-1): 0.75 parts UV absorber (G-1): 0.15 parts Polymerization inhibitor (H-1): 0.0075 parts Leveling agent (M-1): 1.00 parts Organic solvent (L-1): 50.94 parts

[0421] [Examples 2 to 86 and Comparative Example 1] Photosensitive compositions were prepared in the same manner as in Example 1, except that the raw materials and amounts shown in Tables 7 to 15 were used instead of the photosensitive composition of Example 1.

[0422] [Table 7]

[0423] [Table 8]

[0424] [Table 9]

[0425] [Table 10]

[0426] [Table 11]

[0427] [Table 12]

[0428] [Table 13]

[0429] [Table 14]

[0430] [Table 15]

[0431] In Tables 7 to 15, resin (A1) refers to an alkali-soluble resin (A1) having a monomer unit (a1) whose homopolymer glass transition temperature is 0°C or lower. Resin (A2) refers to an alkali-soluble resin (A2) having a blocked isocyanate group-containing monomer unit (a7). Photopolymerization initiator (C1) refers to a photopolymerization initiator (C1) represented by general formula (1). Photopolymerization initiator (C2a) refers to an oxime ester photopolymerization initiator (C2a). Photopolymerization initiator (C2b) refers to other photopolymerization initiators (C2b).

[0432] (Polymerizable compound (B)) B-1: CN9906NS (Arkema, tertiary amine-containing aliphatic multifunctional urethane acrylate; amine-containing polymerizable compound (B1)) B-2: Aronix M-306 (manufactured by Toagosei Co., Ltd., a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate; hydroxyl group-containing polymerizable compound (B2)) B-3: Aronix M-520 (manufactured by Toagosei Co., Ltd., polybasic acid-modified acrylic oligomer; acidic group-containing polymerizable compound (B3)) B-4: KAYARAD DPCA-30 (Nippon Kayaku Co., Ltd., lactone-modified polymerizable compound (B4)) B-5: UA-306H (Kyoeisha Chemical Co., Ltd., acrylate (B5) with urethane bond) B-6: Miramer SP-1106 (manufactured by Miwon Specialty Chemical Co., Ltd., a compound having a dendrimer structure with an average number of 18 acryloyl groups; polymerizable compound (B6) having a dendrimer structure or a hyperbranched structure)

[0433] (Photopolymerization initiator (C1) represented by general formula (1)) C1-1: Compound represented by the above chemical formula (C1) C1-2: Compound represented by the above chemical formula (C6) C1-3: Compound represented by the above chemical formula (C11) C1-4: Compounds represented by the above chemical formula (C20) C1-5: Compounds represented by the above chemical formula (C29) C1-6: Compounds represented by the above chemical formula (C31) C1-7: Compounds represented by the above chemical formula (C35) C1-8: Compounds represented by the above chemical formula (C36) C1-9: Compounds represented by the above chemical formula (C39) C1-10: Compounds represented by the above chemical formula (C44) C1-11: Compounds represented by the above chemical formula (C45) C1-12: Compounds represented by the above chemical formula (C62) (Oxime ester photoinitiator (C2a)) C2-1: The above compound (C2a-1) (absorption coefficient of light at a wavelength of 365 nm is 13,410 L / mol cm) C2-2: The above compound (C2a-2) (absorption coefficient of light at a wavelength of 365 nm is 14,214 L / mol cm) C2-3: The above compound (C2a-10) (absorption coefficient of light at a wavelength of 365 nm is 7,051 L / mol cm) C2-4: The above compound (C2a-14) (absorption coefficient of light at a wavelength of 365 nm is 27,257 L / mol cm) C2-5: The above compound (C2a-3) (absorption coefficient of light at a wavelength of 365 nm is 18,334 L / mol cm) C2-6: The above compound (C2a-4) (absorption coefficient of light at a wavelength of 365 nm is 14,127 L / mol cm) C2-7: The above compound (C2a-5) (absorption coefficient of light at a wavelength of 365 nm is 2,401 L / mol cm) (Other photopolymerization initiators (C2b)) C2-8: NPI-20400 (Changzhou Stronghold Co., Ltd.; compound with a fluorene skeleton (C2b-1))

[0434] (Sensitizer (Q)) Q-1: Kayacure DETX-S (2,4-diethylthioxanthone; manufactured by Nippon Kayaku Co., Ltd.) Q-2: SpeedCure 7010 (a compound having a thioxanthone skeleton represented by the following structure; manufactured by Arkema)

[0435] [ka] Q-3: UVS-1331 (a compound with an anthracene skeleton; manufactured by Kawasaki Kasei Chemical Industries, Ltd.)

[0436] [Thermal polymerization initiator (D)] D1-1: 2,2-bis(4,4-di-tert-butylperoxycyclohexyl); peroxide (D1)

[0437] [Thermal crosslinkable compound (E)] (Blocked isocyanate group-containing compound (E1)) E1-5: BI7982 (manufactured by Baxenden Chemical, a compound blocked with a pyrazole compound, non-volatile content 70% by mass) was diluted with PGMAc to a non-volatile content of 60%. E1-6: BI7984 (manufactured by Baxenden Chemical, a compound blocked with an oxime compound, non-volatile content 75% by mass) was diluted with PGMAc to a non-volatile content of 60%. (Epoxy compound (E2)) E2-1: EHPE-3150 (manufactured by Daicel Corporation, a compound represented by the general formula (50) above, having approximately 15 epoxy groups and an epoxy equivalent of 170 to 190 g / eq.) E2-2: Denacol EX-611 (Nagase ChemteX Corporation, sorbitol polyglycidyl ether, approximately 6 epoxy groups, epoxy equivalent weight 80-90 g / eq.) E2-3: Epolead GT401 (manufactured by Daicel Corporation, butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl) modified ε-caprolactone, epoxy groups approximately 4, epoxy equivalent 190-210g / eq.) E2-4: 1,3,5-tris(2,3-epoxypropyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (3 epoxy groups, 98g / eq. epoxy equivalent)

[0438] [Silane coupling agent (F)] (Compound (F2)) F2-1: KBM-5103 (Shin-Etsu Silicones, 3-acryloxypropyltrimethoxysilane)

[0439] [Ultraviolet absorber (G)] G-1: TINUVIN 326 (BASF Japan, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole)

[0440] [Polymerization inhibitor (H)] H-1: Methylhydroquinone (Fujifilm Wako Pure Chemical Industries, Ltd., alkylhydroquinone compound)

[0441] [Leveling agent (M)] A mixed solution obtained by mixing 2 parts of M1, 0.5 parts of M2, and 0.5 parts of M3 below and dissolving them in 97 parts of PGMAc was used as a leveling agent (M-1). M1: BYK-330 (BYK-Chemie, PGMAc solution with 51% non-volatile content, polyether-modified dimethylsiloxane) M2: Block copolymer having the following structure (n:m = 50:50 (mol%)). In the following structure, * represents the bond.

[0442] [ka] M3: Block copolymer having the following structure (p:q:r=40:40:20 (mol %)). In the following structure, * represents a bond.

[0443] [ka]

[0444] [Organic solvent (L)] 70 parts of propylene glycol monomethyl ether acetate, 10 parts of propylene glycol monomethyl ether, 10 parts of cyclohexanone, and 10 parts of cyclopentanone were mixed to prepare an organic solvent (L-1).

[0445] <Evaluation of Photosensitive Composition> The photosensitive compositions thus obtained were evaluated as follows, and the evaluation results are shown in Table 16.

[0446] [Evaluation of Solvent Resistance] 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 2.5 μm, and then dried on a hot plate at 70° C. for 1 minute. Then, using an ultra-high pressure mercury lamp, the illuminance was 30 mW / cm. 2 , irradiation amount 100mJ / cm 2The substrate was exposed to ultraviolet light through a photomask with a 100 μm square pattern. After cooling to room temperature, the substrate was spray-developed using a potassium hydroxide solution (concentration: 0.04% by mass) at 23°C for 40 seconds, then rinsed with ion-exchanged water, air-dried with clean air, and heated in a clean oven at 100°C for 30 minutes to obtain a substrate for evaluating solvent resistance. The square pattern portion of the substrate was immersed in PGMAc, and the appearance was observed and evaluated after 3, 5, 7, 10, and 15 minutes. The evaluation criteria were as follows, with a score of 3 or higher being practical. [Evaluation criteria] 5: No change in appearance after 15 minutes of immersion, change in appearance after 20 minutes of immersion 4: No change in appearance after 10 minutes of immersion, change in appearance after 15 minutes of immersion 3: No change in appearance after 7 minutes of immersion, change in appearance after 10 minutes of immersion 2: No change in appearance after 5 minutes of immersion, change in appearance after 7 minutes of immersion 1: No change in appearance after 3 minutes of immersion, change in appearance after 5 minutes of immersion

[0447] [Evaluation of heat shock resistance] The obtained photosensitive composition was placed in a sealed container and subjected to a temperature cycle test of 4 hours at 5°C and 2 hours at 30°C for 150 days. The photosensitive composition was then removed from the sealed container and applied to a glass substrate using a spin coater so that the dried film thickness was 0.5 μm. A heat treatment (pre-baking) was performed for 180 seconds using a hot plate at 100°C to produce a film for evaluation. The film on the glass substrate was observed under an optical microscope at a magnification of 100x in a 0.5 mm square area, and the number of defects within the field of view was counted. The same operation was repeated a total of 10 times, with the observation position arbitrarily changed, and the total number of defects was calculated. The evaluation criteria are as follows, with a score of 3 or higher being practical. [Evaluation criteria] 5: 0 defects 4: 1 to 5 defects 3: 5 to less than 30 defects 2: 30 to less than 100 defects 1: 100 or more defects

[0448] [Evaluation of dried precipitate] The obtained photosensitive composition was evaluated through the steps (1) to (4) described below, using a control device that automatically attached a glass test piece (Glass Eagle 2000 manufactured by Corning Incorporated) to the arm of an actuator and repeatedly inserted and removed the tip of the test piece into a bottle filled with the photosensitive composition. (1) At an ambient temperature of 23°C, a 20 mm portion of the longitudinal tip of a glass test piece having a length of 100 mm, a width of 5 mm and a thickness of 0.7 mm was immersed in the photosensitive composition at a speed of 12.5 mm / sec and then maintained therein for 4 seconds. (2) The glass test piece was removed from the photosensitive composition at a speed of 12.5 mm / sec, held vertically with the tip of the glass test piece facing downward, and then dried for 52 seconds under conditions of an atmospheric temperature of 23°C, humidity of 55%, and a wind speed of 0.5±0.2 m / sec. (3) Steps (1) and (2) were repeated a total of 250 times to form deposits (a) derived from the photosensitive composition on the glass test piece. (4) Of the four ridgelines of the glass test piece, the ridgeline with the most deposits was selected, and the weight of the deposits on that ridgeline ("deposit (a)") was measured. The weight of deposit (a) was calculated by first measuring the specific gravity of the film formed using the curable composition, then measuring the volume of deposit (a) with a three-dimensional laser microscope, and then calculating the weight from the product of these. The evaluation criteria were as follows, with a score of 3 or higher being practical. [Evaluation criteria] 5: The weight of the attached matter (a) is less than 1 μg 4: The weight of the deposit (a) is 1 μg or more and less than 2 μg 3: The weight of the attached substance (a) is 2 μg or more and less than 3 μg 2: The weight of the attached substance (a) is 3 μg or more and less than 4 μg 1: The weight of the attached matter (a) is 4 μg or more

[0449] [Outgassing evaluation] 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 2.5 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 , 100mJ / cm 2 The entire glass substrate was exposed to ultraviolet light. After cooling to room temperature, the substrate was spray-developed using a potassium hydroxide solution (concentration: 0.04%) at 23°C for 40 seconds, then washed with ion-exchanged water and air-dried with clean air. The substrate was then heated in a clean oven at 100°C for 60 minutes and then cooled to room temperature. Next, the prepared coating film was scraped off with a glass cutter to obtain a 5 mg test piece. The obtained test piece was subjected to thermogravimetry / differential thermal analysis (TG / DTA) to measure the mass loss rate relative to the initial mass. The evaluation criteria are as follows, with a score of 3 or higher being practical. TG / DTA was measured using Seiko Instruments' EXSTAR TG / DTA6200 with a nitrogen flow rate of 200 ml / min, with a program that increased the temperature from room temperature to 150°C at 5°C / min and held the temperature for 20 minutes. [Evaluation criteria] 5: Mass reduction rate is less than 1% 4: Mass reduction rate is 1% or more and less than 2% 3: Mass reduction rate is 2% or more and less than 3% 2: Mass reduction rate is 3% or more and less than 4% 1: Mass reduction rate is 4% or more

[0450] [Table 16]

Claims

1. A photosensitive composition comprising a binder resin, a polymerizable compound (B), and a photopolymerization initiator (C), The photosensitive composition, wherein the photopolymerization initiator (C) contains a photopolymerization initiator (C1) represented by the following general formula (1): General formula (1) 【Chemistry 1】 (In general formula (1), Ar １ , Ar ２ are each independently a substituent containing an aromatic ring or a heteroaromatic ring, and R １ is a C1 to C20 alkyl group, a C3 to C20 cycloalkyl group, a C1 to C10 alkyl group substituted with a C3 to C8 cycloalkyl group, a C3 to C8 cycloalkyl group substituted with a C1 to C20 alkyl group, a C6 to C20 aryl group, a C6 to C20 aryl group substituted with a C1 to C5 alkyl group, a C4 to C20 heteroaryl group, or a C6 to C20 heteroaryl group substituted with a C1 to C5 alkyl group.

2. The photosensitive composition according to claim 1 , wherein the photopolymerization initiator (C) includes a photopolymerization initiator (C2) (excluding the photopolymerization initiator (C1) represented by the general formula (1)).

3. 3. The photosensitive composition according to claim 2, wherein the mass ratio of the photopolymerization initiator (C1) represented by the general formula (1) to the photopolymerization initiator (C2) is 95:5 to 5:

95.

4. 2. The photosensitive composition according to claim 1, wherein the binder resin comprises an alkali-soluble resin (A1) having a monomer unit (a1) whose homopolymer has a glass transition temperature of 0°C or lower.

5. The photosensitive composition according to claim 1 , further comprising a thermally crosslinkable compound (E).

6. The photosensitive composition according to claim 1 , further comprising a silane coupling agent (F).

7. The photosensitive composition according to claim 1 , wherein the polymerizable compound (B) comprises an amine-containing polymerizable compound (B1).

8. The photosensitive composition according to claim 1 , further comprising an ultraviolet absorber (G) or a polymerization inhibitor (H).

9. A film formed from the photosensitive composition according to any one of claims 1, 2 and 4 to 7.

10. An optical filter comprising the film according to claim 9.

11. A solid-state imaging device comprising the optical filter according to claim 10.

12. An image display device comprising the optical filter according to claim 10.

13. An infrared sensor comprising the optical filter according to claim 10.

Images