Photosensitive composition, film, optical filter, color filter, picture display unit, solid state imaging element, and infrared sensor

Abstract

To provide a photosensitive composition capable of forming a film excellent in storage stability, heat shock resistance and re-melting property, difficult to generate development stain and excellent in solvent resistance after low temperature curing.SOLUTION: A photosensitive composition containing alkaline-soluble resin (A), polymerizable compound (B), photopolymerization initiator (C), and thermal polymerization initiator (D), wherein the photopolymerization initiator (C) includes an oxime ester photopolymerization initiator (C1), and the thermal polymerization initiator (D) includes an oxime sulfonate compound (D1) (excluding compounds in which a carbon atom forming a double bond with the nitrogen atom in the oxime sulfonate structure forms a ring).SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a photosensitive composition that can be used to form optical filters and the like. [Background technology]

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

[0003] Among image display devices, the organic light-emitting layers used in organic EL (Electro-Luminescence) display devices using OLEDs (Organic Light Emitting Diodes) and the like have low heat resistance. Therefore, photosensitive compositions used to form optical filters must be post-baked at lower temperatures than conventional methods, for example, at 150°C or lower. However, low temperatures can result in insufficient film curing and reduced solvent resistance. In addition, the storage stability of photosensitive compositions can be reduced if they contain highly reactive materials (e.g., polymerizable compounds, photopolymerization initiators).

[0004] In addition, as a risk management measure against breakdowns and problems with production lines and refrigerators, it is necessary to consider the quality stability (heat shock resistance) of photosensitive compositions in harsh environments where temperatures fluctuate, rather than at a constant temperature.

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

[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] Japanese Patent Application Laid-Open No. 2013-119568 Summary of the Invention [Problem to be solved by the invention]

[0010] However, conventional photosensitive compositions have not been able to satisfy all of the requirements for storage stability, solvent resistance after low-temperature curing, heat shock resistance, and resolubility. Furthermore, conventional photosensitive compositions have also had the problem of developing stains caused by the developer on the film surface during the development process.

[0011] An object of the present invention is to provide a photosensitive composition that has good storage stability, heat shock resistance, and resolubility, is less likely to cause development stains, and can form a film that has excellent solvent resistance after a low-temperature curing step.

[0012] <1> The photosensitive composition of the present invention is a photosensitive composition comprising an alkali-soluble resin (A), a polymerizable compound (B), a photopolymerization initiator (C), and a thermal polymerization initiator (D), the photopolymerization initiator (C) includes an oxime ester photopolymerization initiator (C1), The thermal polymerization initiator (D) includes an oxime sulfonate compound (D1) (excluding compounds in which a carbon atom forming a double bond with a nitrogen atom in an oxime sulfonate structure forms a ring). <2> The alkali-soluble resin (A) contains an alkali-soluble resin (A1) having a blocked isocyanate group-containing monomer unit (a1). <1> The photosensitive composition according to claim 1. <3> Further, the thermal crosslinking compound (E) <1> The photosensitive composition according to claim 1. <4> The polymerizable compound (B) contains a (meth)acrylate compound (B1) having an amine structure. <1> The photosensitive composition according to claim 1. <5> <1> <2> <3> and <4> 1. A film formed from the photosensitive composition according to any one of claims 1 to 9. <6> <5> An optical filter having the film according to claim 1. <7> <6> A solid-state imaging device having the optical filter according to claim 1. <8> <6> An image display device comprising the optical filter according to claim 1. <9> <6> An infrared sensor having the optical filter according to claim 1. [Effects of the Invention]

[0013] The present invention provides a photosensitive composition capable of forming a film that has good storage stability, heat shock resistance, and resolubility, is less likely to cause development stains, and has excellent solvent resistance after a low-temperature curing step.The present invention also provides a film, an optical filter, a color filter, an image display device, a solid-state imaging device, and an infrared sensor. [Brief explanation of the drawings]

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

[0015] The terms used in this specification are defined below. Unless otherwise specified, the terms "(meth)acryloyl," "(meth)acrylic," "(meth)acrylic acid," "(meth)acrylate," "(meth)allyl," and "(meth)acrylamide" respectively mean "acryloyl and / or methacryloyl," "acrylic and / or methacrylic," "acrylic acid and / or methacrylic acid," "acrylate and / or methacrylate," "allyl and / or methallyl," and "acrylamide and / or methacrylamide." "CI" means Color Index (CI). The polymerizable unsaturated group is an ethylenically unsaturated group such as a vinyl group, a (meth)acryloyl group, or a (meth)allyl group. The monomer is a state before polymerization. The monomer unit is a state that constitutes a resin after polymerization of the monomer. The oxime sulfonate compound is a compound having an oxime sulfonate structure. "C1" means that the number of carbon atoms is 1. For example, when written as C1-C8-alkyl, it means that the number of carbon atoms is 1 to 8.

[0016] The photosensitive composition of the present invention comprises an alkali-soluble resin (A), a polymerizable compound (B), a photopolymerization initiator (C), and a thermal polymerization initiator (D). The photopolymerization initiator (C) comprises an oxime ester photopolymerization initiator (C1), and the thermal polymerization initiator (D) comprises an oxime sulfonate compound (D1) (excluding compounds in which a carbon atom forming a double bond with a nitrogen atom in an oxime sulfonate structure forms a ring).

[0017] The photosensitive composition of the present invention can form a strong film by combining photocrosslinking obtained by the polymerizable compound (B) and the oxime ester photopolymerization initiator (C1) with thermal crosslinking obtained by the polymerizable compound (B) and the oxime sulfonate compound (D1). In particular, during low-temperature curing, the oxime sulfonate compound (D1), which efficiently generates radicals even at low temperatures, allows the thermal crosslinking reaction to proceed at a lower temperature, thereby improving solvent resistance after low-temperature heating. Furthermore, although the mechanism is unclear, the oxime sulfonate compound (D1) exhibits high storage stability and heat shock resistance even when combined with the polymerizable compound (B) and the photopolymerization initiator (C), thereby eliminating the trade-off with solvent resistance and making it superior to conventional photosensitive compositions. Furthermore, the oxime sulfonate compound (D1) has good compatibility with the alkali-soluble resin (A), the polymerizable compound (B), and the photopolymerization initiator (C), resulting in uniform and less variable polarity on the film surface. This reduces the problem of development stains, which occur when highly hydrophilic areas come into contact with a developer. Furthermore, the improved compatibility improves the resolubility of the dried precipitate.

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

[0019] [Alkali-soluble resin (A)] The photosensitive composition of the present invention contains an alkali-soluble resin (A).

[0020] The alkali-soluble resin (A) is not particularly limited as long as it dissolves in the alkali developer described below, and any known resin can be used. Examples of the alkali-soluble resin (A) include (meth)acrylic resins, styrene resins, styrene / (meth)acrylic resins, epoxy resins, urethane resins, polycarbonate resins, polyester resins, polyether resins, polyimide resins, polyamideimide resins, and cyclic olefin resins.

[0021] The weight average molecular weight of the alkali-soluble resin (A) is preferably 3,000 to 100,000.

[0022] The acid value of the alkali-soluble resin (A) is preferably from 20 to 200 mgKOH / g, more preferably from 30 to 180 mgKOH / g.

[0023] The alkali-soluble resin (A) can be used alone or in combination of two or more kinds.

[0024] The alkali-soluble resin (A) preferably accounts for 1 to 90 mass %, more preferably 5 to 80 mass %, of 100 mass % of the nonvolatile content of the photosensitive composition.

[0025] (Alkali-soluble resin (A1) having a thermocrosslinkable group-containing monomer unit (a1)) The alkali-soluble resin (A) can contain an alkali-soluble resin (A1) having a thermocrosslinkable group-containing monomer unit (a1).

[0026] The alkali-soluble resin (A1) having a thermally crosslinkable group-containing monomer unit (a1) (hereinafter also referred to simply as alkali-soluble resin (A1)) is not particularly limited, and known resins can be used. The thermally crosslinkable group is a group that undergoes a crosslinking reaction upon heating to form a crosslink. Examples include a cyclic ether group, a methylol group, an isocyanate group, a blocked isocyanate group, an acetoacetoxy group, an alkoxysilyl group, and a tertiary alkyl group. Among these, from the viewpoints of storage stability and solvent resistance after low-temperature heating, at least one selected from the group consisting of a blocked isocyanate group, an acetoacetoxy group, an alkoxysilyl group, and a tertiary alkyl group is preferred. Examples of the alkali-soluble resin (A1) include a monomer that forms the thermocrosslinkable group-containing monomer unit (a1), and a copolymer of the monomer with any other copolymerizable monomer.

[0027] [Thermal crosslinkable group-containing monomer unit (a1)] From the viewpoints of storage stability and solvent resistance after low-temperature heating, the thermally crosslinkable group-containing monomer unit (a1) is preferably formed from a monomer represented by the following general formulas (1) to (5), more preferably general formulas (1) to (A2), and even more preferably general formula (1).

[0028] General formula (1) [ka]

[0029] In general formula (1), R 1 represents a hydrogen atom or a methyl group.

[0030] In general formula (1), R 2 and R 3 each independently represents an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms is linear or branched. Examples thereof include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, amyl, isoamyl, pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, and decyl groups. Among these, methyl, ethyl, and n-propyl groups are preferred.

[0031] In general formula (1), L 1 represents a single bond or a divalent organic group. Examples of the divalent organic group include an alkylene group having 1 to 20 carbon atoms, and an alkylene group having 1 to 20 carbon atoms having -O- between the carbon-carbon bond. The alkylene group having 1 to 20 carbon atoms is linear or branched. Examples thereof include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, an isopropylene group, a 2-methylpropylene group, a 2-methylhexylene group, and a tetramethylethylene group. Among these, a methylene group, an ethylene group, and an n-propylene group are preferred.

[0032] In general formula (1), L 2 represents a single bond or an oxygen atom.

[0033] In general formula (1), L 3 and L 4each independently represents a single bond or a divalent organic group. Examples of the divalent organic group include alkylene groups having 1 to 20 carbon atoms. The alkylene group having 1 to 20 carbon atoms is the same as above.

[0034] The method for producing the monomer represented by general formula (1) is not particularly limited, and known methods can be used, such as those described in JP-A-10-316643 and WO 2022 / 145298.

[0035] Examples of the monomer represented by general formula (1) include compounds represented by formulas (1-1) to (1-14), but the present invention is not limited to these.

[0036] [ka] JPEG2025117618000004.jpg81150

[0037] From the viewpoint of solvent resistance after low-temperature heating, the monomer represented by general formula (1) is preferably at least one selected from the compounds of formulas (1-1), (1-2), (1-3), (1-4), (1-9), (1-10), (1-11), (1-12), (1-13) and (1-14).

[0038] General formula (2) [ka]

[0039] In general formula (2), R 1 represents a hydrogen atom or a methyl group.

[0040] In general formula (2), R 4 ~R 6 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms is the same as above. 4 and R 5is preferably a hydrogen atom, and R 6 is preferably a methyl group, an ethyl group, or an n-propyl group.

[0041] In general formula (2), L 1 represents a single bond or a divalent organic group. Examples of the divalent organic group include an alkylene group having 1 to 20 carbon atoms, and an alkylene group having 1 to 20 carbon atoms having -O- between the carbon-carbon bond. The alkylene group having 1 to 20 carbon atoms is the same as above.

[0042] The method for producing the monomer represented by general formula (2) is not particularly limited, and known methods can be used, such as those described in WO 2022 / 145298.

[0043] Specific examples of the monomer represented by general formula (2) include compounds represented by formulas (2-1) to (2-6), although the present invention is not limited thereto.

[0044] [ka]

[0045] General formula (3) [ka]

[0046] In general formula (3), R 1 represents a hydrogen atom or a methyl group.

[0047] In general formula (3), R 7 represents an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms is the same as above.

[0048] In general formula (3), L 1 represents a single bond or a divalent organic group. Examples of the divalent organic group include an alkylene group having 1 to 20 carbon atoms, and an alkylene group having 1 to 20 carbon atoms having -O- between the carbon-carbon bond. The alkylene group having 1 to 20 carbon atoms is the same as above.

[0049] The method for producing the monomer represented by general formula (3) is not particularly limited, and known methods can be used, such as those described in Witzeman, JS, and Dell Rector, FJ, Coatings Technology, Vol. 62.

[0050] Examples of the monomer represented by general formula (3) include compounds represented by formulas (3-1) to (3-4), but the present invention is not limited to these.

[0051] [ka]

[0052] General formula (4) [ka]

[0053] In general formula (4), R 1 represents a hydrogen atom or a methyl group.

[0054] In general formula (4), R 8 ~R 10 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, provided that R 8 ~R 10 At least one of them is an alkoxy group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a butyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an isopropyl group, and an isobutyl group. Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an isopropoxy group, etc. Among these, from the viewpoint of solvent resistance after low-temperature heating, a methoxy group and an ethoxy group are preferred. From the viewpoint of solvent resistance after low-temperature heating, R 8 ~R 10 At least two of these are preferably alkoxy groups having 1 to 6 carbon atoms.

[0055] In general formula (4), L 1 represents a single bond or a divalent organic group. Examples of the divalent organic group include an alkylene group having 1 to 20 carbon atoms, and an alkylene group having 1 to 20 carbon atoms having -O- between the carbon-carbon bond. The alkylene group having 1 to 20 carbon atoms is the same as above.

[0056] Specific examples of the monomer represented by general formula (4) include compounds represented by formulas (4-1) to (4-6), although the present invention is not limited thereto.

[0057] [ka]

[0058] Commercially available products of the monomer represented by general formula (4) include, for example, KBM-502, 503, 5103, 5803, KBE-502, 503, etc., manufactured by Shin-Etsu Chemical Co., Ltd.

[0059] General formula (5) [ka]

[0060] In general formula (5), R 1 represents a hydrogen atom or a methyl group.

[0061] In general formula (5), R 11 ~R 13 each independently represents an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms is the same as above. Among these, a methyl group is preferred.

[0062] In general formula (5), L 1 represents a single bond or a divalent organic group. The divalent organic group may be an alkylene group having 1 to 20 carbon atoms, a group having -NH-, or a combination thereof. The alkylene group having 1 to 20 carbon atoms is the same as above.

[0063] Examples of the monomer represented by general formula (5) include compounds represented by formulas (5-1) to (5-6), but the present invention is not limited to these. [ka]

[0064] From the viewpoints of storage stability and solvent resistance after low-temperature heating, the thermally crosslinkable group-containing monomer unit (a1) is more preferably one or more of the monomer unit represented by general formula (1) and the monomer unit represented by general formula (2).

[0065] The thermally crosslinkable group-containing monomer unit (a1) can be formed by using the monomers represented by the general formulae (1) to (5) either alone or in combination of two or more kinds.

[0066] The thermally crosslinkable group-containing monomer unit (a1) can be a combination of a monomer unit formed from a monomer represented by any one of the general formulae (1) to (5) and a monomer unit formed from a monomer other than the monomer represented by any one of the general formulae (1) to (5).

[0067] Examples of the monomer other than the monomers represented by the general formulas (1) to (5) include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxytricyclo[5.2.1.0 2,6] decan-8-yl (meth)acrylate, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decan-9-yl(meth)acrylate, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl(meth)acrylate, 2-[O-(1'-methylpropylideneamino)carboxyamino]ethyl(meth)acrylate, and the like.

[0068] The content of the thermally crosslinkable group-containing monomer unit (a1) is preferably 1 to 80 mol %, more preferably 5 to 70 mol %, of the total monomer units of the alkali-soluble resin (A1), from the viewpoints of storage stability and solvent resistance after low-temperature heating.

[0069] The alkali-soluble resin (A1) may contain, in addition to the thermally crosslinkable group-containing monomer unit (a1), for example, an acidic group-containing monomer unit (a2), a hydroxyl group-containing monomer unit (a3), an aliphatic fused ring structure-containing monomer unit (a4), a polymerizable unsaturated group-containing monomer unit (a5), or other monomer unit (a6).

[0070] [Acidic group-containing monomer unit (a2)] Examples of the acidic group-containing monomer include (meth)acrylic acid, crotonic acid, propiolic acid, cinnamic acid, itaconic acid, itaconic anhydride, maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, maleic anhydride, fumaric acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethylhexylhydrophthalic acid, p-styrenesulfonic acid, vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, and 2-(meth)acryloyloxyethyl acid phosphate.

[0071] From the viewpoint of alkali solubility, the content of the acidic group-containing monomer unit (a2) is preferably from 1 to 40 mol %, more preferably from 5 to 30 mol %, of all the constituent units of the alkali-soluble resin (A1).

[0072] The method for introducing the acidic group-containing monomer unit (a2) into the alkali-soluble resin (A1) may include copolymerizing a thermally crosslinkable group-containing monomer with an acidic group-containing monomer, or adding an acid anhydride (modifying compound) to the hydroxyl groups contained in the resin (precursor). Examples of the acid anhydride include succinic anhydride, phthalic anhydride, and 1,2,3,6-tetrahydrophthalic anhydride.

[0073] [Hydroxyl group-containing monomer unit (a3)] Examples of hydroxyl group-containing monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-acryloyloxyethyl-2-hydroxyethyl phthalate.

[0074] The content of the hydroxyl group-containing monomer units (a3) is preferably 1 to 60 mol %, more preferably 5 to 50 mol %, of all the monomer units in the alkali-soluble resin (A1), from the viewpoint of solvent resistance after low-temperature heating.

[0075] Methods for introducing the hydroxyl group-containing monomer unit (a3) into the alkali-soluble resin (A1) include copolymerizing a thermally crosslinkable group-containing monomer with a hydroxyl group-containing monomer, adding a compound having a carboxyl group (modifying compound) to an epoxy group contained in the resin, and adding a compound having an epoxy group (modifying compound) to a carboxyl group contained in the resin (precursor).

[0076] [Aliphatic fused ring structure-containing monomer unit (a4)] Examples of the aliphatic fused ring structure-containing monomer include isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, adamantyl (meth)acrylate, etc. Among these, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentanyloxyethyl (meth)acrylate are preferred.

[0077] [Polymerizable unsaturated group-containing monomer unit (a5)] The alkali-soluble resin (A1) can be made to contain the polymerizable unsaturated group-containing monomer unit (a5) by, for example, the following methods (i) to (iii).

[0078] <Method (i)> In the method (i), for example, a resin having an epoxy group is first synthesized, and then a monomer having a carboxyl group, among the above-mentioned acid group-containing monomers, is added to the epoxy group of the resin.

[0079] The resin obtained by adding a monomer having a carboxyl group to the epoxy group of the resin can be further reacted with an acid anhydride.

[0080] Examples of the acid anhydride include 1,2,3,6-tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride.

[0081] <Method (ii)> In the method (ii), for example, a resin having an acidic group-containing monomer unit (a2) in which the acidic group is a carboxyl group is first synthesized, and then an epoxy group-containing monomer (modifying compound) is added to the carboxyl group of the resin.

[0082] Examples of epoxy group-containing monomers include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate.

[0083] <Method (iii)> In the method (iii), for example, a resin having a hydroxyl group-containing monomer (a3) is first synthesized, and then the hydroxyl group of the resin is reacted with the isocyanate group of an isocyanate group-containing monomer (modifying compound).

[0084] Examples of the isocyanate group-containing monomer include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate.

[0085] [Other monomer units (a6)] Other monomers include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, and phenoxy Acrylic esters such as ethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, EO-modified (meth)acrylate of phenol, EO- or PO-modified (meth)acrylate of nonylphenol, EO- or PO-modified (meth)acrylate of paracumylphenol, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate; aromatic vinyl compounds such as styrene, α-methylstyrene, p-vinyltoluene, p-chlorostyrene, vinylnaphthalene; (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or acryloylmorpholine; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether; vinyl fatty acid vinyl compounds such as vinyl acetate or vinyl propionate; Phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5 -methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N N-substituted maleimides such as -(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, and 9-maleimidoacridine; Dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, diethyl -2,2'-[oxybis(methylene)]bis-2-propenoate, di(n-propyl )-2,2'-[oxybis(methylene)]bis-2-propenoate, di(isopropyl di(2-ethyl)-2,2'-[oxybis(methylene)]bis-2-propenoate (hexyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, etc. It can be obtained.

[0086] Each monomer unit can be used alone or in combination of two or more kinds.

[0087] The weight average molecular weight of the alkali-soluble resin (A1) is preferably from 3,000 to 50,000, more preferably from 3,000 to 20,000.

[0088] The molecular weight distribution (weight average molecular weight / number average molecular weight) of the alkali-soluble resin (A1) is preferably from 1.2 to 3.0, more preferably from 1.3 to 2.8.

[0089] The acid value of the alkali-soluble resin (A1) is preferably from 20 to 200 mgKOH / g, more preferably from 30 to 180 mgKOH / g.

[0090] The content of the alkali-soluble resin (A1) is preferably 10 to 100 mass %, more preferably 20 to 80 mass %, based on 100 mass % of the alkali-soluble resin (A) from the viewpoints of storage stability and solvent resistance after low-temperature heating.

[0091] (Alkali-soluble resin (A2) not having a thermally crosslinkable group-containing monomer unit (a1)) From the viewpoint of storage stability, the photosensitive composition of the present invention preferably contains, as the alkali-soluble resin (A), an alkali-soluble resin (A2) that does not have a thermally crosslinkable group-containing monomer unit (a1) (hereinafter, also simply referred to as alkali-soluble resin (A2)).

[0092] The alkali-soluble resin (A2) is not particularly limited as long as it does not contain the thermally crosslinkable group-containing monomer unit (a1), and known alkali-soluble resins can be used. For example, alkali-soluble resins containing one or more of the above-mentioned monomer units (a2) to (a6) can be used. Among these, resins containing the polymerizable unsaturated group-containing monomer unit (a5) are preferred from the viewpoint of solvent resistance after low-temperature heating.

[0093] The weight average molecular weight of the alkali-soluble resin (A2) is preferably from 3,000 to 50,000, more preferably from 3,000 to 20,000.

[0094] The acid value of the alkali-soluble resin (A2) is preferably from 20 to 200 mgKOH / g, more preferably from 30 to 180 mgKOH / g.

[0095] The content of the alkali-soluble resin (A2) is preferably 10 to 90 mass %, more preferably 20 to 80 mass %, based on 100 mass % of the alkali-soluble resin (A) from the viewpoints of storage stability and solvent resistance after low-temperature heating.

[0096] The mass ratio of the alkali-soluble resin (A1) to the alkali-soluble resin (A2) is preferably from 90:10 to 10:90, more preferably from 90:10 to 50:50, from the viewpoints of storage stability and solvent resistance after low-temperature heating.

[0097] The alkali-soluble resin (A) can be used alone or in combination of two or more kinds.

[0098] [Polymerizable compound (B)] The photosensitive composition of the present invention contains a polymerizable compound (B).

[0099] 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.

[0100] 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, one or more compounds selected from the group consisting of polymerizable compounds (B1) having an amine structure, polymerizable compounds (B3) having an acidic group, and polymerizable compounds (B6) having a dendrimer structure or hyperbranched structure are preferred.

[0101] (Polymerizable Compound (B1) Having an Amine Structure) The amine structure of the polymerizable compound (B1) having an amine structure may be any of a primary amine, secondary amine, and tertiary amine structures, but from the viewpoint of storage stability, a secondary amine or a tertiary amine is preferred, and a tertiary amine is more preferred. However, 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.

[0102] 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).

[0103] Examples of the (meth)acrylate compound (X) include glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and diglycerides thereof. Examples of the alkylene oxide-modified tri(meth)acrylate include phosphorus tri(meth)acrylate, diglycerin 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, diglycerin alkylene oxide-modified tri- and tetra(meth)acrylate, and dipentaerythritol alkylene oxide-modified tetra-, penta-, and hexa(meth)acrylate. Examples of the alkylene oxide unit in the alkylene oxide modification include ethylene oxide, propylene oxide, and butylene oxide. The (meth)acrylate compound (X) also includes a (meth)acrylate compound having an acidic group.

[0104] The (meth)acrylate compound (X) can be used alone or in combination of two or more kinds.

[0105] 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.

[0106] The amine compound (Y) can be used alone or in combination of two or more kinds.

[0107] The method for producing the Michael addition reaction product of the (meth)acrylate compound (X) and the amine compound (Y) is not particularly limited, and known methods can be used, such as those described in International Publication No. 2006 / 075754, JP-A No. 2008-545859, and JP-A No. 2017-066347.

[0108] The polymerizable compound (B1) having an amine structure may have an acidic group and / or a hydroxyl group. Examples of methods for introducing the acidic group and / or the hydroxyl group include a method 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.

[0109] Commercially available polymerizable compounds (B1) having an amine structure include, for example, Aronix MT-3041 and 3042 manufactured by Toagosei Co., Ltd., EBECRYL80 and 7100 manufactured by Daicel-Allnex Co., Ltd., and CN371NS, 372, 374, 383 and 386 manufactured by Arkema.

[0110] (Multifunctional urethane (meth)acrylate (B1-1) having a secondary amino group or a tertiary amino group) The polymerizable compound (B1) having an amine structure can contain a multifunctional urethane (meth)acrylate (B1-1) having a secondary amino group or a tertiary amino group. This allows for the formation of a chemical crosslinked structure through polymerization, as well as a physical crosslinked structure through intermolecular hydrogen bonds between urethane bonds and between urethane bonds and functional groups on the substrate. The molecular cohesive energy of the intermolecular hydrogen bonds at the urethane bond site is greater than the cohesive energy of other organic structures, such as ether bonds. Therefore, we speculate that the interaction between the urethane bonds makes the film flexible and strong, improving its durability.

[0111] The urethane bond can be introduced, for example, by a urethane reaction between a Michael addition reaction product (resin) of the above-mentioned (meth)acrylate compound (X) and the above-mentioned amine compound (Y) having a hydroxyl group, and a polyisocyanate compound (Z).

[0112] 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; Polyisocyanate 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 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, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, bischloromethyldiphenylmethane diisocyanate, 2,6-diisocyanate-benzyl chloride, and bis(isocyanatomethyl)benzene. Further examples of these compounds include biuret, isocyanurate, adduct and allophanate forms.

[0113] The polyisocyanate compounds (Z) can be used alone or in combination of two or more kinds.

[0114] The method for the urethane reaction between the resin and the polyisocyanate compound (Z) is not particularly limited, and known methods can be used, such as those described in JP-A-2018-517797.

[0115] An example of a commercially available product of the polyfunctional urethane (meth)acrylate (B1-1) having a secondary amino group or a tertiary amino group is CN9906NS manufactured by Arkema.

[0116] The content of the polymerizable compound (B1) having an amine structure is preferably 1 to 80 mass %, more preferably 5 to 60 mass %, based on 100 mass % of the polymerizable compound (B), from the viewpoints of resolubility and solvent resistance after low-temperature heating.

[0117] From the viewpoints of resolubility and solvent resistance after low-temperature heating, it is preferable to use the polymerizable compound (B1) having an amine structure in combination with a polymerizable compound (B2) having a hydroxyl group or a polymerizable compound (B3) having an acidic group, which will be described later. For example, the mass ratio of the polymerizable compound (B1) having an amine structure to the polymerizable compound (B2) having a hydroxyl group or the polymerizable compound (B3) having an acidic group is preferably 5:95 to 95:5, more preferably 10:90 to 50:50.

[0118] (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, and 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, and dipentaerythritol caprolactone-modified penta(meth)acrylate; and epoxy (meth)acrylate obtained by reacting the epoxy group of an epoxy compound with the carboxyl group of (meth)acrylic acid. Among these, glycerol di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate are preferred.

[0119] Examples of commercially available products of the polymerizable compound (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, and Epoxy Ester M-600A, 40EM, 70PA, 200PA, 80MFA, 3002M(N), 3002A(N), and 3000A manufactured by Kyoeisha Chemical Co., Ltd., and OGSOL GA-5060P and GA-2800 manufactured by Osaka Gas Chemical Co., Ltd.

[0120] 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) from the viewpoint of solvent resistance after low-temperature heating.

[0121] (Polymerizable compound (B3) having an acidic group) Examples of the polymerizable compound (B3) having an acidic group include an ester of a dicarboxylic acid with a free hydroxyl group-containing poly(meth)acrylate of a polyhydric alcohol and (meth)acrylic acid; an ester of a polycarboxylic acid with a monohydroxyalkyl (meth)acrylate, and the like.

[0122] Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.

[0123] Examples of the dicarboxylic acid include malonic acid, succinic acid, maleic acid, glutaric acid, phthalic acid, and itaconic acid.

[0124] Examples of the polycarboxylic acid include trimellitic acid and pyromellitic acid. Examples of monohydroxyalkyl (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, pentaerythritol triacrylate, and 2-hydroxy-3-acryloyloxypropyl methacrylate.

[0125] Commercially available polymerizable compounds (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.

[0126] 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 solvent resistance after low-temperature heating.

[0127] (Lactone-modified polymerizable compound (B4)) The lactone-modified polymerizable compound (B4) is a compound having a lactone-modified structure in the molecule. The lactone-modified polymerizable compound (B6) can be obtained by esterifying a polyhydric alcohol such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, tripentaerythritol, glycerin, diglycerol, or trimethylolmelamine with (meth)acrylic acid and ε-caprolactone or another lactone compound.

[0128] 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.

[0129] (Polymerizable compound (B5) having a urethane bond) 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 then reacting the resulting mixture with a hydroxyl group-containing (meth)acrylate.

[0130] 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.

[0131] Examples of the polyfunctional isocyanate include aromatic diisocyanates such as tolylene diisocyanate, diphenylmethylene diisocyanate, and xylene diisocyanate; aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate; and alicyclic diisocyanate such as isophorone diisocyanate; as well as biuret derivatives, isocyanurates, and trimethylolpropane adducts thereof.

[0132] The polymerizable compound (B5) having a urethane bond may have an acidic group. Examples of the acidic group include a sulfonic acid group, a carboxyl group, and a phosphate group. Among these, a carboxyl group is preferred. The polymerizable compound (B5) having a urethane bond does not have an amine structure.

[0133] The acidic group can be introduced into the polymerizable compound (B5) having a urethane bond by, for example, first reacting the hydroxyl group-containing (meth)acrylate with the polyfunctional isocyanate, and then adding a mercapto compound having a carboxyl group to the reaction product.

[0134] 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.

[0135] Examples of commercially available polymerizable compounds (B5) having a urethane bond include AH-600, UA-306H, UA-306T, UA-306I, UA-510H, and UF-8001G manufactured by Kyoeisha Chemical Co., Ltd., UA-1100H, U-6LPA, UA-33H, U-10HA, and U-15HA manufactured by Shin-Nakamura Chemical Co., Ltd., and EBECRYL1290 and KRM8452 manufactured by Daicel-Allnex Corporation.

[0136] (Polymerizable compound (B6) having a dendrimer structure or a hyperbranched structure) A compound with a dendrimer structure has a chemical structure in which branches are regularly repeated outward from a chemical structure constituting a core (hereinafter also referred to as the core part), and polymerizable unsaturated groups are bonded to the ends of the branches, and has a spherical, highly controlled chemical structure and molecular weight. The hyperbranched structure has a chemical structure similar to that of a dendrimer structure.

[0137] 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), and CN2304 (hyperbranched structure, average number of acryloyl groups: 18) manufactured by SARTOMER Co., Ltd.; Examples include Etercure 6361-100 (hyperbranched structure, average number of acryloyl groups: 8), 6362-100 (hyperbranched structure, average number of acryloyl groups: 12), 6363 (hyperbranched structure, average number of acryloyl groups: 16), and DR-E522 (hyperbranched structure, average number of acryloyl groups: 15), all manufactured by Materials Co., Ltd.

[0138] The polymerizable compound (B6) having a dendrimer structure or a hyperbranched structure is preferably contained in an amount of 1 to 90 mass %, more preferably 1 to 50 mass %, based on 100 mass % of the polymerizable compound (B), from the viewpoint of solvent resistance after low-temperature heating.

[0139] (Other polymerizable compounds (B7)) Examples of other polymerizable compounds (B7) include methyl (meth)acrylate, ethyl (meth)acrylate, cyclohexyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane EO or PO modified tri(meth)acrylate, isocyanuric acid Examples of the methacrylic acid ester include EO- or PO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol EO- or PO-modified hexa(meth)acrylate, tricyclodecanyl (meth)acrylate, and (meth)acrylic acid ester of methylolated melamine; styrene, vinyl acetate, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-vinylformamide, and acrylonitrile.

[0140] Other commercially available products of the polymerizable compound (B7) include, for example, KAYARAD NPGDA, PEG400DA, FM-400, HX-200, HX-620, R-551, R-712, R-604, R-684, GPOD-303, TMPTA, T-1420(T), RP-1040, DPEA-12, and D-310 manufactured by Nippon Kayaku Co., Ltd., and Aronix M-101A, M-102, M-111, M-113, M-120, M-140, M-208, and M-21 manufactured by Toagosei Co., Ltd. 1B, M-220, M-225, M-270, M-240, M-309, M-310, M-321, M-350, M-360, M-408, M-460, Viscoat #150, #155, #160, #192, #MTG, #200, #196, #195, #230, #260, #310, #700HV, #295 manufactured by Osaka Organic Chemical Industry Co., Ltd., and OGSOL manufactured by Osaka Gas Chemicals Co., Ltd. EA-0200, EA-0300, Miramer HR6060, 6100, 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, AD-TMP manufactured by Shin-Nakamura Chemical Co., Ltd.

[0141] The polymerizable compound (B) can be used alone or in combination of two or more kinds.

[0142] The content of the polymerizable compound (B) is preferably from 1 to 50 mass %, more preferably from 5 to 30 mass %, of the nonvolatile content of the photosensitive composition.

[0143] [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.

[0144] (Oxime ester photopolymerization initiator (C1)) The photopolymerization initiator (C) contains an oxime ester photopolymerization initiator (C1), which allows the formation of a coating film that is excellent in terms of development stain resistance and solvent resistance at low temperatures.

[0145] Examples of the oxime ester photopolymerization initiator (C1) include compounds represented by the following formulae (C1-1) to (C1-18): However, the present invention is not limited thereto.

[0146] [ka]

[0147] [ka]

[0148] [ka] JPEG2025117618000016.jpg3496

[0149] Among the oxime ester photopolymerization initiators (C1), from the viewpoint of development stains and solvent resistance at low temperatures, an oxime ester photopolymerization initiator with an absorption coefficient of 5.0 × 10 at a wavelength of 365 nm in propylene glycol monomethyl ether acetate is selected. 3 L / mol·cm or higher compounds are preferred.

[0150] From the viewpoint of solvent resistance at low temperatures, the content of the oxime ester photopolymerization initiator (C1) is preferably 1 to 5 mass %, more preferably 1 to 3 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0151] (Photopolymerization initiators (C2) other than oxime ester photopolymerization initiators (C1)) The polymerization initiator (C) can be used in combination with the oxime ester photopolymerization initiator (C1) and a photopolymerization initiator (C2) other than the oxime ester photopolymerization initiator (C1) (hereinafter simply referred to as other photopolymerization initiator (C2)).

[0152] The photopolymerization initiator (C2) is not particularly limited, and known compounds can be used. Other 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-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; triazine-based compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, and 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; acylphosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and diphenyl-2,4,6-trimethylbenzoylphosphine oxide; Examples include quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds; and compounds represented by the following general formula (100).

[0153] The other photopolymerization initiator (C2) is preferably a compound represented by the following general formula (100).

[0154] General formula (100) [ka]

[0155] In general formula (100), R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R3 represents a hydrogen atom or a monovalent substituent.

[0156] In the general formula (100), R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. The alkyl group having 1 to 8 carbon atoms is linear or branched, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a cyclopentyl group, a cyclopentylmethyl group, a cyclohexyl group, a cyclohexylmethyl group, a cyclohexylmethyl group, etc. Among these, a linear alkyl group having 3 to 8 carbon atoms is preferred, and a linear alkyl group having 4 to 6 carbon atoms is more preferred.

[0157] In the general formula (100), R3 represents a hydrogen atom or any monovalent substituent. Examples of the monovalent substituent include alkyl groups having 1 to 20 carbon atoms, such as methyl and ethyl groups; alkoxy groups having 1 to 20 carbon atoms, such as methoxy and ethoxy groups; halogen atoms, such as F, Cl, Br, and I; acyl groups having 1 to 20 carbon atoms; alkyl ester groups having 1 to 20 carbon atoms; alkoxycarbonyl groups having 1 to 20 carbon atoms; halogenated alkyl groups having 1 to 20 carbon atoms, aromatic ring groups having 4 to 20 carbon atoms; amino groups; aminoalkyl groups having 1 to 20 carbon atoms; hydroxyl groups; nitro groups; cyano groups; optionally substituted benzoyl groups; and optionally substituted thenoyl groups. Examples of the substituents that the benzoyl and thenoyl groups may have include alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and alkoxycarbonyl groups having 1 to 10 carbon atoms. Among these, from the viewpoint of radical generation efficiency, a hydrogen atom and a nitro group are preferred, and a hydrogen atom is more preferred.

[0158] Examples of methods for producing the compound represented by general formula (100) include those described in JP-T-2019-507108 and JP-T-2019-528331.

[0159] Specific examples of the compound represented by formula (100) are shown below, but the present invention is not limited to these.

[0160] [ka]

[0161] Other commercially available photopolymerization initiators (C2) include acetophenone-based compounds such as Omnirad 907, 369E, 379EG, 127, 184, 1173, and 2959 manufactured by IGM Resins, and acylphosphine-based compounds such as Omnirad 819 and TPO manufactured by IGM Resins. Further examples include compounds described in JP 2007-210991 A, JP 2009-179619 A, JP 2010-037223 A, JP 2010-215575 A, JP 2011-020998 A, WO 2015 / 036910, JP 2019-507108 A, JP 2019-528331 A, WO 2021 / 175855, etc.

[0162] The photopolymerization initiator (C) can be used alone or in combination of two or more kinds.

[0163] The content of the photopolymerization initiator (C) is preferably from 0.1 to 20 mass %, more preferably from 0.5 to 10 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0164] [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 radical polymerization reactions can be used. In this specification, the thermal polymerization initiator (D) is preferably an oxime sulfonate compound described in Japanese Patent No. 5,955,339 and Japanese Patent No. 6,664,383.

[0165] [Oxime sulfonate compound (D1) represented by general formula (1)] The thermal polymerization initiator (D) includes an oxime sulfonate compound (D1) represented by general formula (1) (hereinafter also referred to as thermal polymerization initiator (D1)). The thermal polymerization initiator (D1) generates radicals upon heating. The thermal polymerization initiator (D1) exhibits higher polymerization efficiency compared to known thermal polymerization initiators such as peroxides and azo compounds. The inclusion of the thermal polymerization initiator (D1) enables the formation of a coating film with excellent solvent resistance after low-temperature heating. Note that the oxime sulfonate compound (D1) used in this specification does not include compounds in which the carbon atom forming a double bond with the nitrogen atom in the oxime sulfonate structure forms a ring, as described in International Publication WO 2014 / 157720 and the like, because such compounds do not solve the problems of the present application.

[0166] General formula (1) QA a B b C c

[0167] In general formula (1), a is 0, 1, 2, 3, or 4. b is 0 or 2. c is 0, 1, or 2. The sum of a+b+c is 1, 2, 3, or 4. A is represented by the following general formula (A), B is represented by the following general formula (B), and C is represented by the following general formula (C). # represents the point of attachment to Q. X is S, SO2, or NR 14 Q is a monovalent organic group when the sum of a+b+c is 1, a divalent organic group when the sum of a+b+c is 2, a trivalent organic group when the sum of a+b+c is 3, and a tetravalent organic group when the sum of a+b+c is 4. [ka] JPEG2025117618000020.jpg4188JPEG2025117618000021.jpg27125

[0168] Among the thermal polymerization initiators (D1), by including a thermal polymerization initiator (D1) represented by the following general formula (2), it is possible to form a coating film with better solvent resistance after low-temperature heating.

[0169] General formula (2) [ka]

[0170] (In the general formula (2), R1 is O(CO)R4, COOR5 or CONR6R7, and n is 1 or 2, R2 is C1-C8-alkyl, C2-C8-alkyl interrupted by one or more O, or C3-C6-cycloalkyl uninterrupted or interrupted by one or more O, or R2 is unsubstituted benzyl or benzyl substituted by one or more C1-C6-alkyl, C1-C4-haloalkyl, halogen, CN, NO2, C1-C6-alkylsulfanyl or C1-C6-alkoxy, R3 is C1-C8-alkyl, C3-C6-cycloalkyl, C1-C8-haloalkyl or C2-C8-alkenyl, or R3 is benzyl, phenyl or naphthyl, which benzyl, phenyl or naphthyl is unsubstituted or substituted by one or more C1-C6-alkyl, C1-C4-haloalkyl, halogen, CN, NO2, C1-C6-alkylsulfanyl, C1-C6-alkoxy, phenyl or COO(C1-C6-alkyl), R4 is C1-C8-alkyl, C3-C6-cycloalkyl, C1-C8-haloalkyl or C2-C8-alkenyl, or R4 is benzyl, phenyl or naphthyl, which is unsubstituted or substituted by one or more C1-C6-alkyl, C1-C4-haloalkyl, halogen, CN, NO2, C1-C6-alkylsulfanyl, phenylsulfanyl, C1-C6-alkoxy, phenoxy, phenyl or COO(C1-C6-alkyl), R5 is alkyl selected from 2,4,4-trimethylpentyl, 2-ethylhexyl, octyl, nonyl, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, and icosyl; or R5 is cyclooctyl, cyclododecyl, cyclotetradecyl, perhydroanthracyl, perhydrophenanthryl, perhydronaphthyl, perhydrofluorenyl, adatomyl, cyclohex ... mantyl, bicyclo[1.1.1]pentyl, bicyclo[4.2.2]decyl, bicyclo[2.2.2]octyl, bicyclo[3.3.2]decyl, bicyclo[4.3.2]undecyl, bicyclo[4.3.3]dodecyl, bicyclo[3.3.3]undecyl, bicyclo[4.3.1]decyl, bicyclo[4.2.1]nonyl, bicyclo[3.3.1]nonyl, bicyclo[3.2.1]octyl, and

[0171] [ka]

[0172] or R5 is a C1-C6 alkyl substituted by one or more halogen, CN, phenylsulfanyl, phenoxy, N(C1-C6 alkyl)2, N(phenyl)2, phthalimido, phenyl or substituted phenyl. 12 -alkyl, and the substituted phenyl is one or more C1-C 12-substituted by alkyl, C1-C4-haloalkyl, halogen, CN, NO2, C1-C6-alkylsulfanyl, phenylsulfanyl, C1-C6-alkoxy, phenoxy, N(C1-C6-alkyl)2 or N(phenyl)2, or R5 is alkyl or cycloalkyl, each of which is interrupted by one or more O or S, where alkyl is selected from pentyl, hexyl, heptyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, octyl, nonyl, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl and icosyl, and cycloalkyl is cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, cyclotetradecyl, perhydroanthracyl, perhydrophenanthryl, perhydronaphthyl, perhydrofluorenyl, adamantyl, bicyclo[1.1.1]pentyl, bicyclo[4.2.2]decyl, bicyclo[2.2.2]octyl, bicyclo[3.3.2]decyl, bicyclo[4.3.2]undecyl, bicyclo[4.3.3]dodecyl, bicyclo[3.3.3]undecyl, bicyclo[4.3.1]decyl, bicyclo[4.2.1]nonyl, bicyclo[3.3.1]nonyl, bicyclo[3.2.1]octyl, and

[0173] [ka]

[0174] or R5 is phenyl or naphthyl, which phenyl or naphthyl is unsubstituted or substituted by one or more C1-C6-alkyl, C1-C4-haloalkyl, halogen, CN, NO2, C1-C6-alkylsulfanyl, C1-C6-alkoxy, phenyl or COO(C1-C6-alkyl), R6 and R7 are each independently hydrogen, C1 to C 12-alkyl, C1-C4-haloalkyl, phenyl-C1-C4-alkyl, C2-C8-alkenyl or C3-C6-cycloalkyl, or R6 and R7 are C2-C alkyl groups interrupted by O, S, N(C1-C8-alkyl) or CO. 12 -alkyl, or R6 and R7 are C2-C4-haloalkyl interrupted by O, S, N(C1-C8-alkyl) or CO, or R6 and R7 are, independently of one another, phenyl-C1-C4-alkyl interrupted by O, S, N(C1-C8-alkyl) or CO, or R6 and R7 are C2-C8-alkenyl interrupted by O, S, N(C1-C8-alkyl) or CO, or R6 and R7 are C3-C6-cycloalkyl interrupted by O, S, N(C1-C8-alkyl) or CO, or R6 and R7 are, independently of one another, independently phenyl or naphthyl, which phenyl or naphthyl is unsubstituted or substituted by one or more C1-C6-alkyl, C1-C4-haloalkyl, halogen, CN, NO2, C1-C6-alkylsulfanyl, C1-C6-alkoxy, phenyl or COO(C1-C6-alkyl), or R6 and R7 together with the N atom to which they are attached form a 5- or 6-membered ring via a C2-C5-alkylene, said C2-C5-alkylene ring being uninterrupted or interrupted by one or more O, S, N(C1-C8-alkyl), NH or CO).

[0175] Examples of the thermal polymerization initiator (D1) represented by the above general formula (2) include compounds represented by formulae (D1-1) to (D1-18).

[0176] [ka] JPEG2025117618000026.jpg52122JPEG2025117618000027.jpg50126JPEG2025117618000028.jpg47119JPEG2025117618000029.jpg49141 JPEG2025117618000030.jpg52136JPEG2025117618000031.jpg55125JPEG2025117618000032.jpg53135JPEG2025117618000033.jpg50119

[0177] [Other thermal polymerization initiators (D2)] The thermal polymerization initiator (D) may contain a thermal polymerization initiator (D2) other than the thermal polymerization initiator (D1) (hereinafter, also simply referred to as other thermal polymerization initiator (D2)).

[0178] Other examples of the thermal polymerization initiator (D2) include peroxide compounds such as 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; 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-tetraphenylethane, 1,2- pinacol compounds such as 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).

[0179] The thermal polymerization initiator (D) can be used alone or in combination of two or more kinds.

[0180] The content of the thermal polymerization initiator (D) is preferably from 0.1 to 15 mass %, more preferably from 1 to 5 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0181] The thermal polymerization initiator (D) is used in combination with the photopolymerization initiator (C), which allows the radical polymerization reaction to proceed in both the exposure step and the post-bake step, further improving solvent resistance.

[0182] The mass ratio of the photopolymerization initiator (C) to the thermal polymerization initiator (D) is preferably (C):(D)=90:10 to 10:90, more preferably 17:83 to 50:50, from the viewpoints of development stains and solvent resistance at low temperatures.

[0183] [Thermal crosslinkable compound (E)] The photosensitive composition of the present invention may contain a thermally crosslinkable compound (E). The thermally crosslinkable compound (E) crosslinks with other components upon heating, further improving solvent resistance during low-temperature curing. The thermally crosslinkable compound (E) does not have a polymerizable unsaturated group and is not alkali-soluble. Therefore, it is a different compound from alkali-soluble resins and polymerizable compounds.

[0184] The thermally crosslinkable compound (E) is not particularly limited as long as it is a compound having a thermally crosslinkable group, and known compounds can be used. Examples include oxetanyl group-containing compounds, methylol group-containing compounds, phenol group-containing compounds, alkoxyalkyl group-containing compounds, blocked isocyanate group-containing compounds (E1) and epoxy compounds (E2) described below. Among these, one or more compounds selected from the group consisting of blocked isocyanate group-containing compounds (E1) and epoxy compounds (E2) are preferred, and blocked isocyanate group-containing compounds are more preferred.

[0185] [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. From the viewpoints of storage stability and solvent resistance after low-temperature heating, 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. The blocked isocyanate group-containing compound (E1) does not have an alkali-soluble group.

[0186] 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 those described in JP-A-52-116420, JP-A-60-149572, JP-A-7-31953, JP-A-10-306136, and JP-A-2012-012567.

[0187] The blocking agent is preferably one or more selected from the group consisting of oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds, more preferably oxime compounds, phenol compounds, active methylene compounds, and pyrazole compounds, and from the viewpoint of solvent resistance after low-temperature heating, active methylene compounds are particularly preferred. The elimination temperature or transesterification temperature of the active methylene compounds is low, at 80 to 110°C, and they react sufficiently even at low temperatures, improving resistance.

[0188] 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 isocyanate include 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, bischloromethyldiphenylmethane diisocyanate, 2,6-diisocyanate-benzyl chloride, and compounds having an aromatic structure such as bis(isocyanatomethyl)benzene. Further examples include biuret, isocyanurate, adduct and allophanate forms of these compounds, and reaction products of these compounds with polyols.

[0189] The compound having an isocyanate group is preferably a biuret, isocyanurate, adduct or allophanate of a compound having an aliphatic structure or a compound having an alicyclic structure, and more preferably a biuret or isocyanurate of a compound having an aliphatic structure.

[0190] Examples of the blocked isocyanate group-containing compound (E1) include compounds represented by formulas (N-1) to (N-7). In the following structural formulas (N-1) to (N-7), X represents a blocked isocyanate group. However, the present invention is not limited to these.

[0191] [ka]

[0192] Among the above, from the viewpoints of stability over time and solvent resistance after low-temperature heating, the compounds represented by (N-1), (N-2), (N-4), and (N-7) are preferred, the compounds represented by (N-1) and (N-2) are more preferred, and the compound represented by (N-1) is even more preferred.

[0193] Examples of the above X (blocked isocyanate group) include the structures shown in the following (X-1) to (X-8). In the following structures, * represents a bond. However, the present invention is not limited to these.

[0194] [ka]

[0195] Among the above structures, from the viewpoints of storage stability and solvent resistance after low-temperature heating, (X-1), (X-4), (X-6), (X-7), and (X-8) are preferred, (X-1) and (X-8) are more preferred, and (X-1) is even more preferred.

[0196] Among the blocked isocyanate group-containing compounds (E1), from the viewpoints of storage stability and solvent resistance after low-temperature heating, combinations of (N-1) and (X-1), (N-1) and (X-4), (N-1) and (X-8), (N-2) and (X-1), (N-2) and (X-4), and (N-2) and (X-8) are preferred, (N-1) and (X-1), (N-2) and (X-1) are more preferred, and (N-1) and (X-1) are more preferred.

[0197] The blocked isocyanate group-containing compound (E1) preferably contains blocked isocyanate groups with different structures. In this specification, for example, the combined use of the above (X-1) and (X-8) is preferred. This allows high levels of both storage stability and solvent resistance after low-temperature heating. The molar ratio of (X-1) to (X-8) is preferably 90:10 to 10:90, more preferably 90:10 to 30:70, and even more preferably 90:10 to 70:30.

[0198] 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.; Similarly, 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.; Similarly, examples of compounds having an aromatic structure include Takenate B-830 and B-815N manufactured by Mitsui Chemicals.

[0199] The blocked isocyanate group-containing compound (E1) preferably has 1 to 20 blocked isocyanate groups, more preferably 2 to 15 blocked isocyanate groups.

[0200] The weight average molecular weight of the blocked isocyanate group-containing compound (E1) is preferably from 300 to 5,000, more preferably from 500 to 3,000.

[0201] The acid value of the blocked isocyanate group-containing compound (E1) is preferably less than 10 mgKOH / g.

[0202] From the viewpoints of storage stability, heat shock resistance, and solvent resistance after low-temperature heating, the content of the blocked isocyanate group-containing compound (E1) is preferably 1 to 20 mass%, more preferably 3 to 15 mass%, and even more preferably 5 to 10 mass%, based on 100 mass% of the nonvolatile content of the photosensitive composition.

[0203] [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) is a compound having no alkoxysilyl group and does not include a vinyl polymer.

[0204] Examples of the epoxy compound (E2) include polyglycidyl ether compounds of bisphenols such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and hydrogenated bisphenol F diglycidyl ether; Polyglycidyl ether compounds of polyhydric alcohols such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether; Polyglycidyl ether compounds of polyether polyols obtained by adding alkylene oxides to polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin; 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl) compounds having two or more 3,4-epoxycyclohexyl groups in the molecule, such as bis(3,4-epoxycyclohexylmethyl)-5,5-spiro-3,4-epoxy)cyclohexane-metadioxane, bis(3,4-epoxycyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, methylenebis(3,4-epoxycyclohexane), ethylenebis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl)-modified ε-caprolactone; Examples include 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol.

[0205] Commercially available epoxy compounds (E2) include, for example, jER807, 815, 825, 827, 828, 190P, 191P, 1004, 1256, 1032H60, 157S65, 157S70, 152, and 154 manufactured by Mitsubishi Chemical Corporation; TECHMORE VG3101L, EPPN-201, 501H, 502H, EOCN-102S, 103S, 104S, 1020 manufactured by Nippon Kayaku Co., Ltd., Celoxide 2021, EHPE-3150, Epolead GT401 manufactured by Daicel Corporation, Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721 manufactured by Nagase ChemteX Corporation, TEPIC-L, H, S manufactured by Nissan Chemical Industries, Ltd., EPICLON manufactured by DIC Corporation Examples include 830, 840, 850, 860, 1050, 3050, 4050, N-660, N-670, N-740, N-770, N865, HP-7200, HP-4700, HP-4770, HP-5000, HP-6000, and HP-9500.

[0206] The epoxy compound (E2) is preferably a compound having 2 to 50 epoxy groups in the molecule.

[0207] 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 developing stains and solvent resistance after low-temperature heating. The epoxy equivalent is defined as the mass of an epoxy compound containing one equivalent of epoxy groups.

[0208] From the viewpoints of developing stains and solvent resistance after low-temperature heating, the epoxy compound (E2) more preferably contains a compound represented by the following general formula (50).

[0209] General formula (50) [ka]

[0210] In the general 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.

[0211] R is preferably a linear or branched alkyl group having 2 to 20 carbon atoms. Examples of the alkyl group having 2 to 20 carbon atoms include ethyl, methyl, propyl, isopropyl, 2,2-dimethylpropyl, butyl, isobutyl, tert-butyl, 3,3-dimethylbutyl, pentyl, isopentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, hexadecyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, cyclohexylmethyl, and cyclohexylmethyl. Among these, branched alkyl groups having 3 to 12 carbon atoms are more preferred. When m is 2 or more, n in each of the groups in parentheses in general formula (50) may be the same or different.

[0212] An example of the compound represented by general formula (50) is a 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol. Commercially available products include EHPE-3150 and EHPE-3150CE manufactured by Daicel Corporation.

[0213] The acid value of the epoxy compound (E2) is preferably 10 mgKOH / g or less.

[0214] The content of the epoxy compound (E2) is preferably from 0.5 to 20 mass%, more preferably from 2 to 7 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.

[0215] From the viewpoint of solvent 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).

[0216] From the viewpoints of storage stability, heat shock resistance, and development stains, the mass ratio of the blocked isocyanate group-containing compound (E1) to the epoxy compound (E2) is preferably (E1):(E2)=5:95 to 95:5, more preferably 37:63 to 91:9, and particularly preferably 55:45 to 77:23.

[0217] The thermally crosslinkable compound (E) can be used alone or in combination of two or more kinds.

[0218] 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.

[0219] [Dye (F)] The photosensitive composition of the present invention may contain a coloring matter (F). Examples of the coloring matter (F) include pigments, dyes, and near-infrared absorbing coloring matters. Examples of the pigments include inorganic pigments and organic pigments. 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.

[0220] Examples of orange pigments include CI Pigment Orange 36, 38, 43, 64, 71, and 73.

[0221] Yellow pigments include, for example, CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, and 118. , 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233, etc. Among these, CI Pigment Yellow 138, 139, 150, 185, 231, 233 are preferred.

[0222] 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.

[0223] 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.

[0224] 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.

[0225] Examples of black pigments include CI Pigment Black 1, 6, 7, 12, 20, and 31.

[0226] Further examples include inorganic pigments such as titanium oxide, barium sulfate, zinc oxide, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, ultramarine, iron blue, chromium oxide green, cobalt green, umber, and synthetic iron black.

[0227] The near-infrared absorbing dye is a compound having a maximum absorption in the wavelength range of 700 to 2,000 nm. Examples of the near-infrared absorbing dye include pigments (also called near-infrared absorbing pigments) and dyes (also called near-infrared absorbing dyes). The near-infrared absorbing pigment and the near-infrared absorbing dye may be used in combination. From the viewpoint of heat resistance, the near-infrared absorbing dye is preferably a near-infrared absorbing pigment. The solubility of the near-infrared absorbing pigment in 100 g of propylene glycol monomethyl ether acetate at 25° C. is preferably less than 2 g, more preferably less than 1 g, and even more preferably 0.5 g or less.

[0228] 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.

[0229] (Squarylium compounds) Examples of squarylium compounds are shown below, but the present invention is not limited to these. [ka]

[0230] [ka]

[0231] (Pyrrolopyrrole compounds) The pyrrolopyrrole compound is preferably, for example, the following compound: In the following formula, Me represents a methyl group and Ph represents a phenyl group, but the present invention is not limited thereto.

[0232] [ka]

[0233] (Naphthalocyanine compounds) The naphthalocyanine compound is preferably, for example, the following compound: However, the present invention is not limited to these. [ka] JPEG2025117618000041.jpg43101JPEG2025117618000042.jpg50102JPEG2025117618000043.jpg51103

[0234] The naphthalocyanine compound is preferably a compound having a maximum absorption wavelength in the wavelength region of 750 to 1500 nm, more preferably a compound having a maximum absorption wavelength in the wavelength region of 780 to 1000 nm.

[0235] The following compounds are also preferred as naphthalocyanine compounds, but the present invention is not limited to these.

[0236] [ka] [ka]

[0237] The near-infrared absorbing dyes can be used alone or in combination of two or more. When using two or more dyes in combination, it is preferable to use compounds with different maximum absorption wavelengths. This broadens the absorption spectrum waveform compared to when a single near-infrared absorbing dye is used, allowing near-infrared rays to be absorbed over a wide wavelength range.

[0238] (dye) Examples of dyes include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, etc. Furthermore, as the dye, derivatives of these dyes or lake pigments obtained by lake-forming dyes can also be used.

[0239] The acid dye preferably has an acidic group such as a sulfonic acid or carboxylic acid. The direct dye preferably forms an inorganic salt of the acid dye, or a salt-forming compound formed between the acid dye and a nitrogen-containing compound such as a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound. Also preferred are salt-forming compounds that are salts of the acid dye and a resin component having these functional groups. Furthermore, the salt-forming compound can be sulfonamidated to modify it into a sulfonic acid amide compound, which makes it easy to obtain a photosensitive composition with excellent resistance (light resistance, solvent resistance). In addition, a salt-forming compound of an acid dye and a compound having an onium salt group is also preferred because it has excellent resistance (light resistance, solvent resistance). The compound having an onium salt group is preferably a resin having a cationic group.

[0240] Although basic dyes can be used as they are, salt-forming compounds that form salts with organic acids, perchloric acid, or metal salts thereof are preferred. Salt-forming compounds of basic dyes are preferred because they have excellent resistance (lightfastness, solvent resistance) and affinity with pigments. Furthermore, in the salt-forming compounds of basic dyes, the anion component that acts as a counter ion is preferably an organic sulfonic acid, organic sulfuric acid, a fluorine-containing phosphorus anion compound, a fluorine-containing boron anion compound, a cyano-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid with a halogenated hydrocarbon group, or a salt-forming compound formed with an acid dye. Furthermore, the resistance of salt-forming compounds is further improved when the salt-forming compound contains a polymerizable unsaturated group in the molecule.

[0241] 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.

[0242] The dye (F) can be used alone or in combination of two or more kinds.

[0243] The content of the dye (F) is preferably from 0.5 to 80% by mass, more preferably from 1 to 60% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0244] (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, wet milling, dry milling, or solution precipitation can be used. Among these, salt milling treatment using a kneader method, which is a type of wet milling, is preferred. The average primary particle diameter of the 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.

[0245] A resin may be added to the salt milling treatment as needed. By adding a resin, the pigment is coated with the resin, improving stability, light resistance, and the like. The type of resin is not particularly limited, and examples include natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. Among these, resins that are solid at room temperature, insoluble in water, and partially soluble in the organic solvents are preferred. The amount of resin added is preferably 2 to 200 parts by mass per 100 parts by mass of the pigment.

[0246] [Pigment derivatives (G)] The photosensitive composition of the present invention may contain a pigment derivative (G).

[0247] The pigment derivative (G) is not particularly limited, and known compounds can be used. For example, compounds having a structure in which a portion of the pigment is substituted with an acidic group, a basic group, a neutral group, or the like can be used. Specific examples include compounds having an acidic substituent such as a sulfo group, a carboxy group, or a phosphate group, and their amine salts; compounds having a basic substituent such as a sulfonamide group or a terminal tertiary amino group; and compounds having a neutral substituent such as a phenyl group or a phthalimidoalkyl group. Examples of pigments include diketopyrrolopyrrole compounds, phthalocyanine compounds, anthraquinone compounds, quinacridone compounds, dioxazine compounds, perinone compounds, perylene compounds, thiazine indigo compounds, triazine compounds, benzimidazolone compounds, benzoisoindole compounds, isoindoline compounds, isoindolinone compounds, quinophthalone compounds, naphthol compounds, squarylium compounds, threne compounds, and naphthalocyanine compounds.

[0248] The pigment derivative (G) is preferably added during the micronization of the above-mentioned colorant (F) or during the dispersion treatment of the colorant (F) described below. The average primary particle size of the pigment derivative (G) is preferably 5 to 200 nm.

[0249] The pigment derivative (G) can be used alone or in combination of two or more kinds.

[0250] The content of the pigment derivative (G) is preferably from 1 to 50 parts by mass, more preferably from 2 to 40 parts by mass, relative to 100 parts by mass of the coloring matter (F).

[0251] [Dispersion resin (H)] The photosensitive composition of the present invention may contain a dispersing resin (H), which is a resin other than an alkali-soluble resin.

[0252] The dispersing resin (H) is preferably a resin having an adsorptive group that has a high affinity for the dye (F). The adsorptive group contains at least one of a basic group and an acidic group.

[0253] 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.

[0254] Examples of the acidic group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group.

[0255] Examples of resin types for the dispersion resin (H) include urethane resins, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphate salts, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, amides formed by the reaction of poly(lower alkylene imines) with polyesters having free carboxyl groups, and salts thereof, water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and polyvinylpyrrolidone, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and phosphate esters.

[0256] 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.

[0257] 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, and 209 manufactured by BYK Japan. 5, 2150, 2155, 2163, 2164, or Anti-Terra-U203, 204, or BYK-P104, P104S, 220S, or Lactimon, Lactimon-WS, or Bykumen, etc.; SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 25000, 26000, 27000, 28000, 29000, 30000, 31000, 32000, 33000, 34000, 35000, 36000, 37000, 38000, 39000, 40000, 41000, 42000, 43000, 44000, 45000, 46000, 47000, 48000, 49000, 50000, 51000, 52000, 53000, 54000, 55000, 56000, 57000, 58000, 59000, 60000, 61000, 62000, 63000, 64000, 65000, 66000, 67000, 68000, 69000, 70000, 71000, 72000, 7 6000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc., and BASF Japan's EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400 , 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., and Ajisper PA111, PB711, PB821, PB822, PB824 manufactured by Ajinomoto Fine-Techno Co., Ltd. Further, the resins described in JP 2008-029901 A, JP 2009-155406 A, JP 2010-185934 A, JP 2011-157416 A, and WO 2013175978 A, paragraphs 0122 to 0155, the resins described in JP 2019-78878 A, paragraphs 0317 to 0321, and the resins described in WO 2018 / 139534 A, paragraph 00 83, the resins described in paragraphs 0167 to 0191 of WO 2019 / 163505, the resins described in paragraphs 0299 to 0310 of WO 2021 / 131927, the resins described in paragraphs 0080 to 0085 of WO 2022 / 102367, and the resins described in paragraphs 0099 to 0109 of WO 2022 / 172607.

[0258] The dispersing resin (H) can be used alone or in combination of two or more kinds.

[0259] The content of the dispersing resin (H) is preferably from 3 to 200 parts by mass, more preferably from 5 to 100 parts by mass, relative to 100 parts by mass of the dye (F).

[0260] [Sensitizer (I)] The photosensitive composition of the present invention may contain a sensitizer (I).

[0261] Examples of the sensitizer (I) include polymethine dyes such as chalcone compounds, unsaturated ketones typified by dibenzalacetone, 1,2-diketone compounds typified by 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. compounds, squarylium compounds, porphyrin compounds, tetraphenylporphyrin compounds, triarylmethane compounds, tetrabenzoporphyrin compounds, tetrapyrazinoporphyrazine compounds, phthalocyanine compounds, tetraazaporphyrazine compounds, tetraquinoxalylporphyrazine compounds, naphthalocyanine compounds, subphthalocyanine compounds, pyrylium compounds, thiopyrylium compounds, tetraphyrin compounds, annulene compounds, spiropyran compounds, spirooxazine compounds, thiospiropyran compounds, metal arene complexes, organic ruthenium complexes, and benzophenone compounds.

[0262] The sensitizer (I) can be used alone or in combination of two or more kinds.

[0263] The content of the sensitizer (I) is preferably from 5 to 200 parts by mass, more preferably from 10 to 150 parts by mass, relative to 100 parts by mass of the photopolymerization initiator (C).

[0264] [Leveling Agent (J)] The photosensitive composition of the present invention may contain a leveling agent (J).

[0265] The leveling agent (J) is not particularly limited and known compounds can be used, such as silicone-based leveling agents, fluorine-based leveling agents, acrylic-based leveling agents, and acetylene diol-based leveling agents.

[0266] Commercially available silicone leveling agents include, for example, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, and 3570 manufactured by BYK-Chemie Co., Ltd., and FZ-7002, 2110, 2122, 2123, 2191, and 5609 manufactured by Toray Dow Corning Co., Ltd. Examples include X-22-4952, X-22-4272, X-22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, and KP-341 manufactured by Shin-Etsu Silicones Co., Ltd., and TegoGlide 432, 440, and 450, and TegoWet 250, 260, 265, 270, and 280 manufactured by Evonik.

[0267] Commercially available fluorine-based leveling agents include, for example, Surflon S-242, 243, 420, 611, 651, and 386 manufactured by AGC Seimi Chemical Co., Ltd.; Megafac F-253, 477, 551, 552, 555, 558, 560, 570, 575, and 576, R-40-LM, R-41, RS-72-K, and DS-21 manufactured by DIC Corporation; FC-4430 and 4432 manufactured by Sumitomo 3M Limited; EF-PP31N09, EF-PP33G1, and EF-PP32C1 manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.; and Futergent 602A manufactured by Neos Corporation.

[0268] Examples of commercially available acrylic leveling agents include BYK-350, 352, 354, 355, 358, 380, 381, 392, and 394 manufactured by BYK-Chemie, and Polyflow 57, 77, and 95 manufactured by Kyoeisha Chemical.

[0269] 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.

[0270] The leveling agent (J) can be used alone or in combination of two or more kinds.

[0271] The content of the leveling agent (J) is preferably from 0.001 to 2.0 mass %, more preferably from 0.005 to 1.0 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0272] [Silane coupling agent (K)] The photosensitive composition of the present invention may contain a silane coupling agent (K).

[0273] 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 group include an epoxy group, an amino group, a vinyl group, a (meth)acryloyl group, an isocyanate group, an isocyanurate group, a mercapto group, an oxetanyl group, a styryl group, and a ureido group. In this specification, the non-photosensitive alkali-soluble resin (A2), the polymerizable compound (B), the thermally crosslinkable compound (E), and the thiol-based chain transfer agent (N) are compounds different from the silane coupling agent (K) because they do not have an alkoxysilyl group.

[0274] 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 thereof include vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, p-styryltrimethoxysilane, and 3-ureidopropyltrialkoxysilane.

[0275] 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 manufactured by Shin-Etsu Chemical Co., Ltd. -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.

[0276] The silane coupling agent (K) may be a polymer, such as a polysiloxane type or an organic polymer type.

[0277] The polysiloxane type is a compound in which the hydrolyzable group and other functional groups are bonded to a polymer having a polysiloxane skeleton in the main chain. Commercially available polysiloxane type products include KR-513, KR-516, KR-517, X-41-1805, and X-41-1810 manufactured by Shin-Etsu Chemical Co., Ltd.

[0278] The organic polymer type is a compound in which an alkoxysilyl group and the other functional groups are bonded to the organic structure of the main chain. 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.

[0279] From the viewpoint of solvent resistance after low-temperature heating, the silane coupling agent (K) is preferably a compound having an epoxy group, more preferably 3-glycidoxypropyltrimethoxysilane or 3-glycidoxypropyldimethoxysilane, and even more preferably 3-glycidoxypropyltriethoxysilane or 3-glycidoxypropyldiethoxysilane.

[0280] The silane coupling agent (K) can be used alone or in combination of two or more kinds.

[0281] The content of the silane coupling agent (K) is preferably 0.1 to 10 mass % in 100 mass % of the nonvolatile content of the photosensitive composition.

[0282] [Curing agent (curing accelerator)] The photosensitive composition of the present invention may contain a curing agent (curing accelerator) to aid in 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, and 4-methyl-N,N-dimethylbenzylamine), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride), blocked isocyanate compounds (e.g., dimethylamine), imidazole derivative bicyclic amidine compounds and their salts (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, Examples of suitable amines include 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc., phosphorus compounds (e.g., triphenylphosphine, etc.), and 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.).

[0283] The curing agents can be used alone or in combination of two or more.

[0284] The content of the curing agent is preferably 0.01 to 15 parts by mass relative to 100 parts by mass of the thermally crosslinkable compound (E).

[0285] [Polymerization inhibitor (L)] The photosensitive composition of the present invention may contain a polymerization inhibitor (L).

[0286] The polymerization inhibitor (L) is not particularly limited, and known compounds can be used. For example, alkyl catechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methyl catechol, 3-methyl catechol, 4-methyl catechol, 2-ethyl catechol, 3-ethyl catechol, 4-ethyl catechol, 2-propyl catechol, 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-tert-butyl catechol, 3-tert-butyl catechol, 4-tert-butyl catechol, and 3,5-di-tert-butyl catechol; 2-methyl resorcinol, 4-methyl resorcinol, 2-ethyl resorcinol, 4-ethyl resorcinol, 2-propyl resorcinol, 4-propyl resorcinol, and 2-n-butyl resorcinol; alkylresorcinol compounds such as resorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, and 4-tert-butylresorcinol; alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, and 2,5-di-tert-butylhydroquinone; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, and tribenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite; pyrogallol; and phloroglucinol.

[0287] The polymerization inhibitor (L) can be used alone or in combination of two or more kinds.

[0288] From the viewpoint of storage stability, the content of the polymerization inhibitor (L) is preferably 0.01 to 0.4% by mass relative to 100% by mass of the nonvolatile content of the photosensitive composition.

[0289] [Antioxidant (M)] The photosensitive composition of the present invention may contain an antioxidant (M).

[0290] The antioxidant (M) is not particularly limited, and known compounds can be used. Examples include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. Among these, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.

[0291] Examples of commercially available hindered phenol antioxidants include ADK STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, and AO-330 manufactured by ADEKA Corporation; KEMINOX 101, 179, 76, and 9425 manufactured by Chemipro Corporation; IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, and 565 manufactured by BASF Japan Ltd.; and Cyanox CY-1790 and CY-2777 manufactured by Sun Chemical Company.

[0292] Examples of commercially available hindered amine antioxidants include ADK STAB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402F, and LA-502XP manufactured by ADEKA CORPORATION; KAMISTAB 29, 62, 77, and 94 manufactured by Chemipro Chemicals; Tinuvin 111FDL, 123, 144, 249, 292, and 5100 manufactured by BASF Japan Ltd.; and Cyasorb UV-3346, UV-3529, and UV-3853 manufactured by Sun Chemical Company.

[0293] 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.

[0294] Examples of commercially available sulfur-based antioxidants include Adekastab AO-412S and AO-503 manufactured by ADEKA Corporation, and KEMINOXPLS manufactured by Chemipro Chemicals.

[0295] The antioxidant (M) can be used alone or in combination of two or more kinds.

[0296] The content of the antioxidant (M) is preferably 0.5 to 5.0% by mass relative to 100% by mass of the nonvolatile content of the photosensitive composition.

[0297] [Thiol-based chain transfer agents (N)] The photosensitive composition of the present invention may contain a thiol chain transfer agent (N). Examples of the thiol chain transfer agent (N) include monofunctional thiol compounds such as thiophenol, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-benzimidazole, butanethiol, octanethiol, 1-dodecanethiol, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate, and 2-ethylhexyl 3-mercaptopropionate; 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.

[0298] The thiol chain transfer agent (N) can be used alone or in combination of two or more kinds.

[0299] The content of the thiol chain transfer agent (N) is preferably 1 to 10% by mass based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0300] [Storage stabilizer (O)] The photosensitive composition of the present invention may contain a storage stabilizer (O).

[0301] The storage stabilizer (O) is not particularly limited and known compounds can be used, for example, quaternary ammonium chlorides such as benzyl trimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as tert-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine, phosphites, etc.

[0302] The content of the storage stabilizer (O) is preferably 0.05 to 5% by mass relative to 100% by mass of the nonvolatile content of the photosensitive composition.

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

[0304] The organic solvent (P) is not particularly limited, and known compounds can be used, such as 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methyl Butyl acetate, 3-methoxy-1-butanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, toluene, o-chlorotoluene, benzene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butyl benzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone,Examples of the esters include dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.

[0305] From an environmental viewpoint, the photosensitive composition of the present invention preferably does not substantially contain organic solvents that are aromatic hydrocarbons (toluene, xylene, benzene, chlorobenzene, etc.) "Substantially not containing" means that the content of such organic solvents in the photosensitive composition is 50 ppm by mass or less, preferably 30 ppm by mass or less, and more preferably 10 ppm by mass or less.

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

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

[0308] [Ultraviolet absorber (Q)] The photosensitive composition of the present invention may contain an ultraviolet absorber (Q).

[0309] The ultraviolet absorber (Q) is a compound having an ultraviolet absorbing function, and examples thereof include benzotriazole compounds, triazine compounds, benzophenone compounds, salicylic acid ester compounds, cyanoacrylate compounds, and salicylate compounds.

[0310] Examples of the benzotriazole compound include 2-(5-tert-butyl-2-hydroxyphenyl)benzotriazole, ester compounds of benzenepropanoic acid and 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy(C7-9 branched and linear alkyl), 2-[5-chloro-(2H)-benzotriazol-2-yl]-4-methyl-6-(tert-butyl)phenol, and 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol. , 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, etc. Commercially available products include Tinuvin PS, 99-2, 326, 384-2, 900, 928, 970, 1130, and UVA-903KT manufactured by BASF Japan, and Adeka STAB LA-31RG and LA-31G manufactured by ADEKA Corporation.

[0311] Examples of benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid trihydrate, 2-hydroxy-4-octyloxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, diethylaminohydroxybenzoylhexyl benzoate, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 2-aminobenzophenone, etc. Commercially available products include Uvinal A, 3049, 3050, UVA-935LH manufactured by BASF Japan, Adeka STAB 1413 manufactured by ADEKA, and Omnirad EMK manufactured by IGM Resins.

[0312] The ultraviolet absorber (Q) can be used alone or in combination of two or more kinds.

[0313] 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 solvent resistance after low-temperature heating.

[0314] When the thermal polymerization initiator (D) is the thermal polymerization initiator (D1), the ultraviolet absorber (Q) is preferably a benzotriazole compound from the viewpoint of re-solubility after drying.

[0315] The photosensitive composition of the present invention may contain components other than those described above. Examples of other components include an acid generator, a salt generator, and a curing catalyst. The content of the other components can be appropriately set within a range that does not impair the effects of the present invention.

[0316] [Specific metal element content] The photosensitive composition of the present invention preferably contains 500 mass ppm or less of Li, Na, K, Mg, Ca, Fe, and Cr (hereinafter also referred to as specific metal elements) in total.

[0317] A photosensitive composition in which the total amount of the specific metal elements is within the above range has excellent dispersion stability and sensitivity even after storage over time. The content of the specific metal elements can be measured by inductively coupled plasma atomic emission spectrometry (ICP).

[0318] [Water content] The photosensitive composition of the present invention preferably has a water content of 2.0% by mass or less. Photosensitive compositions with a water content within the above range have excellent dispersion stability and sensitivity even after storage over time. The water content can be measured by a known method such as the Karl Fischer method.

[0319] [Method for producing photosensitive composition] The photosensitive composition of the present invention can be produced by mixing the above-mentioned components. During production, the components may be mixed together, or the components may be dissolved or dispersed in the polymerizable compound (B) or the organic solvent (P) and then mixed sequentially. 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), and the like and performing a dispersion treatment. The dispersion is then blended with a photosensitive alkali-soluble resin (A1), a polymerizable compound (B), a photopolymerization initiator (C), a thermal polymerization initiator (D), a thermally crosslinkable compound (E), and the like, and mixed to produce the dispersion. The timing of blending each material is optional. The dispersion process can also be performed multiple times.

[0320] 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.

[0321] The average dispersed particle size (secondary particle size) of the pigment particles in the dispersion is preferably 30 to 200 nm, more preferably 40 to 200 nm. If the particle size is appropriate, a photosensitive composition with high dispersion stability is easily obtained.

[0322] The average dispersed particle size (secondary particle size) is measured using, for example, Nikkiso's Microtrac UPA-EX150, which employs dynamic light scattering (FFT power spectrum method). The conditions are particle permeability in absorption mode, particle shape aspherical, and the D50 particle size as the average diameter. The organic solvent used for dispersion is used as the dilution solvent for measurement, and measurements are taken on ultrasonically treated samples immediately after sample preparation to obtain results with little variation.

[0323] The photosensitive composition is preferably subjected to removal of coarse particles of 5 μm or larger, preferably coarse particles of 1 μm or larger, and more preferably coarse particles of 0.5 μm or larger, as well as contaminated dust, by means of centrifugation, filtration through a sintered filter or membrane filter, etc. The photosensitive composition of the present invention preferably contains substantially no particles of 0.5 μm or larger, and more preferably contains no particles of 0.3 μm or smaller.

[0324] The photosensitive composition of the present invention is preferably used for pattern formation by photolithography, although the present invention is not limited thereto.

[0325] <Membrane> The film of the present invention is a film formed from the above-mentioned photosensitive composition. The film is preferably a patterned film, but can also be used as a flat film without forming a pattern.

[0326] [Membrane manufacturing method] The method for producing the film is not particularly limited, and any known method can be used. For example, the film can be produced by applying the colored composition of the present invention onto a substrate and drying the applied composition.

[0327] [Coating process] Examples of the substrate include substrates made of materials such as glass, resin, and silicone. The glass may be colorless and transparent, or colored glass such as blue glass may be used depending on the application. Examples of the resin include polyester-based resins such as polyester terephthalate, polyolefin-based resins such as polypropylene and polyethylene, polycarbonate resins, and epoxy resins. The thickness of the substrate is preferably 0.01 to 10 mm. An organic light-emitting layer may be formed on these substrates. Furthermore, an imaging device such as a CCD or CMOS may be formed on the substrate. Furthermore, an undercoat layer may be provided on the substrate, if necessary, to improve adhesion with the upper layer, prevent diffusion of substances, and flatten the surface.

[0328] Any known coating method can be used, such as a dropping method, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, an inkjet method, flexographic printing, screen printing, gravure printing, or offset printing.

[0329] The thickness of the film can be adjusted appropriately depending on the purpose, and is preferably 0.05 to 20.0 μm, more preferably 0.3 to 10.0 μm.

[0330] [Drying process] The method for drying the film coated on the substrate is not particularly limited, and known methods can be used, such as reduced pressure drying using a vacuum drying device, heat drying using a hot plate, an IR oven, a convection oven, or the like, and a combination of these methods.

[0331] The drying temperature and time can be adjusted as appropriate. The drying temperature is preferably about 50 to 130°C, and the drying time is preferably about 5 seconds to 5 minutes.

[0332] Next, a pattern is formed. Examples of a method for forming a pattern include photolithography and dry etching. Among these, photolithography is preferred. When the film is used as a flat film, the step of forming a pattern is not carried out, and after coating, the film is dried or the entire surface is exposed to light as necessary.

[0333] The method of forming a pattern by photolithography will be described in detail below. In the photolithography method, the photosensitive composition of the present invention is applied to a substrate, the layer formed by drying is exposed to light in a pattern through a mask (exposure step), the unexposed portions are removed by alkaline development (development step), and the pattern is then heat-treated (post-bake step).

[0334] [Exposure process] In the exposure process, the layer formed by coating and drying is exposed to a specific pattern through a mask using an exposure device such as a stepper. This allows the exposed area to harden. Examples of active energy rays used for exposure include ultraviolet rays such as g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), and i-rays (wavelength 365 nm). Light with a wavelength of 300 nm or less can also be used. Examples of light with a wavelength of 300 nm or less include KrF rays (wavelength 248 nm) and ArF rays (wavelength 193 nm). When using light with a specific wavelength, an optical filter can also be used. The exposure may be performed by continuous irradiation with light, or by repeated irradiation and pause in a short cycle (for example, milliseconds or less) (pulse exposure). Furthermore, multiple active energy rays may be used in combination, or multiple exposures may be performed.

[0335] [Development process] Next, an alkaline development treatment is carried out, whereby the unexposed portions of the layer are dissolved in the alkaline developer, leaving only the hardened portions, thereby obtaining a patterned film. Examples of alkaline developers include aqueous solutions containing alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene. Two or more of these alkaline compounds can be used in combination. The alkaline developer may contain a surfactant and an organic solvent in addition to the alkaline compound and water. The concentration of the alkaline developer is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. The pH of the alkaline developer is preferably 11 to 13, more preferably 11.5 to 12.5. When used at an appropriate pH, pattern roughening and peeling are suppressed, and the remaining film rate after development is improved. Examples of the developing method include a dipping method, a spraying method, a puddling method, etc. The developing temperature is preferably 15 to 40° C. After the alkaline development, it is preferable to wash with pure water.

[0336] [Post-baking process] After development, a heat treatment (post-baking) is carried out. 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.

[0337] <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.

[0338] <Solid-state imaging element> The solid-state imaging device of the present invention has the above optical filter. The solid-state imaging device is not particularly limited as long as it has the optical filter of the present invention and functions as a solid-state imaging device, and examples thereof include the following configurations.

[0339] The present invention is configured to include a substrate having a plurality of photodiodes constituting the light-receiving area of a solid-state imaging device (e.g., a CCD image sensor, a CMOS image sensor, etc.) and transfer electrodes made of polysilicon or the like; a light-shielding film, which is open only to the light-receiving portions of the photodiodes, on the photodiodes and transfer electrodes; a device protection film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire light-shielding film and the light-receiving portions of the photodiodes; and an optical filter (color filter) of the present invention on the device protection film. Furthermore, the present invention may also be configured to include a light-focusing means (e.g., a microlens, etc.; the same applies hereinafter) on the device protection film below the optical filter (closer to the substrate), or to include a light-focusing means on the optical filter. The filter may also have a structure in which a cured film forming each color pixel is embedded in spaces partitioned by partition walls, for example, in a lattice pattern. In this case, the partition walls preferably have a low refractive index relative to each color pixel. An imaging device including the solid-state imaging element of the present invention can be used for various purposes, such as digital cameras, electronic devices with imaging functions (such as mobile phones and smartphones), vehicle-mounted cameras, and surveillance cameras.

[0340] <Image display device> The image display device of the present invention includes the optical filter. Examples of the image display device include a liquid crystal display and an organic EL display. The form of the image display device is not particularly limited as long as it functions as an image display device. For example, the following liquid crystal display configurations can be mentioned.

[0341] A liquid crystal display includes a color filter, a counter substrate having a TFT array substrate or the like, and a liquid crystal layer formed between the color filter and the counter substrate. Examples of driving methods for liquid crystal displays include TN, IPS, OCB, and MVA. The counter substrate can be appropriately selected depending on the driving method. The liquid crystal layer can use various liquid crystals with different dielectric anisotropies, or mixtures thereof, depending on the driving method.

[0342] Specifically, it is described in "Next Generation Liquid Crystal Display Technology" (by Uchida Tatsuo, published by Kogyo Chosakai Co., Ltd. in 1994), "Electronic Display Devices" (by Sasaki Akio, published by Kogyo Chosakai Co., Ltd. in 1990), and "Display Devices" (by Ibuki Nobuaki, published by Sangyo Tosho Co., Ltd. in 1989).

[0343] <Infrared sensor> The infrared sensor of the present invention has the above optical filter. The form of the infrared sensor is not particularly limited as long as it has the optical filter of the present invention and functions as an infrared sensor, and examples thereof include the following configurations.

[0344] A substrate has a plurality of photodiodes constituting the light receiving area of a solid-state imaging device (such as a CCD image sensor or a CMOS image sensor) and transfer electrodes made of polysilicon or the like. A light-shielding film, which is open only in the light receiving portions of the photodiodes, is placed on the photodiodes and transfer electrodes. A device protective film is placed on this light-shielding film, and the optical filter of the present invention is placed on this device protective film. Furthermore, the device protective film may have a light-collecting means (e.g., a microlens, etc.; the same applies below) on the device protective film and below the optical filter (on the side closer to the substrate), or the light-collecting means may be placed on the optical filter.

[0345] 1 is a schematic cross-sectional view showing an example of the configuration of an infrared sensor equipped with an optical filter of the present invention, which includes an infrared sensor 100 shown in FIG.

[0346] 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 .

[0347] The infrared cut filter 111 transmits light in the visible light range (for example, light with a wavelength of 400 to 700 nm) and blocks light in the infrared range (for example, light with a wavelength of 800 to 1,300 nm).

[0348] The color filter 112 is a color filter formed with pixels that transmit and absorb light of specific wavelengths in the visible light range. For example, a color filter formed with red (R), green (G), and blue (B) pixels is used.

[0349] 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.

[0350] 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.

[0351] A microlens 115 is disposed on the incident light h side of the color filter 112 and the infrared transmission filter 113. A planarization film 116 is formed to cover the microlens 115.

[0352] 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.

[0353] This infrared sensor can simultaneously capture image information, enabling motion sensing that recognizes the movement of an object. It can also acquire distance information, enabling it to capture images that include 3D information. Furthermore, this infrared sensor can also be used as a biometric authentication sensor. [Example]

[0354] 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 addition, in the present invention, the nonvolatile content or nonvolatile content concentration refers to the mass residue after standing in an oven at 110°C for 3 hours.

[0355] Before describing the examples, each measurement method will be explained.

[0356] 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.

[0357] (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 (Tosoh Corporation), with two separation columns connected in series, both packed with "TSK-GEL SUPER HZM-N" in series. Measurements were performed at an oven temperature of 40°C, with tetrahydrofuran (THF) as the eluent, and a flow rate of 0.35 ml / min. A 1% by mass THF solution of the sample was prepared, and 20 microliters was injected. The molecular weight is expressed in terms of polystyrene.

[0358] (acid number) 80 ml of acetone and 10 ml of water were added to 0.5 to 1 g of sample solution, and the mixture was stirred to dissolve uniformly. The solution was titrated using an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.) with a 0.1 mol / L KOH aqueous solution as the titrant, 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.

[0359] (amine value) The amine value is a value obtained by converting the total amine value (mgKOH / g) measured in accordance with the method of ASTM D 2074 into nonvolatile content.

[0360] <Production of alkali-soluble resin (A)> (Solution of alkali-soluble resin (A1-1) having thermocrosslinkable group-containing monomer unit (a1)) 100 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAc) was placed in a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, and the mixture was stirred while replacing the atmosphere with nitrogen and heated to 78°C. Next, a mixture of 25.2 parts of Karenz MOI-DEM (2-[[[[(2-methyl-1-oxo-2-propenyl)oxy]ethyl]amino]carbonyl]-1,3-diethyl ester malonate, manufactured by Showa Denko K.K.), 31.2 parts of 2-hydroxyethyl methacrylate (hereinafter, 2HEMA), 37.5 parts of dicyclopentanyl methacrylate (hereinafter, DCPMA), 20.7 parts of methacrylic acid (hereinafter, MAA), and 27.0 parts of methyl methacrylate (hereinafter, MMA), and 12.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) dissolved in 50 parts of PGMAc, was added dropwise from the dropping funnel to the flask and reacted. After the dropwise addition, the mixture was stirred at 78 ° C for 3 hours. Thereafter, PGMAc was added so that the nonvolatile content became 30% by mass, thereby preparing an alkali-soluble resin (A1-1) solution. The alkali-soluble resin (A1-1) had an acid value of 74 mgKOH / g and a weight-average molecular weight of 8,000.

[0361] (Solution of alkali-soluble resin (A1-2) having thermocrosslinkable group-containing monomer unit (a1)) An alkali-soluble resin (A1-2) was synthesized to have the composition ratio and weight average molecular weight shown in Table 2, similarly to the alkali-soluble resin (A1-1), except that part of the DCPMA was replaced with glycidyl methacrylate (hereinafter, GMA). Thereafter, PGMAc was added so that the nonvolatile content became 30% by mass, thereby preparing an alkali-soluble resin (A1-2) solution. The weight-average molecular weight of the resin was adjusted by changing the amount of polymerization initiator used.

[0362] (Solution of alkali-soluble resin (A1-3) having thermocrosslinkable group-containing monomer unit (a1)) A resin (resin) was synthesized in the same manner as for alkali-soluble resin (A1-1), except that some of the DCPMA was replaced with GMA. The atmosphere in the flask was then purged with air, and acrylic acid (AA), triphenylphosphine, and methylhydroquinone were added and reacted at 110°C for 10 hours. This resulted in the introduction of a monomer unit (GMA+AA) in which the epoxy group derived from GMA in the resin reacted with the carboxyl group of AA. GMA+AA is the polymerizable unsaturated group-containing monomer unit (b5). Thereafter, PGMAc was added so that the nonvolatile content became 30% by mass, thereby preparing an alkali-soluble resin (A1-3) solution.

[0363] (Solution of alkali-soluble resin (A1-4) having thermocrosslinkable group-containing monomer unit (a1)) 28.5 parts of diethyl malate, 0.01 parts of 2,6-di-tert-butyl-4-methylphenol, and 0.05 parts of dibutyltin dilaurate were added to a four-neck flask equipped with a stirrer, thermometer, dropping funnel, and reflux condenser, and the mixture was stirred and cooled to 15-20°C. Then, while maintaining the temperature at 15-20°C and stirring, 23.3 parts of 2-methacryloyloxyethyl isocyanate were added dropwise from the dropping funnel. After the addition was completed, the mixture was stirred at 25°C for 13 hours to allow the reaction to proceed. The disappearance of the isocyanate group peak was confirmed by IR, and the compound of the following chemical formula (16), which is a monomer represented by general formula (1), was obtained.

[0364] Chemical formula (16) [ka]

[0365] 200 parts of PGMAc were placed in a four-neck flask equipped with a stirrer, thermometer, dropping funnel, reflux condenser, and gas inlet tube, and the mixture was stirred while purging with nitrogen and heated to 90°C. Next, a mixture of 41.7 parts of the compound of formula (16), 14 parts of MAA, 86 parts of n-butyl acrylate (nBMA), and 76 parts of MMA, and a mixture of 24 parts of 2,2'-azobis(isobutyrate)dimethyl (V-601) as a polymerization initiator dissolved in 50 parts of PGMAc were each added dropwise from the dropping funnel to the flask. After the addition was complete, a solution of 4 parts of V-601 in 16 parts of PGMAc was added dropwise, and the mixture was allowed to react for 3 hours. Thereafter, PGMAc was added so that the nonvolatile content became 30% by mass, thereby preparing an alkali-soluble resin (A1-4) solution.

[0366] (Solution of alkali-soluble resin (A1-5) having thermocrosslinkable group-containing monomer unit (a1)) To 100 parts of alkali-soluble resin (A1-4), 0.1 parts of 1,8-diazabicyclo[5.4.0]undecene-7 was added, and the mixture was heated to 80°C with stirring. After reacting at 80°C for 30 minutes, the mixture was cooled to terminate the reaction. This yielded alkali-soluble resin (A1-5) having a thermally crosslinkable group-containing monomer unit (a1) formed from the compound of the following chemical formula (17), which is a monomer represented by general formula (2).

[0367] Chemical formula (17) [ka]

[0368] (Solution of alkali-soluble resin (A1-6) having thermocrosslinkable group-containing monomer unit (a1)) A four-neck flask equipped with a stirrer, thermometer, dropping funnel, and reflux condenser was charged with 190.2 parts of diethyl malate, 0.17 parts of 2,6-di-tert-butyl-4-methylphenol, and 0.33 parts of dibutyltin dilaurate, and the mixture was stirred and cooled to 15-20°C. The temperature was then maintained at 15-20°C, and 141.1 parts of 2-acryloyloxyethyl isocyanate was added dropwise from the dropping funnel with stirring. After the addition was complete, the mixture was stirred at 25°C for 13 hours to allow the reaction to proceed. The disappearance of the isocyanate group peak was confirmed by IR, yielding the compound of the following chemical formula (18), which is a monomer represented by general formula (1).

[0369] Chemical formula (18) [ka]

[0370] A flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube was charged with 80 parts of PGMAc, and the mixture was stirred while purging with nitrogen and heated to 78 ° C. Next, 48.8 parts of the compound of formula (18), 24.7 parts of Karenz MOI-BP (2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate manufactured by Showa Denko K.K.), 25.5 parts of 2HEMA, 8.6 parts of 2-ethylhexyl acrylate (hereinafter referred to as 2EHA), and 17.4 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) were mixed and added dropwise to the flask from the dropping funnel. After the addition was completed, the mixture was stirred at 78 ° C for 3 hours to react, and then 0.2 parts of 1,8-diazabicyclo[5.4.0]-undecene-7 was added and stirred at 78 ° C for an additional 30 minutes. In this way, a thermally crosslinkable group-containing monomer unit (a1) formed from the compound of the following chemical formula (19), which is a monomer represented by general formula (2), was synthesized.

[0371] Chemical formula (19) [ka]

[0372] Next, 9.9 parts of succinic anhydride (hereinafter referred to as SA) and 0.5 parts of lithium naphthenate (catalyst) were added and stirred at 78°C for 1 hour. This resulted in the introduction of a monomer unit in which SA was added to the hydroxyl group of 2HEMA (hereinafter referred to as 2HEMA+SA). 2HEMA+SA is the acidic group-containing monomer unit (a2). Thereafter, PGMAc was added so that the nonvolatile content became 30% by mass, thereby preparing an alkali-soluble resin (A1-6) solution.

[0373] (Solution of alkali-soluble resin (A1-7) having thermocrosslinkable group-containing monomer unit (a1)) Karenz MOI-BP was replaced with Karenz MOI-BM (2-[O-(1'-methylpropylideneamino)carboxyamino]ethyl methacrylate manufactured by Showa Denko K.K.), and alkali-soluble resin (A1-7) was synthesized in the same manner as alkali-soluble resin (A1-6) so as to have the composition ratio and weight-average molecular weight listed in Table 2. Thereafter, PGMAc was added so that the nonvolatile content became 30% by mass, thereby preparing an alkali-soluble resin (A1-7) solution.

[0374] (Solution of alkali-soluble resin (A1-8) having thermocrosslinkable group-containing monomer unit (a1)) A flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube was charged with 70 parts of PGMAc, and the mixture was stirred while purging with nitrogen and heated to 90°C. Next, a mixture of 20.7 parts of 2-(acetoacetoxy)ethyl methacrylate (hereinafter, 2AAEM), a monomer represented by general formula (3), 26.7 parts of MAA, and 52.6 parts of DCPMA, and a solution of 5.0 parts of V-601 dissolved in 30 parts of PGMAc, were each added dropwise from the dropping funnel to the flask. After the addition was completed, the mixture was stirred at 90°C for 6 hours to react. The mixture was then cooled to 40°C, and 0.12 parts of 4-methoxyphenol, 17.6 parts of 3,4-epoxycyclohexylmethyl acrylate (hereinafter referred to as ECHA), and 4.7 parts of triphenylphosphine were added. The mixture was then heated to 110°C and reacted with stirring for 10 hours. This resulted in the introduction of a monomer unit in which the epoxy group of ECHA was added to the carboxyl group of MAA (hereinafter referred to as MAA+ECHA). MAA+ECHA is the polymerizable unsaturated group-containing monomer unit (a5). Thereafter, PGMAc was added so that the nonvolatile content became 30% by mass, thereby preparing an alkali-soluble resin (A1-8) solution.

[0375] (Solution of alkali-soluble resin (A1-9) having thermocrosslinkable group-containing monomer unit (a1)) 300 parts of PGMAc was added to a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube, and the mixture was stirred while purging with nitrogen and heated to 105°C. Next, a mixture of 106.9 parts of 3-methacryloyloxypropyltrimethoxysilane (hereinafter referred to as Monomer A), a monomer represented by general formula (4), 40.8 parts of MAA, and 125 parts of MMA, plus 27.3 parts of V-601, was added dropwise from the dropping funnel to the flask. After the addition was complete, the mixture was allowed to react for 2 hours with stirring at 105°C. Thereafter, PGMAc was added so that the nonvolatile content became 30% by mass, to prepare an alkali-soluble resin (A1-9) solution.

[0376] (Solution of alkali-soluble resin (A1-10) having thermally crosslinkable group-containing monomer unit (a1)) Monomer A was replaced with 3-methacryloyloxypropylmethyldiethoxysilane (hereinafter referred to as monomer B), and alkali-soluble resin (A1-10) was synthesized in the same manner as alkali-soluble resin (A1-9) so as to have the composition ratio and weight-average molecular weight shown in Table 2. Thereafter, PGMAc was added so that the nonvolatile content became 30% by mass, thereby preparing an alkali-soluble resin (A1-10) solution.

[0377] (Solution of alkali-soluble resin (A1-11) having thermally crosslinkable group-containing monomer unit (a1)) A flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube was charged with 100 parts of PGMAc, which was then stirred while purging with nitrogen and heated to 90°C. Next, a mixture of 35 parts of tert-butyl methacrylate (hereinafter referred to as tBMA), 5 parts of 2AAEM, 10 parts of N-benzylmaleimide (hereinafter referred to as BzMI), 20 parts of 2HEMA, 17.1 parts of MAA, and 2 parts of t-butylperoxy-2-ethylhexanoate (polymerization initiator), which is a monomer represented by general formula (5), and a mixture of 0.6 parts of n-dodecyl mercaptan and 20 parts of PGMAc were each added dropwise from the dropping funnel to the flask. After the addition was completed, the mixture was maintained at 90°C for 30 minutes, then heated to 115°C, and reacted with stirring for 90 minutes. Thereafter, PGMAc was added so that the nonvolatile content became 30% by mass, thereby preparing an alkali-soluble resin (A1-11) solution.

[0378] (Solution of alkali-soluble resin (A-12) having thermocrosslinkable group-containing monomer unit (a1)) Karenz MOI-DEM was replaced with Karenz MOI-BP, and an alkali-soluble resin (A1-12) was synthesized to have the composition ratio and weight-average molecular weight shown in Table 2, similar to that of the alkali-soluble resin (A1-1). Thereafter, PGMAc was added so that the nonvolatile content became 30% by mass, thereby preparing an alkali-soluble resin (A1-12) solution.

[0379] (Solution of alkali-soluble resin (A1-13) having thermocrosslinkable group-containing monomer unit (a1)) Karenz MOI-DEM was replaced with GMA, and an alkali-soluble resin (A1-13) was synthesized to have the composition ratio and weight-average molecular weight shown in Table 2, similarly to the alkali-soluble resin (A1-1). Thereafter, PGMAc was added so that the nonvolatile content became 30% by mass, thereby preparing an alkali-soluble resin (A1-13) solution.

[0380] (Solution of alkali-soluble resin (A1-14) having thermocrosslinkable group-containing monomer unit (a1)) Karenz MOI-DEM 3,4-epoxytricyclo[5.2.1.0 2,6 ]decan-8-yl acrylate (hereinafter referred to as Monomer C) and 3,4-epoxytricyclo[5.2.1.0 2,6 ] Alkali-soluble resin (A1-14) was synthesized in the same manner as alkali-soluble resin (A1-1), except that a mixture (molar ratio 1:1) of decan-9-yl acrylate (hereinafter referred to as monomer D) was used instead, so as to have the composition ratio and weight-average molecular weight shown in Table 2. Thereafter, PGMAc was added so that the nonvolatile content became 30% by mass, thereby preparing an alkali-soluble resin (A1-14) solution.

[0381] [Table 1]

[0382] [Table 2]

[0383] The amount of each component in Tables 1 and 2 is expressed in mol %.

[0384] (Solution of alkali-soluble resin (A2-1) not having thermally crosslinkable group-containing monomer unit (a1)) A separable four-neck flask was fitted with a thermometer, condenser, nitrogen gas inlet, and stirrer. 100 parts of 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 56.86 parts of GMA, 66.09 parts of DCPMA, and 31.25 parts of styrene (hereinafter referred to as St), and a mixture of 5.0 parts of azobisisobutyronitrile dissolved in PGMAc as a polymerization initiator, was added dropwise over 2.5 hours via a dropping tube to carry out the polymerization reaction. After the addition was complete, the mixture was stirred for another 2 hours at 120 °C. Next, the atmosphere in the flask was purged with air, and 28.82 parts of AA, 0.3 parts of tris(dimethylaminomethyl)phenol, and 0.3 parts of hydroquinone were added. The mixture was stirred at 120 °C for 5 hours. Further, 48.68 parts of tetrahydrophthalic anhydride (hereinafter referred to as THPA) and 0.5 parts of triethylamine were added, and the mixture was stirred at 120° C. for 4 hours to carry out the reaction. Thereafter, PGMAc was added so that the nonvolatile content was 30% by mass, to prepare an alkali-soluble resin (A2-1) solution. The resin had an acid value of 77 mgKOH / g and a weight-average molecular weight of 10,000.

[0385] <(Production of Blocked Isocyanate Group-Containing Compound (E1)> (Production of Blocked Isocyanate Group-Containing Compound E1-1) A four-neck flask equipped with a thermometer, stirring blade, and reflux condenser was charged with 100 parts by mass of hexamethylene diisocyanate (hereinafter referred to as HDI) under a nitrogen stream. The temperature inside the reactor was maintained at 60°C with stirring, and 0.095 parts by mass of trimethylbenzylammonium hydroxide was added to carry out the reaction. After 4.5 hours, when the conversion rate reached 40% by mass, 0.02 parts by mass of phosphoric acid was added to terminate the reaction. The reaction solution was filtered, and unreacted HDI was removed using a thin-film evaporator to obtain an isocyanurate-type polyisocyanate (hereinafter referred to as "E1 precursor"). The NCO content of the obtained E1-1 precursor was 22.0% by mass, the number-average molecular weight was 655, and the average number of isocyanate groups was 3.43. Furthermore, the obtained E1 precursor 1 H-NMR analysis confirmed the presence of isocyanurate groups. A four-neck flask equipped with a thermometer, a stirring blade, and a reflux condenser was charged with 100 parts by mass of the E1 precursor and diethyl malonate (100 mol% relative to 100 mol% of NCO groups) under a nitrogen stream, and butyl acetate was added to adjust the solid content to 60% by mass. Next, 1.0 part by mass of a methanol solution containing sodium methylate (28% by mass relative to the total mass of the solution) was added dropwise with stirring, and the external bath was adjusted so that the solution temperature was 55°C. A blocking reaction was carried out at 55°C for 5 hours to obtain a blocked isocyanate group-containing compound E1-1 with a nonvolatile content of 60% by mass and containing the above (X-1) as the blocked isocyanate group.

[0386] (Production of Blocked Isocyanate Group-Containing Compound E1-2) A four-neck flask equipped with a thermometer, a stirring blade, and a reflux condenser was charged with 100 parts by mass of the E1 precursor, diethyl malonate (70 mol% relative to 100 mol% of NCO groups), and dibutyl malonate (30 mol% relative to 100 mol% of NCO groups) under a nitrogen stream. Then, butyl acetate was added to adjust the solid content to 60% by mass. Next, 1.0 part by mass of a methanol solution containing sodium methylate (28% by mass relative to the total mass of the solution) was added dropwise with stirring. The external bath was then adjusted to a solution temperature of 55°C, and the blocking reaction was carried out at 55°C for 5 hours to obtain a blocked isocyanate group-containing compound E1-2 with a nonvolatile content of 60% by mass and containing the blocked isocyanate groups (X-1) and (X-8) in a molar ratio of 70:30.

[0387] (Production of Blocked Isocyanate Group-Containing Compound E1-3) A four-neck flask equipped with a thermometer, a stirring blade, and a reflux condenser was charged with 100 parts by mass of the E1 precursor, diethyl malonate (30 mol% relative to 100 mol% of NCO groups), and dibutyl malonate (70 mol% relative to 100 mol% of NCO groups) under a nitrogen stream. Then, butyl acetate was added to adjust the solid content to 60% by mass. Next, 1.0 part by mass of a methanol solution containing sodium methylate (28% by mass relative to the total mass of the solution) was added dropwise with stirring. The external bath was then adjusted to a solution temperature of 55°C, and the blocking reaction was carried out at 55°C for 5 hours to obtain a blocked isocyanate group-containing compound E1-3 with a nonvolatile content of 60% by mass and containing the blocked isocyanate groups (X-1) and (X-8) in a molar ratio of 30:70.

[0388] (Production of Blocked Isocyanate Group-Containing Compound E1-4) A four-necked flask equipped with a thermometer, a stirring blade, and a reflux condenser was charged with 100 parts by weight of E1 precursor, diisopropyl malonate (70 mol% relative to 100 mol% of NCO groups), and di-tert-butyl malonate (30 mol% relative to 100 mol% of NCO groups) under a nitrogen stream. Then, butyl acetate was added to adjust the solids content to 60% by weight. Next, 1.0 part by weight of a methanol solution containing sodium methylate (28% by weight relative to the total weight of the solution) was added dropwise with stirring. The external bath was adjusted to raise the solution temperature to 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 with a nonvolatile content of 60% by weight and containing the blocked isocyanate groups (X-4) and (X-7) in a molar ratio of 70:30.

[0389] <Production of dye (F)> (Yellow pigment (f16)) In a reaction vessel, 46.2 parts of diazobarbituric acid and 38.4 parts of barbituric acid were added to 1,100 parts of distilled water at 85° C. Next, an aqueous potassium hydroxide solution was added to adjust the pH to about 5, and the mixture was stirred for 90 minutes to synthesize an azobarbituric acid precursor. 0.3 mol of the resulting azobarbituric acid precursor was mixed with 1,500 parts of distilled water at 82°C, and 10 parts of 30% hydrochloric acid was added dropwise. Then, 0.6 mol of melamine was added. 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. Potassium hydroxide was then added to adjust the pH to approximately 5.2, and 100 parts of distilled water was added and the mixture was heated to 90°C. Next, 21 parts of 30% hydrochloric acid was added dropwise, and the mixture was stirred for 12 hours to react. Potassium hydroxide was then added to adjust the pH to approximately 5, and the product was filtered. The product was washed with ion-exchanged water and filtered. After drying at 80°C and pulverizing, colorant (f16) with a Ni, Zn, and Cu molar ratio of 65:30:5 was obtained.

[0390] <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-A-2022-96687.

[0391] Chemical formula (400) [ka]

[0392] (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-A-2022-96687.

[0393] Chemical formula (401) [ka]

[0394] (Production of near-infrared absorbing dyes (F-NIR31), (F-NIR32), and (F-NIR33)) By the method described in JP 2022-72558 A, a micronized 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.

[0395] [ka]

[0396] 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).

[0397] (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.

[0398] Chemical formula (406) [ka]

[0399] <Production of Dispersion Resin (H)> (Dispersed resin (H-1) solution) A reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer was charged with 108 parts of 1-thioglycerol, 174 parts of pyromellitic anhydride, 650 parts of PGMAc (propylene glycol monomethyl ether acetate), and 0.2 parts of monobutyltin oxide as a catalyst. After purging with nitrogen gas, the mixture was reacted at 120°C for 5 hours (first step). Acid value measurement confirmed that 95% or more of the acid anhydride had been half-esterified. Next, 160 parts of the compound obtained in the first step (based on nonvolatile 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 into a reaction vessel, heated to 80 °C, and 1.2 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) was added. The reaction was continued for 12 hours (step 2). Measurement of the nonvolatile content confirmed that more than 95% had reacted. Finally, 500 parts of a 50% PGMAc solution of the compound obtained in step 2, 27.0 parts of 2-methacryloyloxyethyl isocyanate, and 0.1 parts of hydroquinone were charged, and the reaction was continued until the disappearance of the peak at 2270 cm-1 due to the isocyanate group was confirmed by IR (step 3). After confirming the disappearance of the peak, the reaction solution was cooled and the nonvolatile 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 nonvolatile 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.

[0400] <Preparation of Dispersion> (Dispersion 1) The following raw materials were mixed and stirred until uniform, and then dispersed in an Eiger mill (Eiger Japan Co., Ltd., "Mini Model M-250 MKII") using zirconia beads with a diameter of 0.5 mm for 3 hours, followed by filtration through a filter with a pore size of 1.0 μm to produce Dispersion 1. The nonvolatile content was 20% by mass. Red coloring material (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

[0401] (Dispersion 2~16) Dispersions 2 to 16 were produced in the same manner as Dispersion 1, except that the raw materials and amounts were changed as shown in Tables 3 and 4. The values in the tables indicate the non-volatile content ratio. The solvent used was PGMAc, and the non-volatile content of Dispersions 2 to 16 was 30%.

[0402] The components listed in Tables 3 and 4 are as follows:

[0403] [Table 3]

[0404] [Table 4]

[0405] [Dye (F)] (red pigment) F-1: CI Pigment Red 177 (Shinic, "Shinilex Red SR3C") F-2: CI Pigment Red 254 (BASF Japan, "Irgajin Red L 3630") F-3: CI Pigment Red 264 (BASF Japan, "Irgazin Rubin L4025") (green pigment) F-4: CI Pigment Green 36 (Toyo Color Co., Ltd., "Lionol 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 Co., Ltd.) F-8: CI Pigment Green 63 (Toyo Color Co., Ltd.) (blue pigment) F-9: CI Pigment Blue 15:3 (Toyo Color Co., Ltd., "Lionor Blue FG7351") F-10: CI Pigment Blue 15:6 (Toyo Color Co., Ltd., "Lionol Blue ES") (purple pigment) F-11: CI Pigment Violet 23 (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 (Toyo Color Co., Ltd.) F-16: Yellow pigment (f16) (near infrared absorbing dye) F-17: F-NIR1 F-18: F-NIR2 F-19: F-NIR3 F-20: F-NIR4

[0406] All of the pigments (F-1) to (F-20) were pulverized by salt milling, thoroughly washed, and dried before use.

[0407] [Pigment derivatives (G)] [ka]

[0408] <Production of silane coupling agent (K)> (Silane coupling agent (K-2)) A 1-L separable flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer was charged with 116 parts of hydroxyethyl acrylate and heated to 80°C. 205 parts of 3-isocyanatopropyltrimethoxysilane was added dropwise and the mixture was stirred at 80°C for 4 hours to allow the reaction to proceed. Subsequently, IR measurement confirmed that the absorption peaks derived from the isocyanate groups of the raw material had completely disappeared, and instead, absorption peaks derived from urethane bonds had appeared, yielding a silane coupling agent (K-2) whose main component is represented by the following chemical formula (20). Note that a dimer to decamer, which is a condensation product of chemical formula (20), was included as a secondary component.

[0409] Chemical formula (20) [ka]

[0410] <Production of Photosensitive Composition> [Example 1] The following raw materials were mixed and stirred, and then filtered through a filter with a pore size of 1.0 μm to obtain 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 (A2-1) solution: 6.01 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 Epoxy compound (E2-1): 0.75 parts Silane coupling agent (K-1): 0.75 parts UV absorber (Q-1): 0.15 parts Polymerization inhibitor (L-1): 0.0075 parts Leveling agent (J-1): 1.00 parts Organic solvent (P-1): 53.09 parts

[0411] [Examples 2 to 86 and Comparative Examples 1 to 3] Photosensitive compositions of Examples 2 to 86 and Comparative Examples 1 to 3 were prepared in the same manner as in Example 1, except that the raw materials and amounts of the photosensitive composition of Example 1 were changed to those shown in Tables 5 to 13.

[0412] [Table 5]

[0413] [Table 6]

[0414] [Table 7]

[0415] [Table 8]

[0416] [Table 9]

[0417] [Table 10]

[0418] [Table 11]

[0419] [Table 12]

[0420] [Table 13]

[0421] In Tables 5 to 13, resin (A1) represents an alkali-soluble resin (A1) having a thermally crosslinkable group-containing monomer unit (a1), and resin (A2) represents an alkali-soluble resin (A2) not having a thermally crosslinkable group-containing monomer unit (a1).

[0422] (Polymerizable compound (B)) B1-1: CN9906NS (Arkema, aliphatic multifunctional urethane acrylate having a tertiary amine structure; polymerizable compound (B1) having an amine structure) B1-2: Aronix M-306 (manufactured by Toagosei Co., Ltd., a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate; a polymerizable compound (B2) having a hydroxyl group) B1-3: Aronix M-520 (manufactured by Toagosei Co., Ltd., polybasic acid-modified acrylic oligomer; polymerizable compound (B3) having an acidic group) B1-4: 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) B1-5: KAYARAD DPCA-30 (Nippon Kayaku Co., Ltd., lactone-modified polymerizable compound (B4))

[0423] [Photopolymerization initiator (C)] C1-1: The above compound (C1-1) (absorption coefficient of light at a wavelength of 365 nm is 13,410 L / mol cm) C1-2: The above compound (C1-2) (absorption coefficient of light at a wavelength of 365 nm is 14,214 L / mol cm) C1-3: The above compound (C1-3) (absorption coefficient of light at a wavelength of 365 nm is 7,051 L / mol cm) C1-4: The above compound (C1-4) (absorption coefficient of light at a wavelength of 365 nm is 27,257 L / mol cm) C1-5: The above compound (C1-5) (absorption coefficient of light at a wavelength of 365 nm is 18,334 L / mol cm) C1-6: The above compound (C1-6) (absorption coefficient of light at a wavelength of 365 nm is 14,127 L / mol cm) C1-7: The above compound (C1-7) (absorption coefficient of light at a wavelength of 365 nm is 2,401 L / mol cm) C2-1: NPI-20400 (α-aminoalkylphenone; Changzhou Strong Co., Ltd.; other photopolymerization initiators (C2))

[0424] [Thermal polymerization initiator (D)] (Oxime sulfonate compound (D1)) D1-1: The above-mentioned compound (D1-1) (thermal polymerization initiator (D1) represented by general formula (2)) D1-2: The above-mentioned compound (D1-2) (thermal polymerization initiator (D1) represented by general formula (2)) D1-3: The above-mentioned compound (D1-3) (thermal polymerization initiator (D1) represented by general formula (2)) D1-4: The above-mentioned compound (D1-4) (thermal polymerization initiator (D1) represented by general formula (2)) D1-5: The above-mentioned compound (D1-5) (thermal polymerization initiator (D1) represented by general formula (2)) D1-6: The above-mentioned compound (D1-6) (thermal polymerization initiator (D1) represented by general formula (2)) D1-7: The above-mentioned compound (D1-7) (thermal polymerization initiator (D1) represented by general formula (2)) D1-8: The above-mentioned compound (D1-8) (thermal polymerization initiator (D1) represented by general formula (2)) D1-9: The above-mentioned compound (D1-9) (thermal polymerization initiator (D1) represented by general formula (2)) D1-10: The above-mentioned compound (D1-10) (thermal polymerization initiator (D1) represented by general formula (2)) D1-11: The above-mentioned compound (D1-11) (thermal polymerization initiator (D1) represented by general formula (2)) D1-12: The above-mentioned compound (D1-12) (thermal polymerization initiator (D1) represented by general formula (2)) D1-13: The above-mentioned compound (D1-13) (thermal polymerization initiator (D1) represented by general formula (2)) D1-14: The above-mentioned compound (D1-14) (thermal polymerization initiator (D1) represented by general formula (2)) D1-15: The above-mentioned compound (D1-15) (thermal polymerization initiator (D1) represented by general formula (2)) D1-16: The above-mentioned compound (D1-16) (thermal polymerization initiator (D1) represented by general formula (2)) D1-17: The above-mentioned compound (D1-17) (thermal polymerization initiator (D1) represented by general formula (2)) D1-18: The above-mentioned compound (D1-18) (thermal polymerization initiator (D1) represented by general formula (2)) (Other thermal polymerization initiators (D2)) D2-1: 2,2-bis(4,4-di-tert-butylperoxycyclohexyl)

[0425] [Compounds in which the nitrogen atom in the oxime sulfonate structure and the carbon atom forming a double bond form a ring] d1: the following photoacid generator A-1 described in WO 2014 / 157720 (Photoacid generator d1) [ka]

[0426] [Thermal crosslinkable compound (E)] 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 approximately 15 epoxy groups and an epoxy equivalent of 170 to 190 g / eq.); E2-2: Denacol EX-611 (manufactured by Nagase ChemteX Corporation, sorbitol polyglycidyl ether, having approximately 6 epoxy groups and an epoxy equivalent of 80 to 90 g / eq.). E2-3: Epolead GT401 (manufactured by Daicel Corporation, butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl) modified ε-caprolactone, epoxy groups approximately 4, epoxy equivalent 190-210g / eq.) E2-4: 1,3,5-tris(2,3-epoxypropyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (3 epoxy groups, 98g / eq. epoxy equivalent)

[0427] [Silane coupling agent (K)] K-1: KBE-403 (Shin-Etsu Silicone Co., Ltd., compound with epoxy group, 3-glycidoxypropyltriethoxysilane)

[0428] [Ultraviolet absorber (Q)] Q-1: TINUVIN 326 (BASF Japan, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole) Q-2: Omnirad EMK (IGM Resins, 4,4'-bis(diethylamino)benzophenone)

[0429] [Polymerization inhibitor (L)] L-1: Methylhydroquinone (Fujifilm Wako Pure Chemical Industries, Ltd., alkylhydroquinone compound)

[0430] [Leveling Agent (J)] A mixed solution obtained by mixing 2 parts of the following J1 and 1 part of J2 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%))

[0431] [ka]

[0432] [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 prepare an organic solvent (P-1).

[0433] <Evaluation of Photosensitive Composition> The following evaluations were carried out for Examples 1 to 83 and Comparative Examples 1 to 3. The evaluation results are shown in Tables 14 to 22.

[0434] [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. A value of 3 or higher is practical. [Viscosity change rate] = |([Initial viscosity] - [Temporal viscosity]) / [Initial viscosity]| × 100 [Evaluation criteria] 5: Viscosity change rate: 0% to less than 3% 4: Viscosity change rate: 3% or more but less than 5% 3: Viscosity change rate: 5% or more but less than 10% 2: Viscosity change rate of 10% or more but less than 20% 1: Viscosity change rate of 20% or more

[0435] [Development stain evaluation] The obtained photosensitive composition was applied to a glass substrate (Corning Eagle 2000) measuring 100 mm in length, 100 mm in width, and 0.7 mm in thickness using a spin coater so that the dry film thickness was 2.5 μm, and then dried on a hot plate at 70° C. for 1 minute. Then, an ultra-high pressure mercury lamp was used to apply the coating with an illuminance of 30 mW / cm. 2 , 100mJ / cm 2 The substrate was exposed to ultraviolet light through a photomask with a 100 μm-wide stripe pattern. After cooling to room temperature, the substrate was spray-developed using a potassium hydroxide solution (concentration: 0.04%) at 23°C for 40 seconds, washed with ion-exchanged water, and air-dried with clean air to obtain a substrate for evaluation. The photocured portion remaining after development was observed within a 5 x 5 cm area at the center of the substrate using an optical microscope at 50x magnification. The area of the entire photocured portion was taken as 100%, and any locally discolored areas were considered to be development stains and evaluated. The evaluation criteria were as follows, with a score of 3 or higher being practical. [Evaluation criteria] 5: No development stains are generated over the entire area. 4: Less than 10% of the total area was stained by development. 3: 10% or more but less than 20% of the total area was stained by development. 2: 20% or more but less than 50% of the total area was stained by development. 1: 50% or more of the total area was stained by development.

[0436] [Redissolution evaluation] The obtained photosensitive composition was evaluated through the steps (1) to (4) described below. A control device was used that automatically attached a glass test piece (Glass Eagle 2000 manufactured by Corning Incorporated) to the arm of a driving device and repeatedly inserted and removed the tip of the test piece into a bottle filled with the photosensitive composition. (1) At an ambient temperature of 23°C, a 20 mm portion of the longitudinal tip of a glass test piece having a length of 100 mm, a width of 5 mm and a thickness of 0.7 mm was immersed in the photosensitive composition at a speed of 12.5 mm / sec and then maintained therein for 4 seconds. (2) The glass test piece was removed from the photosensitive composition at a speed of 12.5 mm / sec, held vertically with the tip of the glass test piece facing downward, and then dried for 52 seconds under conditions of an atmospheric temperature of 23°C, humidity of 55%, and a wind speed of 0.5±0.2 m / sec. (3) Steps (1) and (2) were repeated a total of 250 times to form deposits (a) derived from the photosensitive composition on the glass test piece. (4) Of the four ridgelines of the glass test piece, the ridgeline with the most deposits was selected, and the weight of the deposits on that ridgeline ("deposit (a)") was measured. The weight of deposit (a) was calculated by first measuring the specific gravity of the film formed using the curable composition, then measuring the volume of deposit (a) with a three-dimensional laser microscope, and then calculating the weight from the product of these. The evaluation criteria were as follows, with a score of 3 or higher being practical. [Evaluation criteria] 5: The weight of the attached matter (a) is less than 1 μg 4: The weight of the deposit (a) is 1 μg or more and less than 2 μg 3: The weight of the attached substance (a) is 2 μg or more and less than 3 μg 2: The weight of the attached substance (a) is 3 μg or more and less than 4 μg 1: The weight of the attached matter (a) is 4 μg or more

[0437] [Evaluation of heat shock resistance] The obtained photosensitive composition was placed in a sealed container and subjected to a temperature cycle test of 4 hours at 5°C and 2 hours at 30°C for 150 days. The photosensitive composition was then removed from the sealed container and applied to a glass substrate using a spin coater so that the dried film thickness was 0.5 μm. A heat treatment (pre-baking) was performed for 180 seconds using a hot plate at 100°C to produce a film for evaluation. The film on the glass substrate was observed under an optical microscope at a magnification of 100x in a 0.5 mm square area, and the number of defects within the field of view was counted. The same operation was repeated a total of 10 times, with the observation position arbitrarily changed, and the total number of defects was calculated. The evaluation criteria are as follows, with a score of 3 or higher being practical. [Evaluation criteria] 5: 0 defects 4: 1 to 5 defects 3: 5 to less than 30 defects 2: 30 to less than 100 defects 1: 100 or more defects

[0438] [Evaluation of solvent resistance] The obtained photosensitive composition was applied to a glass substrate (Corning Eagle 2000) measuring 100 mm in length, 100 mm in width, and 0.7 mm in thickness using a spin coater so that the dry film thickness was 2 μm, and then dried on a hot plate at 70° C. for 1 minute. Then, an ultra-high pressure mercury lamp was used to apply the coating with an illuminance of 30 mW / cm. 2 , irradiation amount 100mJ / cm 2 The substrate was exposed to ultraviolet light through a photomask with a 100 μm square pattern. After cooling to room temperature, the substrate was spray-developed using a potassium hydroxide solution (concentration: 0.04% by mass) at 23°C for 40 seconds, then 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 for 3, 5, 7, 10, 15, and 20 minutes to create substrates, which were then evaluated by visual observation. The evaluation criteria were as follows, with a score of 3 or higher being practical. [Evaluation Criteria] 5: No change in appearance for substrates immersed for 15 minutes or less, change in appearance for substrates immersed for 20 minutes 4: No change in appearance for substrates immersed for 10 minutes or less, change in appearance for substrates immersed for 15 minutes or more 3: No change in appearance for substrates immersed for 7 minutes or less, change in appearance for substrates immersed for 10 minutes or more 2: No change in appearance for substrates immersed for 5 minutes or less, change in appearance for substrates immersed for 7 minutes or more 1: No change in appearance for the substrate after immersion for 3 minutes, change in appearance for the substrate after immersion for 7 minutes or more

[0439] [Table 14]

Claims

1. A photosensitive composition comprising an alkali-soluble resin (A), a polymerizable compound (B), a photopolymerization initiator (C), and a thermal polymerization initiator (D), the photopolymerization initiator (C) includes an oxime ester photopolymerization initiator (C1), The photosensitive composition, wherein the thermal polymerization initiator (D) comprises an oxime sulfonate compound (D1) (excluding compounds in which a carbon atom forming a double bond with a nitrogen atom in an oxime sulfonate structure forms a ring).

2. The photosensitive composition according to claim 1 , wherein the alkali-soluble resin (A) comprises an alkali-soluble resin (A1) having a thermocrosslinkable group-containing monomer unit (a1).

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

4. The photosensitive composition according to claim 1 , wherein the polymerizable compound (B) comprises a (meth)acrylate compound (B1) having an amine structure.

5. A film formed from the photosensitive composition according to any one of claims 1 to 4.

6. An optical filter comprising the film according to claim 5 .

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

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

9. An infrared sensor comprising the optical filter according to claim 6.

Images