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

Abstract

To provide a photosensitive composition capable of forming a film which offers superior temporal stability, heat shock resistance, and resolubility, which is less prone to cause development stains, and exhibits superior chemical resistance following a low-temperature curing process.SOLUTION: A photosensitive composition comprises: a photosensitive alkali-soluble resin (A), a polymerizable compound (B), a photopolymerization initiator (C), a thermal polymerization initiator (D), and a thermally crosslinkable compound (E), wherein the thermally crosslinkable compound (E) comprises a compound (E1) containing a blocked isocyanate group.SELECTED DRAWING: Figure 1

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 layer used in an organic EL (Electro-Luminescence) display device using an OLED (Organic Light Emitting Diode) or the like has low heat resistance. Therefore, the photosensitive composition used in forming the optical filter needs to be post-baked at a lower temperature than before, for example, 150°C or lower. However, at low temperatures, the film is not cured sufficiently, and there is a problem that the chemical resistance is deteriorated. In addition, there is a problem that the stability over time of the photosensitive composition is deteriorated when a highly reactive composition is contained.

[0004] Furthermore, as a risk management measure against breakdowns or problems in production lines or refrigerators, there are cases where the photosensitive composition is required to have quality stability (heat shock resistance) not at a constant temperature but in harsh environments where the temperature fluctuates.

[0005] Furthermore, when the photosensitive composition is applied, there is a problem that precipitates that dry and adhere to the coater part of the application device are mixed into the coating film, resulting in a decrease in image quality (hereinafter referred to as re-dissolvability).

[0006] In view of this, as an approach to producing 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.

[0007] Furthermore, as an effort to improve heat shock resistance, Patent Document 2 discloses a coloring composition containing a metal azo pigment.

[0008] Furthermore, as an effort to improve the resolubility of precipitates, Patent Document 3 discloses a coloring composition containing a block copolymer having a block containing a lactone-modified (meth)acrylate moiety and a block containing an amino group-containing (meth)acrylate moiety. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] International Publication No. 2019 / 026547 [Patent Document 2] International Publication No. 2019 / 077913 [Patent Document 3] JP 2013-119568 A Summary of the Invention [Problem to be solved by the invention]

[0010] However, the conventional compositions did not satisfy all of the requirements for stability over time, chemical resistance after low-temperature curing, heat shock resistance, and resolubility. Furthermore, the conventional compositions had a problem that development stains originating from the developer occurred on the film surface during the development process.

[0011] An object of the present invention is to provide a photosensitive composition which has good stability over time, heat shock resistance and resolubility, is less likely to cause development stains, and can form a film which has excellent chemical resistance after a low-temperature curing step. [Means for solving the problem]

[0012] <1> The photosensitive composition of the present invention contains a photosensitive alkali-soluble resin (A1), a polymerizable compound (B), a photopolymerization initiator (C), a thermal polymerization initiator (D) and a thermal crosslinkable compound (E), and the thermal crosslinkable compound (E) contains a blocked isocyanate group-containing compound (E1). <2> The blocking agent for the blocked isocyanate group is an active methylene compound. <1> The photosensitive composition according to claim 1. <3> The thermally crosslinkable compound (E) further contains an epoxy compound (E2). <1> The photosensitive composition according to claim 1. <4> In addition, the dye (F) <1> The photosensitive composition according to claim 1. <5> The thermal polymerization initiator (D) contains a peroxide (D1). <1> The photosensitive composition according to claim 1. <6> <1> ~ <5> 2. A film formed from the photosensitive composition according to claim 1. <7> <6> An optical filter having the film according to claim 1. <8> <7> A solid-state imaging device comprising the optical filter according to claim 1. <9> <7> An image display device comprising the optical filter according to claim 1. <10> <7> An infrared sensor having the optical filter according to claim 1. Effect of the Invention

[0013] According to the present invention, it is possible to provide a photosensitive composition capable of forming a film having good stability over time, heat shock resistance and resolubility, which is less likely to cause development stains and has excellent chemical resistance after a low-temperature curing process. The present invention also provides a cured film, an optical filter, a color filter, an image display device, a solid-state imaging device, and an infrared sensor. [Brief description of the drawings]

[0014] [Figure 1] FIG. 1 is a schematic cross-sectional view of an infrared sensor. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] The terms used in this specification are defined below. When "(meth)acryloyl", "(meth)acryl", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" is used, it means "acryloyl and / or methacryloyl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamide", respectively, unless otherwise specified. 「C.I.」 means Color Index (C.I.). The polymerizable unsaturated group is an ethylenically unsaturated group such as a vinyl group, a (meth)acryloyl group, a (meth)allyl group, etc. A monomer is a state before polymerization. A monomer unit is a state that constitutes a resin after polymerization of the monomer.

[0016] The photosensitive composition of the present invention contains a photosensitive alkali-soluble resin (A1), a polymerizable compound (B), a photopolymerization initiator (C), a thermal polymerization initiator (D), and a thermally crosslinkable compound (E), and the thermally crosslinkable compound (E) contains a blocked isocyanate group-containing compound (E1).

[0017] In addition to the photocrosslinking obtained by the photosensitive alkali-soluble resin (A1), the polymerizable compound (B), and the photopolymerization initiator (C), the photosensitive composition of the present invention combines the thermal crosslinking obtained by the thermal polymerization initiator (D) and the thermally crosslinkable compound (E) to form a strong film. In particular, in low-temperature curing, the thermal crosslinking reaction by the blocked isocyanate group-containing compound (E1) proceeds at a lower temperature, so the chemical resistance after low-temperature heating can be improved. Also, although the mechanism is unclear, the blocked isocyanate group-containing compound (E1) exhibits high stability over time and heat shock resistance even when combined with the thermal polymerization initiator (D), so it is superior to conventional photosensitive compositions in that there is no trade-off with chemical resistance. Furthermore, since the blocked isocyanate group-containing compound (E1) has good compatibility with the photosensitive alkali-soluble resin (A1), the polymerizable compound (B), the photopolymerization initiator (C), and the thermal polymerization initiator (D), the polarity of the coating film surface is less likely to vary and becomes uniform. For this reason, the problem of developing stains where highly hydrophilic portions become stains when in contact with the developer hardly occurs. Also, the redissolubility of the dry deposit is improved due to the above improvement in compatibility.

[0018] In this specification, low-temperature curing is 150°C or lower, preferably 110°C or lower, and more preferably 95°C or lower. Also, low-temperature curing is preferably 60°C or higher.

[0019] [Photosensitive alkali-soluble resin (A1)] The photosensitive composition of the present invention includes a photosensitive alkali-soluble resin (A1). The photosensitive alkali-soluble resin (A1) may be any resin that contains a polymerizable unsaturated group and dissolves in an alkaline developer, and any known resin may be used. The photosensitive alkali-soluble resin (A1) has an alkali-soluble group such as a carboxyl group, a phosphoric acid group, a sulfo group, a hydroxyl group, or a phenolic hydroxyl group. Among these, a carboxyl group is preferred. The photosensitive alkali-soluble resin (A1) may also contain a thermosetting group such as an epoxy group or an oxetanyl group. The alkali-soluble resin is preferably a chain-like random polymer. The chain-like group includes a branched chain.

[0020] The photosensitive alkali-soluble resin (A1) is preferably a resin synthesized by the following method (i) or (ii), which further improves the crosslink density of the film formed from the photosensitive composition by light irradiation and improves the chemical resistance during low-temperature curing.

[0021] [Method (i)] In the method (i), for example, a polymer of an epoxy group-containing monomer and other monomers is first synthesized, and then a monocarboxyl group-containing monomer is added to the epoxy group of the polymer, and a polybasic acid anhydride is reacted with the resulting hydroxyl group to obtain a photosensitive alkali-soluble resin (A1) containing a polymerizable unsaturated group.

[0022] 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.

[0023] Examples of other monomers include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, and ethoxypolyethylene glycol (meth)acrylate; (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, acryloylmorpholine, and other (meth)acrylamides; styrene, α-methylstyrene, and other styrenes; ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and other isobutyl vinyl ether; vinyl acetate, vinyl propionate, and other fatty acid vinyls; Cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide Examples of the benzoate include N-substituted maleimides such as N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide and 9-maleimidoacridine, EO-modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, and PO-modified (meth)acrylate of nonylphenol. Further, there may be mentioned a phosphate group-containing monomer obtained by reacting a phosphate esterifying agent such as phosphorus pentoxide or polyphosphoric acid with the hydroxyl group of a hydroxyl group-containing monomer.

[0024] Examples of monocarboxyl group-containing monomers include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, and (meth)acrylic acid substituted with haloalkyl, alkoxyl, halogen, nitro or cyano at the α-position.

[0025] Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. The polybasic acid anhydride may have a carboxyl group that does not form an acid anhydride. From the viewpoint of development stains, tetrahydrophthalic anhydride is preferred.

[0026] As a method similar to the method (i), for example, a polymer of a monocarboxyl group-containing monomer and other monomers is synthesized, and then an epoxy group-containing monomer is added to a part of the carboxyl groups of the polymer to obtain a photosensitive alkali-soluble resin (A1) containing a polymerizable unsaturated group.

[0027] [Method (ii)] In the method (ii), for example, a hydroxyl group-containing monomer, a monocarboxyl group-containing monomer, and other monomers are synthesized to prepare a polymer, and then the hydroxyl group of the polymer is reacted with an isocyanate group of an isocyanate group-containing monomer to synthesize a resin.

[0028] Examples of the hydroxyl group-containing monomer include hydroxyalkyl methacrylates 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. Other examples include polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to hydroxyalkyl (meth)acrylates, and polyester mono(meth)acrylates obtained by addition of polyγ-valerolactone, polyε-caprolactone, and / or poly12-hydroxystearic acid. Among these, 2-hydroxyethyl methacrylate and glycerol mono(meth)acrylate are preferred, and glycerol mono(meth)acrylate is more preferred.

[0029] Examples of the isocyanate group-containing monomer include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate.

[0030] Examples of monomers that can be used other than the above monomers include the other monomers exemplified in the above method (i).

[0031] [Non-photosensitive alkali-soluble resin (A2)] The photosensitive composition of the present invention may further contain a non-photosensitive alkali-soluble resin (A2). The non-photosensitive alkali-soluble resin (A2) is an alkali-soluble resin that does not have a polymerizable unsaturated group. The non-photosensitive alkali-soluble resin (A2) may contain a reactive group other than the polymerizable unsaturated group.

[0032] [Alkali-soluble resin containing blocked isocyanate groups (A2-1)] The non-photosensitive alkali-soluble resin (A2) may contain a blocked isocyanate group-containing alkali-soluble resin (A2-1). The blocked isocyanate group-containing alkali-soluble resin (A2-1) has excellent low-temperature curing properties and improves chemical resistance. The blocked isocyanate group-containing compound (E1) is not soluble in alkali, and is therefore a different compound from the non-photosensitive alkali-soluble resin (A2).

[0033] The blocked isocyanate group-containing alkali-soluble resin (A2-1) has a blocked isocyanate group-containing monomer unit. The blocked isocyanate group is a group in which an isocyanate group is protected with a blocking agent described below. The reaction of the blocked isocyanate group may be (a) a case in which the blocking agent is thermally eliminated to regenerate an isocyanate, and the regenerated isocyanate group undergoes a crosslinking reaction, or (b) a case in which a crosslinking reaction occurs by an ester exchange reaction. The temperature at which the blocking agent is eliminated or the ester exchange reaction proceeds is preferably 60 to 160°C, more preferably 70 to 130°C, and particularly preferably 80 to 110°C. The blocked isocyanate group-containing monomer unit can be prepared by protecting the isocyanate group with a blocking agent after polymerization of the blocked isocyanate group-containing monomer, or the blocked isocyanate group-containing monomer may be polymerized after protecting the isocyanate group.

[0034] 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. Also usable are equimolar reaction products of 2-hydroxyalkyl (meth)acrylate and diisocyanate compound. Among these, 2-isocyanatoethyl (meth)acrylate and 2-isocyanatopropyl (meth)acrylate are preferred.

[0035] 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, and from the viewpoint of the protection reaction and the deprotection reaction, is more preferably one or more selected from the group consisting of oxime compounds, phenol compounds, active methylene compounds, and pyrazole compounds.

[0036] 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 the lactam compound 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, dibutyl malonate, diisopropyl malonate, di-tert-butyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone, etc. Among these, diethyl malonate, dibutyl malonate, diisopropyl malonate, and di-tert-butyl malonate are preferred. Examples of the pyrazole compound include pyrazole, methylpyrazole, 3,5-dimethylpyrazole, etc. Among these, 3,5-dimethylpyrazole is 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 ethyleneurea. Examples of the imine compound include ethyleneimine and polyethyleneimine. Examples of the bisulfite compound include sodium bisulfite and potassium bisulfite.

[0037] The blocking agent can be used alone or in combination of two or more.

[0038] Examples of the blocked isocyanate group-containing monomer include the following compounds. However, the present invention is not limited thereto.

[0039] [Chemical formula]

[0040] Commercially available products of the blocked isocyanate group-containing monomer include Karens MOI-DEM (desorption temperature of the blocking agent: 85 to 95 °C), MOI-BP (desorption temperature of the blocking agent: 105 to 115 °C), MOI-BM (desorption temperature of the blocking agent: 125 to 135 °C), etc. manufactured by Resonaak.

[0041] From the viewpoints of stability over time and chemical resistance in low-temperature curing, the content of the blocked isocyanate group-containing monomer unit is preferably 1 to 50 mol%, more preferably 5 to 40 mol%, based on all the monomer units of the blocked isocyanate group-containing alkali-soluble resin (A2-1).

[0042] The weight average molecular weight (Mw) of the photosensitive alkali-soluble resin (A1) and the non-photosensitive alkali-soluble resin (A2) is preferably 2,000 to 40,000, more preferably 3,000 to 300,000, and even more preferably 5,000 to 25,000. Also, the value of Mw / Mn (number average molecular weight) is preferably 10 or less.

[0043] The acid value of the photosensitive alkali-soluble resin (A1) and the non-photosensitive alkali-soluble resin (A2) is preferably 20 to 200 mgKOH / g, more preferably 30 to 180 mgKOH / g.

[0044] The photosensitive alkali-soluble resin (A1) and the non-photosensitive alkali-soluble resin (A2) can be used alone or in combination of two or more kinds.

[0045] The content of the photosensitive alkali-soluble resin (A1) and the non-photosensitive alkali-soluble resin (A2) is preferably from 10 to 500 parts by mass, more preferably from 30 to 250 parts by mass, based on 100 parts by mass of the polymerizable compound (B).

[0046] When a non-photosensitive alkali-soluble resin (A2) is used, the mass ratio to the photosensitive alkali-soluble resin (A1), A1:A2, is preferably from 90:10 to 10:90, more preferably from 90:10 to 50:50.

[0047] [Polymerizable compound (B)] The photosensitive composition of the present invention contains a polymerizable compound (B).

[0048] The polymerizable compound (B) is a monomer or oligomer having a polymerizable unsaturated group, such as a vinyl group, a (meth)allyl group, a (meth)acryloyl group, a (meth)acryloyloxy group, or a styryl group.

[0049] Examples of the polymerizable compound (B) include a polymerizable compound (B1) having an amine structure, a polymerizable compound (B2) having a hydroxyl group, a polymerizable compound (B3) having an acidic group, a lactone-modified polymerizable compound (B4), a polymerizable compound (B5) having a urethane bond, a polymerizable compound (B6) having a dendrimer structure or a hyperbranched structure, and other polymerizable compounds (B7). Among these, it is preferable to include at least one selected from the group consisting of a polymerizable compound (B1) having an amine structure, a polymerizable compound (B3) having an acidic group, and a polymerizable compound (B6) having a dendrimer structure or a hyperbranched structure.

[0050] (Polymerizable compound (B1) having an amine structure) The amine structure of the polymerizable compound (B1) having an amine structure may be any of primary amine, secondary amine, and tertiary amine structures, but is preferably a secondary amine or tertiary amine, provided that the amine structure of the polymerizable compound (B1) having an amine structure does not include an amide structure, an imide structure, or a urethane structure in which a carbonyl group is directly bonded to a nitrogen atom.

[0051] Examples of the polymerizable compound (B1) having an amine structure include tris(acryloyloxyethyl)amine, tris(methacryloyloxyethyl)amine, tris(2-hydroxy-3-methacryloyloxypropyl)amine, and a Michael addition reaction product of a (meth)acrylate compound (X) and an amine compound (Y).

[0052] Examples of the (meth)acrylate compound (X) include glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, diglycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, penta ...hexa(meth)acrylate, diglycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol hexa(meth)acrylate, diglycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol hexa(meth)acrylate, diglycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol hexa(meth)acrylate, diglycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol hexa(meth)acrylate, diglycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, Examples of the alkylene oxide-modified tetra(meth)acrylate include phosphorus tri(meth)acrylate, diglycerol tetra(meth)acrylate, trimethylolpropane alkylene oxide-modified tri(meth)acrylate, ditrimethylolpropane alkylene oxide-modified tri- and tetra(meth)acrylate, pentaerythritol alkylene oxide-modified tri- and tetra(meth)acrylate, diglycerol alkylene oxide-modified tri- and tetra(meth)acrylate, and dipentaerythritol alkylene oxide-modified tetra-, penta- and hexa(meth)acrylate. Examples of the alkylene oxide unit in the alkylene oxide modification include ethylene oxide, propylene oxide, and butylene oxide. The (meth)acrylate compound (X) also includes a (meth)acrylate compound having an acidic group.

[0053] The (meth)acrylate compounds (X) can be used alone or in combination of two or more.

[0054] Examples of the amine compound (Y) include primary amines such as n-propylamine, n-butylamine, n-hexylamine, benzylamine, aminocaproic acid, monoethanolamine, 2-(2-aminoethoxy)ethanol, o-aminophenol, m-aminophenol, and p-aminophenol; Examples of the secondary amines include dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, cyclohexylamine, morpholine, piperidine, 1-methylpiperazine, proline, N-merylethanolamine, N-acetylethanolamine, diethanolamine, 3-anilinephenol, and 4-anilinephenol.

[0055] The amine compound (Y) can be used alone or in combination of two or more kinds.

[0056] The method for producing the Michael addition reaction product of the (meth)acrylate compound (X) and the amine compound (Y) is not particularly limited, and a known method can be used. For example, the methods described in International Publication No. 2006 / 075754, JP-A-2008-545859, JP-A-2017-066347, etc. can be mentioned.

[0057] The polymerizable compound (B1) having an amine structure may have an acidic group and / or a hydroxyl group. Examples of a method for introducing an acidic group and / or a hydroxyl group include a method of using a compound having an acidic group and / or a hydroxyl group in the (meth)acrylate compound (X) or the amine compound (Y), and a method of adding an acid anhydride after a Michael addition reaction.

[0058] Commercially available polymerizable compounds (B1) having an amine structure include, for example, ARONIX MT-3041 and 3042 manufactured by Toagosei Co., Ltd., EBECRYL 80 and 7100 manufactured by Daicel-Allnex Corporation, and CN371NS, 372, 374, 383 and 386 manufactured by Arkema.

[0059] The polymerizable compound (B1) having an amine structure preferably further has a urethane bond. This forms a chemical crosslinked structure by polymerization as well as a physical crosslinked structure by intermolecular hydrogen bonds between the urethane bonds and between the urethane bonds and the functional groups of the substrate. The molecular cohesive energy of the intermolecular hydrogen bonds in the urethane bonds is greater than the cohesive energy of other organic structures such as ether bonds. Therefore, it is presumed that the film becomes flexible and strong due to the interaction between the urethane bonds, improving its resistance.

[0060] The urethane bond can be introduced, for example, by a urethane reaction between a Michael addition reaction product (precursor) of the above-mentioned (meth)acrylate compound (X) and the above-mentioned amine compound (Y) having a hydroxyl group, and a polyisocyanate compound (Z).

[0061] Examples of the polyisocyanate compound (Z) include polyisocyanate compounds having an aliphatic structure, such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate; Cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dimethylcyclohexyl diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatemethyl)cyclo polyisocyanate compounds having an alicyclic structure, such as norbornane diisocyanate, methylcyclohexane diisocyanate, norbornane diisocyanate, and bis(isocyanatomethyl)cyclohexane; Examples of the polyisocyanate compound include polyisocyanate compounds having an aromatic structure, such as 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyl diphenylmethane diisocyanate, tetraalkyl diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylylene diisocyanate, m-tetramethyl xylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, bischloromethyl diphenylmethane diisocyanate, 2,6-diisocyanate-benzyl chloride, and bis(isocyanate methyl)benzene. Further, biuret, isocyanurate, adduct and allophanate forms of these compounds are also included.

[0062] The polyisocyanate compounds (Z) can be used alone or in combination of two or more kinds.

[0063] The method of the urethane reaction between the precursor and the polyisocyanate compound (Z) is not particularly limited, and a known method can be used. For example, the method described in JP-A-2018-517797 can be mentioned.

[0064] An example of a commercially available polymerizable compound (B1) having an amine structure and a urethane bond is CN9906NS manufactured by Arkema.

[0065] The polymerizable compound (B1) having an amine structure can be used alone or in combination of two or more kinds.

[0066] The content of the polymerizable compound (B1) having an amine structure is preferably 1 to 80 mass%, more preferably 5 to 60 mass%, in 100 mass% of the polymerizable compound (B) from the viewpoints of resolubility and chemical resistance after low-temperature heating.

[0067] From the viewpoint of resolubility, the polymerizable compound (B1) having an amine structure is preferably used in combination with the polymerizable compound (B2) having a hydroxyl group or the polymerizable compound (B3) having an acidic group, which will be described later. 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.

[0068] (Polymerizable compound (B2) having a hydroxyl group) Examples of the polymerizable compound (B2) having a hydroxyl group 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, EO isocyanuric acid, or the like. Examples of the acrylic acid ester include 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, and epoxy (meth)acrylate obtained by reacting an epoxy group of an epoxy compound with a carboxyl group of (meth)acrylic acid. Among these, glycerol di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate are preferred.

[0069] Examples of commercially available polymerizable compounds (B2) having a hydroxyl group 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, 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.

[0070] The polymerizable compound (B2) having a hydroxyl group can be used alone or in combination of two or more kinds.

[0071] The content of the polymerizable compound (B2) having a hydroxyl group is preferably 10 to 99 mass%, more preferably 20 to 90 mass%, in 100 mass% of the polymerizable compound (B).

[0072] (Polymerizable compound having an acidic group (B3)) Examples of the polymerizable compound (B3) having an acidic group include an esterification product of a free hydroxyl group-containing poly(meth)acrylate of a polyhydric alcohol and (meth)acrylic acid with a dicarboxylic acid; an esterification product of a polycarboxylic acid with a monohydroxyalkyl (meth)acrylate, and the like.

[0073] Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.

[0074] Examples of the dicarboxylic acid include malonic acid, succinic acid, maleic acid, glutaric acid, phthalic acid, and itaconic acid.

[0075] Examples of the polyvalent carboxylic 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.

[0076] Commercially available products of the polymerizable compound (B3) having an acidic group include Aronix M-5300, M-5400, M-510, M-520, and M-521 manufactured by Toagosei Co., Ltd., and β-CEA manufactured by Daicel Allnex Corporation.

[0077] The polymerizable compound (B3) having an acidic group can be used alone or in combination of two or more kinds.

[0078] The content of the polymerizable compound (B3) having an acidic group is preferably 1 to 90 mass%, more preferably 1 to 50 mass%, in 100 mass% of the polymerizable compound (B) from the viewpoint of chemical resistance after low-temperature heating.

[0079] (Lactone-modified polymerizable compound (B4)) The lactone-modified polymerizable compound (B4) is a compound having a structure modified with lactone in the molecule. The lactone-modified polymerizable compound (B6) is obtained by esterifying a polyhydric alcohol such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaethylthritol, tripentaerythritol, glycerin, diglycerol, or trimethololmelamine with (meth)acrylic acid and ε-caprolactone or other lactone compounds.

[0080] 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.

[0081] (Polymerizable compound having a urethane bond (B5)) Examples of the polymerizable compound (B5) having a urethane bond include urethane (meth)acrylates obtained by reacting a hydroxyl group-containing (meth)acrylate with a polyfunctional isocyanate, and urethane (meth)acrylates obtained by reacting a polyhydric alcohol with a polyfunctional isocyanate and further reacting the polyhydric alcohol with a hydroxyl group-containing (meth)acrylate.

[0082] 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.

[0083] 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 forms, isocyanurate forms, and trimethylolpropane adducts thereof.

[0084] 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 phosphoric acid group. Among them, a carboxyl group is preferable. The polymerizable compound (B5) having a urethane bond does not have an amine structure.

[0085] The method for introducing an acidic group into the polymerizable compound (B5) having a urethane bond can be, for example, synthesized by first reacting the hydroxyl group-containing (meth)acrylate with the polyfunctional isocyanate, and then adding a mercapto compound having a carboxyl group to the product.

[0086] 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.

[0087] Commercially available polymerizable compounds (B5) having a urethane bond include, for example, 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.

[0088] (Polymerizable compound (B6) having a dendrimer structure or a hyperbranched structure) A compound having a dendrimer structure has a chemical structure in which the core-constituting chemical structure (hereinafter also referred to as the core portion) is regularly branched outward, and a polymerizable unsaturated group is bonded to the end of the branch, and the compound has a highly controlled spherical chemical structure and molecular weight. The hyperbranched structure has a chemical structure similar to that of the dendrimer structure.

[0089] 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 Co., Ltd., CN2301 (hyperbranched structure, average number of acryloyl groups: 9), CN2302 (hyperbranched structure, average number of acryloyl groups: 16), CN2303 (hyperbranched structure, average number of acryloyl groups: 6), CN2304 (hyperbranched structure, average number of acryloyl groups: 18), and Eternal 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.

[0090] The polymerizable compound (B6) having a dendrimer structure or a hyperbranched structure can be used alone or in combination of two or more kinds.

[0091] The polymerizable compound (B6) having a dendrimer structure or a hyperbranched structure is preferably present in an amount of 1 to 90 mass %, more preferably 1 to 50 mass %, in 100 mass % of the polymerizable compound (B) from the viewpoint of chemical resistance after low-temperature heating.

[0092] (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-vinyl formamide, and acrylonitrile.

[0093] 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., OGSOL manufactured by Osaka Gas Chemical 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.

[0094] The other polymerizable compounds (B7) can be used alone or in combination of two or more kinds.

[0095] The content of the polymerizable compound (B) is preferably from 1 to 50 mass %, more preferably from 5 to 30 mass %, of the non-volatile content of the photosensitive composition.

[0096] [Photopolymerization initiator (C)] The photosensitive composition of the present invention contains a photopolymerization initiator (C). The photopolymerization initiator (C) is not particularly limited, and known compounds can be used.

[0097] [Oxime ester photoinitiator (C1)] The photopolymerization initiator (C) may contain an oxime ester-based photopolymerization initiator (C1) (hereinafter, also referred to as photopolymerization initiator (C1)). The photopolymerization initiator (C1) absorbs ultraviolet light, causing cleavage of the NO bond of the oxime, generating iminyl radicals and alkyloxy radicals. These radicals further decompose to generate highly active radicals, so that a pattern can be formed with a small amount of exposure. Therefore, even when the dye concentration of the photosensitive composition is high, the photopolymerization initiator (C1) does not reduce the curability of the film. Examples of the photopolymerization initiator (C1) include compounds represented by the following general formulae (C11) to (C15).

[0098] (Oxime ester photopolymerization initiator (C11) represented by general formula (C11)) General formula (C11) [ka]

[0099] In general formula (C11), R 1 and R 2 R each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, or a phenyl group. 3 -COR 5 R represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an acyl group, a nitro group, or a sulfo group. 5 R represents a phenyl group which may have a substituent. 4 is a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms. 1 ~R 4 The alkyl group, cyclic alkyl group, acyl group, and phenyl group in R may be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 10 carbon atoms, and a phenyl group. 1 ~R 4 The hydrogen atoms of the substituents in 6 may be substituted with R6 represents a halogen atom, a fluorine atom, an alkyl group, a cyclic alkyl group, an acyl group, a nitro group, a sulfo group, or a phenyl group.

[0100] The oxime ester photopolymerization initiator (C11) represented by the general formula (C11) is, for example, 1-[9-ethyl-6-benzoyl-9H-carbazol-3-yl]-octan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9.H.-carbazol-3-yl]-ethan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2,4,6-trimethylbenzoyl]- )-9H-carbazol-3-yl]-ethan-1-one oxime-O-benzoate, 1-[9-n-butyl-6-(2-ethylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-O-benzoate, ethanone,1-[9-ethyl-6-(3-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime), ethanone,1-(9-ethyl-6-benzoyl-9H-carbazol-3-yl)-,1-(O-acetyloxime), ethanone,1-[9-ethyl-6-(2-methyl-4-tetramethylbenzoyl)- 1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), ethanone, 1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), ethanone, 1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), ethanone, 1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylbenzoyl)-9H-carbazol-3 -yl]-,1-(O-acetyl oxime), ethanone,1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)benzoyl}-9H-carbazol-3-yl]-,1-(O-acetyl oxime), ethanone,1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranyl methoxybenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyl oxime), ethanone,1-[9-ethyl-6-(2-methyl-4-tetrahydropyranyl methoxybenzoyl)-9H-carbazol-3-yl]-,Examples of the compounds include 1-(O-acetyl oxime), ethanone, 1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranyl methoxybenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime), ethanone, 1-[9-ethyl-6-(2-methyl-5-tetrahydropyranyl methoxybenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime), ethanone, 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl}-9H-carbazol-3-yl]-, 1-(O-acetyl oxime), and the compounds represented by the following chemical formulas (C11-1) to (C11-9).

[0101] [ka] JPEG2025079765000005.jpg53123 JPEG2025079765000006.jpg47123 JPEG2025079765000007.jpg48113 JPEG2025079765000008.jpg5354

[0102] (Oxime ester photopolymerization initiator (C12) represented by general formula (C12)) General formula (C12) [ka]

[0103] In general formula (C12), R 1 and R 2 R each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, an alkyl group having 3 to 20 carbon atoms which may have a cyclic substituent, or a phenyl group. 3 represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an acyl group, a nitro group, or a sulfo group.1 ~R 3 The alkyl group, cyclic alkyl group, acyl group, and phenyl group of R may be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 10 carbon atoms, and a phenyl group. 4 R is a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. 4 The hydrogen atoms of the aryl group and arylalkyl group represented by 21 , -OR 21 , -COR 21 , hydroxyl group, nitro group, cyano group, halogen atom, or COOR 21 and R 21 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms; R 21 The hydrogen atoms of the alkyl group, aryl group, and arylalkyl group represented by the formula (I) may be further substituted with a hydroxyl group, a nitro group, a cyano group, a halogen atom, a hydroxyl group, or a carboxyl group. The alkyl group, acyl group, and phenyl group may be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 10 carbon atoms, and a phenyl group. 1 ~R 4 The hydrogen atom of the substituent in may be further substituted with another substituent.

[0104] In the above general formula (C12), R 1 ~R 4 Examples of the linear or branched alkyl group having 1 to 20 carbon atoms represented by the formula (I) include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl, cyclohexylmethyl, and cyclohexylethyl.

[0105] In the above general formula (C12), R 1 ~R 4 Examples of the cyclic alkyl group having 3 to 20 carbon atoms represented by the formula (I) include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclododecyl group.

[0106] In the above general formula (C12), R 4 , R 21 Examples of the aryl group having 6 to 30 carbon atoms represented by the formula (I) include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl, phenyl substituted with one or more of the above-mentioned alkyl groups, biphenylyl, naphthyl, and anthryl.

[0107] In the above general formula (C12), R 4 Examples of the arylalkyl group having 7 to 30 carbon atoms include benzyl, α-methylbenzyl, α,α-dimethylbenzyl, and phenylethyl.

[0108] Examples of the oxime ester photopolymerization initiator (C12) represented by general formula (C12) include the compounds represented by the following chemical formulas (C12-1) to (C12-10).

[0109] [ka] JPEG2025079765000011.jpg4391 JPEG2025079765000012.jpg4192 JPEG2025079765000013.jpg104134 [ka] JPEG2025079765000015.jpg9184

[0110] (The oxime ester-based photoinitiator (C13) represented by the general formula (C13)) General formula (C13)

Chemical formula

[0111] In the general formula (C13), R 1 and R 2 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, or a phenyl group. R 3 , R 5 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an acyl group, a nitro group, or a sulfo group. The alkyl groups, acyl groups, and phenyl groups of the above R 1 ~R 3 may be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 10 carbon atoms, and a phenyl group. R 4 represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a heterocyclic group having 4 to 20 carbon atoms, or -COR 6 . R 6 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms. Note that the hydrogen atoms of the substituents in R 1 ~R 6 may be further substituted with other substituents.

[0112] Among the above general formula (C13), R 1 ~R 5Examples of the linear or branched alkyl group having 1 to 20 carbon atoms represented by the formula (I) include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl, cyclohexylmethyl, and cyclohexylethyl.

[0113] In the above general formula (C13), R 1 ~R 5 Examples of the cyclic alkyl group having 3 to 20 carbon atoms represented by the formula (I) include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclododecyl group.

[0114] In the above general formula (C13), R 4 and R 7 Examples of the heterocyclic group having 4 to 20 carbon atoms represented by the formula (I) include 5- to 7-membered heterocyclic rings such as benzofuran, isobenzofuran, pyridyl, pyrimidyl, furyl, thienyl, tetrahydrofuryl, dioxolanyl, benzoxazol-2-yl, tetrahydropyranyl, pyrrolidyl, imidazolidyl, pyrazolidyl, thiazolidyl, isothiazolidyl, oxazolidyl, isoxazolidyl, piperidyl, piperazyl, and morpholinyl.

[0115] In the above general formula (C13), R 6 Examples of the aryl group having 6 to 30 carbon atoms represented by the formula (I) include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl, phenyl substituted with one or more of the above-mentioned alkyl groups, biphenylyl, naphthyl, and anthryl.

[0116] In the above general formula (C13), R 6Examples of the arylalkyl group having 7 to 30 carbon atoms include benzyl, α-methylbenzyl, α,α-dimethylbenzyl, and phenylethyl.

[0117] Examples of the oxime ester photopolymerization initiator (C13) represented by general formula (C13) include the compounds represented by the following chemical formulas (C13-1) to (C13-3).

[0118] [ka] JPEG2025079765000018.jpg4376

[0119] (Oxime ester photopolymerization initiator (C14) represented by general formula (C14)) General formula (C14) [ka]

[0120] In general formula (C14), R 1 and R 2 R each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, or a phenyl group. 3 , R 5 R each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, an acyl group, a nitro group, or a sulfo group. 4 is a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or an alkoxy group which may be interrupted by a hydroxyl group. The above alkyl group, acyl group, and phenyl group may be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxy group having 1 to 10 carbon atoms, and a phenyl group. 1 ~R 5 The hydrogen atom of the substituent in may be further substituted with another substituent.

[0121] In the above general formula (C14), R 1 ~R 5 Examples of the linear or branched alkyl group having 1 to 20 carbon atoms represented by the formula (I) include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl, cyclohexylmethyl, and cyclohexylethyl.

[0122] In the above general formula (C14), R 1 , R 2 , R 3 and R 5 Examples of the cyclic alkyl group having 3 to 20 carbon atoms represented by the formula (I) include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclododecyl group.

[0123] Examples of the oxime ester photopolymerization initiator (C1-4) represented by the general formula (C14) include 1,2-heptanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime), 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime), 1,2-octanedione, 1-[4-(benzoyl)phenyl]-, 2-(O-benzoyloxime), ethanone, 1-[4-(phenylthio)phenyl]-octan-1-one-2-one oxime-O-acetate, 1-[4-(2-methylphenylthio)phenyl]-octan-1-one-2-one oxime-O-acetate, 1-[4-(2,4,6-trimethylphenylthio)phenyl]-octan- Examples of the compound include 1-one-2-one oxime-O-acetate, 1-[4-(2-ethylphenylthio)phenyl]-octan-1-one-2-one oxime-O-acetate, 1-[4-(phenylthio)phenyl]-octan-1-one-2-one oxime-O-benzoate, 1-[4-(2-methylphenylthio)phenyl]-octan-1-one-2-one oxime-O-benzoate, 1-[4-(2,4,6-trimethylphenylthio)phenyl]-octan-1-one-2-one oxime-O-benzoate, 1-[4-(2-ethylphenylthio)phenyl]-octan-1-one-2-one oxime-O-benzoate, and the compounds represented by the following chemical formulae (C14-1) to (C14-6).

[0124] [ka] JPEG2025079765000021.jpg6990 JPEG2025079765000022.jpg6990

[0125] (Oxime ester photopolymerization initiator (C15) represented by general formula (C15)) General formula (C15) [ka]

[0126] In general formula (C15), R 1 and R 2 are each independently R 11 or COR 11 represents R 11 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms; R 11 The alkyl moiety of the alkyl group, aryl group, arylalkyl group or heterocyclic group represented by the formula (I) may have a branched side chain or may be a cyclic alkyl group, R 3 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms; R 3 The alkyl moiety of the alkyl group, aryl group, arylalkyl group or heterocyclic group represented by the formula (I) may have a branched side chain or may be a cyclic alkyl group, and R 3 The hydrogen atom of the aryl group, arylalkyl group or heterocyclic group represented by 21 , -OR 21 , -COR 21 , -SR 21 , -NR 22 R 23 , -CONR 22 R 23 , -NR 22 -OR 23 , -NCOR 22 -OCOR 23 , -NR 22 COR 21 , -OCOR 21 , -SCOR 21 , -OCSR 21 , -COSR 21 , -CSOR 21 , hydroxyl group, nitro group, cyano group, halogen atom, or COOR 21 may be substituted with R 21 , R 22 and R 23each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms; R 21 , R 22 and R 23 The hydrogen atoms of the alkyl group, aryl group, arylalkyl group or heterocyclic group represented by the formula (I) may be further substituted with a hydroxyl group, a nitro group, a cyano group, a halogen atom, a hydroxyl group or a carboxyl group, and R 21 , R 22 and R 23 The alkyl group, aryl group, arylalkyl group, or alkylene portion of the heterocyclic group represented by the formula: 24 -, -NR 24 CO-, -NR 24 COO-, -OCONR 24 The oxygen atom may be interrupted 1 to 5 times by -, -SCO-, -COS-, -OCS- or CSO-, provided that the oxygen atom is not adjacent to another oxygen atom; R 24 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms; R 24 The alkyl moiety of the alkyl group, aryl group, arylalkyl group or heterocyclic group represented by the formula (I) may have a branched side chain or may be a cyclic alkyl group, R 4 represents a hydrogen atom, a hydroxyl group, a cyano group, a nitro group, or a halogen atom, and n represents 0 or 1.

[0127] In the above general formula (C15), R 3 , R 11 , R 21 , R 22 , R 23 and R 24Examples of the alkyl group having 1 to 20 carbon atoms represented by the formula (I) include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl, cyclohexylmethyl, and cyclohexylethyl.

[0128] In the above general formula (C15), R 3 , R 11 , R 21 , R 22 , R 23 and R 24 Examples of the aryl group having 6 to 30 carbon atoms represented by the formula (I) include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl, phenyl substituted with one or more of the above-mentioned alkyl groups, biphenylyl, naphthyl, and anthryl.

[0129] In the above general formula (C15), R 3 , R 11 , R 21 , R 22 , R 23 and R 24 Examples of the arylalkyl group having 7 to 30 carbon atoms represented by the formula (I) include benzyl, α-methylbenzyl, α,α-dimethylbenzyl, and phenylethyl.

[0130] In the above general formula (C15), R 3 , R 11 , R 21 , R 22 , R 23 and R 24Examples of the heterocyclic group having 2 to 20 carbon atoms represented by the formula (I) include 5- to 7-membered heterocyclic rings such as pyridyl, pyrimidyl, furyl, thienyl, tetrahydrofuryl, dioxolanyl, benzoxazol-2-yl, tetrahydropyranyl, pyrrolidyl, imidazolidyl, pyrazolidyl, thiazolidyl, isothiazolidyl, oxazolidyl, isoxazolidyl, piperidyl, piperazyl, and morpholinyl.

[0131] The method for producing the oxime ester photopolymerization initiator (C1) represented by the general formula (C15) is not particularly limited, and a known method can be used. For example, the method described in International Publication No. 2015 / 152153 can be used.

[0132] Examples of the oxime ester photopolymerization initiator (C15) represented by general formula (C15) include the compounds represented by the following chemical formulas (C15-1) to (C15-8).

[0133] [ka] JPEG2025079765000025.jpg56101 JPEG2025079765000026.jpg56124

[0134] Among these photopolymerization initiators (C1), 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), ethanone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxybenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), and ethanone, 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl}-9H-carbazol-3-yl]-, 1-(O-acetyloxime) are preferred.

[0135] Commercially available products include 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] (IRGACURE OXE-01), IRGACURE OXE-03, and IRGACURE OXE-04 manufactured by BASF Japan Ltd., N-1919, NCI-730, NCI-831, and NCI-930 manufactured by ADEKA Corporation, and TRONLY TR-PBG-304, TRONLY TR-PBG-305, TRONLY TR-PBG-3057, TRONLY TR-PBG-309, TRONLY TR-PBG-345, and TRONLY TR-PBG-3054 manufactured by Changzhou Strong New Materials Co., Ltd. Among these, from the viewpoint of chemical resistance after low-temperature heating, TRONLY TR-PBG-345, NCI-730, and NCI-930 are more preferable, and IRGACURE OXE-04 and NCI-831 are even more preferable. Also, from the viewpoint of resolubility, IRGACURE OXE-04 and NCI-831 are preferable.

[0136] The content of the photopolymerization initiator (C1) is preferably from 0.5 to 4 mass %, more preferably from 1 to 2 mass %, in the non-volatile content of the photosensitive composition.

[0137] [Other photopolymerization initiators (C2)] The photopolymerization initiator (C) may contain a photopolymerization initiator (C2) other than the above (hereinafter, also referred to as photopolymerization initiator (C2)). Examples of the photopolymerization initiator (C2) 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; benzoin, benzoin methyl; benzoin compounds such as benzoyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzil dimethyl ketal; benzophenone compounds such as benzophenone, benzoylbenzoic acid, benzoylbenzoic acid methyl, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone;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) Examples of the compounds include triazine-based compounds such as -s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, and 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; phosphine-based compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and diphenyl-2,4,6-trimethylbenzoylphosphine oxide; quinone-based compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate-based compounds; carbazole-based compounds; imidazole-based compounds; and titanocene-based compounds.

[0138] Commercially available photopolymerization initiators (C2) include acetophenone-based compounds, all manufactured by IGM Resins, such as "Omnirad 907" (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one), "Omnirad 369E" (2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone), and "Omnirad 379EG" (2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone), and phosphine-based compounds, all manufactured by IGM Resins, such as "Omnirad 819" (bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide) and "Omnirad TPO" (diphenyl-2,4,6-trimethylbenzoylphosphine oxide).

[0139] The content of the photopolymerization initiator (C1) is preferably from 0.5 to 4 mass %, more preferably from 0.6 to 2 mass %, in the non-volatile content of the photosensitive composition.

[0140] The content of the photopolymerization initiator (C2) is preferably from 0.5 to 10 mass %, more preferably from 3 to 7 mass %, in the non-volatile content of the photosensitive composition.

[0141] [Thermal polymerization initiator (D)] The photosensitive composition of the present invention contains a thermal polymerization initiator (D). The thermal polymerization initiator (D) is not particularly limited, and known compounds can be used. For example, compounds that generate radicals by the action of heat to initiate or promote a radical polymerization reaction can be mentioned. By containing a peroxide (D1), the photosensitive composition of the present invention can form a coating film with good chemical resistance after low-temperature heating. The peroxide (D1) is preferably an organic peroxide.

[0142] [Peroxide (D1)] The thermal polymerization initiator (D) may contain a peroxide (D1). By containing the peroxide (D1), a coating film having excellent chemical resistance after low-temperature heating can be formed.

[0143] 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.

[0144] [Other thermal polymerization initiators (D2)] The photosensitive composition of the present invention may contain a thermal polymerization initiator (D2) other than the peroxide (D1).

[0145] 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, 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).

[0146] The thermal polymerization initiator (D) can be used alone or in combination of two or more kinds.

[0147] The content of the thermal polymerization initiator (D) is preferably from 0.1 to 15 mass %, and more preferably from 1 to 5 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0148] It is preferable to use the thermal polymerization initiator (D) in combination with the photopolymerization initiator (C). It is presumed that resistance is further improved by carrying out a radical polymerization reaction in both the exposure step and the post-bake step.

[0149] The mass ratio of the photopolymerization initiator (C) to the thermal polymerization initiator (D) is preferably from 90:10 to 10:90, and more preferably from 17:83 to 50:50, from the viewpoints of development stains and chemical resistance to low-temperature heating.

[0150] [Thermal crosslinkable compound (E)] The photosensitive composition of the present invention contains a thermally crosslinkable compound (E). The thermally crosslinkable compound (E) crosslinks with other components by heating, and the chemical resistance in low-temperature curing is improved. 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.

[0151] The thermally crosslinkable compound (E) is not particularly limited as long as it is a compound having a thermally crosslinkable group, and a known compound can be used. For example, an oxetanyl group-containing compound, a methylol group-containing compound, a phenol group-containing compound, an alkoxyalkyl group-containing compound, a blocked isocyanate group-containing compound (E1) described later, an epoxy compound (E2), etc. can be mentioned. Among these, it is preferable to contain one or more compounds selected from the group consisting of a blocked isocyanate group-containing compound (E1) and an epoxy compound (E2), and it is more preferable to contain a blocked isocyanate group-containing compound.

[0152] [Blocked isocyanate group-containing compound (E1)] The blocked isocyanate group-containing compound (E1) is a compound having a blocked isocyanate group. The blocked isocyanate group-containing compound (E1) is a compound in which the isocyanate group of a compound having an isocyanate group is protected with a blocking agent. The desorption temperature of the blocking agent is preferably 60 to 160°C, more preferably 70 to 130°C, and particularly preferably 80 to 110°C, from the viewpoints of storage stability and chemical resistance after low-temperature heating.

[0153] The blocked isocyanate group-containing compound (E1) is synthesized by reacting a compound having an isocyanate group with a blocking agent by a known method, such as the methods described in JP-A-52-116420, JP-A-60-149572, JP-A-7-31953, JP-A-10-306136, and JP-A-2012-012567.

[0154] 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 particularly preferably active methylene compounds from the viewpoint of chemical resistance after low-temperature heating. The elimination temperature of the active methylene compound or the temperature of the ester exchange reaction is low at 80 to 110°C, and the reaction is sufficient even at low temperatures, improving resistance.

[0155] Examples of the compound having an isocyanate group include compounds having an aliphatic structure, such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate; Compounds having an alicyclic structure, 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 compounds include 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyl diphenylmethane diisocyanate, tetraalkyl diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylylene diisocyanate, m-tetramethyl xylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, bischloromethyl diphenylmethane diisocyanate, 2,6-diisocyanate-benzyl chloride, and bis(isocyanate methyl)benzene. Further examples include biuret forms, isocyanurate forms, adduct forms, allophanate forms, and reaction products of these compounds with polyols.

[0156] The compound having an isocyanate group is preferably a biuret, isocyanurate, adduct, or allophanate of a compound having an aliphatic structure or an alicyclic structure, and more preferably a biuret or isocyanurate of a compound having an aliphatic structure.

[0157] 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.

[0158] [ka]

[0159] Among the above structures, from the viewpoints of stability over time and chemical resistance after low-temperature heating, (N-1), (N-2), (N-4) and (N-7) are preferred, (N-1) and (N-2) are more preferred, and (N-1) is even more preferred.

[0160] 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.

[0161] [ka]

[0162] Among the above structures, from the viewpoints of stability over time and chemical resistance after low-temperature heating, (X-4), (X-6) and (X-7) are preferred, (X-8) is more preferred, and (X-1) is even more preferred.

[0163] Among the blocked isocyanate group-containing compounds (E1), from the viewpoints of stability over time and chemical resistance after low-temperature heating, structures of (N-1) or (N-2) and (X-1), (X-4) or (X-8) are preferred.

[0164] By using the above (X-1) and (X-8) in combination, it is possible to achieve high levels of both stability over time and chemical 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.

[0165] Commercially available blocked isocyanate group-containing compounds (E1) having an aliphatic structure 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 compounds having an alicyclic structure 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 compounds having an aromatic structure include Takenate B-830 and B-815N manufactured by Mitsui Chemicals.

[0166] The blocked isocyanate group-containing compound (E1) preferably has 1 to 20 blocked isocyanate groups, and more preferably has 2 to 15 blocked isocyanate groups.

[0167] The weight average molecular weight of the blocked isocyanate group-containing compound (E1) is preferably from 300 to 5,000, and more preferably from 500 to 3,000.

[0168] The acid value of the blocked isocyanate group-containing compound (E1) is preferably less than 10 mgKOH / g.

[0169] The blocked isocyanate group-containing compound (E1) can be used alone or in combination of two or more kinds.

[0170] From the viewpoints of stability over time, heat shock resistance, and chemical 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.

[0171] [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 structure, and also includes an alicyclic epoxy group. The epoxy compound (E2) does not have an alkoxysilyl group and does not include a (meth)acrylic polymer.

[0172] 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, methylene bis(3,4-epoxycyclohexane), ethylene bis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, butanetetracarboxylate tetra(3,4-epoxycyclohexylmethyl) modified ε-caprolactone; Examples include an adduct of 2,2-bis(hydroxymethyl)-1-butanol with 1,2-epoxy-4-(2-oxiranyl)cyclohexane.

[0173] Commercially available products of the epoxy compound (E2) include, for example, Epicoat 807, 815, 825, 827, 828, 190P, and 191P manufactured by Mitsubishi Chemical Corporation, and TECHMORE manufactured by Mitsui Chemicals, Inc. VG3101L, EPPN-201, 501H, 502H, EOCN-102S, 103S, 104S, 1020 manufactured by Nippon Kayaku Co., Ltd., Epicoat 1004, 1256, JER1032H60, 157S65, 157S70, 152, 154 manufactured by Mitsubishi Chemical Co., Ltd., Celloxide 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, and EPICLON manufactured by DIC Corporation Examples include 830, 840, 850, 860, 1050, 3050, 4050, N-660, N-670, N-740, N-770, N865, HP-7200, HP-4700, HP-4770, HP-5000, HP-6000, and HP-9500.

[0174] The epoxy compound (E2) is preferably a compound having 2 to 50 epoxy groups in the molecule.

[0175] 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 development stains and chemical resistance after low-temperature heating. The epoxy equivalent is defined as the mass of an epoxy compound containing one equivalent of an epoxy group.

[0176] From the viewpoints of development stains and chemical resistance after low-temperature heating, the epoxy compound (E2) more preferably contains a compound represented by the following general formula (50).

[0177] General formula (50) [ka]

[0178] In formula (50), R represents a group obtained by removing m hydroxyl groups from an m-hydric alcohol, m represents an integer of 1 to 6, and n represents an integer of 1 to 30.

[0179] R is preferably an alkyl group having 2 to 20 carbon atoms, and may be linear, branched, or cyclic, or a group in which they are bonded. Examples of the alkyl group having 2 to 20 carbon atoms include an ethyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a 2,2-dimethylpropyl group, a butyl group, an isobutyl group, a tert-butyl group, a 3,3-dimethylbutyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group, a 2-ethylhexyl group, a nonyl group, an isononyl group, a decyl group, an isodecyl group, an undecyl group, a dodecyl group, a hexadecyl group, a cyclopentyl group, a cyclopentylmethyl group, a cyclohexyl group, a cyclohexylmethyl group, and a cyclohexylmethyl group. Among these, a branched alkyl group having 3 to 12 carbon atoms is more preferable. When m is 2 or more, n in each group in parentheses in general formula (50) may be the same or different.

[0180] The compound represented by the general formula (50) is, for example, 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.

[0181] The acid value of the epoxy compound (E2) is preferably 10 mgKOH / g or less.

[0182] The epoxy compound (E2) can be used alone or in combination of two or more kinds.

[0183] The content of the epoxy compound (E2) is preferably from 0.5 to 20 mass%, more preferably from 1 to 8 mass%, particularly preferably from 3 to 5 mass%, based on 100 mass% of the nonvolatile content of the photosensitive composition, from the viewpoints of resolubility and development stains.

[0184] From the viewpoint of chemical resistance after low-temperature heating, 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).

[0185] 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 stability over time, heat shock resistance, and development stains.

[0186] The thermally crosslinkable compound (E) can be used alone or in combination of two or more kinds.

[0187] The content of the thermally crosslinkable compound (E) is preferably from 0.5 to 40 mass %, more preferably from 1 to 30 mass %, particularly preferably from 5 to 20 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0188] [Dye (F)] The colorant (F) may be a pigment, a dye, or a near-infrared absorbing colorant. 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.

[0189] Examples of orange pigments include CI Pigment Orange 36, 38, 43, 64, 71, and 73.

[0190] Yellow pigments include, for example, CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118 , 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 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 is preferable.

[0191] 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.

[0192] 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.

[0193] 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.

[0194] Examples of black pigments include CI Pigment Black 1, 6, 7, 12, 20, and 31.

[0195] 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)), cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, umber, and synthetic iron black.

[0196] The near infrared absorbing dye is a compound having a maximum absorption in the wavelength range of 700 to 2,000 nm. The near infrared absorbing dye may be a pigment (also called a near infrared absorbing pigment) or a dye (also called a near infrared absorbing dye). In addition, the near infrared absorbing pigment and the near infrared absorbing dye may be used in combination. In addition, the near infrared absorbing dye is preferably a near infrared absorbing pigment from the viewpoint of heat resistance. 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.

[0197] 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.

[0198] (Squarylium Compounds)

[0199] Specific examples of squarylium compounds are shown below, but the present invention is not limited to these. [ka]

[0200] [ka]

[0201] (Pyrrolopyrrole Compounds) The pyrrolopyrrole compound is preferably a compound represented by the following general formula (5).

[0202] General formula (5) [ka]

[0203] (In general formula (5), 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 is a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BR 4X R 4Y or a metal atom, R 4 is R 1X , R 1Y and R 3 R 4X R 4Y each independently represents a substituent. Compounds represented by general formula (5) are described in JP2009-263614A, JP2011-68731A, and WO2015 / 166873A.

[0204] Specific examples of pyrrolopyrrole compounds are shown below. In the following structural formulae, ME represents a methyl group and PH represents a phenyl group. However, the present invention is not limited to these.

[0205] [ka]

[0206] (Naphthalocyanine compounds) The naphthalocyanine compound is preferably a compound represented by the following general formula (6).

[0207] General formula (6) [ka]

[0208] In general formula (6), 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 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 (6) 1 ~R 24 Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0209] In the general formula (6), 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 the general formula (6) is represented by two NH. Examples of the metal atom represented by M in the general formula (6) include iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium, and tin. Examples of the metal oxide represented by M in the general formula (6) include titanyl and vanadyl. Examples of the metal halide represented by M in the general formula (6) include aluminum chloride, indium chloride, germanium chloride, tin(II) chloride, tin(IV) chloride, and silicon chloride. In the formula (1), 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.

[0210] Specific examples of the compound represented by formula (6) are shown below, but the present invention is not limited to these. [ka] JPEG2025079765000036.jpg43101 [ka] [ka]

[0211] The naphthalocyanine compounds represented by the general formula (6) can be used alone or in combination of two or more.

[0212] The naphthalocyanine compound represented by formula (6) is preferably a compound having a maximum absorption wavelength in the wavelength region of 750 to 1500 nm, and more preferably a compound having a maximum absorption wavelength in the wavelength region of 780 to 1000 nm.

[0213] The naphthalocyanine compound is preferably a compound represented by the following general formula (7).

[0214] General formula (7) [ka]

[0215] In general formula (7), 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 (8) or a phosphorus compound moiety represented by general formula (9).

[0216] [ka]

[0217] In the general formula (8), X is -CONH-R 25 -,-COO-R 26 -,-CONH-R 27 -O-, -COO-R 28 -O-, R 25 ~R 28 R represents an alkylene group or an arylene group, in which the carbon atoms may be linked by -O-, -CO-, -COO-, -OCO-, -CONH-, or -NHCO-. 31 represents hydrogen or a methyl group, and n is an integer of 0 or 1 to 10. * represents a bond to Al. In general formula (9), R 29 and R 30each 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 R 30 may be bonded to each other to form a ring. * is a bond to Al.

[0218] Specific examples of the compound represented by formula (7) are shown below, but the present invention is not limited to these.

[0219] [ka] [ka] JPEG2025079765000043.jpg6352

[0220] The near-infrared absorbing dyes can be used alone or in combination of two or more. When using two or more, it is preferable to use compounds with different maximum absorption wavelengths. This broadens the waveform of the absorption spectrum compared to when one type of near-infrared absorbing dye is used, and near-infrared rays can be absorbed in a wide wavelength range.

[0221] (dye) Examples of the dye 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, the dye may be a derivative of these dyes or a lake pigment obtained by converting the dye into a lake.

[0222] The acid dye preferably has an acid group such as sulfonic acid or carboxylic acid. The direct dye preferably forms an inorganic salt of the acid dye, or a salt-forming compound 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 which are salts between a resin component having such a functional group and the acid dye. The salt-forming compound is also sulfonamidated to modify it into a sulfonamide compound, which makes it easy to obtain a photosensitive composition with excellent resistance (light resistance, chemical resistance). In addition, a salt-forming compound of an acid dye and a compound having an onium salt group is also preferable because it has excellent resistance (light resistance, solvent resistance). The compound having an onium salt group is preferably a resin having a cationic group.

[0223] Although the 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. The salt-forming compounds of basic dyes are preferred because they have excellent resistance (light resistance, chemical resistance) and affinity with pigments. In addition, the anion component that acts as a counter ion in the salt-forming compounds of basic dyes is preferably an organic sulfonic acid, an organic sulfuric acid, a fluorine group-containing phosphorus anion compound, a fluorine group-containing boron anion compound, a cyano group-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, or a salt-forming compound formed with an acid dye. The resistance of the salt-forming compounds is further improved when the salt-forming compounds contain a polymerizable unsaturated group in the molecule.

[0224] 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.

[0225] The dye (F) can be used alone or in combination of two or more kinds.

[0226] The content of the dye (F) is preferably from 0.5 to 80% by mass, and more preferably from 1 to 60% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0227] (Micronization of organic pigments) The organic pigment is preferably used in a finely divided state. The method of finely dividing is not particularly limited, and for example, any of wet grinding, dry grinding, and dissolution precipitation can be used. Among these, salt milling treatment by a kneader method, which is a type of wet grinding, is preferred. The average primary particle diameter of the finely divided pigment determined by TEM (transmission electron microscope) is preferably 5 to 90 nm. From the viewpoints of dispersibility and contrast ratio, the average primary particle diameter is more preferably 10 to 70 nm.

[0228] In the salt milling treatment, a resin may be added as necessary. By adding a resin, the pigment is coated with the resin, and the stability, light resistance, etc. are improved. The type of the resin is not particularly limited, and examples thereof include natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. Among these, it is preferable that the resin is solid at room temperature, insoluble in water, and partially soluble in the organic solvent. The amount of the resin added is preferably 2 to 200 parts by mass relative to 100 parts by mass of the pigment.

[0229] [Pigment derivatives (G)] The photosensitive composition of the present invention can contain a pigment derivative (G).

[0230] The pigment derivative (G) is not particularly limited, and known compounds can be used. For example, compounds having a structure in which a part of the pigment is substituted with an acidic group, a basic group, a neutral group, etc. can be mentioned. Specifically, compounds having acidic substituents such as sulfo groups, carboxy groups, and phosphoric acid groups, and amine salts thereof, compounds having basic substituents such as sulfonamide groups or tertiary amino groups at the terminals, and compounds having neutral substituents such as phenyl groups and phthalimidoalkyl groups can be mentioned. 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.

[0231] The pigment derivative (G) is preferably added during the micronization of the colorant (A) described above, or during the dispersion treatment of the colorant (A) described below. The average primary particle size of the pigment derivative (G) is preferably 5 to 200 nm.

[0232] The pigment derivative (G) can be used alone or in combination of two or more kinds.

[0233] The content of the pigment derivative (G) is preferably from 1 to 50 parts by mass, and more preferably from 2 to 40 parts by mass, based on 100 parts by mass of the colorant (A).

[0234] [Dispersion resin (H)] The photosensitive composition of the present invention may contain a dispersing resin (H). The dispersing resin (H) is a resin other than an alkali-soluble resin.

[0235] The dispersing resin (H) is preferably a resin having an adsorptive group having a high affinity for the dye (F). The adsorptive group contains at least one of a basic group and an acidic group.

[0236] 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.

[0237] Examples of the acidic group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group.

[0238] Examples of the resin type of the dispersion resin (H) include urethane resins, polycarboxylates such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylate (partial) amine salts, polycarboxylate ammonium salts, polycarboxylate alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl-containing polycarboxylates, and modified products thereof, amides and salts thereof formed by the reaction of poly(lower alkylene imines) with polyesters having free carboxyl groups, 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 alcohols, and polyvinylpyrrolidone, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and phosphates.

[0239] Examples of the structure of the dispersing resin (H) 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.

[0240] Commercially available dispersion resins (H) 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, 209 manufactured by BYK Japan Co., Ltd. 5, 2150, 2155, 2163, 2164, Anti-Terra-U203, 204, BYK-P104, P104S, 220S, Lactimon, Lactimon-WS, Bykumen, 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, 5000, 51000, 52000, 53000, 54000, 55000, 56000, 57000, 58000, 59000, 60000, 61000, 62000, 63000, 64000, 65000, 66000, 67000, 68000, 69000, 70000, 71000, 72000, 73000, 74 6000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400 manufactured by BASF Japan , 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., and Ajinomoto Fine-Techno Co., Ltd.'s Ajisper PA111, PB711, PB821, PB822, PB824, etc. Further, the resins described in JP 2008-029901 A, JP 2009-155406 A, JP 2010-185934 A, JP 2011-157416 A, and paragraphs 0122 to 0155 of WO 2013175978 A, the resins described in paragraphs 0317 to 0321 of JP 2019-78878 A, and paragraph 00 of WO 2018 / 139534 A are also usable. 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.

[0241] The dispersing resin (H) can be used alone or in combination of two or more kinds.

[0242] The content of the dispersing resin (H) is preferably from 3 to 200 parts by mass, and more preferably from 5 to 100 parts by mass, based on 100 parts by mass of the colorant (F).

[0243] [Sensitizer (R)] The photosensitive composition of the present invention can contain a sensitizer (R).

[0244] Examples of the sensitizer (R) include polymethine dyes such as chalcone compounds, unsaturated ketones such as dibenzalacetone, 1,2-diketone compounds such as benzil and camphorquinone, benzoin compounds, fluorene compounds, naphthoquinone compounds, anthraquinone compounds, xanthene compounds, thioxanthene compounds, xanthone compounds, thioxanthone compounds, coumarin compounds, ketocoumarin compounds, cyanine compounds, merocyanine compounds, and oxonol compounds, acridine compounds, azine compounds, thiazine compounds, oxazine compounds, indoline compounds, azulene compounds, and azulenium compounds. Examples of the compounds include compounds having a fluorine atom, ...

[0245] The sensitizers (R) can be used alone or in combination of two or more kinds.

[0246] The content of the sensitizer (R) is preferably from 5 to 200 parts by mass, and more preferably from 10 to 150 parts by mass, based on 100 parts by mass of the photopolymerization initiator (C).

[0247] [Hardening agent (curing accelerator)] In the photosensitive composition of the present invention, a curing agent (curing accelerator) can be used in combination to assist the curing of the thermally crosslinkable compound (E). Examples of the curing agent include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, and sulfonic acid compounds. Examples of the curing agent include amine compounds (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives, bicyclic amidine compounds and their salts (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc.), phosphorus compounds (e.g., triphenylphosphine, etc.), S-triazine derivatives (e.g., 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine·isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine·isocyanuric acid adduct, etc.).

[0248] The curing agents can be used alone or in combination of two or more kinds.

[0249] The content of the curing agent is preferably 0.01 to 15 parts by mass based on 100 parts by mass of the thermally crosslinkable compound (E).

[0250] [Thiol-based chain transfer agents (N)] The photosensitive composition of the present invention may contain a thiol-based chain transfer agent (N). Examples of the thiol-based 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; Monofunctional thiol compounds having a hydroxyl group or an acidic group, 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.

[0251] The thiol chain transfer agent (N) can be used alone or in combination of two or more kinds.

[0252] The content of the thiol chain transfer agent (N) is preferably from 1 to 10% by mass in 100% by mass of the nonvolatile content of the photosensitive composition.

[0253] [Silane coupling agent (K)] The photosensitive composition of the present invention may contain a silane coupling agent (K).

[0254] The silane coupling agent (K) is a compound having an alkoxysilyl group and other functional groups. Examples of the alkoxysilyl group include a methoxysilyl group and an ethoxysilyl group. Examples of the other functional groups 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. In this specification, the silane coupling agent (K) is not included in the non-photosensitive alkali-soluble resin (A2), the polymerizable compound (B), the thermally crosslinkable compound (E), and the thiol-based chain transfer agent (N).

[0255] The silane coupling agent (K) is not particularly limited, and known compounds can be used. For example, 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, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, vinyl Examples of the silyl trimethoxysilane include vinyl triethoxysilane, 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyl diethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-acryloxypropyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, tris-(trimethoxysilylpropyl) isocyanurate, 3-mercaptopropyl methyl dimethoxysilane, 3-mercaptopropyl trimethoxysilane, p-styryl trimethoxysilane, and 3-ureidopropyl trialkoxysilane.

[0256] Commercially available silane coupling agents (K) 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, and 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, KBE-585A, X-12-1048, X-12-50, etc.

[0257] The silane coupling agent (K) may be a polymer, such as a polysiloxane type or an organic polymer type.

[0258] The polysiloxane type is a compound in which the hydrolyzable group and the 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 Chemical Co., Ltd.

[0259] The organic polymer type is a silane coupling agent (K) in which the hydrolyzable group and the other functional groups are bonded to an organic polymer whose main chain is 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 Chemical Co., Ltd.

[0260] From the viewpoint of chemical resistance after low-temperature heating, the silane coupling agent (K) is preferably a compound having an epoxy group, more preferably 3-glycidoxypropyltrimethoxysilane, and particularly preferably 3-glycidoxypropyltriethoxysilane.

[0261] The silane coupling agent (K) can be used alone or in combination of two or more kinds.

[0262] The content of the silane coupling agent (K) is preferably from 0.1 to 10 mass % in 100 mass % of the nonvolatile content of the photosensitive composition.

[0263] [Polymerization inhibitor (I)] The photosensitive composition of the present invention may contain a polymerization inhibitor (I).

[0264] The polymerization inhibitor (I) is not particularly limited, and known compounds can be used. For example, alkylcatechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert-butylcatechol, 3,5-di-tert-butylcatechol, etc.; alkylresorcinol compounds such as 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, 4-tert-butylresorcinol, etc.; alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, etc.; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine, etc.; phosphine oxide compounds such as trioctylphosphine oxide, triphenylphosphine oxide, etc.; phosphite compounds such as triphenylphosphite, trisnonylphenylphosphite, etc.; pyrogallol, phloroglucin, etc.

[0265] The polymerization inhibitor (I) can be used alone or in combination of two or more.

[0266] From the viewpoint of stability over time, the content of the polymerization inhibitor (I) is preferably 0.01 to 0.4% by mass in 100% by mass of the non-volatile content of the photosensitive composition.

[0267] [Antioxidant (M)] The photosensitive composition of the present invention can contain an antioxidant (M).

[0268] The antioxidant (M) is not particularly limited and may be a known compound. For example, hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds may be mentioned. Among these, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.

[0269] Examples of commercially available hindered phenol-based antioxidants include Adeka 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.

[0270] 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 Co., Ltd., 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 Co., Ltd.

[0271] 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.

[0272] Examples of commercially available sulfur-based antioxidants include Adeka STAB AO-412S and AO-503 manufactured by ADEKA CORPORATION, and KEMINOXPLS manufactured by Chemipro Chemicals.

[0273] The antioxidants (M) can be used alone or in combination of two or more kinds.

[0274] The content of the antioxidant (M) is preferably from 0.5 to 5.0% by mass based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0275] [Leveling agent (J)] The photosensitive composition of the present invention can contain a leveling agent (J).

[0276] The leveling agent (J) is not particularly limited and any known compound can be used, such as a silicone-based leveling agent, a fluorine-based leveling agent, an acrylic-based leveling agent, or an acetylene diol-based leveling agent.

[0277] 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.; FZ-7002, 2110, 2122, 2123, 2191, and 5609 manufactured by Dow Corning Toray Co., Ltd.; Examples of such silicone rubbers 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, TegoWet 250, 260, 265, 270, and 280 manufactured by Evonik Corporation.

[0278] Examples of commercially available fluorine-based leveling agents include Surflon S-242, 243, 420, 611, 651, and 386 manufactured by AGC Seimi Chemical Co., Ltd., Megafac F-253, 477, 551, 552, 555, 558, 560, 570, 575, and 576, R-40-LM, R-41, RS-72-K, and DS-21 manufactured by DIC Corporation, FC-4430 and 4432 manufactured by Sumitomo 3M Limited, EF-PP31N09, EF-PP33G1, and EF-PP32C1 manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd., and Futergent 602A manufactured by Neos Corporation.

[0279] Commercially available acrylic leveling agents include, for example, BYK-350, 352, 354, 355, 358, 380, 381, 392, and 394 manufactured by BYK-Chemie Co., Ltd., and Polyflow 57, 77, and 95 manufactured by Kyoeisha Chemical Co., Ltd.

[0280] 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.

[0281] The leveling agent (J) can be used alone or in combination of two or more kinds.

[0282] The content of the leveling agent (J) is preferably from 0.001 to 2.0 mass %, and more preferably from 0.005 to 1.0 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0283] [Storage stabilizer (O)] The photosensitive composition of the present invention may contain a storage stabilizer (O).

[0284] The storage stabilizer (O) is not particularly limited and may be a known compound, for example, benzyl trimethyl chloride, quaternary ammonium chloride such as diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as tert-butylpyrocatechol, tetraethylphosphine and tetraphenyl, phosphites, etc.

[0285] The content of the storage stabilizer (O) is preferably from 0.05 to 5% by mass based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0286] [Organic solvent (P)] The photosensitive composition of the present invention can contain an organic solvent (P).

[0287] The organic solvent (P) is not particularly limited, and known compounds can be used. For example, 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-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-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone,Dipropylene glycol dimethyl ether, 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, dibasic acid esters, etc.,

[0288] From the viewpoint of the environment, 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.

[0289] The organic solvent (P) can be used alone or in combination of two or more kinds.

[0290] The content of the organic solvent (P) is preferably such that the nonvolatile content of the photosensitive composition is 5 to 60% by mass.

[0291] [Ultraviolet absorber (Q)] The photosensitive composition of the present invention may contain an ultraviolet absorber (Q).

[0292] The ultraviolet absorber (Q) is a compound having an ultraviolet absorption function, and examples thereof include benzotriazole compounds, triazine compounds, benzophenone compounds, salicylic acid ester compounds, cyanoacrylate compounds, and salicylate compounds.

[0293] Examples of the benzotriazole compound include 2-(5-tert-butyl-2-hydroxyphenyl)benzotriazole, benzenepropanoic acid, and an ester compound of 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy (C7-9 side chain and linear alkyl), 2-[5-chloro-(2H)-benzotriazol-2-yl]-4-methyl-6-(tert-butyl)phenol, 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, and the like. Commercially available products include, for example, Tinuvin PS, 99-2, 326, 384-2, 900, 928, 970, 1130 manufactured by BASF Japan, UVA-903KT, and Adeka Stab LA-31RG, LA-31G manufactured by ADEKA Corporation.

[0294] Benzophenone compounds include, for example, 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, and 2-aminobenzophenone. Examples of commercially available products include Ubinal A, 3049, 3050, and UVA-935LH manufactured by BASF Japan Ltd., Adeka STAB 1413 manufactured by ADEKA Corporation, and Omnirad EMK manufactured by IGM Resins.

[0295] The ultraviolet absorbents (Q) can be used alone or in combination of two or more kinds.

[0296] The content of the ultraviolet absorber (Q) 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, from the viewpoints of resolubility and chemical resistance after low-temperature heating.

[0297] When the thermal polymerization initiator (D) is a peroxide (D1), the ultraviolet absorber (Q) is preferably a benzotriazole compound from the viewpoint of resolubility.

[0298] The photosensitive composition of the present invention may contain components other than those described above. Examples of the other components include an acid generator, a salt generator, a curing catalyst, etc. The content of the other components may be appropriately set within a range that does not impair the effects of the present invention.

[0299] [Specific metal element content] The photosensitive composition of the present invention preferably has a total content of Li, Na, K, Mg, Ca, Fe, and Cr (hereinafter also referred to as specific metal elements) of 500 mass ppm or less.

[0300] 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 emission spectrometry (ICP).

[0301] [Water content] The photosensitive composition of the present invention preferably has a water content of 2.0% by mass or less. Photosensitive compositions having 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.

[0302] [Method of producing photosensitive composition] The photosensitive composition of the present invention can be prepared by mixing the above-mentioned components. When preparing the composition, the components may be mixed at once, or each component may be dissolved or dispersed in the polymerizable compound (B) or the organic solvent (P) and then mixed successively. When a pigment is used as the coloring matter (F), it is preferable to disperse the pigment. For example, a dispersion is produced by adding a dye (F), a dispersing resin (H), an organic solvent (P), etc., and carrying out a dispersion treatment. Then, a photosensitive alkali-soluble resin (A1), a polymerizable compound (B), a photopolymerization initiator (C), a thermal polymerization initiator (D), a thermal crosslinking compound (E), etc. are blended and mixed with the dispersion to produce the dispersion. The timing of blending each material is arbitrary. The dispersion process can also be carried out multiple times.

[0303] 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.

[0304] The average dispersed particle size (secondary particle size) of the pigment particles in the dispersion is preferably from 30 to 200 nm, more preferably from 40 to 200 nm. If the pigment particles have an appropriate particle size, a photosensitive composition having high dispersion stability is easily obtained.

[0305] The average dispersed particle size (secondary particle size) is measured, for example, using Nikkiso's Microtrack UPA-EX150, which employs dynamic light scattering (FFT power spectrum method), with particle permeability set to absorption mode, particle shape set to non-spherical, and D50 particle size set to average size. The dilution solvent used for measurement is the organic solvent used for dispersion, and measurements are made on samples treated with ultrasound immediately after sample preparation to obtain results with little variation.

[0306] The photosensitive composition is preferably subjected to removal of coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more, and mixed dust by means of centrifugation, filtration with a sintered filter or membrane filter, etc. The photosensitive composition of the present invention preferably does not substantially contain particles of 0.5 μm or more, and more preferably does not contain particles of 0.3 μm or less.

[0307] The photosensitive composition of the present invention is preferably used for pattern formation in a photolithography method, although the present invention is not limited thereto.

[0308] <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 may also be used as a flat film without forming a pattern.

[0309] [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 through a step of applying the coloring composition of the present invention onto a substrate and a step of drying the applied composition.

[0310] [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. Also, an imaging element such as a CCD or a CMOS may be formed on the substrate. Also, an undercoat layer may be provided on the substrate as necessary to improve adhesion with the upper layer, prevent diffusion of substances, and flatten the surface.

[0311] The coating method may be a known method, 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.

[0312] The thickness of the membrane can be appropriately adjusted depending on the purpose, and is preferably 0.05 to 20.0 μm, more preferably 0.3 to 10.0 μm.

[0313] [Drying process] The method for drying the film applied to the substrate is not particularly limited, and any known method can be used. For example, a reduced pressure drying method using a vacuum drying device, a heat drying method using a hot plate, an IR oven, a convection oven, or the like, and a combination of these methods can be used.

[0314] The drying temperature and time can be appropriately adjusted. The drying temperature is preferably about 50 to 130° C., and the drying time is preferably about 5 seconds to 5 minutes.

[0315] Next, a pattern is formed. Examples of methods for forming a pattern include photolithography and dry etching. Among these, photolithography is preferred. When used as a planar film, the step of forming a pattern is not performed. After coating, drying and overall exposure are performed as necessary.

[0316] Hereinafter, a method for forming a pattern by photolithography will be described in detail. In the photolithography method, a layer formed by coating and drying the photosensitive composition of the present invention on a substrate is exposed in a pattern through a mask (exposure step), and the unexposed portion is removed by alkali development (development step), and then the pattern is heat-treated (post-bake step).

[0317] 〔Exposure step〕 In the exposure step, the layer formed by coating and drying is exposed to a specific pattern through a mask using an exposure apparatus such as a stepper. Thereby, the exposed portion can be cured. Examples of the active energy ray used for exposure include ultraviolet rays such as g-line (wavelength 436 nm), h-line (wavelength 405 nm), and i-line (wavelength 365 nm). Further, light having a wavelength of 300 nm or less can also be used. Examples of light having a wavelength of 300 nm or less include KrF line (wavelength 248 nm), ArF line (wavelength 193 nm), etc. When using light of a specific wavelength for irradiation, an optical filter can also be used. Further, at the time of exposure, the light may be continuously irradiated for exposure, or the light irradiation and pause may be repeated in a short time (for example, at the millisecond level or less) cycle for exposure (pulse exposure). In addition, a plurality of active energy rays can be used in combination or exposure can be performed in multiple times.

[0318] 〔Development step〕 Next, by performing alkali development treatment, the layer of the unexposed portion is eluted in the alkali developer, and only the cured portion remains to obtain a patterned film. Examples of the alkaline developer 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, 1,8-diazabicyclo-[5.4.0]-7-undecene, etc. 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, it suppresses roughening and peeling of the pattern and improves the remaining film rate after development. Examples of the developing method include a dipping method, a spraying method, a puddle method, etc. The developing temperature is preferably 15 to 40° C. After the alkaline development, it is preferable to wash with pure water.

[0319] [Post-bake process] After development, a heat treatment (post-baking) is performed. Post-baking improves the resistance of the film. The temperature is preferably 60 to 150° C., more preferably 80 to 130° C. The time is preferably about 2 minutes to 2 hours.

[0320] <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.

[0321] <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 includes the optical filter of the present invention and functions as a solid-state imaging device. For example, the following configurations can be mentioned.

[0322] The substrate has a plurality of photodiodes constituting a light receiving area of ​​a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) and a transfer electrode made of polysilicon or the like, a light shielding film with only the light receiving portion of the photodiode open on the photodiode and the transfer electrode, 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 portion of the photodiode, and the optical filter (color filter) of the present invention on the device protection film. Furthermore, the device protection film may have a light collecting means (e.g., a microlens, etc., the same below) on the device protection film and below the optical filter (the side closer to the substrate), or a light collecting means on the optical filter. The filter may have a structure in which a cured film forming each color pixel is embedded in a space partitioned by partitions, for example, in a lattice shape. In this case, the partitions preferably have a low refractive index with respect to each color pixel. An imaging device including a 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.

[0323] <Image display device> The image display device of the present invention includes the above 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 configuration can be given.

[0324] The 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 the TN method, the IPS method, the OCB method, and the MVA method. The counter substrate can be appropriately selected according to the driving method. The liquid crystal layer can use various liquid crystals with different dielectric anisotropy and mixtures thereof according to the driving method.

[0325] 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 Yoshiaki, published by Sangyo Tosho Co., Ltd. in 1989).

[0326] <Infrared sensor> The infrared sensor of the present invention has the above optical filter. The form of the infrared sensor used is not particularly limited as long as it is provided with the optical filter of the present invention and functions as an infrared sensor, and examples thereof include the following configurations.

[0327] A substrate has a plurality of photodiodes constituting a light receiving area of ​​a solid-state imaging element (CCD image sensor, CMOS image sensor, etc.) and a transfer electrode made of polysilicon or the like. A light shielding film with only the light receiving portion of the photodiodes open is provided on the photodiodes and the transfer electrodes. A device protection film is provided on this light shielding film, and the optical filter of the present invention is provided on this device protection film. Furthermore, the device protection film may have a light collecting means (e.g., a microlens, etc., the same applies below) below the optical filter (the side closer to the substrate) on the device protection film, or the light collecting means may be provided on the optical filter.

[0328] 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. The infrared sensor shown in FIG.

[0329] 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 .

[0330] The infrared cut filter 111 transmits light in the visible light region (for example, light with a wavelength of 400 to 700 nm) and blocks light in the infrared region (for example, light with a wavelength of 800 to 1,300 nm).

[0331] The color filter 112 is a color filter having pixels formed therein that transmit and absorb light of specific wavelengths in the visible light region, and for example, a color filter having red (R), green (G), and blue (B) pixels formed therein is used.

[0332] 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.

[0333] 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.

[0334] 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 so as to cover the microlens 115.

[0335] 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.

[0336] This infrared sensor can simultaneously capture image information, making it possible to perform motion sensing that recognizes the object whose movement is to be detected. In addition, this infrared sensor can obtain distance information, making it possible to capture images that include 3D information. Furthermore, this infrared sensor can also be used as a biometric authentication sensor. EXAMPLES

[0337] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these examples. Note that "parts" means "parts by mass" and "%" means "% by mass". In the present invention, the non-volatile content or non-volatile content concentration refers to the mass residue after standing in an oven at 110°C for 3 hours.

[0338] Before describing the examples, each measurement method will be described.

[0339] The weight average molecular weight (Mw), number average molecular weight (Mn), acid value (mgKOH / g), amine value (mgKOH / g), and extinction coefficient (L / mol cm) of the resin are measured as follows.

[0340] (Molecular weight) Number average molecular weight (Mn) and weight average molecular weight (Mw) were measured by gel permeation chromatography (GPC) equipped with an RI detector. The instrument used was an HLC-8220GPC (manufactured by Tosoh Corporation), with two separation columns connected in series, and both packings were "TSK-GEL SUPER HZM-N" connected in series. The oven temperature was 40°C, tetrahydrofuran (THF) was used as the eluent, and the flow rate was 0.35 ml / min. A 1% by mass THF solution was prepared as the sample, and 20 microliters were injected. The molecular weight is a polystyrene equivalent value.

[0341] (Acid value) 80 ml of acetone and 10 ml of water were added to 0.5 to 1 g of sample solution, and the solution was stirred to dissolve uniformly. The solution was titrated with an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.) using a 0.1 mol / L KOH aqueous solution as the titrant, and the acid value (mgKOH / g) was measured. The acid value per unit of nonvolatile content was calculated from the acid value of the solution and the concentration of nonvolatile content in the solution.

[0342] (amine value) The amine value is the total amine value (mgKOH / g) measured according to the method of ASTM D 2074 and converted into non-volatile content.

[0343] <Preparation of photosensitive alkali-soluble resin (A1) solution> (Preparation of Photosensitive Alkali-Soluble Resin (A1-1) Solution) A separable 4-neck flask was fitted with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer to form a reaction vessel. 100 parts of propylene glycol monomethyl ether (hereinafter referred to as PGMAc) was placed in the reaction vessel, which was heated to 120°C while injecting nitrogen gas into the vessel. At the same temperature, a mixture of 10.4 parts of styrene (hereinafter referred to as St), 85.3 parts of glycidyl methacrylate (hereinafter referred to as GMA), 67.2 parts of dicyclopentanyl methacrylate (hereinafter referred to as DCPMA), and 1.0 parts of azobisisobutyronitrile (hereinafter referred to as AIBN) was added dropwise over 2.5 hours from the dropping tube to carry out a polymerization reaction. Next, the flask was substituted with air, and 43.2 parts of acrylic acid (hereinafter referred to as AA), 0.3 parts of trisdimethylaminomethylphenol, and 0.3 parts of hydroquinone were added, and the reaction was carried out at 120°C for 5 hours. In this way, the epoxy group of GMA and the carboxyl group of AA were reacted to synthesize a polymerizable unsaturated group-containing monomer unit (hereinafter referred to as GMA+AA). Further, 60.8 parts of tetrahydrophthalic anhydride (hereinafter, THPA) and 0.5 parts of triethylamine were added and reacted at 120°C for 4 hours. As a result, the hydroxyl groups of GMA+AA and THPA were esterified to synthesize a structure derived from a polybasic acid anhydride modified with a fatty acid anhydride (hereinafter, represented as GMA+AA+THPA). After cooling to room temperature, PGMAc was added so that the non-volatile content was 30%, and an alkali-soluble resin (A1-1) solution of a chain random polymer was prepared. The weight average molecular weight of the obtained resin was 8,000 and the acid value was 75 KOHmg / g. In Table 1, the content of the monomer unit is shown in mol%.

[0344] <Production of Non-Photosensitive Alkali-Soluble Resin (A2)> (Preparation of Non-Photosensitive Alkali-Soluble Resin (A2-1) Solution) In a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 149.3 parts of propylene glycol monomethyl ether (hereinafter also referred to as "PGME") was placed, and the mixture was stirred while replacing with nitrogen and heated to 78°C. Next, a monomer mixture consisting of 20.2 parts (10 mol%) of malonic acid-2-[[[2-methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3 diethyl ester (Karenz MOI-DEM, manufactured by Resonac), 6.7 g (10 mol%) of styrene, 28.2 parts (20 mol%) of dicyclopentanyl methacrylate, 11.0 parts (20 mol%) of methacrylic acid, 25.3 parts of 2-ethylhexyl methacrylate (20 mol%), and 12.8 parts (20 mol%) of methyl methacrylate, and 11.2 parts of 2,2'-azobis(2,4-dimethylbutadiene) was added. The mixture obtained by dissolving 62.8 parts of ethylhexyl nitrile (polymerization initiator) in 62.8 parts of PGMAc was dropped into the flask from the dropping funnel. After the dropping was completed, the reaction was carried out at 78°C for 3 hours to synthesize a linear random copolymer. After cooling to room temperature, PGMAc was added so that the non-volatile content was 30%, and a non-photosensitive alkali-soluble resin (A2-1) solution was obtained. The weight average molecular weight of the obtained resin was 8,000 and the acid value was 75 KOHmg / g. In Table 1, the content of the monomer unit is shown in mol%.

[0345] [Table 1]

[0346] <(Production of Blocked Isocyanate Group-Containing Compound (E1)> (Production of Blocked Isocyanate Group-Containing Compound E1-1) In a four-neck flask equipped with a thermometer, stirring blade, and reflux condenser, 100 parts by mass of hexamethylene diisocyanate (hereinafter also referred to as HDI) was charged under a nitrogen gas flow, and the temperature inside the reactor was maintained at 60°C while 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 stop the reaction. After filtering the reaction liquid, 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. In addition, the obtained E1 precursor 1 H-NMR analysis was performed to confirm the presence of isocyanurate groups. In a four-neck flask equipped with a thermometer, a stirring blade, and a reflux condenser, 100 parts by mass of the above E1 precursor and diethyl malonate (100 mol% relative to 100 mol% NCO groups) were charged under a nitrogen stream, and butyl acetate was further added to adjust the solid content to 60% by mass. Next, while stirring, 1.0 part by mass of a methanol solution containing sodium methylate (28% by mass relative to the total mass of the solution) was dropped, and the external bath was adjusted so that the solution temperature was 55°C, and a blocking reaction was carried out at 55°C for 5 hours to obtain a blocked isocyanate group-containing compound E1-1 with a solid content of 60% by mass and containing the above (X-1) as a blocked isocyanate group.

[0347] (Production of Blocked Isocyanate Group-Containing Compound E1-2) In a four-neck flask equipped with a thermometer, a stirring blade and a reflux condenser, 100 parts by mass of the above 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) were charged under a nitrogen stream, and butyl acetate was further added to adjust the solid content to 60% by mass. Next, while stirring, 1.0 part by mass of a methanol solution containing sodium methylate (28% by mass relative to the total mass of the solution) was dropped, and the external bath was adjusted so that the solution temperature was 55°C, and a blocking reaction was carried out at 55°C for 5 hours to obtain a blocked isocyanate group-containing compound E1-2 having a solid content of 60% by mass and containing the above (X-1) and (X-8) in a molar ratio of 70:30 as blocked isocyanate groups.

[0348] (Production of Blocked Isocyanate Group-Containing Compound E1-3) In a four-neck flask equipped with a thermometer, a stirring blade and a reflux condenser, 100 parts by mass of the above 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) were charged under a nitrogen stream, and butyl acetate was further added to adjust the solid content to 60% by mass. Next, while stirring, 1.0 part by mass of a methanol solution containing sodium methylate (28% by mass relative to the total mass of the solution) was dropped, and the external bath was adjusted so that the solution temperature was 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 having a solid content of 60% by mass and containing the above (X-1) and (X-8) in a molar ratio of 30:70 as blocked isocyanate groups.

[0349] (Production of Blocked Isocyanate Group-Containing Compound E1-4) In a four-neck flask equipped with a thermometer, a stirring blade and a reflux condenser, 100 parts by mass of E1 precursor, diisopropyl malonate (70 mol% relative to 100 mol% of NCO group), and di-tert-butyl malonate (30 mol% relative to 100 mol% of NCO group) were charged under nitrogen gas flow, and butyl acetate was further added to adjust the solid content to 60% by mass. Next, while stirring, 1.0 part by mass of a methanol solution containing sodium methylate (28% by mass relative to the total mass of the solution) was dropped, and the external bath was adjusted so that the solution temperature was 55°C, and the blocking reaction was carried out at 55°C for 5 hours to obtain a blocked isocyanate group-containing compound E1-4 having a solid content of 60% by mass and containing the above (X-4) and (X-7) in a molar ratio of 70:30 as blocked isocyanate groups.

[0350] <Production of dye (F)> (Yellow pigment (f12)) 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 obtained 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 adding 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 react. Then, potassium hydroxide was added to adjust the pH to about 5.2, 100 parts of distilled water was added, and the mixture was heated to 90 ° C. Next, 21 parts of 30% hydrochloric acid was added dropwise, and the mixture was stirred for 12 hours to react. Then, potassium hydroxide was added to adjust the pH to about 5, and the product was taken out by filtration. The product was washed with ion-exchanged water and filtered. After drying at 80 ° C., it was pulverized to obtain a colorant (f12) having a molar ratio of Ni, Zn, and Cu of 65:30:5.

[0351] <Production of near-infrared absorbing dye> (Production of near infrared absorbing dye (F-NIR1)) A near-infrared absorbing dye (F-NIR1) represented by the following chemical formula (400) was obtained by the method described in JP 2022-96687 A.

[0352] Chemical formula (400) [ka]

[0353] (Production of near infrared absorbing dye (F-NIR2)) A near-infrared absorbing dye (F-NIR2) represented by the following chemical formula (401) was obtained by the method described in JP 2022-96687 A.

[0354] Chemical formula (401) [ka]

[0355] (Production of near-infrared absorbing dyes (F-NIR31), (F-NIR32), and (F-NIR33)) By the method described in JP 2022-72558 A, a finely divided near-infrared absorbing dye (F-NIR31) represented by the following chemical formula (403), a near-infrared absorbing dye (F-NIR32) represented by the following chemical formula (404), and a near-infrared absorbing dye (F-NIR33) represented by the following chemical formula (405) were obtained.

[0356] [ka]

[0357] The near-infrared absorbing dyes (F-NIR31) to (F-NIR33) were mixed in a ratio of 1:1:1 to obtain the near-infrared absorbing dye (F-NIR3).

[0358] (Production of near infrared absorbing dye (F-NIR4)) According to the description in WO 2019 / 058882, a near-infrared absorbing dye (F-NIR4) represented by chemical formula (406) was obtained.

[0359] Chemical formula (406) [ka]

[0360] <Production of Dispersion Resin (H)> (Dispersion resin (H-1) solution) In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 108 parts of 1-thioglycerol, 174 parts of pyromellitic anhydride, 650 parts of PGMAc (propylene glycol monomethyl ether acetate), and 0.2 parts of monobutyltin oxide as a catalyst were charged, and after replacing with nitrogen gas, the reaction was carried out at 120°C for 5 hours (first step). It was confirmed by measuring the acid value that 95% or more of the acid anhydride was half-esterified. Next, 160 parts of the compound obtained in the first step, calculated as non-volatile content, 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of t-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, 200 parts of methyl acrylate, 50 parts of methacrylic acid, and 663 parts of PGMAc were charged, and the inside of the reaction vessel was heated to 80 ° C., and 1.2 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) were added, and the reaction was carried out for 12 hours (second step). It was confirmed that 95% or more had reacted by measuring the non-volatile content. Finally, 500 parts of a 50% PGMAc solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate, and 0.1 parts of hydroquinone were charged, and the reaction was carried out until the disappearance of the peak at 2270 cm-1 due to the isocyanate group was confirmed by IR (third step). After confirming the disappearance of the peak, the reaction solution was cooled and the non-volatile content was adjusted with PGMAc to obtain a solution of dispersion resin (H-1), a comb-shaped acidic resin-type dispersant with photocrosslinkability and a non-volatile content of 30%. The acid value of dispersion resin (H-1) was 68 KOHmg / g, the double bond equivalent was 1,593 g / eq., and the weight average molecular weight was 13,000.

[0361] <Preparation of Dispersion> (Dispersion 1) After stirring and mixing the following raw materials to make them uniform, they were dispersed for 3 hours using a zirconia bead with a diameter of 0.5 mm in an Eiger mill (Mini Model M-250 MKII manufactured by Eiger Japan Co., Ltd.), and then filtered through a filter with a pore size of 1.0 μm to prepare Dispersion 1. The non-volatile content was 20% by mass. Red pigment (F-1): 14.0 parts Dispersion resin (H-1) solution: 16.7 parts Pigment derivative (G-4): 1.0 part Organic solvent (propylene glycol monomethyl ether acetate): 63.3 parts

[0362] (Dispersions 2 to 16) Dispersions 2 to 16 were produced in the same manner as Dispersion 1, except that the raw materials and amounts described in Tables 2 and 3 were changed. The numerical values in the table are non-volatile content ratios. The solvent is PGMAc in all cases, and the non-volatile content of Dispersions 2 to 16 is 30%.

[0363] Each component described in Tables 2 and 3 is as follows.

[0364]

Table 2

[0365]

Table 3

[0366] [Dye (F)] (Red pigment) F-1: C.I. Pigment Red 177 (manufactured by Sinic Co., Ltd., "Sinilex Red SR3C") F-2: C.I. Pigment Red 254 (manufactured by BASF Co., Ltd., "Irgajin Red L3630") F-3: C.I. Pigment Red 264 (manufactured by BASF Co., Ltd., "Irgazin Rubine L4025") (Green pigment) F-4: C.I. Pigment Green 36 (manufactured by Toyo Color Co., Ltd., "Leonol Green 6YK") F-5: CI Pigment Green 58 (DIC, FASTOGEN Green A110) F-6: CI Pigment Green 59 (DIC) F-7: CI Pigment Green 62 (Toyo Color) F-8: CI Pigment Green 63 (Toyo Color) (Blue pigment) F-9: CI Pigment Blue 15:3 (Toyo Color Co., Ltd., "Leonor Blue FG7351") F-10: CI Pigment Blue 15:6 (manufactured by Toyo Color Co., Ltd., "Leonor Blue ES") (purple pigment) F-11: CI Pigment Violet 23 (manufactured by Toyo Color Co., Ltd., "Lionogen Violet FG6140") (Yellow pigment) F-12: CI Pigment Yellow 138 (BASF Japan, "Paliothol Yellow K0960-HD") F-13: CI Pigment Yellow 139 (BASF Japan, "Paliotol Yellow D1819") F-14: CI Pigment Yellow 150 (LANXESS, "Yellow Pigment E4GN") F-15: CI Pigment Yellow 231 (manufactured by Toyo Color Co., Ltd.) F-16: The yellow pigment (f12 (Near infrared absorbing dye) F-17: F-NIR1 F-18: F-NIR2 F-19: F-NIR3 F-20: F-NIR4

[0367] All of the pigments (F-1) to (F-20) were finely milled by salt milling, and thoroughly washed and dried before use.

[0368] [Pigment derivatives (G)] [ka]

[0369] <Production of silane coupling agent (K)> (Silane coupling agent (K-1)) In a 1L separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 116 parts of hydroxyethyl acrylate was charged and heated to 80°C. 205 parts of 3-isocyanatepropyltrimethoxysilane was added dropwise thereto and stirred at 80°C for 4 hours to react. After that, it was confirmed by IR measurement that the absorption peak derived from the isocyanate group of the raw material had completely disappeared and instead an absorption peak derived from a urethane bond had been generated, and a silane coupling agent (K-1) whose main component is represented by the following chemical formula (20) was obtained. In addition, as a secondary component, a dimer to decamer which is a condensation product of the chemical formula (20) was included.

[0370] Chemical formula (20) [ka]

[0371] <Production of Photosensitive Composition> [Example 1] (Photosensitive composition 1) The following raw materials were mixed, stirred, and filtered through a filter with a pore size of 1.0 μm to obtain a photosensitive composition with a nonvolatile content of 15%. Dispersion 6: 16.07 parts Dispersion 7: 3.21 parts Dispersion 11: 3.21 parts Dispersion 12: 9.64 parts Alkali-soluble resin (A1-1) solution: 11.01 parts Polymerizable compound (B-1): 3.00 parts Photopolymerization initiator (C1-1): 0.15 parts Thermal polymerization initiator (D1-1): 0.45 parts Blocked isocyanate group-containing compound (E1-1): 2.50 parts Silane coupling agent (K-1): 0.75 parts UV absorber (Q-1): 0.15 parts Polymerization inhibitor (I-1): 0.0075 parts Leveling agent (J-1): 1.00 parts Organic solvent (P-1): 48.84 parts

[0372] [Examples 2 to 52 and Comparative Examples 1 to 2] Photosensitive compositions of Examples 2 to 52 and Comparative Examples 1 and 2 were prepared in the same manner as in Example 1, except that the raw materials and amounts shown in Tables 4 to 9 were used in place of those in Example 1.

[0373] [Table 4]

[0374] [Table 5]

[0375] [Table 6]

[0376] [Table 7]

[0377] [Table 8]

[0378] [Table 9]

[0379] In Tables 4 to 9, resin (A1) represents the photosensitive alkali-soluble resin (A1), and resin (A2) represents the non-photosensitive alkali-soluble resin (A2).

[0380] (Polymerizable compound (B)) B-1: CN9906NS (Arkema, aliphatic multifunctional urethane acrylate having a tertiary amine structure; polymerizable compound (B1) having an amine structure) B-2: Aronix M-306 (manufactured by Toagosei Co., Ltd., a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate; a polymerizable compound having a hydroxyl group (B2)) B-3: Aronix M-520 (manufactured by Toagosei Co., Ltd., polybasic acid modified acrylic oligomer; polymerizable compound having an acidic group (B3)) B-4: 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)

[0381] [Photopolymerization initiator (C)] C1-1: Adeka Arcles NCI-831 (manufactured by ADEKA Corporation; oxime-based photopolymerization initiator (C11) represented by the chemical formula (C11-2) C1-2: PBG-345 (manufactured by Changzhou Strong Co., Ltd.; oxime-based photopolymerization initiator (C12) represented by the chemical formula (C12-1)) C1-3: Irgacure OXE-04 (manufactured by BASF Japan; oxime-based photopolymerization initiator (C13) represented by the chemical formula (C13-1)) C1-4: Adeka Cruise NCI-930 (manufactured by BASF Japan; oxime-based photopolymerization initiator (C14) represented by the chemical formula (C14-4)) C1-5: Adeka Cruise NCI-730 (manufactured by ADEKA Corporation; oxime-based photopolymerization initiator (C15) represented by the chemical formula (C15-6) C2-1: NPI-20400 (α-aminoalkylphenone; Changzhou Strong Co., Ltd.; other photopolymerization initiators (C2))

[0382] [Thermal polymerization initiator (D)] (Peroxide (D1)) D1-1: 2,2-bis(4,4-di-tert-butylperoxycyclohexyl) D1-2: 1,1-bis(tert-hexylperoxy)cyclohexane D1-3: Di-tert-hexyl peroxide (Other thermal polymerization initiators (D2)) D2-1: Benzopiconal

[0383] [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), having about 15 epoxy groups and an epoxy equivalent of 170 to 190 g / eq.) E2-2: Denacol EX-611 (Nagase ChemteX Corporation, sorbitol polyglycidyl ether, epoxy group number approximately 6, epoxy equivalent 80-90g / 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, epoxy equivalent: 98g / eq.)

[0384] [Silane coupling agent (K)] K-1: KBE-403 (Shin-Etsu Silicone Co., Ltd., compound with epoxy group, 3-glycidoxypropyltriethoxysilane)

[0385] [Ultraviolet absorber (Q)] Q-1: TINUVIN326 (BASF Japan, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole) Q-2: Omnirad EMK (IGM Resins, 4,4'-bis(diethylamino)benzophenone)

[0386] [Polymerization inhibitor (I)] I-1: Methylhydroquinone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., an alkylhydroquinone compound)

[0387] [Leveling agent (J)] A mixed solution obtained by mixing 2 parts of J1 and 1 part of J2 below and dissolving the mixture in 97 parts of PGMAc was used as a leveling agent (J-1). J1: BYK-330 (BYK-Chemie, PGMAc solution with 51% non-volatile content, polyether-modified dimethylsiloxane) J2: Block copolymer having the following structure (n:m = 50:50 (mol%))

[0388] [ka]

[0389] [Organic solvent (P)] 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 obtain an organic solvent (P-1).

[0390] <Evaluation of Photosensitive Composition> The photosensitive compositions thus obtained were subjected to the following evaluations, and the evaluation results are shown in Table 10.

[0391] [Development stain evaluation] The obtained photosensitive composition was applied to a glass substrate (Corning Eagle 2000) having a length of 100 mm, width of 100 mm, and thickness of 0.7 mm 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 illumination intensity of 30 mW / cm. 2 , 100mJ / cm 2 The substrate was exposed to ultraviolet light through a photomask with a 100 μm wide stripe pattern. After cooling the substrate to room temperature, it was spray-developed with a potassium hydroxide solution (concentration: 0.04%) at 23°C for 40 seconds, washed with ion-exchanged water, and dried with clean air to obtain a substrate for evaluation. The photocured portion remaining after development was observed with an optical microscope at 50x magnification within a 5 x 5 cm area at the center of the substrate, and locally colored areas were observed as development stains. The evaluation criteria are as follows, with 3 or higher being practical. 5: No development stains are observed in the entire light-cured area. 4: The area of ​​the entire photocured portion was taken as 100%, and less than 10% was observed as development stains. 3: The area of ​​the entire photocured portion was taken as 100%, and 10% or more but less than 20% of the area was observed as development stains. 2: The area of ​​the entire photocured portion was taken as 100%, and 20% or more but less than 50% of the area was observed as development stains. 1: The total area of ​​the photocured portion is taken as 100%, and 50% or more was observed as development stains.

[0392] [Evaluation of dried precipitate] The obtained photosensitive composition was evaluated through the steps (1) to (4) described below. A control device was used that automatically performed the operation of attaching a glass test piece (Corning Glass Eagle 2000) to the arm of a driving device and repeatedly inserting and removing the tip of the test piece into and from a bottle filled with the photosensitive composition. (1) At an atmospheric 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 down, and then dried for 52 seconds under conditions of an atmospheric temperature of 23°C, a humidity of 55%, and a wind speed of 0.5±0.2 m / sec. (3) The steps (1) and (2) were repeated a total of 250 times to form a deposit (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 multiplying these values. The evaluation criteria are as follows, with 3 or more being practical. [Evaluation Criteria] 5: The weight of the attached matter (a) is less than 1 μg 4: The weight of the attached matter (a) is 1 μg or more and less than 2 μg 3: The weight of the attached matter (a) is 2 μg or more and less than 3 μg. 2: The weight of the attached matter (a) is 3 μg or more and less than 4 μg 1: The weight of the attached matter (a) is 4 μg or more

[0393] [Evaluation of heat shock resistance] The obtained photosensitive composition was placed in a sealed container, and a temperature cycle test was performed for 150 days at 5°C for 4 hours and 30°C for 2 hours. Thereafter, the photosensitive composition was taken out of the sealed container, and the photosensitive composition was applied to a glass substrate using a spin coater so that the film thickness after drying was 0.5 μm, and a heat treatment (pre-baking) was performed for 180 seconds using a hot plate at 100°C to produce a coating film for evaluation. The coating film on the glass substrate was magnified 100 times in a 0.5 mm square area with an optical microscope, and the number of defects in the field of view was counted. The same operation was repeated a total of 10 times by arbitrarily changing the observation position, and the total number of defects was calculated. The evaluation criteria are as follows, and 3 or more is 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

[0394] [Evaluation of Solvent Resistance] The obtained photosensitive composition was applied to a glass substrate (Corning Eagle 2000) having a length of 100 mm, width of 100 mm, and thickness of 0.7 mm using a spin coater so that the dry film thickness was 2 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 illumination intensity of 30 mW / cm. 2 , irradiation amount 100mJ / cm 2 The substrate was exposed to ultraviolet light through a photomask with a square pattern of 100 μm squares. After cooling the substrate to room temperature, it was spray-developed using a potassium hydroxide solution (concentration: 0.04% by mass) at 23° C. for a development time of 40 seconds, then washed 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. The evaluation criteria are as follows, with 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

[0395] [Storage stability evaluation: Viscosity change rate] The obtained photosensitive composition was placed in a sealed container and stored at 40°C for one week, and the rate of change in viscosity before and after storage was calculated and evaluated using the following formula. The viscosity was measured using an E-type viscometer ("ELD-type viscometer" manufactured by Toki Sangyo Co., Ltd.) at 25°C and a rotation speed of 50 rpm. The evaluation criteria are as follows, with 3 or more being practical. [Change rate of viscosity over time] = |([Initial viscosity] - [Viscosity over time]) / [Initial viscosity]| x 100 [Evaluation Criteria] 5: Less than 2% change 4: Change rate is 2% or more but less than 5% 3: Change rate is 5% or more but less than 10% 2: Change rate is 10% or more but less than 20% 1: Change rate 20% or more

[0396] [Table 10]

Claims

1. A photosensitive composition comprising a photosensitive alkali-soluble resin (A1), a polymerizable compound (B), a photopolymerization initiator (C), a thermal polymerization initiator (D), and a thermal crosslinking compound (E), The thermally crosslinkable compound (E) is a photosensitive composition containing a blocked isocyanate group-containing compound (E1).

2. 2. The photosensitive composition according to claim 1, wherein the blocking agent for the blocked isocyanate group is an active methylene compound.

3. The photosensitive composition according to claim 1 , wherein the thermally crosslinkable compound (E) further comprises an epoxy compound (E2).

4. The photosensitive composition according to claim 1 , further comprising a dye (F).

5. 2. The photosensitive composition according to claim 1, wherein the thermal polymerization initiator (D) comprises a peroxide (D1).

6. A film formed from the photosensitive composition according to any one of claims 1 to 5.

7. An optical filter comprising the film according to claim 6.

8. A solid-state imaging device comprising the optical filter according to claim 7.

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

10. An infrared sensor comprising the optical filter according to claim 7.

Images