Photosensitive compositions, films, optical filters, solid-state image sensors, image display devices, and infrared sensors

Abstract

The present invention aims to provide a photosensitive composition that exhibits excellent alkali developability and can form a film with excellent resistance to heating over a wide temperature range from low to high temperatures. [Solution] The above problem is solved by a photosensitive composition comprising an alkali-soluble resin (A), a polymerizable compound (B), and a polymerization initiator (C), The alkali-soluble resin (A) can be solved by a photosensitive composition comprising an alkali-soluble resin (A1) having a phenolic hydroxyl group-containing monomer unit (a1), and an alkali-soluble resin (A2) having a hydroxyl group-containing monomer unit (a2) other than the phenolic hydroxyl group-containing monomer unit (a1) (excluding the alkali-soluble resin (A1)).

Description

[Technical Field]

[0001] The present invention relates to a photosensitive composition used for forming optical filters used in solid-state image sensors, image display devices, and infrared sensors, etc. [Background technology]

[0002] With the widespread use of liquid crystal displays, digital cameras, smartphones, image sensors, infrared sensors, etc., the demand for optical filters used in these devices is growing. In the manufacturing process of optical filters and devices using optical filters, a process is being considered in which a film is formed using a photosensitive composition, and then heated at various temperatures ranging from low temperatures (e.g., below 130°C) to high temperatures (e.g., above 280°C). For example, Patent Document 1 discloses a coloring composition that can form a cured film in which mixing with other colors is suppressed even when an image is formed by a low-temperature process, and includes a red coloring agent, a resin having repeating units containing blocked isocyanate groups, a polymerizable compound, and a photopolymerizable initiator. Patent Document 2 also discloses a coloring resin composition that can expand the process window for processes after the film is manufactured, and includes a resin A containing a specific repeating unit (A), a colorant, and an organic solvent. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] International Publication No. 2021 / 054248 [Patent Document 2] International Publication No. 2021 / 149595 [Overview of the project] [Problems that the invention aims to solve]

[0004] However, the compositions of Patent Document 1 and Patent Document 2 were not sufficiently resistant to heating in a wide temperature range from low temperature to high temperature. Also, the alkali developability of the compositions was not sufficient.

[0005] An object of the present invention is to provide a photosensitive composition that has excellent alkali developability and can form a film having excellent resistance to heating in a wide temperature range from low temperature to high temperature.

Means for Solving the Problems

[0006] The photosensitive composition of the present invention contains an alkali-soluble resin (A), a polymerizable compound (B), and a polymerization initiator (C). The alkali-soluble resin (A) includes an alkali-soluble resin (A1) having a phenolic hydroxyl group-containing monomer unit (a1) and an alkali-soluble resin (A2) (excluding the alkali-soluble resin (A1)) having a hydroxyl group-containing monomer unit (a2) other than the phenolic hydroxyl group-containing monomer unit (a1), and is a photosensitive composition.

Effects of the Invention

[0007] According to the present invention as described above, it is possible to provide a photosensitive composition that has excellent alkali developability and can form a film having excellent resistance to heating in a wide temperature range from low temperature to high temperature. Further, the present invention can provide a film, an optical filter, a solid-state imaging device, an image display device, and an infrared sensor using the same.

Brief Description of the Drawings

[0008] [Figure 1] FIG. 1 shows a schematic cross-sectional view of an infrared sensor having the optical filter of the present invention.

Embodiments for Carrying Out the Invention

[0009] Hereinafter, embodiments of the photosensitive composition of the present invention will be described in detail. Note that the present invention is not limited to the following embodiments and can be modified and implemented within the range capable of solving the problems.

[0010] In this specification, unless otherwise specified, "(meth)acryloyl," "(meth)acrylic," "(meth)acrylic acid," "(meth)acrylate," or "(meth)acrylamide" means "acryloyl and / or methacryloyl," "acrylic and / or methacrylic," "acrylic acid and / or methacrylic acid," "acrylate and / or methacrylate," or "acrylamide and / or methacrylamide," respectively. In this specification, "CI" refers to the Color Index (published by The Society of Dyers and Colourists). In this specification, a polymerizable unsaturated group is an ethylenically unsaturated double bond. Regarding the molecular weight of the compounds in this invention, for low molecular weight compounds whose molecular weight can be specified, the molecular weight is calculated by formula weight or measured by ESI-MS (electrospray ionization mass spectrometry), while for compounds with a molecular weight distribution, the weight-average molecular weight in polystyrene terms is measured by gel permeation chromatography using tetrahydrofuran as the solvent. In this specification, a monomer is a compound that forms a resin by polymerization. A monomer is in an unreacted state, and a monomer unit is in a state where the monomer has formed a resin after polymerization. In this specification, a numerical range represented by "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively.

[0011] <Photosensitive composition> A photosensitive composition according to one embodiment of the present invention is a photosensitive composition comprising an alkali-soluble resin (A), a polymerizable compound (B), and a polymerization initiator (C), The alkali-soluble resin (A) includes an alkali-soluble resin (A1) having a phenolic hydroxyl group-containing monomer unit (a1), and an alkali-soluble resin (A2) having a hydroxyl group-containing monomer unit (a2) other than the phenolic hydroxyl group-containing monomer unit (a1) (excluding the alkali-soluble resin (A1)).

[0012] The mechanism by which the above-described photosensitive composition can solve the problems of the present invention is not clear, but we speculate as follows.

[0013] It is hypothesized that the alkali-soluble resin (A1) containing phenolic hydroxyl group monomer units (a1) generates hydrogen bonds due to the phenolic hydroxyl groups and stacking interactions between aromatic rings within the film, thereby forming a strong film. Therefore, it is hypothesized that it has excellent resistance to heating over a wide temperature range. On the other hand, it is hypothesized that it tends to aggregate and leave residue during alkaline development. However, it is hypothesized that by using an alkali-soluble resin (A2) containing hydroxyl group monomer units other than phenolic hydroxyl group monomer units (a1) in combination, the stacking interactions between aromatic rings are moderately weakened, suppressing aggregation and improving alkaline developability.

[0014] The components included in or potentially included in one embodiment of the photosensitive composition will be described in detail below.

[0015] [Alkali-soluble resin (A)] The photosensitive composition of the present invention comprises an alkali-soluble resin (A).

[0016] Alkali-soluble resin (A) is a resin that dissolves in an alkaline developer, and any known resin can be used. Examples of alkali-soluble resins (A) include (meth)acrylic resins, styrene resins, styrene / (meth)acrylic resins, epoxy resins, urethane resins, polycarbonate resins, polyester resins, polyether resins, polyimide resins, polyamide-imide resins, cyclic olefin resins, polysiloxane resins, and the like.

[0017] The alkali-soluble resin (A) preferably has alkali-soluble groups such as carboxyl groups, phosphate groups, sulfonic acid groups, and phenolic hydroxyl groups.

[0018] The molecular structure of the alkali-soluble resin (A) can be, for example, a chain-like random structure, a chain-like block structure, a graft structure, a comb-like structure, or a star-shaped structure. Among these, a chain-like random structure is preferred from the viewpoint of film resistance.

[0019] The weight-average molecular weight of the alkali-soluble resin (A) is preferably 3,000 to 50,000, and more preferably 4,000 to 40,000.

[0020] The acid value of the alkali-soluble resin (A) is preferably 30 to 200 mg KOH / g, and more preferably 40 to 180 mg KOH / g.

[0021] Alkali-soluble resin (A) can be used alone or in combination of two or more types.

[0022] The alkali-soluble resin (A) is preferably present in an amount of 1 to 95% by mass, and more preferably 3 to 80% by mass, of 100% by mass of the non-volatile content of the photosensitive composition.

[0023] (Alkali-soluble resin (A1) having a monomer unit (a1) containing phenolic hydroxyl groups) The alkali-soluble resin (A) includes an alkali-soluble resin (A1) having a monomer unit (a1) containing a phenolic hydroxyl group.

[0024] The alkali-soluble resin (A1) having a phenolic hydroxyl group-containing monomer unit (a1) (hereinafter also simply referred to as alkali-soluble resin (A1)) is not limited and any known resin can be used. Examples of alkali-soluble resin (A1) include monomers that form phenolic hydroxyl group-containing monomer units (a1) and copolymers with other monomers that can be optionally copolymerized.

[0025] [Phenolenic hydroxyl group-containing monomer unit (a1)] The phenolic hydroxyl group-containing monomer unit (a1) is not limited to any monomer that has a phenolic hydroxyl group. Examples of monomers that form the phenolic hydroxyl group-containing monomer unit (a1) include 4-vinylphenol, 4-vinylcatechol, 6-vinylnaphthalene-2-ol, 4-allyl-2-methoxyphenol, 5-allyl-2-hydroxy-3-methoxybenzaldehyde, 4-hydroxyphenyl(meth)acrylate, dopamine(meth)acrylamide, and N-(4-hydroxyphenyl)(meth)acrylamide.

[0026] Furthermore, the monomer unit containing phenolic hydroxyl groups (a1) is the monomer unit represented by the following general formula (1).

[0027] [ka]

[0028] In general formula (1), R1 independently represents a hydrogen atom or a methyl group. L1 represents a trivalent hydrocarbon group. Examples of trivalent hydrocarbon groups include trivalent aliphatic hydrocarbon groups. Trivalent aliphatic hydrocarbon groups can be linear, branched, cyclic, or combinations thereof. Furthermore, trivalent aliphatic hydrocarbon groups can be partially substituted with alkoxy groups, allyloxy groups, allyloxythio groups, halogen atoms, etc. The number of carbon atoms in the trivalent aliphatic hydrocarbon group is preferably 1 to 15, and more preferably 3 to 10. Examples of trivalent aliphatic hydrocarbon groups include the group represented by the following formula (L1-1) and the group represented by the following formula (L1-2).

[0029] [ka]

[0030] In formulas (L1-1) and (L1-2), * represents a bond with the oxygen atom in general formula (1).

[0031] In general formula (1), n ​​represents an integer between 1 and 3.

[0032] Monomers that form monomer units represented by general formula (1) include, for example, monomers obtained by adding a carboxyl group of an aromatic ring-containing compound substituted with a hydroxyl group and a carboxyl group to the epoxy group of an epoxy group-containing monomer. Examples of the epoxy group-containing monomers include glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, 2-oxyranylethyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and 3,4-epoxytricyclo[5.2.1.0 2,6 ] Decane-8-yl(meth)acrylate, 3,4-epoxytricyclo[5.2.1.0 2,6 Examples include decane-9-yl(meth)acrylate. Among these, glycidyl(meth)acrylate is preferred. Examples of aromatic ring-containing compounds in which the hydroxyl group and carboxyl group are substituted include 2-hydroxybenzoic acid, 4-hydroxybenzoic acid, 4-(4-hydroxyphenoxy)benzoic acid, 2,3-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, and 3,4,5-trihydroxybenzoic acid. Among these, 3,4,5-trihydroxybenzoic acid is preferred.

[0033] The monomer unit represented by general formula (1) can also be obtained by adding a carboxyl group of an aromatic ring-containing compound substituted with a hydroxyl group and a carboxyl group to the epoxy group of a resin (precursor) having an epoxy group-containing monomer (a4), which will be described later.

[0034] The phenolic hydroxyl group-containing monomer unit (a1) is preferably a monomer unit obtained from 4-hydroxyphenyl (meth)acrylate, dopamine (meth)acrylamide, or a monomer unit represented by general formula (1).

[0035] From the viewpoint of alkali developability and resistance, the content of phenolic hydroxyl group-containing monomer units (a1) is preferably 1 to 50 mol%, and more preferably 3 to 30 mol%, of the total constituent units of the alkali-soluble resin (A1).

[0036] The alkali-soluble resin (A1) may have monomer units other than the phenolic hydroxyl group-containing monomer unit (a1). The monomer units other than the phenolic hydroxyl group-containing monomer unit (a1) are not limited and include, for example, hydroxyl group-containing monomer units (a2) (excluding the phenolic hydroxyl group-containing monomer unit (a1)), acidic group-containing monomer units (a3), epoxy group-containing monomer units (a4), aliphatic condensed ring structure-containing monomer units (a5), blocked isocyanate group-containing monomer units (a6), and other monomer units (a7).

[0037] [Hydroxyl group-containing monomer unit (a2)] Examples of monomers that form a hydroxyl group-containing monomer unit (a2) 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 (meth)acrylate, and 2-acryloyloxyethyl-2-hydroxyethyl phthalic acid.

[0038] Furthermore, the hydroxyl group-containing monomer unit (a2) can also be the monomer unit represented by the following general formula (2).

[0039] [ka]

[0040] In general formula (2), R2 and R3 each independently represent a hydrogen atom or a methyl group.

[0041] In general formula (2), L2 represents a trivalent hydrocarbon group. Examples of trivalent hydrocarbon groups include trivalent aliphatic hydrocarbon groups. Trivalent aliphatic hydrocarbon groups can be linear, branched, cyclic, or combinations thereof. Furthermore, trivalent aliphatic hydrocarbon groups can be partially substituted with alkoxy groups, allyloxy groups, allyloxythio groups, halogen atoms, etc. The number of carbon atoms in the trivalent aliphatic hydrocarbon group is preferably 1 to 15, and more preferably 3 to 10. Examples of trivalent aliphatic hydrocarbon groups include the group represented by the following formula (L2-1) and the group represented by the following formula (L2-2).

[0042] [ka]

[0043] In formulas (L2-1) and (L2-2), * represents a bond with the oxygen atom in general formula (2).

[0044] The monomer unit represented by general formula (2) can be synthesized, for example, by adding an unsaturated monobasic acid (modified compound) such as (meth)acrylic acid to at least a portion of the epoxy groups contained in an alkali-soluble resin (A1). Furthermore, monomer units represented by general formula (2) can also be obtained by adding (meth)acrylate (modified compound) having epoxy groups to some of the carboxyl groups contained in alkali-soluble resin (A1).

[0045] [Acidic group-containing monomer unit (a3)] Monomers that form an acidic group-containing monomer unit (a3) ​​include, for example, (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-acryloyloxyethylhexyl hydrophthalic acid, p-styrene sulfonic acid, vinyl sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, and 2-(meth)acryloyloxyethyl acid phosphate.

[0046] Furthermore, the monomer unit containing an acidic group (a3) ​​can also be the monomer unit represented by the following general formula (3).

[0047] [ka]

[0048] In general formula (3), R4 and R5 each independently represent a hydrogen atom or a methyl group. L3 represents a trivalent hydrocarbon group. Examples of trivalent hydrocarbon groups include trivalent aliphatic hydrocarbon groups. Trivalent aliphatic hydrocarbon groups can be linear, branched, cyclic, or combinations thereof. Furthermore, trivalent aliphatic hydrocarbon groups can be partially substituted with alkoxy groups, allyloxy groups, allyloxythio groups, halogen atoms, etc. The number of carbon atoms in the trivalent aliphatic hydrocarbon group is preferably 1 to 15, and more preferably 3 to 10. Examples of trivalent aliphatic hydrocarbon groups include the group represented by the following formula (L3-1) and the group represented by the following formula (L3-2).

[0049] [ka]

[0050] In formulas (L3-1) and (L3-2), * represents a bond with the oxygen atom in general formula (3).

[0051] In general formula (3), L4 represents a divalent hydrocarbon group. Examples of divalent hydrocarbon groups include divalent aliphatic hydrocarbon groups and divalent aromatic hydrocarbon ring groups. Divalent aliphatic hydrocarbon groups can be linear, branched, cyclic, or combinations thereof. Furthermore, divalent aliphatic hydrocarbon groups can be partially substituted with alkoxy groups, carboxyl groups, halogen atoms, etc. The number of carbon atoms in the divalent aliphatic hydrocarbon group is preferably 1 to 15, and more preferably 3 to 10. Examples of divalent aliphatic hydrocarbon groups include ethylene, propylene, ethenylene, cyclohexa-4-ene-1,2-diyl, and cyclohexa-1,2-diyl. Divalent aromatic hydrocarbon ring groups are monocyclic or fused rings. Divalent aromatic hydrocarbon ring groups can be partially substituted with alkoxy groups, carboxyl groups, halogen atoms, etc. Examples of divalent aromatic hydrocarbon ring groups include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, pyrene rings, and fluorene rings.

[0052] The monomer unit represented by general formula (3) is obtained by adding a polybasic acid anhydride (modified compound) to the hydroxyl group of the monomer unit represented by general formula (2). Examples of the aforementioned polybasic acid anhydrides include 1,2,3,6-tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, and the like.

[0053] [Epoxy group-containing monomer unit (a4)] Examples of monomers that form epoxy group-containing monomer units (a4) include oxyranyl (meth)acrylate, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, 2-oxyranyl ethyl (meth)acrylate, 2-glycidyl oxyethyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexyl methyl (meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate, 2-(3,4-epoxycyclohexyl methyloxy)ethyl (meth)acrylate, and 3-(3,4-epoxycyclohexyl methyloxy)propyl (meth)acrylate.

[0054] [Aliphatic condensed ring structure-containing monomer unit (a5)] Monomers that form an aliphatic condensed ring structure-containing monomer unit (a5) include, for example, isobolonyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and adamantyl (meth)acrylate. Among these, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentanyloxyethyl (meth)acrylate are preferred.

[0055] [Blocked isocyanate group-containing monomer unit (a6)] The monomer that forms the blocked isocyanate group-containing monomer unit (a6) is a compound in which the compound having an isocyanate group in the monomer is protected with a compound that is eliminated by heat (hereinafter also referred to as a blocking agent). The elimination temperature of the blocking agent is preferably 60 to 160°C, and more preferably 80 to 140°C.

[0056] Examples of compounds having an isocyanate group include 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, and methacryloyl isocyanate. Equimolar reaction products of 2-hydroxyalkyl (meth)acrylate and diisocyanate compounds can also be used. Among these, 2-isocyanatoethyl (meth)acrylate and 2-isocyanatopropyl (meth)acrylate are preferred.

[0057] Examples of blocking agents include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, imide compounds, urea compounds, imine compounds, and bisulfite compounds.

[0058] Examples of oxime compounds include formaldehyde oxime, acetaldehyde oxime, acetoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, cyclohexanone oxime, and benzophenone oxime. Among these, methyl ethyl ketoxime is preferred. Examples of lactam compounds include ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam. Examples of phenolic compounds include phenol, cresol, 2,6-xylenol, 3,5-xylenol, ethylphenol, p-tert-butylphenol, nonylphenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, p-naphthol, and p-nitrophenol. Among these, 3,5-xylenol, methyl 2-hydroxybenzoate, and methyl 4-hydroxybenzoate are preferred. Examples of alcohol compounds include methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, and furfuryl alcohol. Examples of amine compounds include diphenylamine, phenylnaphthylamine, aniline, and carbazole. Examples of active methylene compounds include dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone, with diethyl malonate being preferred. Examples of pyrazole compounds include pyrazole, methylpyrazole, and 3,5-dimethylpyrazole, with 3,5-dimethylpyrazole being preferred. Examples of mercaptan compounds include butyl mercaptan, thiophenol, and tert-dodecyl mercaptan. Examples of imidazole compounds include imidazole, 2-methylimidazole, 2-ethylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, and 1-benzyl-2-phenylimidazole. Examples of imide compounds include succinimide, maleimide, maleimide, and phthalimide. Examples of urea compounds include urea, thiourea, and ethyleneurea. Examples of imine compounds include ethyleneimine and polyethyleneimine. Examples of bisulfite compounds include sodium bisulfite and potassium bisulfite.

[0059] Blocking agents can be used alone or in combination of two or more types.

[0060] The blocking agent is preferably one or more selected from the group consisting of oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds, and more preferably one or more selected from the group consisting of oxime compounds, phenol compounds, active methylene compounds, and pyrazole compounds from the viewpoint of protective and deprotective reactions.

[0061] Examples of monomer units containing blocked isocyanate groups (a6) include monomer units represented by the following general formula (4) and monomer units represented by the following general formula (5).

[0062] [ka]

[0063] In general formula (4), R6 represents a hydrogen atom or a methyl group. R7 and R8 each independently represent an alkyl group having 1 to 10 carbon atoms. C1-C10 alkyl groups can be linear or branched, and examples include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, amyl, isoamyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, and decyl groups. Among these, methyl, ethyl, and n-propyl groups are preferred.

[0064] In general formula (4), L5, L7, and L8 each independently represent a single bond or a divalent organic group. Examples of divalent organic groups include alkylene groups having 1 to 20 carbon atoms, or groups of alkylene groups having 1 to 20 carbon atoms with -O- between the carbon-carbon bonds. Alkylene groups having 1 to 20 carbon atoms can be linear or branched, and examples include methylene, ethylene, n-propyl, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, isopropylene, 2-methylpropylene, 2-methylhexylene, and tetramethylethylene. Among these, methylene, ethylene, and n-propylene groups are preferred.

[0065] In general formula (4), L6 represents a single bond or an oxygen atom.

[0066] In general formula (5), R9 represents a hydrogen atom or a methyl group. R 10 ~R 12 Each of these independently represents either a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Alkyl groups having 1 to 10 carbon atoms can be linear or branched, and examples include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, isopropyl group, isobutyl group, amyl group, isoamyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, decyl group, etc. Among these, R 10 and R 11 A hydrogen atom is preferred, R 12 The preferred group is a methyl group, an ethyl group, or an n-propyl group.

[0067] In general formula (5), L9 represents a single bond or a divalent organic group. Examples of divalent organic groups include alkylene groups having 1 to 20 carbon atoms, or groups of alkylene groups having 1 to 20 carbon atoms with -O- between the carbon-carbon bonds. Alkylene groups having 1 to 20 carbon atoms can be linear or branched, and examples include methylene, ethylene, n-propyl, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, isopropylene, 2-methylpropylene, 2-methylhexylene, and tetramethylethylene. Among these, methylene, ethylene, and n-propylene groups are preferred.

[0068] Examples of monomers that form monomer units represented by general formula (4) include the following compounds.

[0069] [ka]

[0070] Examples of monomers that form monomer units represented by general formula (5) include the following compounds.

[0071] [ka]

[0072] [Other monomer units (a7)] Other monomers that form monomer units (a7) 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, and benzyl (meth)acrylate. Sulfate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenol modified with ethylene oxide (meth)acrylate, nonylphenol modified with ethylene oxide or propylene oxide (meth)acrylate, paracumylphenol modified with ethylene oxide or propylene oxide (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, styrene, α-methylstyrene, p-vinyltoluene, p-chlorostyrene, vinylnaphthalene, (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, acryloylmorpholine, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimide ethane 1,6-bismaley Midohexane, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-Dichloromaleimide, N-Succinimidyl-3-Maleimide Benzoate, N-Succinimidyl-3-Maleimide Propionate, N-Succinimidyl-4-Maleimide Butyrate, N-Succinimidyl-6-Maleimide Hexanoate, N-[4-(2-Benzimidazolyl)phenyl]Maleimide, 9-Maleimide Acridine, Dimethyl-2,2'-[Oxybis(methylene)]Bis-2-Propenoate, Diethyl-2,2'-[Oxybis(methylene)]Bis-2-Propenoate, Di(n-Propyl)-2,2'-[Oxybis(methylene)]Bis-2-Propenoate, Di(Isopropyl)-2,2'-[Oxybis(methylene)]Bis Examples include -2-propenoate, di(2-ethylhexyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, 2-(acetoacetoxy)ethyl (meth)acrylate, 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropylethyldimethoxysilane, 3-(meth)acryloyloxypropylmethyldiethoxysilane, 3-(meth)acryloyloxypropylethyldiethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, and 8-(meth)acryloyloxyoctyltrimethoxysilane.

[0073] From the viewpoint of resistance, the alkali-soluble resin (A1) preferably has aliphatic condensed ring structure-containing monomer units (a5). The aliphatic condensed ring structure-containing monomer unit (a5) is preferably present in an amount of 1 to 50 mol%, and more preferably 3 to 40 mol%, of the total constituent units of the alkali-soluble resin (A1).

[0074] The weight-average molecular weight of the alkali-soluble resin (A1) is preferably 3,000 to 50,000, and more preferably 3,000 to 20,000.

[0075] The molecular weight distribution (weight-average molecular weight / number-average molecular weight) of the alkali-soluble resin (A1) is preferably 1.3 to 3.0, and more preferably 1.5 to 2.8.

[0076] The acid value of the alkali-soluble resin (A1) is preferably 20 to 200 mg KOH / g, and more preferably 30 to 180 mg KOH / g.

[0077] Alkali-soluble resin (A1) can be used alone or in combination of two or more types.

[0078] The content of alkali-soluble resin (A1) is preferably 10 to 90% by mass, and more preferably 20 to 80% by mass, based on 100% by mass of alkali-soluble resin (A).

[0079] (Alkali-soluble resin (A2) having hydroxyl group-containing monomer units (a2)) The photosensitive composition of the present invention comprises an alkali-soluble resin (A2) having a hydroxyl group-containing monomer unit (a2) as the alkali-soluble resin (A) (excluding alkali-soluble resin (A1)).

[0080] The alkali-soluble resin (A2) having hydroxyl group-containing monomer units (a2) (hereinafter also simply referred to as alkali-soluble resin (A2)) is not limited and any known resin can be used. Examples of alkali-soluble resins (A2) include monomers that form hydroxyl group-containing monomer units (a2) and copolymers with other monomers that can be optionally copolymerized.

[0081] The hydroxyl group-containing monomer unit (a2) is equivalent to the one described above for the alkali-soluble resin (A1).

[0082] From the viewpoint of alkali developability and resistance, the content of hydroxyl group-containing monomer units (a2) is preferably 1 to 60 mol%, and more preferably 3 to 55 mol%, of the total constituent units of the alkali-soluble resin (A2).

[0083] The alkali-soluble resin (A2) may have monomer units other than the hydroxyl group-containing monomer unit (a2). The monomer units other than the hydroxyl group-containing monomer unit (a2) are not limited and include, for example, the acidic group-containing monomer unit (a3), epoxy group-containing monomer unit (a4), aliphatic condensed ring structure-containing monomer unit (a5), blocked isocyanate group-containing monomer unit (a6), and other monomer units (a7) as described above for the alkali-soluble resin (A1). However, the phenolic hydroxyl group-containing monomer unit (a1) is excluded. Among these, it is preferable that the alkali-soluble resin (A2) has either the acidic group-containing monomer unit (a3) ​​or the blocked isocyanate group-containing monomer unit (a6).

[0084] From the viewpoint of alkali developability and resistance, the alkali-soluble resin (A2) more preferably has at least one selected from the group consisting of monomer units represented by general formula (3) of acidic group-containing monomer units (a3) ​​and monomer units represented by general formula (4) of blocked isocyanate group-containing monomer units (a6). The content of monomer units represented by general formula (3) is preferably 1 to 80 mol%, and more preferably 3 to 60 mol%, of the total constituent units of the alkali-soluble resin (A2). The content of monomer units represented by general formula (4) is preferably 1 to 80 mol%, and more preferably 3 to 60 mol%, of the total constituent units of the alkali-soluble resin (A2).

[0085] The weight-average molecular weight of the alkali-soluble resin (A2) is preferably 3,000 to 50,000, and more preferably 3,000 to 20,000.

[0086] The molecular weight distribution (weight-average molecular weight / number-average molecular weight) of the alkali-soluble resin (A2) is preferably 1.3 to 3.0, and more preferably 1.5 to 2.8.

[0087] The acid value of the alkali-soluble resin (A2) is preferably 20 to 200 mg KOH / g, and more preferably 30 to 180 mg KOH / g.

[0088] Alkali-soluble resin (A2) can be used alone or in combination of two or more types.

[0089] The content of alkali-soluble resin (A2) is preferably 10 to 90% by mass, and more preferably 20 to 80% by mass, based on 100% by mass of alkali-soluble resin (A).

[0090] (Alkali-soluble resin (A1), alkali-soluble resin (A3) other than alkali-soluble resin (A2)) Alkali-soluble resin (A) may contain alkali-soluble resin (A1) and alkali-soluble resin (A2) other than alkali-soluble resin (A3) (hereinafter also simply referred to as alkali-soluble resin (A3)).

[0091] [Polymerizable compound (B)] The photosensitive composition of the present invention contains a polymerizable compound (B).

[0092] Polymerizable compound (B) is not limited to known compounds. Examples of polymerizable compound (B) include monomers and oligomers having polymerizable unsaturated groups. Examples of polymerizable unsaturated groups include vinyl groups, (meth)allyl groups, (meth)acryloyl groups, acryloyloxy groups, and styryl groups. Polymerizable compound (B) is a compound with a weight-average molecular weight (or formula weight) of less than 3,000.

[0093] Polymerizable compound (B) can be used alone or in combination of two or more types.

[0094] The content of polymerizable compound (B) is preferably 1 to 80% by mass, and more preferably 5 to 70% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0095] (A polymerizable compound (B1) having at least one selected from the group consisting of a hydroxyl group, an acidic group, and an alkylene oxide group) From the viewpoint of alkali developability, polymerizable compound (B) preferably includes polymerizable compound (B1) (hereinafter also simply referred to as polymerizable compound (B1)) having at least one selected from the group consisting of a hydroxyl group, an acidic group, and an alkylene oxide group.

[0096] [Polymerizable compounds containing hydroxyl groups] Polymerizable compounds having a hydroxyl group include, for example, acrylic acid esters such as 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, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and polypentaerythritol penta(meth)acrylate, as well as epoxy(meth)acrylates obtained by reacting the epoxy group of an epoxy compound with the carboxyl group of (meth)acrylic acid.

[0097] Examples of commercially available polymerizable compounds containing hydroxyl groups include KAYARAD R-128H and R-167 from Nippon Kayaku Co., Ltd., Bremmer GLM, GLM-R, GMR-M, GMR-R, GAM, GAM-R, and G-FA80 from NOF Corporation, Aronix M-5700 and M-920 from Toagosei Co., Ltd., NK Ester 701A from Shin Nakamura Chemical Co., Ltd., Light Ester HOP(N), HOA(N), HOP-A(N), HOB(N), and G-201P from Kyoeisha Chemical Co., Ltd., and Epoxy Ester M-600A, 40EM, 70PA, 200PA, 80MFA, 3002M(N), 3002A(N), and 3000A from Osaka Gas Chemical Co., Ltd., and OGSOL GA-5060P and GA-2800 from Osaka Gas Chemical Co., Ltd.

[0098] [Polymerizable compounds containing acidic groups] Polymerizable compounds having acidic groups include, for example, esterifications of polyhydric alcohols and (meth)acrylic acid, containing free hydroxyl groups, with dicarboxylic acids; Examples include esterified products of polycarboxylic acids and monohydroxyalkyl (meth)acrylates.

[0099] Examples of the polyhydric alcohols include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.

[0100] Examples of the dicarboxylic acid include malonic acid, succinic acid, maleic acid, glutaric acid, phthalic acid, and itaconic acid.

[0101] 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.

[0102] Examples of commercially available polymerizable compounds containing acidic groups include Aronics M-5300, M-5400, M-510, M-520, and M-521 from Toagosei Co., Ltd., Light Acrylate HOA-MS(N), HOA-HH(N), HOA-MPE(N), and P-1A(N) from Kyoeisha Chemical Co., Ltd., and β-CEA from Daicel Ornex Co., Ltd.

[0103] Furthermore, polymerizable compounds having acidic groups are compounds obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, and then adding a mercapto compound having a carboxyl group to the product; A compound obtained by reacting a polyhydric alcohol with a polyfunctional isocyanate, adding a (meth)acrylate having a hydroxyl group, and then adding a mercapto compound having a carboxyl group to the product; Examples include compounds obtained by reacting a polyhydric alcohol having a carboxyl group with a polyfunctional isocyanate, and then reacting it with a (meth)acrylate having a hydroxyl group.

[0104] 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, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, reaction products of epoxy group-containing compounds and carboxy(meth)acrylate, hydroxyl group-containing polyol polyacrylate, and the like.

[0105] The aforementioned polyfunctional isocyanates include, for example, 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyli isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylenediisocyanate, 1,4-phenylenediisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, bis-chloromethyl-diphenylmethane-diisocyanate, and 2,6-diisocyanate. Examples include anneto-benzyl chloride, bis(isocyanate-methyl)benzene, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dimethylcyclohexyl diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanate-methyl)cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, bis(isocyanate-methyl)cyclohexane, etc. Also, examples include their biuret, isocyanurate, adduct, and allophanate forms.

[0106] Examples of mercapto compounds having a carboxyl group include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid, and mercaptosuccinic acid.

[0107] Examples of the polyhydric alcohols include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.

[0108] Examples of polyhydric alcohols having a carboxyl group include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolpentanoic acid, and 2,2-dimethylolhexanoic acid.

[0109] [Polymerizable compounds containing alkylene oxide groups] Polymerizable compounds having an alkylene oxide group include, for example, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, trimethylol alkylene oxide-modified di(meth)acrylate, ditrimethylolpropane alkylene oxide-modified di(meth)acrylate, dipentaerythritol alkylene oxide-modified di(meth)acrylate, isocyanuric acid alkylene oxide-modified di(meth)acrylate, isocyanuric acid alkylene oxide-modified tri(meth)acrylate, bisphenol A alkylene oxide-modified di(meth)acrylate, trimethylolpropane alkylene oxide-modified tri(meth)acrylate, and glycerin alkylene oxide-modified tri(meth)acrylate. Examples include pentaerythritol alkylene oxide modified tri(meth)acrylate, pentaerythritol alkylene oxide modified tetra(meth)acrylate, ditrimethylolpropane alkylene oxide modified tri(meth)acrylate, ditrimethylolpropane alkylene oxide modified tetra(meth)acrylate, diglycerin alkylene oxide modified tri(meth)acrylate, diglycerin alkylene oxide modified tetra(meth)acrylate, dipentaerythritol alkylene oxide modified tri(meth)acrylate, dipentaerythritol alkylene oxide modified tetra(meth)acrylate, dipentaerythritol alkylene oxide modified penta(meth)acrylate, and dipentaerythritol alkylene oxide modified hexa(meth)acrylate.

[0110] Examples of alkylene oxides modified with alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and tetramethylene oxide. The repeating units of the alkylene oxide are preferably 1 to 8, and more preferably 1 to 6.

[0111] Examples of commercially available polymerizable compounds having alkylene oxide groups include Aronix M-208, M-220, M-211B, M-240, M-310, M-321, M-350, M-360, M-313, M-315, and M-460 from Toagosei Co., Ltd., and KAYARAD GPO-303, RP-1040, and DPEA-12 from Nippon Kayaku Co., Ltd.

[0112] Polymerizable compound (B1) may contain two or more groups selected from the group consisting of hydroxyl groups, acidic groups, and alkylene oxide groups within the same molecule.

[0113] The content of polymerizable compound (B1) is preferably 10 to 100% by mass, and more preferably 10 to 95% by mass, based on 100% by mass of polymerizable compound (B).

[0114] (Polymerizable compounds other than polymerizable compound (B1) (B2)) Polymerizable compound (B) may contain polymerizable compound (B2) other than polymerizable compound (B1) (hereinafter also simply referred to as polymerizable compound (B2)).

[0115] [Polymerizable compounds having an amine structure] From the viewpoint of resistance, it is preferable that the polymerizable compound (B2) contains a polymerizable compound having an amine structure.

[0116] The amine structures of polymerizable compounds having an amine structure include primary amines, secondary amines, and tertiary amines. Among these, secondary amines or tertiary amines are preferred. However, the amine structures do not include amide structures, imide structures, urethane structures, or cyclic amine structures in which the carbonyl group is directly bonded to a nitrogen atom.

[0117] Polymerizable compounds having an amine structure include, for example, tris(acryloyloxyethyl)amine, tris(methacryloyloxyethyl)amine, tris(2-hydroxy-3-methacryloyloxypropyl)amine, and the products of Michael addition reactions between (meth)acrylate compounds (X) and amine compounds (Y).

[0118] (Meth)acrylate compound (X) is, for example, glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, diglycerin Examples include lint 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 dipenerythritol alkylene oxide-modified tetra, penta, and hexa(meth)acrylate. Examples of alkylene oxide units in the alkylene oxide modification include ethylene oxide, propylene oxide, and butylene oxide. Furthermore, (meth)acrylate compound (X) may also include (meth)acrylate compounds having an acidic group.

[0119] (Meth)acrylate compound (X) can be used alone or in combination of two or more types.

[0120] Examples of amine compounds (Y) include n-propylamine, n-butylamine, n-hexylamine, benzylamine, aminocaproic acid, ethanolamine, butanolamine, diethylene glycolamine, 2-(2-aminoethoxy)ethanol, o-aminophenol, m-aminophenol, p-aminophenol, 2-aminobenzyl alcohol, N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-isopropylethanolamine, N-butylethanolamine, N-isobutylethanolamine, N-methylbutanolamine, N-ethylbutanolamine, N-butyl-4-hydroxybutylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, cyclohexylamine, N-acetylethanolamine, diethanolamine, 3-anilynphenol, and 4-anilynphenol.

[0121] Amine compound (Y) can be used alone or in combination of two or more types.

[0122] The preparation of the product of the Michael addition reaction between a (meth)acrylate compound (X) and an amine compound (Y) is not particularly limited, and known methods can be used. For example, the methods described in International Publication No. 2006 / 075754, Japanese Patent Publication No. 2008-545859, and Japanese Patent Application Publication No. 2017-066347 are examples of such methods.

[0123] Polymerizable compounds having an amine structure may also have an acidic group and / or a hydroxyl group. Methods for introducing an acidic group and / or a hydroxyl group include, for example, using a compound having an acidic group and / or a hydroxyl group with a (meth)acrylate compound (X) or an amine compound (Y), or adding an acid anhydride after a Michael addition reaction.

[0124] Examples of commercially available polymerizable compounds having an amine structure include Arronix MT-3041 and 3042 from Toagosei Co., Ltd., EBECRYL80 and 7100 from Daicel Ornex Corporation, CN371NS, 372, 374, 383, and 386 from Arkema Corporation, and Photomer4250, 4771, 4775, 4967, and 5006 from IGM Resins.

[0125] Polymerizable compounds having an amine structure preferably also have urethane bonds. This allows for the formation of both chemical crosslinking structures through polymerization and physical crosslinking structures through intermolecular hydrogen bonding between urethane bonds and between urethane bonds and functional groups of the substrate. The molecular cohesion energy of the intermolecular hydrogen bonds in these urethane bond portions is greater than that of other organic structures such as ether bonds. Therefore, it is presumed that the film becomes flexible and strong due to the interactions between the urethane bonds.

[0126] A method for introducing urethane bonds can be used, for example, by a urethane reaction between a Michael addition reaction product (precursor) of the above-mentioned (meth)acrylate compound (X) and the above-mentioned hydroxyl group-containing amine compound (Y), and a polyisocyanate compound (Z).

[0127] Polyisocyanate compounds (Z) are polyisocyanate compounds having an aliphatic structure, such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropyl 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(isocyanate-methyl)cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, and bis(isocyanate-methyl)cyclohexane; Examples of polyisocyanate compounds having aromatic structures include 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyli isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylenedi isocyanate, 1,4-phenylenedi isocyanate, 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(isocyanatemethyl)benzene. Other examples of these compounds include biuret, isocyanurate, adduct, and allophanate forms.

[0128] Polyisocyanate compounds (Z) can be used alone or in combination of two or more.

[0129] The urethane reaction between the precursor and the polyisocyanate compound (Z) is not limited, and known methods can be used. For example, the method described in Japanese Patent Publication No. 2018-517797 is one such example.

[0130] Examples of commercially available polymerizable compounds having an amine structure and a urethane bond include CN9906NS manufactured by Arkema.

[0131] Polymerizable compounds having an amine structure can be used alone or in combination of two or more types.

[0132] The content of the polymerizable compound having an amine structure is preferably 0.1 to 80% by mass, and more preferably 0.5 to 60% by mass, based on 100% by mass of polymerizable compound (B).

[0133] Examples of polymerizable compounds (B2) other than polymerizable compounds having an amine structure include methyl (meth)acrylate, ethyl (meth)acrylate, cyclohexyl (meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. Commercially available products include, for example, KAYARAD DPCA-20, DPCA-30, DPCA-60, DPCA-120 from Nippon Kayaku Co., Ltd., AH-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G from Kyoeisha Chemical Co., Ltd., UA-1100H, U-6LPA, UA-33H, U-10HA, U-15HA from Shin Nakamura Chemical Co., Ltd., EBECRYL1290, KRM8452 from Daicel Ornex Co., Ltd., Viscoat #1000LT, SIRUS-501 from Osaka Organic Chemical Industry Co., Ltd., Miramer SP-1106, SP-1108 from Miwon Specialty Chemical Co., Ltd., CN2301, CN2302, CN2303, CN2304 from SARTOMER, and Eternal Examples include Etercure 6361-100, 6362-100, 6363, and DR-E522 from Materials Inc.

[0134] [Polymerization initiator (C)] The photosensitive composition of the present invention contains a polymerization initiator (C).

[0135] Polymerization initiators (C) include, for example, compounds that generate radicals by the action of light or heat, thereby initiating or promoting a radical polymerization reaction. A polymerization initiator that generates radicals in response to light (hereinafter also simply referred to as a photopolymerization initiator) is preferably a compound that generates radicals in response to light from ultraviolet to visible light. A polymerization initiator that generates radicals by heat (hereinafter also simply referred to as a thermal polymerization initiator) may be a compound that generates radicals by the action of heat and light.

[0136] Photopolymerization initiators include, for example, α-hydroxyketone compounds such as 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methylpropiophenone, and 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone; Alpha-aminoketone compounds such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-(dimethylamino)-4'-morpholinobtyrophenone, and 2-dimethylamino-2-(4-methylbenzyl)-1-[4-(morpholinophenyl)-butan-1-one; Acylphosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and diphenyl-2,4,6-trimethylbenzoylphosphine oxide; Oxime compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyl oxime)], etanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole3-yl]-,1-(O-acetyl oxime); Triazine 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-(naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, and 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; Examples include quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone.

[0137] Commercially available products include: α-hydroxyketone compounds such as Omnirad 127, 184, 1173, 2959 from IGM Resins; α-aminoketone compounds such as Omnirad 907, 369E, 379EG from IGM Resins; acylphosphine compounds such as Omnirad 819, TPO from IGM Resins; oxime compounds such as IRGACURE OXE-01, 02, 03, 04, 05 from BASF Japan; ADEKA Arclus N-1919, NCI-730, 831E, 930 from ADEKA; and TRONLY TR-PBG-301, 304, 305, 309, 314, 345, 358, 380, 365, 610, 3054, 3057 from Changzhou Strong New Materials Co., Ltd. Examples include Omnirad 1312, 1314, and 1316 from Resins, SPI-02, 03, 04, 05, 06, and 07 from Samyang Corporation, and DFI-020, 306, and EOX-01 from Daito Chemix. Also, examples include compounds described in Japanese Patent Publication No. 2007-210991, Japanese Patent Publication No. 2009-179619, Japanese Patent Publication No. 2010-037223, Japanese Patent Publication No. 2010-215575, Japanese Patent Publication No. 2011-020998, International Publication No. 2015 / 036910, Japanese Patent Publication No. 2019-507108, Japanese Patent Publication No. 2019-528331, International Publication No. 2021 / 175855, Japanese Patent Publication No. 2022-5115524, etc. Among these, polymerization initiators (C1) having two oxime ester groups are preferred. Having two oxime ester groups results in high radical generation ability and resistance to oxygen inhibition. Therefore, photocuring progresses and film resistance is further improved.

[0138] The following are specific examples of polymerization initiators (C1) having two oxime ester groups, represented by compounds of formulas (C1-1) to (C1-5). However, the present invention is not limited to these examples.

[0139] [ka]

[0140] The content of the polymerization initiator (C1) having two oxime ester groups is preferably 10 to 100% by mass of the polymerization initiator (C) at 100% by mass.

[0141] Examples of thermal polymerization initiators include benzopinacol, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-diphenoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetra(4-methylphenyl)ethane, 1,2-diphenoxy-1,1,2,2-tetra(4-methoxyphenyl)ethane, and 1,2-bis(trimethylsiloxy)-1,1,2,2-tetraphenylethane. Pinacol compounds such as 1,2-bis(triethylsiloxy)-1,1,2,2-tetraphenylethane, 1,2-bis(tert-butyldimethylsiloxy)-1,1,2,2-tetraphenylethane, 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-triethylsiloxy-1,1,2,2-tetraphenylethane, and 1-hydroxy-2-tert-butyldimethylsiloxy-1,1,2,2-tetraphenylethane; Azo compounds such as 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-carbonnitrile), 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); Examples include organic peroxides 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 acid peroxide, and benzoyl peroxide.

[0142] Polymerization initiator (C) can be used alone or in combination of two or more types.

[0143] The content of polymerization initiator (C) is preferably 0.1 to 20% by mass, and more preferably 0.5 to 10% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0144] [Coloring agent (D)] The photosensitive composition of the present invention may contain a coloring agent (D).

[0145] Colorants (D) include pigments and dyes. Pigments include organic pigments and inorganic pigments, and for optical filter applications, it is preferable to include pigments from the viewpoint of resistance.

[0146] (Pigment) Pigments are not limited to those listed above, and include, for example, compounds classified as pigments in the color index.

[0147] Red pigments include, for example, CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1,63:2,64,64:1,68,69,81,81:1,81:2,81:3,81:4,83,88,90:1,101,101:1,104,108,108:1,109,112,113,114,122,123,144,146,147,149,151,166,168,169,170,172,173,174,175,176,177,178,179 ,181,184,185,187,188,190,193,194,200,202,206,207,208,209,210,214,216,220,221,224,230,231,232,233,235,236,237,238,239,242,243,245,247,249,250,251,253,254,255,256,257,258,259, Examples include pigments 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, pigments described in Japanese Patent Publication No. 2014-134712, pigments described in Japanese Patent Publication No. 6368844, and the like.

[0148] Examples of orange pigments include CI Pigment Orange 36, 38, 43, 64, 71, and 73.

[0149] Yellow pigments include, for example, CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123 Examples include pigments described in JP 2012-226110, 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.

[0150] Furthermore, yellow pigments include pigments containing an azo compound represented by the following general formula (6) and one or more anions selected from the group consisting of mono, di, tri, and tetraanions of azo compounds with tautomer structures thereof, two or more metal ions selected from Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn, and a compound represented by the following general formula (7).

[0151] [ka]

[0152] In general formula (6), the two R1s each independently represent -OH, -NH2, -NH-CN, an acylamino group, an alkylamino group, or an arylamino group.

[0153] In general formula (6), the two R2s each independently represent either -OH or -NH2.

[0154] [ka]

[0155] In general formula (7), the three R3s each independently represent a hydrogen atom or an alkyl group.

[0156] 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, 63, etc.

[0157] 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, 79, etc.

[0158] 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.

[0159] Examples of black pigments include CI Pigment Black 1, 6, 7, 12, 20, and 31.

[0160] Other examples of inorganic pigments include silica, talc, titanium dioxide, zinc oxide, barium sulfate, zinc oxide, lead sulfate, lead yellow, zinc yellow, red iron(III) oxide, cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, amber, and synthetic iron black.

[0161] It is preferable to use the pigment in a finely milled form. The milling method is not limited and can be any of the following: wet milling, dry milling, or dissolution milling. Among these, salt milling by the kneader method, which is a type of wet milling, is preferred. The average primary particle size of the milled pigment, as determined by TEM (transmission electron microscopy), is preferably 5 to 90 nm. However, from the viewpoint of dispersibility and contrast ratio, an average primary particle size of 10 to 70 nm is more preferable.

[0162] Resin may be added to the salt milling process as needed. By adding resin, the pigment is coated with resin, improving stability, lightfastness, etc. The type of resin is not particularly limited and includes natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. Among these, it is preferable that the resin is solid at room temperature, insoluble in water, and partially soluble in organic solvents. The amount of resin added is preferably 2 to 200 parts by mass per 100 parts by mass of pigment.

[0163] (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, and sulfur dyes. Derivatives of these dyes, as well as lake pigments (dyes obtained by lake formation), are also examples.

[0164] Acid dyes preferably have acidic groups such as sulfonic acid or carboxylic acid. Salt compounds are also preferred, which are salts of acid dyes with nitrogen-containing compounds such as quaternary ammonium salts, tertiary amines, secondary amines, or primary amines. Salt compounds are also preferred, which are salts of resin components having these functional groups with acid dyes. Furthermore, by sulfonamidating the salt compounds to convert them into sulfonic acid amide compounds, it is easy to obtain photosensitive compositions with excellent resistance (lightfastness, solvent resistance). Furthermore, salt-forming compounds of acid dyes and compounds containing an onium base are also preferred due to their excellent resistance (light resistance and solvent resistance). The compound containing the onium base is preferably a resin having a cationic group.

[0165] Basic dyes can be used as is, but salt-forming compounds that form salts with organic acids, perchloric acid, or their metal salts are preferred. Salt-forming compounds of basic dyes are preferred because they have excellent resistance (lightfastness, solvent resistance) and affinity with pigments. Furthermore, in salt-forming compounds of basic dyes, preferred anionic components that act as counterions are salt-forming compounds obtained by salting with organic sulfonic acids, organic sulfuric acids, fluorine-containing phosphorus anionic compounds, fluorine-containing boron anionic compounds, cyano-containing nitrogen anionic compounds, anionic compounds having a conjugate base of an organic acid with a halogenated hydrocarbon group, and acid dyes. Note that the resistance of the salt-forming compound is further improved if it contains polymerizable unsaturated groups in its molecule.

[0166] From the viewpoint of color characteristics such as hue, color separation, and color unevenness, the chemical structure of the dye can be derived from pigments selected from azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes. Among these, pigment structures derived from pigments selected from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyromethene dyes, and phthalocyanine dyes are more preferred.

[0167] Coloring agent (D) can be used alone or in combination of two or more types.

[0168] The content of the coloring agent (D) is preferably 1 to 70% by mass, and more preferably 5 to 60% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0169] [Near-infrared absorbing compound (E)] The photosensitive composition of the present invention may contain a near-infrared absorbing compound (E).

[0170] Near-infrared absorbing compounds (E) are compounds that have maximum absorption at wavelengths of 700 to 2,000 nm. Examples of near-infrared absorbing compounds (E) include pigments (also called near-infrared absorbing pigments) or dyes (also called near-infrared absorbing dyes). Near-infrared absorbing pigments are preferred from the viewpoint of heat resistance and light resistance. These can be used in combination. In this specification, the near-infrared absorbing pigment preferably has a solubility of less than 2 g, more preferably less than 1 g, and particularly preferably 0.5 g or less in 100 g of propylene glycol monomethyl ether acetate at 25°C.

[0171] Examples of near-infrared absorbing compounds (E) include cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, indigo compounds, immonium compounds, anthraquinone compounds, pyrrolopyrrole compounds, squarylium compounds, crokonium compounds, indium tin oxide, antimony tin oxide, zinc oxide, Al-doped zinc oxide, fluorine-doped tin dioxide, niobium-doped titanium dioxide, cesium tungsten oxide, copper, nickel, silver, gold, and other metal oxide particles or metal particles.

[0172] Cyanine compounds are described in International Publication No. 2006 / 006573, International Publication No. 2010 / 073857, Japanese Patent Publication No. 2013-241598, Japanese Patent Publication No. 2016-113501, Japanese Patent Publication No. 2016-113504, etc.; Phthalocyanine compounds are described in Japanese Patent Publication No. Hei 4-23868, Japanese Patent Publication No. Hei 06-192584, Japanese Patent Publication No. 2000-63691, International Publication No. 2014 / 208514, etc.; Naphthalocyanine For indigo compounds, see Japanese Patent Publication No. 11-152414, Japanese Patent Publication No. 2000-86919, Japanese Patent Publication No. 2009-29955, International Publication No. 2018 / 186490, Japanese Patent Publication No. 2022-91099, Japanese Patent Publication No. 2022-072558, etc.; for indigo compounds, see Japanese Patent Publication No. 2012-224593, Japanese Patent Publication No. 2013-87233, Japanese Patent Publication No. 2013-230412, etc.; for immonium compounds, see Japanese Patent Publication No. 200 Japanese Patent Publication No. 5-336150, Japanese Patent Publication No. 2007-197492, Japanese Patent Publication No. 2008-88426, etc.; for anthraquinone compounds, Japanese Patent Publication No. Sho 62-903, Japanese Patent Publication No. Hei 1-172458, etc.; for pyrrolopyrrole compounds, Japanese Patent Publication No. 2009-263614, Japanese Patent Publication No. 2010-90313, Japanese Patent Publication No. 2011-068731, Japanese Patent Publication No. 2014-130348, International Publication No. 2015 / 166873 Examples of squarylium compounds include those described in Japanese Patent Publication No. 2011-132361, Japanese Patent Publication No. 2016-142891, International Publication No. 2017 / 135359, International Publication No. 2018 / 225837, Japanese Patent Publication No. 2019-001987, International Publication No. 2020 / 054718, International Publication No. 2021 / 029195, etc.; examples of croconium compounds include those described in International Publication No. 2019 / 021767, etc. Among these, from the viewpoint of light resistance, it is preferable to include at least one selected from the group consisting of phthalocyanine compounds, naphthalocyanine compounds, indigo compounds, pyrrolopyrrole compounds, and squarylium compounds.

[0173] Near-infrared absorbing compounds (E) can be used alone or in combination of two or more. When using two or more compounds in combination, it is preferable to use at least two compounds with different maximum absorption wavelengths. This broadens the waveform of the absorption spectrum compared to using a single near-infrared absorbing compound (E), allowing for absorption of near-infrared light over a wide wavelength range.

[0174] From the viewpoint of near-infrared absorption, the content of the near-infrared absorbing compound (E) is preferably 0.1 to 70% by mass, and more preferably 0.5 to 50% by mass, based on 100% by mass of the non-volatile content of the photosensitive composition.

[0175] [Dye derivative (F)] The photosensitive composition of the present invention may contain a colorant (D) and a near-infrared absorbing compound (E) together with a dye derivative (F). The use of the dye derivative (F) allows for stable dispersion of these components.

[0176] The dye derivative (F) is not limited, and any known compound can be used. For example, this includes compounds having a structure in which part of the dye is substituted with an acidic group, a basic group, a neutral group, etc. Specifically, this includes compounds having acidic substituents such as sulfo groups, carboxyl groups, and phosphate groups, as well as their amine salts, compounds having basic substituents such as sulfonamide groups or tertiary amino groups at the terminal, and compounds having neutral substituents such as phenyl groups or phthalimidoalkyl groups. Examples of pigments include diketopyrrolopyrrole compounds, phthalocyanine compounds, anthraquinone compounds, quinacridone compounds, dioxazine compounds, perinone compounds, perylene compounds, thiaidine indigo compounds, triazine compounds, benzimidazolon compounds, benzoisoindole compounds, isoindoline compounds, isoindolinone compounds, quinophthalone compounds, naphthol compounds, squarylium compounds, surene compounds, and naphthalocyanine compounds.

[0177] The dye derivative (F) can be used alone or in combination of two or more types.

[0178] The content of the pigment derivative (F) is preferably 1 to 50 parts by mass, and more preferably 2 to 40 parts by mass, based on 100 parts by mass of the total of the colorant (D) and the near-infrared absorbing compound (E).

[0179] [Dispersion resin (G)] The photosensitive composition of the present invention may contain a dispersion resin (G). The dispersion resin (G) is used for the purpose of stably dispersing the colorant (D) and near-infrared absorbing compound (E), which are raw materials of the photosensitive composition. In this specification, the dispersion resin (G) is not included in the alkali-soluble resin (A).

[0180] The dispersion resin (G) is preferably a resin having adsorption groups that have a high affinity for the colorant (D) and the near-infrared absorbing compound (E). The adsorption groups preferably have one or more basic and acidic groups.

[0181] Basic groups include, for example, primary amino groups, secondary amino groups, tertiary amino groups, quaternary ammonium bases, and nitrogen-containing heterocycles and other groups containing nitrogen atoms.

[0182] Examples of acidic groups include carboxyl groups, phosphate groups, and sulfonic acid groups.

[0183] Examples of the resin types of the dispersed resin (G) include urethane resins, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial)amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, and modified products thereof, amides and salts thereof formed by the reaction of poly(lower alkyleneimines) with polyesters having free carboxyl groups, water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and polyvinylpyrrolidone, polyester systems, modified polyacrylate systems, ethylene oxide / propylene oxide adduct compounds, and phosphate ester systems.

[0184] Examples of the structure of the dispersed resin (G) include random structures, block structures, graft structures, comb structures, and star structures. Among these, block structures and comb structures are preferred from the viewpoint of dispersion stability.

[0185] From the viewpoint of resistance, the dispersion resin (G) preferably has thermosetting groups and / or polymerizable unsaturated groups. Examples of thermosetting groups include hydroxyl groups, epoxy groups, oxetanyl groups, tert-butyl groups, and blocked isocyanate groups.

[0186] Examples of the dispersed resin (G) include the resin described in paragraphs 0122 to 0155 of International Publication No. 2013 / 175978, the resin described in paragraphs 0317 to 0321 of Japanese Patent Publication No. 2019-78878, the resin described in paragraph 0083 of International Publication No. 2018 / 139534, the resin described in paragraphs 0167 to 0191 of International Publication No. 2019 / 163505, the resin described in paragraphs 0299 ​​to 0310 of International Publication No. 2021 / 131927, the resin described in paragraphs 0080 to 0085 of International Publication No. 2022 / 102367, and the resin described in paragraphs 0099 to 0109 of International Publication No. 2022 / 172607.

[0187] Commercially available dispersion resins (G) include, for example, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164, or Anti-Terra-U203, 204, or BYK-P1, all manufactured by BYK Chemie Japan. SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 7 (manufactured by Lubrizol Japan Co., Ltd.) 6500, etc., 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 Ajinomoto Fine Techno's Ajisupu Examples of resins include PA111, PB711, PB821, PB822, PB824, etc., as described in Japanese Patent Publication No. 2008-029901, Japanese Patent Publication No. 2009-155406, Japanese Patent Publication No. 2010-185934, Japanese Patent Publication No. 2011-157416, International Publication No. 2008 / 007776, Japanese Patent Publication No. 2008-029901, Japanese Patent Publication No. 2009-155406, Japanese Patent Publication No. 2010-185934, Japanese Patent Publication No. 2011-157416, Japanese Patent Publication No. 2009-251481, Japanese Patent Publication No. 2007-23195, Japanese Patent Publication No. 1996-143651, etc.

[0188] The dispersion resin (G) can be used alone or in combination of two or more types.

[0189] From the viewpoint of dispersion stability, the content of the dispersion resin (G) is preferably 3 to 200 parts by mass, and more preferably 5 to 150 parts by mass, per 100 parts by mass of the total of the colorant (D) and the near-infrared absorbing compound (E).

[0190] The dispersion resin (G) preferably contains a dispersion resin (G1) (hereinafter also simply referred to as dispersion resin (G1)) having one or more monomer units selected from the group consisting of monomer units represented by the following general formulas (8) to (10).

[0191] [ka]

[0192] In general formula (8), R1 to R3 each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group, and two or more of R1 to R3 may bond to each other to form a cyclic structure. R4 represents a hydrogen atom or a methyl group, X1 represents a divalent linking group, and Y1 - This represents the paired anion.

[0193] The alkyl groups in R1 to R3 of general formula (8) can be linear, branched, cyclic, or a combination thereof. Examples of these alkyl groups include methyl, ethyl, propyl, butyl, pentyl, octyl, cyclohexyl, and cyclohexylmethyl groups. Among these, methyl, ethyl, propyl, and butyl groups are preferred.

[0194] Examples of aryl groups in R1 to R3 of general formula (8) include phenyl, naphthyl, biphenyl, and anthracenyl groups. Among these, the phenyl group is preferred.

[0195] The aralkyl groups in R1 to R3 of the general formula (8) include, for example, benzyl group, phenethyl group, phenylpropyl group, phenylbutyl group, phenylisopropyl group and the like. Among these, benzyl group and phenethyl group are preferred.

[0196] When the alkyl group, aryl group or aralkyl group of R1 to R3 in the general formula (8) has a substituent, the substituent includes, for example, halogen atom, alkoxy group, benzoyl group and the like.

[0197] The cyclic structure formed by the bonding of two or more of R1 to R3 includes, for example, a 5- to 7-membered nitrogen-containing heterocyclic ring. Examples of the cyclic structure include the following cyclic structures. R in the following formula is the substituent described for R1 to R3 above.

[0198]

Chemical formula

[0199] These cyclic structures can contain substituents. Examples of the substituent include halogen atom, alkoxy group, hydroxyl group and the like.

[0200] The divalent linking group X1 in the general formula (8) includes, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, -CONH-R5-, or -COO-R6- (wherein R5 and R6 are each independently a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 2 to 10 carbon atoms (alkyloxyalkyl group)). Among these, -COO-R6- in which R6 is an alkylene group having 1 to 3 carbon atoms is preferred.

[0201] The counter anion Y1 of the general formula (8) - is, for example, Cl - 、Br - 、I - 、ClO4 - 、BF4 - 、CH3COO - 、PF6 - 、SO3 -Examples include aromatic dicarboxylate imide anions, aromatic sulfonate anions, aromatic phosphonate anions, and aromatic carboxylate anions.

[0202] Monomers that form monomer units represented by general formula (8) include, for example, alkyl (meth)acrylate quaternary ammonium salts such as (meth)acryloyloxyethyltrimethylammonium chloride, (meth)acryloyloxyethyltriethylammonium chloride, (meth)acryloyloxyethyldimethylbenzylammonium chloride, and (meth)acryloyloxyethylmethylmorpholinoammonium chloride; alkyl (meth)acryloylamide quaternary ammonium salts such as (meth)acryloylaminopropyltrimethylammonium chloride, (meth)acryloylaminoethyltriethylammonium chloride, and (meth)acryloylaminoethyldimethylbenzylammonium chloride; dimethyldiallylammonium methyl sulfate; and trimethylvinylphenylammonium chloride.

[0203] In general formula (9), R7 and R8 each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group, and R7 and R8 may bond to each other to form a cyclic structure. R9 represents a hydrogen atom or a methyl group, and X2 represents a divalent linking group.

[0204] The alkyl groups in R7 and R8 of general formula (9) are linear, branched, cyclic, or a combination thereof. Examples of the alkyl groups include methyl, ethyl, propyl, butyl, pentyl, octyl, cyclohexyl, and cyclohexylmethyl groups. Among these, methyl, ethyl, propyl, and butyl groups are preferred.

[0205] Examples of aryl groups in R7 and R8 of general formula (9) include phenyl, naphthyl, biphenyl, and anthracenyl groups. Among these, the phenyl group is preferred.

[0206] Examples of aralkyl groups in R7 and R8 of general formula (9) include benzyl, phenethyl, phenylpropyl, phenylbutyl, and phenylisopropyl groups. Among these, benzyl and phenethyl groups are preferred.

[0207] If the alkyl, aryl, or aralkyl groups of R7 and R8 in general formula (9) have substituents, examples of substituents include halogen atoms, alkoxy groups, benzoyl groups, hydroxyl groups, and so on.

[0208] The cyclic structures formed by the bonding of R7 and R8 include, for example, 5- to 7-membered nitrogen-containing heterocycles. These include, for example, the following cyclic structures.

[0209] [ka]

[0210] These cyclic structures may have substituents. Examples of substituents include halogen atoms and alkoxy groups.

[0211] The divalent linking group X2 in general formula (9) can preferably be the group listed as the divalent linking group X1 in general formula (8).

[0212] Monomers that form monomer units represented by general formula (9) include, for example, (meth)acrylates having a tertiary amino group, such as N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, and N,N-diethylaminopropyl (meth)acrylate; Examples include (meth)acrylamides having a tertiary amino group, such as N,N-dimethylaminoethyl(meth)acrylamide, N,N-diethylaminoethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, and N,N-diethylaminopropyl(meth)acrylamide.

[0213] In general formula (10), R 10 This includes a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an acyl group, an oxy radical group, or -OR 16 Represents R 16 R represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, or an acyl group. 11 ~R 14 Each of these independently represents a methyl group, an ethyl group, or a phenyl group, and R 15 represents a hydrogen atom or a methyl group, and X3 represents a divalent linking group.

[0214] R in general formula (10) 10 The alkyl group in the formula is linear, branched, cyclic, or a combination thereof. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-hexyl, cyclohexyl, n-octyl, and hexadecyl groups. Among these, methyl, ethyl, n-propyl, isopropyl, and n-butyl groups are preferred.

[0215] R in general formula (10) 10 Examples of aryl groups in this context include phenyl groups, 1-naphthyl groups, and 2-naphthyl groups.

[0216] R in general formula (10) 10 Examples of aralkyl groups in this context include benzyl, phenethyl, phenylpropyl, phenylbutyl, and phenylisopropyl groups.

[0217] R in general formula (10) 10 Examples of acyl groups in this context include acetyl groups and benzoyl groups.

[0218] R in general formula (10) 10When the alkyl group, aryl group, or aralkyl group has a substituent, examples of the substituent include a halogen atom, an alkoxy group, a benzoyl group, and the like.

[0219] -OR 16 The R in 16 is preferably an alkyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, or a group exemplified as an acyl group. 10

[0220] As the divalent linking group X3 in the general formula (10), the groups exemplified as the divalent linking group X1 in the general formula (8) can be used.

[0221] Examples of the monomer forming the monomer unit represented by the general formula (10) include the following monomers and the like. In the following structural formulas, R 15 represents a hydrogen atom or a methyl group.

[0222]

Chemical formula

[0223] Among the above monomers, 2,2,6,6-tetramethylpiperidyl methacrylate and 1,2,2,6,6-pentamethylpiperidyl methacrylate are preferred, and 1,2,2,6,6-pentamethylpiperidyl methacrylate is more preferred.

[0224] The monomer units represented by the general formulas (8) to (1​​​​​​​​​

[0227] Other monomer units include, for example, 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, 2-Acryloyloxyethyl-2-hydroxyethyl phthalate, 4-Vinylphenol, 4-Isopropenylphenol, Isobolonyl (meth)acrylate, Dicyclopentanyl (meth)acrylate, Dicyclopentenyl (meth)acrylate, Dicyclopentanyloxyethyl (meth)acrylate, Dicyclopentenyloxyethyl ( Meth)acrylate, adamantyl(meth)acrylate, (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-acryloyloxyethylhexyl hydrophthalic acid, p-styrene sulfonic acid, vinyl sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamide Sulfonic acid, 2-(meth)acryloyloxyethyl acid phosphate, 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, pheno Xyethyl (meth)acrylate, phenoxyethylene glycol (meth)acrylate, phenol modified with ethylene oxide (EO) (meth)acrylate, nonylphenol modified with EO or propylene oxide (PO) (meth)acrylate, paracumylphenol modified with EO or PO (meth)acrylate, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, 2-oxyranylethyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 3,4-Epoxycyclohexyl (meth)acrylate, 3,4-Epoxycyclohexylmethyl (meth)acrylate, 3,4-Epoxytricyclo[5.2.1.0, 2,6 ] Decane-8-yl(meth)acrylate, 3,4-epoxytricyclo[5.2.1.0 2,6Decan-9-yl (meth)acrylate, 3-((meth)acryloyloxymethyl)oxetane, 3-((meth)acryloyloxymethyl)-3-ethyloxetane, 3-((meth)acryloyloxymethyl)-2-methyloxetane, 3-((meth)acryloyloxyethyl)-3-ethyloxetane, 2-ethyl-3-((meth)acryloyloxyethyl)oxetane, 3-methyl-3-(meth)acryloyloxymethyloxetane, 3-ethyl-3-(meth)acryloyl Royloxymethyl oxetane, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (MOI-BP from Resonaq), 2-[O-(1'-methylpropyrideneamino)carboxyamino]ethyl methacrylate (MOI-BM from Resonaq), 2-[[[[(2-methyl-1-oxo-2-propenyl)oxy]ethyl]amino]carbonyl]-1,3-diethyl malonate (MOI-DEM from Resonaq), 2-(acetate Cethoxy)ethyl methacrylate, 2-(acetoacetoxy)ethyl acrylate, 3-methacryloyloxypropyl methyldiethoxysilane, 3-methacryloyloxypropyl trimethoxysilane, styrene, α-methylstyrene, p-vinyltoluene, p-chlorostyrene, vinylnaphthalene, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, vinyl acetate, or vinyl propionate. Examples of monomer units derived from monomers such as dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, diethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, di(n-propyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(isopropyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, and di(2-ethylhexyl)-2,2'-[oxybis(methylene)]bis-2-propenoate.

[0228] Examples of the structure of the dispersion resin (G1) include random structure, block structure, graft structure, comb structure, and star structure. Among these, block structure or graft structure is preferred from the viewpoint of dispersibility.

[0229] The amine value of the dispersion resin (G1) is preferably 20 to 250 mg KOH / g, and more preferably 30 to 150 mg KOH / g, from the viewpoint of dispersibility. In this specification, the amine value refers to the amine value when quaternary ammonium bases are also considered as amino groups, and can be calculated by the method described in paragraphs 0039 to 0040 of International Publication No. 2022 / 172607.

[0230] The weight-average molecular weight of the dispersion resin (G1) is preferably 2,000 to 60,000, and more preferably 4,000 to 50,000.

[0231] The dispersion resin (G) may include dispersion resins other than dispersion resin (G1), such as (G2) (hereinafter also simply referred to as dispersion resin (G2)).

[0232] [Sensitizer (H)] The photosensitive composition of the present invention may contain a sensitizer (H).

[0233] The sensitizer (H) is preferably, for example, a thioxanthone compound or a benzophenone compound.

[0234] Examples of thioxanthone compounds include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, and 1-chloro-4-propoxythioxanthone. Among these, 2,4-diethylthioxanthone is preferred.

[0235] Examples of the benzophenone-based compound include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 2-aminobenzophenone, etc. Among these, 4,4'-bis(diethylamino)benzophenone is preferred.

[0236] The sensitizer (H) can be used alone or in combination of two or more kinds.

[0237] The content of the sensitizer (H) is preferably 10 to 400 parts by mass, more preferably 20 to 300 parts by mass, relative to 100 parts by mass of the polymerization initiator (C).

[0238] [Thermally crosslinkable compound (I)] The photosensitive composition of the present invention can contain a thermally crosslinkable compound (I).

[0239] The thermally crosslinkable compound (I) is a compound having a thermally crosslinkable group, and examples thereof include a compound having an epoxy group, a compound having a blocked isocyanate group, a compound having an oxetanyl group, a compound having a methylol group, a compound having a phenol group, etc. Among these, a compound having an epoxy group and a compound having a blocked isocyanate group are preferred. Note that the thermally crosslinkable compound (I) is a compound having no alkali-soluble group.

[0240] The thermally crosslinkable compound (I) can be used alone or in combination of two or more kinds.

[0241] The content of the thermally crosslinkable compound (I) is preferably 0.5 to 40% by mass, more preferably 1 to 30% by mass, in 100% by mass of the non-volatile content of the photosensitive composition.

[0242] (Compound having an epoxy group) An epoxy group is a group having a three-membered ring cyclic ether structure, and includes alicyclic epoxy groups. Compounds containing epoxy groups include, for example, 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 their molecule, such as ru-5,5-spiro-3,4-epoxy)cyclohexane-methadioxane, 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, and tetra(3,4-epoxycyclohexylmethyl)-modified ε-caprolactone butanetetracarboxylic acid; Examples include the 1,2-epoxy-4-(2-oxyranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol.

[0243] Examples of commercially available compounds containing epoxy groups include Epicote 807, 815, 825, 827, 828, 190P, and 191P from Shell Epoxy Corporation, and TECHMORE from Mitsui Chemicals Corporation. VG3101L, EPPN-201, 501H, 502H, EOCN-102S, 103S, 104S, 1020 from Nippon Kayaku Co., Ltd., Epicote 1004, 1256, JER1032H60, 157S65, 157S70, 152, 154 from Japan Epoxy Resin Co., Ltd., Celoxide 2021, EHPE-3150, Epolid GT401 from Daicel Chemical Industries, Ltd., Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721 from Nagase ChemteX Corporation, TEPIC-L, H, S from Nissan Chemical Industries, Ltd., EPICLON from 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, HP-9500, etc.

[0244] (Compounds having a blocked isocyanate group) A compound having a blocked isocyanate group is a compound in which the isocyanate group of an isocyanate group is protected with a blocking agent. The desorption temperature of the blocking agent for the blocked isocyanate group is preferably 60 to 160°C, more preferably 70 to 130°C, and particularly preferably 80 to 100°C.

[0245] 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, with oxime compounds, phenol compounds, active methylene compounds, and pyrazole compounds being more preferred, and active methylene compounds being particularly preferred. The elimination temperature of the active methylene compound, or the temperature of the transesterification reaction, is low, at 80 to 110°C, allowing for sufficient reaction.

[0246] Compounds having an isocyanate group include, for example, aliphatic compounds such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropyl 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(isocyanate-methyl)cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, and bis(isocyanate-methyl)cyclohexane; Examples of aromatic compounds include 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyli isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylenedi isocyanate, 1,4-phenylenedi isocyanate, 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(isocyanatemethyl)benzene. Other examples include biuret forms, isocyanurate forms, adduct forms, allophanate forms of these compounds, and reaction products of these compounds with polyols.

[0247] The compounds having an isocyanate group are preferably in the form of a biuret, isocyanurate, adduct, or allophanate compounds, which are compounds having an aliphatic structure or an alicyclic structure.

[0248] Examples of commercially available compounds containing a blocked isocyanate group and having an aliphatic structure include, for example, Asahi Kasei's Duranate SBN-70D, SBB-70P, SBF-70E, TPA-B80E, 17B-60P, MF-B60B, E402-B80B, MF-K60B, WM44-L70G; Mitsui Chemicals' Takenate B-882; and Baxenden Chemical's BI7960, BI7961, BI7982, BI7991, BI7992, etc. Examples of compounds having an alicyclic structure include Takenate B-846N from Mitsui Chemicals, Coronate BI-301, 2507, 2554 from Tosoh Corporation, and BI7950, BI7951, BI7990 from Baxenden Chemical. Examples of compounds having an aromatic structure include Takenate B-830 and B-815N, manufactured by Mitsui Chemicals, Inc.

[0249] (Compounds containing an oxetanyl group) Compounds having an oxetanyl group include, for example, (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, 3-ethyl-3-hydroxymethyloxetan, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetan, 3-ethyl-3-(phenoxymethyl)oxetan, 3-ethyl-3-(2-methacryloxymethyl)oxetan, and 3-ethyl Lu-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane, 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-)methyl ether, di[1-ethyl(3-) Oxetanyl) methyl ether 3-ethyl-3-hydroxymethyl oxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycos(3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl(3-ethyl-3-oxetanylmethyl) ether, triethylene glycol(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol(3-ethyl-3-oxetanylmethyl) ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-Bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO) modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO) modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, PO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tris(3-ethyl-3-oxetanylmethyl) Examples include dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, and ditrimethylolpropanetetrakis(3-ethyl-3-oxetanylmethyl) ether.

[0250] Examples of commercially available compounds containing an oxetanyl group include OXE-10 and 30 from Osaka Organic Chemical Industry Co., Ltd., OXT-101, 121, 212, and 221 from Toagosei Co., Ltd., and OXBP and OXTP from Ube Industries, Ltd.

[0251] [Thiol-based chain transfer agent (J)] The photosensitive composition of the present invention may contain a thiol-based chain transfer agent (J).

[0252] Thiol chain transfer agents (J) include, for example, monofunctional thiol compounds such as thiophenol, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-benzimidazole, butanethiol, octanthiol, 1-dodecanethiol, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate, and 2-ethylhexyl 3-mercaptopropionate; Monofunctional thiol compounds having a hydroxyl group or 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 tetrakisthioglycolate, pentaerythritol tetrakis(3-mercaptopropionate), tris(2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, and 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine.

[0253] Thiol-based chain transfer agents (J) can be used alone or in combination of two or more types.

[0254] The content of the thiol-based chain transfer agent (J) is preferably 0.5 to 10% by mass of 100% by mass of the non-volatile content of the photosensitive composition.

[0255] [Silane coupling agent (K)] The photosensitive composition of the present invention may contain a silane coupling agent (K).

[0256] The silane coupling agent (K) is a compound having a hydrolyzable group. The hydrolyzable group is a group that is directly bonded to a silicon atom and forms a siloxane bond through at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include halogen atoms, alkoxy groups, and acyloxy groups. Among these, alkoxy groups are preferred. From the viewpoint of reactivity, methoxy groups and ethoxy groups are preferred among alkoxy groups. The silane coupling agent (K) may have functional groups other than the hydrolyzable group. Examples of functional groups include epoxy groups, amino groups, vinyl groups, (meth)acryloyl groups, isocyanate groups, isocyanurate groups, mercapto groups, oxetanyl groups, styryl groups, ureido groups, and the like.

[0257] Silane coupling agents (K) include, 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, hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyl Examples include pyrtrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatetopropyltriethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, p-styryltrimethoxysilane, 3-ureidopropyltrialkoxysilane, N,N-bis[3-(trimethoxysilyl)propyl]ethylenediamine, bis(3-triethoxysilyl)propyl)tetrasulfide, 1,6-bis(trimethoxysilyl)hexane, 1,8-bis(trimethoxysilyl)octane, and tris(-trimethoxysilylpropyl)isocyanate.

[0258] 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, KBE-1003, and KBM-5, all manufactured by Shin-Etsu Chemical Co., Ltd. Examples include 02, KBM-503, KBE-502, KBE-503, KBM-5803, X-12-1048, X-12-1050, KBE-9007N, KBM-9659, KBM-802, KBM-803, KBM-1043, KBM-3086, KBE-585A, X-12-1048, X-12-50, X-12-5263HP, etc.

[0259] Furthermore, the silane coupling agent (K) may be of polymer type. Examples of polymer types include polysiloxane type and organic polymer type.

[0260] Polysiloxane-type compounds are compounds in which the hydrolyzable group is bonded to a polymer having a polysiloxane skeleton in its main chain. Commercially available polysiloxane-type compounds include KR-513, KR-516, KR-517, X-41-1805, and X-41-1810, manufactured by Shin-Etsu Chemical Co., Ltd.

[0261] The organic polymer type is a silane coupling agent (K) in which the hydrolyzable group is bonded to an organic polymer whose main chain has an organic structure. Commercially available organic polymer type products include X-12-9815, X-12-9845, X-12-1154, X-12-972F, X-12-1159L, etc., manufactured by Shin-Etsu Chemical Co., Ltd.

[0262] Silane coupling agents (K) can be used alone or in combination of two or more types.

[0263] The content of the silane coupling agent (K) is preferably 0.1 to 10% by mass of 100% by mass of the nonvolatile content of the photosensitive composition.

[0264] The silane coupling agent (K) preferably contains a silane coupling agent (K1) represented by the following general formula (11) (hereinafter also simply referred to as silane coupling agent (K1)). Since the silane coupling agent (K1) has urethane bonds, it forms hydrogen bonds between the urethane bonds and with the functional groups of other components contained in the photosensitive composition, resulting in a strong film. Furthermore, since the urethane bonds are flexible, it is presumed that the resulting film will be both strong and flexible.

[0265] [ka]

[0266] In general formula (11), R1 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R2 represents an alkylene group having 1 to 8 carbon atoms, X is a group represented by any of the following general formulas (X-1) to (X-4), and n is an integer from 1 to 10.

[0267] [ka]

[0268] In general formula (X-1), R3 represents an alkylene group having 1 to 8 carbon atoms. In general formulas (X-1) to (X-4), R4 independently represents either a hydrogen atom or a methyl group. * indicates a bond with an oxygen atom.

[0269] In general formula (11), R1 is preferably a methyl group.

[0270] Silane coupling agents (K1) can be used alone or in combination of two or more types.

[0271] [UV absorber (R)] The photosensitive composition of the present invention may contain an ultraviolet absorber (R).

[0272] The ultraviolet absorber (R) is not limited, and known compounds can be used. For example, compounds having the maximum absorption wavelength in the range of 300 to 400 nm are preferred, and examples include benzophenone compounds, benzotriazole compounds, triazine compounds, conjugated diene compounds, methyldibenzoyl compounds, coumarin compounds, acrylonitrile compounds, benzothiazole compounds, salicylate compounds, and the like.

[0273] Examples of commercially available benzophenone compounds include Ubinal A, 3049, 3050, and UVA-935LH from BASF Japan, and Adeka Stab 1413 from ADEKA.

[0274] Examples of commercially available benzotriazole compounds include Chinuvin PS, 99-2, 326, 384-2, 900, 928, 970, 1130, and UVA-903KT from BASF Japan, and Adeka Stab LA-31RG and LA-31G from ADEKA.

[0275] Examples of commercially available triazine compounds include Chinuvin 400, 405, 406, 477, and 479 from BASF Japan, and Adeka Stab LA-46 and LA-F70 from ADEKA.

[0276] UV absorbers (K) can be used alone or in combination of two or more types.

[0277] The content of the ultraviolet absorber (K) is preferably 0.01 to 5% by mass of 100% by mass of the nonvolatile content of the photosensitive composition. [Polymerization inhibitor (L)] The photosensitive composition of the present invention may contain a polymerization inhibitor (L).

[0278] The polymerization inhibitor (L) is not limited and any known compound can be used. For example, alkylcatechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert-butylcatechol, 3,5-di-tert-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, 2-n-butyl Examples include alkylresorcinol compounds such as zolcinol, 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 tripenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphite compounds such as triphenylphosphine and trisnonylphenylphosphine; pyrogallol and phloroglucin.

[0279] Polymerization inhibitors (L) can be used alone or in combination of two or more types.

[0280] The polymerization inhibitor (L) content is preferably 0.01 to 0.5% by mass of 100% by mass of the nonvolatile content of the photosensitive composition.

[0281] [Antioxidant (M)] The photosensitive composition of the present invention may contain an antioxidant (M).

[0282] The antioxidant (M) is not limited, and known compounds can be used, such as hindered phenol, hindered amine, phosphorus, sulfur, and hydroxylamine compounds. Among these, hindered phenol antioxidants, hindered amine antioxidants, phosphorus antioxidants, and sulfur antioxidants are preferred.

[0283] Examples of commercially available hindered phenol antioxidants include ADEKA's ADEKA Stab AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, and AO-330; Chemipro's KEMINOX 101, 179, 76, and 9425; BASF Japan's IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, and 565; and Sun Chemical's Cyanox CY-1790 and CY-2777.

[0284] Examples of commercially available hindered amine antioxidants include ADEKA's ADEKA Stab LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402F, LA-502XP; KAMISTAB29, 62, 77, 94 from Chemipro Chemical; Tinuvin111FDL, 123, 144, 249, 292, 5100 from BASF Japan; and Siasorb UV-3346, UV-3529, UV-3853 from Sun Chemical.

[0285] Examples of commercially available phosphorus-based antioxidants include ADEKA's ADEKA Stab PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, and TPP; BASF Japan's IRGAFOS168; and Clariant Chemicals' Hostanox P-EPQ.

[0286] Examples of commercially available sulfur-based antioxidants include ADEKA's ADEKA Stab AO-412S and AO-503, and KEMINOXPLS from Chemipro Chemical Co., Ltd.

[0287] Antioxidants (M) can be used alone or in combination of two or more types.

[0288] The antioxidant (M) content is preferably 0.5 to 5.0% by mass of 100% by mass of the nonvolatile content of the photosensitive composition.

[0289] [Leveling agent (N)] The photosensitive composition of the present invention may contain a leveling agent (N).

[0290] The leveling agent (N) is not limited, and any known leveling agent can be used. Examples include silicone-based leveling agents, fluorine-based leveling agents, acrylic-based leveling agents, acetylenediol-based leveling agents, and the like.

[0291] Commercially available silicone-based 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, 3570 from Bic Chemie, and FZ-7002, 2110, 2122, 2123, 2191, 5609 from Toray Dow Corning, and Shin-Etsu Chemical. 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, KP-341 from Gaku Kogyo Co., Ltd., TegoGlide 432, 440, 450, TegoWet 250, 260, 265, 270, 280 from Evonik Corporation, and MEGAFACE EFS-131, EFS-321, EFS-521, EFS-801 from DIC Corporation.

[0292] Examples of commercially available fluorine-based leveling agents include Surflon S-242, 243, 420, 611, 651, and 386 from AGC Seimi Chemical; Megafac F-253, 477, 551, 552, 554, 555, 556, 558, 559, 560, 561, 570, 575, 576, R-01, R-40, R-40-LM, R-41, and RS-72-K from DIC; FC-4430 and 4432 from Sumitomo 3M; EF-PP31N09, EF-PP33G1, and EF-PP32C1 from Mitsubishi Materials Electronic Chemicals; and Futergent 602A from Neos.

[0293] Examples of commercially available acrylic leveling agents include BYK-350, 352, 354, 355, 358, 380, 381, 392, and 394 from BIC Chemie, and Polyflow 57, 77, and 95 from Kyoeisha Chemical.

[0294] Examples of commercially available acetylenediol-based leveling agents include Surfinol 420, 440, 465, 485, SE, DF110D, DE85, and Orfin E1004, 1010, all manufactured by Nisshin Chemical Industry Co., Ltd.

[0295] Leveling agent (N) can be used alone or in combination of two or more types.

[0296] The leveling agent (N) content is preferably 0.001 to 2.0% by mass of 100% by mass of the nonvolatile content of the photosensitive composition.

[0297] The leveling agent (N) preferably includes a leveling agent (N1) having monomer units represented by the following general formula (12) (hereinafter also simply referred to as leveling agent (N1)).

[0298] [ka]

[0299] In general formula (12), R1 is a hydrogen atom or a methyl group.

[0300] In general formula (12), R2 is independently an alkyl group having 1 to 6 carbon atoms, or a group represented as -OSi(R5)3 (where R5 is independently an alkyl group having 1 to 3 carbon atoms). R2 is preferably a methyl group or a trimethylsiloxy group.

[0301] In general formula (12), R3 is independently an alkyl group having 1 to 6 carbon atoms. R3 is preferably a methyl group.

[0302] In general formula (12), R4 is an alkyl group having 1 to 6 carbon atoms. R4 is preferably an alkyl group having 1 to 4 carbon atoms.

[0303] In general formula (12), L1 is a divalent organic group or a single bond. Among these, L1 is preferably a divalent organic group, and more preferably an alkylene group having 1 to 50 carbon atoms, or an alkylene oxy group having 1 to 50 carbon atoms. Examples of alkylene groups having 1 to 50 carbon atoms include methylene, ethylene, n-propyl, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, isopropylene, 2-methylpropylene, 2-methylhexylene, and tetramethylethylene. Among these, methylene, ethylene, n-propylene, and isopropylene are preferred. Examples of alkylene oxy groups having 1 to 50 carbon atoms include methylene oxy group, ethylene oxy group, propylene oxy group, oxytrimethylene group, butylene oxy group, oxytetramethylene group, pentylene oxy group, and heptylene oxy group.

[0304] A portion of the -CH2- group of the alkylene group having 1 to 50 carbon atoms, or the alkyleneoxy group having 1 to 50 carbon atoms, may be substituted with a carbonyl group, a phenylene group, an amide bond, or a urethane bond, and further, a hydroxyl group or the like may be substituted on the carbon atom.

[0305] In general formula (12), n is an integer between 1 and 70. Preferably, n is an integer between 2 and 50.

[0306] Monomers that form monomer units represented by general formula (12) include, for example, α-(3-methacryloyloxy)propyl polydimethylsiloxane and 3-(methacryloyloxy)propyltris(trimethylsiloxy)silane. Commercially available products include Cyraplane FM-0711, FM-0721, FM-0725, and FM-0701T from JNC Corporation, and X-22-174ASX, X-22-174BX, X-22-2426, and X-22-2404 from Shin-Etsu Chemical Co., Ltd. These can be used individually or in combination of two or more types.

[0307] The content of monomer units represented by general formula (12) is preferably 30 to 95% by mass, and more preferably 40 to 85% by mass, of the total monomer units of the leveling agent (N1).

[0308] The leveling agent (N1) preferably contains at least one selected from the group consisting of monomer units represented by general formula (13) and monomer units represented by general formula (14), in addition to monomer units represented by general formula (12).

[0309] [ka]

[0310] In general formula (13), R6 is a hydrogen atom or a methyl group.

[0311] In general formula (13), R7 is an alicyclic hydrocarbon group having 3 to 20 carbon atoms. Alicyclic hydrocarbon groups having 3 to 20 carbon atoms may have substituents. Examples of substituents include alkyl groups, hydroxyl groups, nitro groups, amino groups, alkoxy groups, halogen atoms, and combinations thereof. Examples of alicyclic hydrocarbon groups having 3 to 20 carbon atoms include monocyclic or polycyclic alicyclic hydrocarbon groups. Examples of monocyclic alicyclic hydrocarbon groups include cyclopentyl groups, cyclohexyl groups, cycloheptyl groups, and cyclooctyl groups. Polycyclic alicyclic hydrocarbon groups include isobornyl, norbornyl, adamantyl, tricyclodecyl, dicyclopentanyl, dicyclopentenyl, tricyclopentenyl, tricyclopentadiene, and dicyclopentadiene groups. Among these, polycyclic alicyclic hydrocarbon groups are preferred, isobornyl, dicyclopentanyl, and adamantyl groups are more preferred, and adamantyl groups are even more preferred.

[0312] Monomers that form monomer units represented by general formula (13) include, for example, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, 2-isopropyl-2-adamantyl (meth)acrylate, and dimethyladamantyl (meth)acrylate. These can be used individually or in combination of two or more.

[0313] In general formula (14), R8 is a hydrogen atom or a methyl group.

[0314] In general formula (14), R9 is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. The alkyl group having 1 to 18 carbon atoms may be linear, branched, cyclic, or a combination thereof. Examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl, isoamyl, pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl groups. Among these, R6 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, with a hydrogen atom being more preferred.

[0315] In general formula (14), m is an integer between 1 and 4. m is preferably 3 or 4.

[0316] In general formula (14), o is an integer between 2 and 200. Preferably, o is an integer between 3 and 50.

[0317] Monomers that form monomer units represented by general formula (14) include, for example, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polytrimethylene glycol mono(meth)acrylate, polytetramethylene glycol mono(meth)acrylate, poly(ethylene glycol-propylene glycol) mono(meth)acrylate, polyethylene glycol-polypropylene glycol mono(meth)acrylate, poly(ethylene glycol-tetramethylene glycol) mono(meth)acrylate, polyethylene glycol-polytetramethylene glycol mono(meth)acrylate, poly(propylene glycol-tetramethylene glycol) mono(meth)acrylate, polypropylene glycol-polytetramethylene glycol mono(meth)acrylate, poly(propylene glycol-1,2-butylene glycol) mono(meth)acrylate, polypropylene glycol-poly1,2-butylene glycol mono(meth)acrylate, and poly(ethylene glycol-1,2-butyl Polyethylene glycol mono(meth)acrylate, polyethylene glycol / poly-1,2-butylene glycol mono(meth)acrylate, poly(tetramethylene glycol / 1,2-butylene glycol) mono(meth)acrylate, polytetraethylene glycol / poly-1,2-butylene glycol mono(meth)acrylate, poly-1,2-butylene glycol mono(meth)acrylate, poly(ethylene glycol / trimethylene glycol) mono(meth)acrylate, polyethylene glycol / polytrimethylene Examples include glycol mono(meth)acrylate, poly(propylene glycol / trimethylene glycol) mono(meth)acrylate, poly(1,2-butylene glycol / trimethylene glycol) mono(meth)acrylate, poly1,2-butylene glycol / polytrimethylene glycol mono(meth)acrylate, poly(1,2-butylene glycol / tetramethylene glycol) mono(meth)acrylate, and poly1,2-butylene glycol / polytetramethylene glycol mono(meth)acrylate.Note that "poly(ethylene glycol / propylene glycol)" above refers to a random copolymer of ethylene glycol and propylene glycol, and "polyethylene glycol / polyethylene glycol" refers to a block copolymer of ethylene glycol and propylene glycol. Commercially available products include NK Ester M-20G, M-40G, M-90G, M-130G, M-230G, AM-90G, AM-130G, AM-230G from Shin Nakamura Chemical Industry Co., Ltd., and Bremmer PE-90, PE-200, PE-350, PP-500, PP-800, PP-1000, 50PEP-300, 55PET-800, 10PPB-500B, AE-200, AE-400, AP-400 from NOF Corporation. These can be used individually or in combination of two or more types.

[0318] The content of monomer units represented by general formula (13) and monomer units represented by general formula (14) is preferably 5 to 70% by mass, and more preferably 15 to 60% by mass, of the total monomer units of the leveling agent (N1).

[0319] The leveling agent (N1) may contain monomer units other than those represented by general formula (12), general formula (13), and general formula (14) (hereinafter also referred to as other monomer units).

[0320] Other monomers that form monomer units 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, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, and Examples include methyl(meth)acrylate, 2-phenoxymethyl(meth)acrylate, 2-phenoxyethyl(meth)acrylate, 2-hydroxy-3-phenoxypropyl(meth)acrylate, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, glycerol monoallyl ether, styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-isopropylacrylamide, acroylmorpholine, methyl maleimide, ethyl maleimide, propyl maleimide, and butyl maleimide. These can be used individually or in combination of two or more types.

[0321] The structure of the leveling agent (N1) can include, for example, a random structure, a block structure, or a graft structure. Among these, the block structure is preferred.

[0322] When the leveling agent (N1) has a block structure, the number and arrangement of each block are not limited. For example, if block A consists of monomer units represented by general formula (12), and block B consists of monomer units represented by general formula (13), or monomer units represented by general formula (14), the leveling agent (N1) can be arranged in configurations such as AB block structure, ABA block structure, or BAB block structure.

[0323] The method for manufacturing the block structure is not limited, and known methods can be used. Examples include living polymerization methods such as living radical polymerization and living anionic polymerization. Among these, reversible addition-cleavage chain transfer polymerization (RAFT), atom transfer radical polymerization (ATRP), living radical polymerization using iodine compounds, and living radical polymerization using organotellurium compounds (TERP) are preferred. Specifically, the leveling agent (N1) can be synthesized by methods described in, for example, International Publication No. 2021 / 131726, International Publication No. 2022 / 050062, International Publication No. 2022 / 244586, etc.

[0324] The weight-average molecular weight of the leveling agent (N1) is preferably 5,000 to 40,000.

[0325] The number-average molecular weight of the leveling agent (N1) is preferably 2,000 to 20,000.

[0326] The average molecular weight distribution (weight-average molecular weight / number-average molecular weight) of the leveling agent (N1) is preferably between 1.0 and 3.0.

[0327] Leveling agent (N1) can be used alone or in combination of two or more types.

[0328] [Storage stabilizer (O)] The photosensitive composition of the present invention may contain a storage stabilizer (O).

[0329] The storage stabilizer (O) is not limited, and any known compound can be used. Examples include benzyl trimethyl chloride, quaternary ammonium chlorides such as diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organophosphines such as tert-butylpyrocatechol, tetraethylphosphine, and tetraphenyl, and phosphates.

[0330] The storage stabilizer (O) content is preferably 0.05 to 5.0% by mass of 100% by mass of the nonvolatile content of the photosensitive composition.

[0331] [Organic solvent (P)] The photosensitive composition of the present invention may contain an organic solvent (P).

[0332] The organic solvent (P) is not limited and any known compound can be used. For example, 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-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 Dibenzene, 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 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, dibasic acid esters, etc.

[0333] From an environmental standpoint, the photosensitive composition of the present invention preferably contains substantially no organic solvents, such as aromatic hydrocarbons (toluene, xylene, benzene, chlorobenzene, etc.). Substantially no organic solvents means that the concentration 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.

[0334] Organic solvents (P) can be used alone or in combination of two or more types.

[0335] The amount of organic solvent (P) is preferably such that the non-volatile content of the photosensitive composition is 5 to 60% by mass.

[0336] [Other ingredients (Q)] The photosensitive composition of the present invention may contain components other than those listed above (hereinafter also simply referred to as other components (Q)). Examples of other components (Q) include surfactants, acid generators, salt generators, curing agents, curing catalysts, quenching agents, semiconductor nanocrystals, semiconductor materials, organic electroluminescent materials, insulating materials, and the like. The content of other components can be appropriately set within a range that solves the problems of the present invention.

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

[0338] Photosensitive compositions containing a total amount of specific metal elements within the above range exhibit excellent stability and sensitivity even after storage over time. The content of specific metal elements can be measured by inductively coupled plasma atomic emission spectrometry (ICP).

[0339] [Water content] The photosensitive composition of the present invention preferably contains 2.0% by mass or less of water.

[0340] Photosensitive compositions with a water content within the above range exhibit excellent stability and sensitivity even after storage over time. The water content can be measured by known methods such as the Karl Fischer method.

[0341] [Method for producing a photosensitive composition] The photosensitive composition of the present invention can be prepared by mixing the above-mentioned components. During preparation, the components may be combined all at once, or they may be dissolved or dispersed in a polymerizable compound (B) or an organic solvent (P) before being added sequentially. When using components with low solubility, such as pigments as colorants (D), it is preferable to first perform a dispersion treatment. For example, a dispersion can be produced by adding a colorant (D), a dispersion resin (G), and an organic solvent (P), etc., and performing a dispersion treatment. Subsequently, the dispersion can be mixed with an alkali-soluble resin (A), a polymerizable compound (B), and a polymerization initiator (C), etc. The timing of adding each material is arbitrary. Furthermore, the dispersion process can be performed multiple times.

[0342] Examples of distributed processing machines include two-roll mills, three-roll mills, ball mills, horizontal sand mills, vertical sand mills, annular bead mills, or attritors.

[0343] The average dispersed particle diameter (secondary particle diameter) of the particles in the dispersion is preferably 30 to 200 nm, and more preferably 40 to 200 nm.

[0344] The method for measuring the average dispersed particle diameter (secondary particle diameter) is, for example, to use Nikkiso's Microtrac UPA-EX150, which employs dynamic light scattering (FFT power-spectrum method), with particle permeability set to absorption mode, particle shape to non-spherical, and D50 particle diameter as the average diameter. The diluent solvent for measurement is the same organic solvent used for dispersion, and it is preferable to measure immediately after sample preparation of ultrasonically treated samples to obtain results with less variation.

[0345] The photosensitive composition is preferably subjected to centrifugation, sintering filter filtration or membrane filter filtration to remove coarse particles of 5 μm or larger, preferably 1 μm or larger, more preferably 0.5 μm or larger, and any mixed dust. 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.

[0346] <Membrane> The film of the present invention is formed using the photosensitive composition described above. While a patterned film is preferred, it can also be used as a flat film.

[0347] [Membrane manufacturing method] The method for manufacturing the film is not limited, and known methods can be used. For example, it can be manufactured by a step of coating the photosensitive composition of the present invention onto a substrate, and a step of drying it.

[0348] [Coating process] Examples of substrates include those 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 resins include polyester resins such as polyester terephthalate, polyolefin 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 image sensor such as a CCD or CMOS may be formed on the substrate. Additionally, a primer layer may be provided on the substrate as needed to improve adhesion with the upper layer, prevent diffusion of materials, and flatten the surface.

[0349] The coating method is not limited, and known methods can be used. Examples include the drop method, slit coating method, spray method, roll coating method, rotary coating method, casting coating method, inkjet method, flexographic printing, screen printing, gravure printing, and offset printing.

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

[0351] [Drying process] The drying of the film coated on the substrate is not limited, and known methods can be used. Examples include vacuum drying using a vacuum drying apparatus, heating drying using a hot plate, IR oven, convection oven, etc., and methods combining these.

[0352] The drying temperature and drying time can be adjusted as appropriate. A drying temperature of approximately 50 to 130°C is preferred, and a drying time of approximately 5 seconds to 5 minutes is preferred.

[0353] Next, a pattern is formed. Methods for forming the pattern include photolithography and dry etching. Of these, photolithography is preferred. Note that if the film is to be used as a flat film, the pattern formation step is not necessary.

[0354] [Exposure process] The exposure process involves exposing the layer formed by coating and drying to a specific pattern via 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 of a specific wavelength, optical filters can also be used. Furthermore, exposure may be performed by continuously irradiating with light, or by repeatedly irradiating and pausing with light in short cycles (for example, at the millisecond level or less) (pulsed exposure). Furthermore, multiple active energy rays can be used in combination, and exposure can be performed in multiple stages.

[0355] [Development process] Next, by performing an alkaline development treatment, the unexposed layers dissolve in the alkaline developer, leaving only the hardened parts and resulting in 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. Alkaline developers may contain surfactants and organic solvents in addition to alkaline compounds and water. The concentration of the alkaline developer is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass. The pH of the alkaline developer is preferably 11 to 13, and more preferably 11.5 to 12.5. Using an appropriate pH suppresses pattern roughness and peeling, and improves the residual film rate after development. Development methods include, for example, the dip method, spray method, and paddle method. The development temperature is preferably 15 to 40°C. After alkaline development, it is preferable to wash with pure water.

[0356] [Post-baking process] After development, heat treatment (post-bake) is performed. Post-bake improves the film's durability. The temperature is preferably between 70 and 260°C, and more preferably between 80 and 240°C. The duration is preferably between 2 minutes and 2 hours. When a material with low heat resistance is used as the substrate, when a substrate having an organic electroluminescent element as the light-emitting layer is used, or from the viewpoint of reducing environmental impact, a temperature of 180°C or lower is preferable, 150°C or lower is more preferable, and 130°C or lower is particularly preferable.

[0357] <Optical filters> The optical filter of the present invention has the above-described film. Optical filters are used, for example, in color filters, black matrices, light-shielding filters, anti-reflective filters, infrared cut filters, infrared transmission filters, microlenses, and the like. The optical filter of the present invention can be manufactured in the same manner as the above-described film.

[0358] <Solid-state image sensor> The solid-state image sensor of the present invention has the above-mentioned optical filter. The solid-state image sensor is not particularly limited as long as it is equipped with the optical filter of the present invention and functions as a solid-state image sensor, but for example, the following configuration is possible.

[0359] The present invention has a configuration in which a substrate has a plurality of photodiodes that constitute the light-receiving area of ​​a solid-state image sensor (CCD image sensor, CMOS image sensor, etc.) and transfer electrodes made of polysilicone or the like, a light-shielding film with an opening only for the light-receiving portion of the photodiode on the photodiode and transfer electrodes, a device protective film made of silicone nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the light-receiving portion of the photodiode, and the optical filter (color filter) of the present invention is on the device protective film. Furthermore, the device protective film may have a configuration in which a light-gathering means (for example, a microlens, etc.; the same applies hereinafter) is provided on the device protective film and below the optical filter (on the side closer to the substrate), or a configuration in which the light-gathering means is provided on the optical filter. The filter may also have a structure in which a hardened film forming each colored pixel is embedded in a space partitioned, for example, in a grid pattern by partition walls. In this case, it is preferable that the partition walls have a low refractive index with respect to each colored pixel. The imaging device equipped with the solid-state image sensor of the present invention can be used in a variety of applications, such as digital cameras, electronic devices with imaging capabilities (mobile phones, smartphones, etc.), in-vehicle cameras, and surveillance cameras.

[0360] <Image display device> The image display device of the present invention has the above-mentioned optical filter. Examples of image display devices include liquid crystal displays and organic EL displays. The form used in an image display device is not particularly limited, as long as it functions as an image display device. For example, the configuration described in "Next-Generation Liquid Crystal Display Technology" (by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd. in 1994) can be used. For definitions of image display devices and details of various image display devices, see, for example, "Electronic Display Devices" (by Akio Sasaki, Kogyo Chosakai Co., Ltd., published in 1990) and "Display Devices" (by Junsho Ibuki, Sangyo Tosho Co., Ltd., published in 1989).

[0361] <Infrared sensor> The infrared sensor of the present invention has the above-mentioned optical filter. The form used in the infrared sensor is not particularly limited as long as it incorporates the optical filter of the present invention and functions as an infrared sensor, but for example, the following configurations can be given.

[0362] The substrate has multiple photodiodes that constitute the light-receiving area of ​​a solid-state image sensor (CCD image sensor, CMOS image sensor, etc.) and transfer electrodes made of polysilicone or the like. A light-shielding film is provided on these photodiodes and transfer electrodes, with openings only in the light-receiving portions of the photodiodes. A device protective film is provided on this light-shielding film, and the optical filter of the present invention is provided on this device protective film. Furthermore, the configuration may include a light-gathering means (for example, a microlens, etc.; the same applies hereinafter) on the device protective film and below the optical filter (closer to the substrate), or a configuration in which the light-gathering means is provided on the optical filter.

[0363] Figure 1 is a schematic cross-sectional view showing an example configuration of an infrared sensor equipped with the optical filter of the present invention. The infrared sensor shown in Figure 1 comprises a 100 and a solid-state image sensor 110.

[0364] The imaging area on the solid-state image sensor 110 is formed by combining an infrared cut filter 111 and a color filter 112.

[0365] The infrared cut filter 111 transmits light in the visible light region (for example, light with a wavelength of 400 to 700 nm) and blocks light in the infrared region (for example, light with a wavelength of 800 to 1,300 nm).

[0366] The color filter 112 is a color filter in which pixels that transmit and absorb light of specific wavelengths in the visible light region are formed. For example, a color filter in which red (R), green (G), and blue (B) pixels are formed is used.

[0367] Between the infrared transmission filter 113 and the solid-state image sensor 110, a resin film 114 is placed that can transmit light of wavelengths that have passed through the infrared transmission filter 113.

[0368] The infrared transmission filter 113 is a filter that has visible light shielding properties and transmits infrared rays of a specific wavelength. Preferably, the infrared transmission filter 113 shields light with wavelengths of 400 to 830 nm and transmits light with wavelengths of 900 to 1,300 nm.

[0369] A microlens 115 is positioned 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.

[0370] In the configuration shown in Figure 1, a resin film 114 is arranged, but an infrared transmission filter 113 may be formed instead of the resin film 114.

[0371] This infrared sensor can simultaneously capture image information, enabling motion sensing and other applications that recognize moving objects. Furthermore, because it can acquire distance information, it can capture images containing 3D data. In addition, this infrared sensor can also be used as a biometric authentication sensor.

[0372] [Example of an embodiment] Examples of embodiments of the present invention are given below. The present invention is not limited to the following.

[0373] <1> A photosensitive composition comprising an alkali-soluble resin (A), a polymerizable compound (B), and a polymerization initiator (C), A photosensitive composition in which the alkali-soluble resin (A) comprises an alkali-soluble resin (A1) having a phenolic hydroxyl group-containing monomer unit (a1), and an alkali-soluble resin (A2) having a hydroxyl group-containing monomer unit (a2) other than the phenolic hydroxyl group-containing monomer unit (a1) (excluding the alkali-soluble resin (A1)). <2> The content of the alkali-soluble resin (A1) is 10 to 90% by mass of 100% by mass of the alkali-soluble resin (A). <1> The photosensitive composition described in [reference]. <3> The content of the phenolic hydroxyl group-containing monomer unit (a1) is 1 to 50 mol% of the total constituent units of the alkali-soluble resin (A1). <1> or <2> The photosensitive composition described in [reference]. <4> The content of the hydroxyl group-containing monomer unit (a2) is 1 to 60 mol% of the total constituent units of the alkali-soluble resin (A2). <1> ~ <3> A photosensitive composition as described in any one of the following. <5> The alkali-soluble resin (A2) has at least one selected from the group consisting of monomer units represented by the following general formula (3) and monomer units represented by the following general formula (4). <1> ~ <4> A photosensitive composition as described in any one of the following. [ka] (In general formula (3), R4 and R5 each independently represent a hydrogen atom or a methyl group.) L3 represents a trivalent hydrocarbon group. L4 represents a divalent hydrocarbon group. In general formula (4), R6 represents a hydrogen atom or a methyl group. R7 and R8 each independently represent an alkyl group having 1 to 10 carbon atoms. L5, L7, and L8 each independently represent a single bond or a divalent organic group. L6 represents a single bond or an oxygen atom. <6> The polymerizable compound (B) includes polymerizable compound (B1) having at least one selected from the group consisting of a hydroxyl group, an acidic group, and an alkylene oxide group. <1> ~ <5> A photosensitive composition as described in any one of the following. <7> <1> ~ <6> A film formed from any one of the photosensitive compositions described in the following. <8> <7> An optical filter having the film described above. <9> <8> A solid-state image sensor having the optical filter described above. <10> <8> An image display device having the optical filter described above. <11> <8> An infrared sensor having the optical filter described above. [Examples]

[0374] 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" refers to "parts by mass" and "%" refers to "percentage by mass". Furthermore, in this invention, non-volatile content or non-volatile content concentration refers to the mass residue after standing in an oven at 110°C for 3 hours.

[0375] Prior to the examples, each measurement method will be described.

[0376] The weight-average molecular weight (Mw), number-average molecular weight (Mn), acid value (mgKOH / g), and amine value (mgKOH / g) of the resin are measured as follows.

[0377] (Molecular weight of resin) The number-average molecular weight (Mn) and weight-average molecular weight (Mw) were measured by gel permeation chromatography (GPC) equipped with an RI detector. An HLC-8220GPC (manufactured by Tosoh Corporation) was used as the instrument, with two separation columns connected in series and two TSK-GEL SUPER HZM-N packing materials connected in series for both columns. The oven temperature was 40°C, tetrahydrofuran (THF) solution was used as the eluent, and measurements were taken at a flow rate of 0.35 ml / min. The sample was dissolved in a solvent consisting of 1% by mass of the above eluent and injected in 20 microliters. Molecular weight is expressed as polystyrene equivalent.

[0378] (Acid value of resin) 0.5 to 1 g of resin solution was mixed with 80 ml of acetone and 10 ml of water and stirred to dissolve uniformly. A 0.1 mol / L aqueous KOH solution was used as the titrant, and the solution was titrated using an automatic titrator ("COM-555," manufactured by Hiranuma Sangyo Co., Ltd.) to measure the acid value (mg KOH / g). The acid value per unit of non-volatile content of the resin was then calculated from the acid value of the resin solution and the concentration of non-volatile content of the resin solution.

[0379] (Amine value of resin) The amine value of the resin is the total amine value (mgKOH / g) measured according to the ASTM D 2074 method, converted to non-volatile content. In this specification, the amine value is calculated assuming that quaternary ammonium bases are also considered as amino groups.

[0380] <Manufacturing of alkali-soluble resin (A)> (Alkali-soluble resin (A1-1) solution) 200 parts of propylene glycol monomethyl ether acetate (PGMAc) were placed in a reaction vessel equipped with a thermometer, condenser, nitrogen gas inlet tube, and stirrer. Nitrogen gas was injected into the reaction vessel while stirring, and the temperature was raised to 120°C. At the same temperature, a mixture of 44.0 parts of dicyclopentanyl methacrylate, 17.8 parts of 4-hydroxyphenyl methacrylate, 50.4 parts of acrylic acid (AA), and the polymerization initiator tert-butyl peroxy-2-ethylhexanoate was added dropwise from a dropping tube over 2.5 hours. After the dropwise addition was complete, the reaction was carried out at 120°C for a further 2 hours with stirring to obtain a copolymer. Then, the reaction vessel was replaced with dry air, and 42.6 parts of glycidyl methacrylate (GMA) and 0.45 parts of the catalyst triphenylphosphine were added and the reaction was carried out at 110°C for 10 hours. This reacted the carboxyl groups derived from AA in the copolymer with the epoxy groups of GMA, generating monomer units (AA+GMA) represented by general formula (2). Subsequently, PGMAc was added to achieve a non-volatile content of 30% by mass to prepare an alkali-soluble resin solution (A1-1) containing phenolic hydroxyl group-containing monomer units (a1) and monomer units represented by general formula (2). The acid value was 110 mgKOH / g, and the weight-average molecular weight was 16,000. Note that the composition ratios in Table 1 are expressed in mol%.

[0381] (Alkali-soluble resin (A1-2)~(A1-7) solution) Alkali-soluble resins (A1-2) to (A1-7) were synthesized by varying the type and amount of monomers and the amount of polymerization initiator to achieve the constituent molar ratios and weight-average molecular weights shown in Table 1, and PGMAc was added to bring the non-volatile content to 30% by mass.

[0382] [Table 1]

[0383] The compound with chemical formula (15) listed in Table 1 is the following compound

[0384] [ka]

[0385] (Alkali-soluble resin (A1-8) solution) 200 parts of PGMAc were placed in a reaction vessel equipped with a thermometer, condenser, nitrogen gas inlet tube, and stirrer. Nitrogen gas was injected into the reaction vessel while stirring, and the temperature was raised to 120°C. At the same temperature, a mixture of 55.0 parts dicyclopentanyl methacrylate, 17.8 parts 4-hydroxyphenyl methacrylate, 92.4 parts glycidyl methacrylate (GMA), and the polymerization initiator tert-butyl peroxy-2-ethylhexanoate was added dropwise from a dropping tube over 2.5 hours. After the dropwise addition was complete, the reaction was carried out at 120°C for a further 2 hours with stirring to obtain a copolymer. Subsequently, the reaction vessel was replaced with dry air, and 46.8 parts of acrylic acid (AA) and 0.45 parts of the catalyst triphenylphosphine were added, and the reaction was carried out at 110°C for 10 hours. This reacted the epoxy groups derived from GMA in the copolymer with the carboxyl groups of AA, generating monomer units (GMA + AA) represented by general formula (2). Next, 30 parts of succinic anhydride (SHA) were added and the mixture was reacted at 110°C for 4 hours. This reacted some of the hydroxyl groups of GMA+AA with SHA to produce monomer units (GMA+AA+SHA) represented by general formula (3). Subsequently, PGMAc was added to achieve a non-volatile content of 30% by mass to prepare an alkali-soluble resin solution (A1-8) containing phenolic hydroxyl group-containing monomer units (a1), monomer units represented by general formula (2), and monomers represented by general formula (3). The acid value was 75 mgKOH / g and the weight-average molecular weight was 14,000.

[0386] (Alkali-soluble resin (A1-9) solution) 200 parts of PGMAc were placed in a reaction vessel equipped with a thermometer, condenser, nitrogen gas inlet tube, and stirrer. Nitrogen gas was injected into the reaction vessel while stirring, and the temperature was raised to 120°C. At the same temperature, a mixture of 55.0 parts dicyclopentanyl methacrylate, 31.3 parts of the compound of chemical formula (15), 92.4 parts glycidyl methacrylate (GMA), and the polymerization initiator tert-butyl peroxy-2-ethylhexanoate was added dropwise from a dropping tube over 2.5 hours. After the dropwise addition was complete, the reaction was carried out at 120°C for a further 2 hours with stirring to obtain a copolymer. Subsequently, the reaction vessel was replaced with dry air, and 46.8 parts of acrylic acid (AA) and 0.45 parts of the catalyst triphenylphosphine were added, and the reaction was carried out at 110°C for 10 hours. This reacted the epoxy groups derived from GMA in the copolymer with the carboxyl groups of AA, generating monomer units (GMA + AA) represented by general formula (2). Next, 45.6 parts of tetrahydrophthalic anhydride (THPA) were added and the mixture was reacted at 110°C for 4 hours. This reacted some of the hydroxyl groups of GMA+AA with THPA to produce monomer units represented by general formula (3) (GMA+AA+THPA). Subsequently, PGMAc was added to achieve a non-volatile content of 30% by mass to prepare an alkali-soluble resin solution (A1-9) containing phenolic hydroxyl group-containing monomer units (a1), monomer units represented by general formula (2), and monomers represented by general formula (3). The acid value was 75 mgKOH / g and the weight-average molecular weight was 14,000.

[0387] (Alkali-soluble resin (A2-1) solution) 200 parts of PGMAc were placed in a reaction vessel equipped with a thermometer, condenser, nitrogen gas inlet tube, and stirrer. Nitrogen gas was injected into the reaction vessel while stirring, and the temperature was raised to 120°C. At the same temperature, 53.5 parts of 2-ethylhexyl acrylate, 99.5 parts of glycidyl methacrylate (GMA), 2.2 parts of dicyclopentanyl methacrylate, a polymerization initiator tert-butyl peroxy-2-ethylhexanoate, and a mixture of PGMAc were added dropwise from a dropping tube over 2.5 hours. After the dropwise addition was complete, the reaction was carried out at 120°C for a further 2 hours with stirring to obtain a copolymer. Then, the reaction vessel was replaced with air, and 50.8 parts of acrylic acid (AA), 0.6 parts of the catalyst triphenylphosphine, and 0.2 parts of methylhydroquinone were added, and the reaction was carried out at 110°C for 10 hours. This reacted the epoxy groups derived from GMA in the copolymer with the carboxyl groups of AA to produce monomer units (GMA+AA) represented by general formula (2). Next, 17.0 parts of succinic anhydride (SHA) were added and the mixture was reacted at 110°C for 4 hours. This reacted some of the hydroxyl groups of GMA+AA with SHA to produce monomer units (GMA+AA+SHA) represented by general formula (3). Subsequently, PGMAc was added to achieve a non-volatile content of 30% by mass to prepare an alkali-soluble resin solution (A2-1) containing hydroxyl group-containing monomer units (a2) and monomer units represented by general formula (3). The acid value was 45 mgKOH / g and the weight-average molecular weight was 15,000.

[0388] (Alkali-soluble resin (A2-2) solution) 200 parts of PGMAc were placed in a reaction vessel equipped with a thermometer, condenser, nitrogen gas inlet tube, and stirrer. Nitrogen gas was injected into the reaction vessel while stirring, and the temperature was raised to 78°C. Next, a mixture of 25.2 parts of the compound of chemical formula (16) below, 31.2 parts of 2-hydroxyethyl methacrylate, 37.5 parts of dicyclopentanyl methacrylate, 20.7 parts of methacrylic acid, and 27.0 parts of methyl methacrylate, along with 2,2'-azobis(2,4-dimethylvaleronitrile), a polymerization initiator, dissolved in 50 parts of PGMAc, was added dropwise to the reaction vessel from a dropping funnel. After the dropwise addition was complete, the reaction was carried out at 78°C for 3 hours with stirring to obtain a copolymer. Subsequently, PGMAc was added to achieve a non-volatile content of 30% by mass to prepare an alkali-soluble resin (A2-2) solution containing hydroxyl group-containing monomer units (a2) and monomer units represented by general formula (4). The acid value was 74 mgKOH / g and the weight-average molecular weight was 8,000.

[0389] [ka]

[0390] (Alkali-soluble resin (A2-3) solution) 200 parts of PGMAc were placed in a reaction vessel equipped with a thermometer, condenser, nitrogen gas inlet tube, and stirrer, and the mixture was stirred while nitrogen gas was injected into the reaction vessel, raising the temperature to 78°C. Next, a mixture of 25.2 parts of the compound of chemical formula (16), 31.2 parts of 2-hydroxyethyl methacrylate, 37.5 parts of dicyclopentanyl methacrylate, 12.1 parts of methacrylic acid, 27.0 parts of methyl methacrylate, and 14.2 parts of glycidyl methacrylate (GMA), along with 2,2'-azobis(2,4-dimethylvaleronitrile), a polymerization initiator, was added to 50 parts of PGMAc and dissolved. These mixtures were then added dropwise to the reaction vessel from a dropping funnel. After the dropwise addition was complete, the reaction was carried out at 78°C for 3 hours with stirring to obtain a copolymer. Subsequently, the reaction vessel was replaced with air, and 7.2 parts of acrylic acid (AA), 0.6 parts of the catalyst triphenylphosphine, and 0.2 parts of methylhydroquinone were added, and the reaction was carried out at 78°C for 10 hours. This reacted the epoxy groups derived from GMA in the copolymer with the carboxyl groups of AA to produce monomer units (GMA+AA) represented by general formula (2). Next, 10.0 parts of succinic anhydride (SHA) were added and the mixture was reacted at 78°C for 4 hours. This reacted some of the hydroxyl groups of GMA+AA with SHA to produce the monomer unit (GMA+AA+SHA) represented by general formula (3). Subsequently, PGMAc was added to achieve a non-volatile content of 30% by mass to prepare an alkali-soluble resin (A2-3) solution containing hydroxyl group-containing monomer units (a2), monomer units represented by general formula (3), and monomer units represented by general formula (4). The acid value was 71 mgKOH / g and the weight-average molecular weight was 8,800.

[0391] (Alkali-soluble resin (A2-4) solution) 200 parts of PGMAc were placed in a reaction vessel equipped with a thermometer, condenser, nitrogen gas inlet tube, and stirrer. Nitrogen gas was injected into the reaction vessel while stirring, and the temperature was raised to 78°C. Next, a mixture of 27.6 parts of the compound of chemical formula (17) below, 31.2 parts of 2-hydroxyethyl methacrylate, 37.5 parts of dicyclopentanyl methacrylate, 20.7 parts of methacrylic acid, and 27.0 parts of methyl methacrylate, along with 2,2'-azobis(2,4-dimethylvaleronitrile), a polymerization initiator, dissolved in 50 parts of PGMAc, was added dropwise to the reaction vessel from a dropping funnel. After the dropwise addition was complete, the reaction was carried out at 78°C for 3 hours with stirring to obtain a copolymer. Subsequently, PGMAc was added to achieve a non-volatile content of 30% by mass to prepare an alkali-soluble resin solution (A2-4) containing hydroxyl group-containing monomer units (a2) and monomer units represented by general formula (4). The acid value was 74 mgKOH / g and the weight-average molecular weight was 8,000.

[0392] [ka]

[0393] (Alkali-soluble resin (A2-5) solution) 200 parts of PGMAc were placed in a reaction vessel equipped with a thermometer, condenser, nitrogen gas inlet tube, and stirrer. Nitrogen gas was injected into the reaction vessel while stirring, and the temperature was raised to 80°C. Next, a mixture of 20.2 parts methacrylic acid, 21.8 parts 2-hydroxyethyl methacrylate, 38.9 parts Aronics M-110 (manufactured by Toagosei Co., Ltd., paracumylphenol ethylene oxide modified acrylate), 35.8 parts n-butyl methacrylate, 39.0 parts benzyl methacrylate, and 2,2'-azobisisobutyronitrile, a polymerization initiator, was added dropwise over 2 hours. After the dropwise addition was complete, the reaction was continued for another 3 hours with stirring to obtain a copolymer. Subsequently, PGMAc was added to achieve a non-volatile content of 30% by mass to prepare an alkali-soluble resin (A2-5) solution containing hydroxyl group monomer units (a2). The acid value was 81 mgKOH / g and the weight-average molecular weight was 28,000.

[0394] (Alkali-soluble resin (A3-1) solution) 200 parts of PGMAc were placed in a reaction vessel equipped with a thermometer, condenser, nitrogen gas inlet tube, and stirrer. Nitrogen gas was injected into the reaction vessel while stirring, and the temperature was raised to 120°C. Next, a mixture of 109.3 parts benzyl methacrylate, 24.1 parts methacrylic acid, 22.0 parts dicyclopentanyl methacrylate, azobisisobutyronitrile (a polymerization initiator), and PGMAc was added dropwise from a dropping funnel to the reaction vessel over 2.5 hours. After the addition was complete, the reaction was carried out at 120°C for a further 2 hours with stirring to obtain the copolymer. Subsequently, PGMAc was added to achieve a non-volatile content of 30% by mass to prepare an alkali-soluble resin (A3-1) solution. The acid value was 98 mgKOH / g, and the weight-average molecular weight was 17,500.

[0395] In the production of alkali-soluble resin (A), the amount of polymerization initiator added was appropriately adjusted to match the weight-average molecular weight of each resin.

[0396] <Production of polymerizable compound (B)> (Polymerizable compound (B1-4)) A five-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping tube was charged with 400 parts dipentaerythritol pentaacrylate, 100 parts PGMAc, and 0.5 parts N,N-dimethylbenzylamine. The temperature was raised to 70°C, and a mixture of 66 parts toluene diisocyanate and 66 parts PGMAc was added dropwise from the dropping tube over 2 hours. After addition, the mixture was reacted at a temperature of 50-70°C for 8 hours, and the reaction was measured at 2,180 cm³ by infrared radiation. -1 The disappearance of the absorption of the isocyanate was confirmed. Next, 35 parts of mercaptoacetic acid and 0.6 parts of 4-methoxyphenol were charged, and the reaction was carried out with stirring at a temperature of 50-60°C for 6 hours, after which the reaction was terminated. The non-volatile content was adjusted to 50% by mass, and a polyfunctional acrylate having acidic groups and urethane bonds was obtained.

[0397] (Polymerizable compound (B2-2)) A flask equipped with a stirrer, dropping funnel, condenser, thermometer, and air inlet tube contained 634.7 parts trimethylolpropane triacrylate, 2.0 parts 4-methoxyphenol, 2.0 parts triphenyl phosphite, and 2.0 parts phenothiazine. The mixture was then heated to 50°C while stirring. Next, 160.8 parts N-methylethanolamine was gradually added dropwise into the flask from the dropping funnel. After the addition was complete, the mixture was stirred at 50°C for 2 hours. Next, the temperature was raised to 100°C, and 198.3 parts of isophorone diisocyanate were gradually added dropwise into the flask from a dropping funnel. After the addition was complete, the reaction was carried out at 100°C for 4 hours with stirring, and then terminated. This yielded a polyfunctional acrylate having an amine structure and a urethane bond.

[0398] (Polymerizable compound (B2-3)) A flask equipped with a stirrer, dropping funnel, condenser, thermometer, and air inlet tube contained 998.4 parts ditrimethylolpropanetetraacrylate, 2.0 parts 4-methoxyphenol, 2.0 parts triphenyl phosphite, and 2.0 parts phenothiazine. The mixture was then heated to 50°C while stirring. Next, 160.8 parts N-methylethanolamine was gradually added dropwise into the flask from the dropping funnel. After the addition was complete, the mixture was stirred at 50°C for 2 hours. Next, the temperature was raised to 100°C, and 198.3 parts of isophorone diisocyanate were gradually added dropwise into the flask from a dropping funnel. After the addition was complete, the reaction was carried out at 100°C for 4 hours with stirring, and then terminated. This yielded a polyfunctional acrylate having an amine structure and a urethane bond.

[0399] (Polymerizable compound (B2-4)) A flask equipped with a stirrer, dropping funnel, condenser, thermometer, and air inlet tube contained 754.0 parts pentaerythritol tetraacrylate, 2.0 parts 4-methoxyphenol, 2.0 parts triphenyl phosphite, and 2.0 parts phenothiazine. The mixture was then heated to 50°C while stirring. Next, 160.8 parts N-methylethanolamine was gradually added dropwise into the flask from the dropping funnel. After the addition was complete, the mixture was stirred at 50°C for 2 hours. Next, the temperature was raised to 100°C, and 149.7 parts of hexamethylene diisocyanate were gradually added dropwise into the flask from a dropping funnel. After the addition was complete, the reaction was carried out at 100°C for 4 hours with stirring, and then terminated. This yielded a polyfunctional acrylate having an amine structure and a urethane bond.

[0400] (Polymerizable compound (B2-6)) 250 parts of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate were added to a four-necked flask equipped with a thermometer, stirrer, and reflux tubing. Then, 17.3 parts of di-n-butylamine were added at room temperature, and the reaction was carried out at 50°C for 4 hours with stirring, after which the reaction was terminated. This yielded a polyfunctional acrylate having an amine structure. The reaction was carried out under a mixed atmosphere of air / nitrogen.

[0401] (Polymerizable compound (B2-7)) In a five-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping tube, 400 parts of dipentaerythritol pentaacrylate, 100 parts of PGMAc, and 0.5 parts of N,N-dimethylbenzylamine were charged. The temperature was raised to 70°C, and a mixture of 64 parts of hexamethylene diisocyanate and 64 parts of PGMAc was added dropwise from the dropping tube over 2 hours. After addition, the mixture was allowed to react with stirring at a temperature of 50-70°C for 8 hours, and the reaction was measured at 2,180 cm³ by infrared radiation. -1 The reaction was terminated after confirming the disappearance of the isocyanate absorption. PGMAc was added to achieve a non-volatile content of 50% by mass to obtain a polyfunctional acrylate having urethane bonds.

[0402] <Manufacturing of near-infrared absorbing compounds (E)> (Near-infrared absorbing compound (E-1)) 400 parts toluene, 40.0 parts 1,8-diaminonaphthalene, 32.2 parts 3,5-dimethylcyclohexanone, and 0.087 parts p-toluenesulfonic acid monohydrate were mixed and heated and stirred under a nitrogen atmosphere, reacting under reflux for 3 hours. The water produced during the reaction was removed from the reaction system by azeotropic distillation. After the reaction was complete, the toluene was distilled to obtain a dark brown solid, which was extracted with acetone and purified by recrystallization in a mixed solvent of acetone and ethanol. The obtained brown solid was dissolved in a mixed solvent of 240 parts toluene and 160 parts n-butanol, and 13.8 parts 3,4-dihydroxy-3-cyclobutene-1,2-dione were added. The mixture was heated and stirred under a nitrogen atmosphere, reacting under reflux for 8 hours. The water produced during the reaction was removed from the reaction system by azeotropic distillation. After the reaction was complete, the solvent was distilled, and 200 parts of hexane were added to the resulting reaction mixture while stirring. The resulting dark brown precipitate was filtered off, and then washed sequentially with hexane, ethanol, and acetone. The mixture was dried under reduced pressure to obtain the near-infrared absorbing compound (E-1) represented by the following chemical formula (18). 50 parts of the obtained near-infrared absorbing compound (E-1), 500 parts of sodium chloride, and 60 parts of diethylene glycol were charged into a stainless steel gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60°C for 12 hours. Next, the kneaded mixture was added to warm water and stirred for 1 hour while heating to approximately 80°C to form a slurry. After repeated filtration and washing with deionized water, the mixture was dried overnight at 80°C and then pulverized to finely grind the mixture.

[0403] [ka]

[0404] <Manufacturing of Dispersed Resin (G)> (Dispersion resin (G1-1) solution) In a reactor equipped with a gas inlet pipe, condenser, stirring blades, and thermometer, 40.0 parts of methyl methacrylate, 10.0 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine as a catalyst were charged. The mixture was stirred at 50°C for 1 hour while flowing nitrogen, and the reactor was then purged with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate as a polymerization initiator, 5.6 parts of cuprous chloride as a catalyst, and 100 parts of PGMAc were charged. The mixture was heated to 110°C under a nitrogen stream to start polymerization of the first block (block B). After 4 hours of polymerization, the polymerization solution was sampled and its non-volatile content was measured. Based on the non-volatile content, it was confirmed that the polymerization conversion rate was 98% or higher. Next, 50 parts of PGMAc, 40.0 parts of dimethylaminoethyl methacrylate as the second block (Block A) monomer, and 10.0 parts of methacryloyloxyethyl benzyldimethylammonium chloride were added to the reaction apparatus. The reaction was continued with stirring while maintaining a temperature of 110°C and a nitrogen atmosphere. Two hours after the addition of the compounds, the polymerization solution was sampled and the non-volatile content was measured. Based on the non-volatile content, it was confirmed that the polymerization conversion rate of the second block (Block A) was 98% or higher. After cooling, PGMAc was added to the non-volatile content to 30% by mass to prepare a dispersed resin (G1-1) solution with a block structure having monomer units represented by general formulas (8) and (9). The amine value was 169.8 mg KOH / g.

[0405] (Dispersed resin (G1-2) solution) In a reactor equipped with a gas inlet tube, condenser, stirring blade, and thermometer, 250 parts of tetrahydrofuran and 5.8 parts of the polymerization initiator dimethylketene methyltrimethylsilyl acetal were added, and the reactor was purged with nitrogen. 0.5 parts of a 1 mol / L acetonitrile solution of the catalyst tetrabutylammonium m-chlorobenzoate was injected using a syringe, and 19.7 parts of 2-hydroxyethyl methacrylate, 7.5 parts of 2-ethylhexyl methacrylate, 12.9 parts of n-butyl methacrylate, 10.7 parts of benzyl methacrylate, and 30.9 parts of methyl methacrylate were added dropwise over 60 minutes using a dropping funnel to carry out the reaction. During the reaction, the temperature was kept below 40°C by cooling the reaction vessel in an ice bath. After 1 hour, 18.3 parts of dimethylaminopropyl methacrylamide were added dropwise over 20 minutes. After reacting for 1 hour, 1.0 part of methanol was added to stop the reaction. The resulting copolymer was reprecipitated in hexane and purified by filtration and vacuum drying. Next, 15.0 parts of the obtained copolymer was dissolved in 35 parts of PGMAc in a 100 mL round-bottom flask, and 1.1 parts of phenylphosphinic acid (0.5 molar equivalent relative to dimethylaminopropyl methacrylamide), which is the salt-forming component, was added. The reaction was carried out at a reaction temperature of 30°C for 20 hours with stirring, and then terminated. Subsequently, PGMAc was added to the mixture until the non-volatile content was 30%, and a dispersion resin (G1-2) solution with a block structure having monomer units represented by general formulas (8) and (9) was prepared.

[0406] (Dispersion resin (G1-3) solution) In a reactor equipped with a gas inlet pipe, condenser, stirring blades, and thermometer, 30.0 parts methyl methacrylate, 30.0 parts n-butyl methacrylate, 20.0 parts hydroxyethyl methacrylate, and 13.2 parts tetramethylethylenediamine were charged. The mixture was stirred at 50°C for 1 hour while flowing nitrogen, and the reactor was then purged with nitrogen. Next, 9.3 parts ethyl bromoisobutyrate, 5.6 parts cuprous chloride, and 133 parts PGMAc were charged, and the temperature was raised to 110°C under a nitrogen stream to begin polymerization of the first block (block B). After 4 hours of polymerization, the polymerization solution was sampled and the non-volatile content was measured. Based on the non-volatile content, a polymerization conversion rate of 98% or higher was confirmed. Next, 61 parts of PGMAc and 20.0 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate (manufactured by Hitachi Chemical Co., Ltd., Funcryl FA-711MM) were added to the reaction apparatus as the monomer for the second block (block A). The reaction was continued by stirring while maintaining a temperature of 110°C and a nitrogen atmosphere. Two hours after the addition of 1,2,2,6,6-pentamethylpiperidyl methacrylate, the polymerization solution was sampled and the non-volatile content was measured. Based on the non-volatile content, it was confirmed that the polymerization conversion rate of the second block (block A) was 98% or higher, and the reaction solution was cooled to room temperature to stop the polymerization. Subsequently, PGMAc was added to bring the non-volatile content to 30%, and a dispersion resin (G1-3) solution with a block structure having monomer units represented by general formula (10) was prepared. The amine value was 57 mgKOH / g.

[0407] (Dispersed resin (G2-1) solution) In a reaction vessel equipped with a thermometer, reflux condenser, nitrogen gas inlet tube, and stirrer, 108 parts of 1-thioglycerol, 174 parts of pyromellitic dianhydride, 650 parts of PGMAc, and 0.2 parts of monobutyltin(IV) oxide as a catalyst were charged. After purging with nitrogen gas, the mixture was reacted at 120°C for 5 hours (first step). Acid value measurement confirmed that more than 95% of the acid anhydride had undergone half-esterification. Next, 160 parts of the compound obtained in the first step (based on non-volatile content), 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of tert-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, 200 parts of methyl acrylate, 50 parts of methacrylic acid, and 663 parts of PGMAc were charged. The reaction vessel was heated to 80°C, and 2,2'-azobis(2,4-dimethylvaleronitrile), a polymerization initiator, was added and the mixture was reacted for 12 hours (second step). Non-volatile content measurement confirmed that more than 95% had reacted. Finally, 500 parts of a 50% PGMAc solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate (MOI), and 0.1 parts of hydroquinone were charged, and IR measurement showed a reading of 2,270 cm based on the isocyanate group. -1The reaction was carried out until the peak disappeared (third step). After cooling, PGMAc was added to a dispersion resin (G2-1) solution so that the non-volatile content was 30% by mass. The acid value was 68 mgKOH / g and the weight-average molecular weight was 13,000.

[0408] <Manufacturing of silane coupling agent (K)> (Silane coupling agent (K1-1)) 116 parts of hydroxyethyl acrylate were placed in a 1 L separable flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, and heated to 80°C. 205 parts of 3-isocyanatepropyltrimethoxysilane were added dropwise, and the mixture was heated and stirred at 80°C for 4 hours. Subsequently, IR measurement confirmed that the absorption peak derived from the isocyanate group of the starting material had completely disappeared, and instead, an absorption peak derived from the urethane bond had been generated, yielding a silane coupling agent (K1-1) whose main component is represented by the following chemical formula (19). As a minor component, the mixture contains condensates of chemical formula (19), specifically 2-10 commensals (compounds where n in general formula (11) is 2-10).

[0409] [ka]

[0410] (Silane coupling agent (K1-2)) 524 parts of dipentaerythritol pentaacrylate were charged into a 1 L separable flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, and heated to 80°C. 205 parts of 3-isocyanate propyltrimethoxysilane were added dropwise, and the mixture was heated and stirred at 80°C for 4 hours. Subsequently, IR measurement confirmed that the absorption peak derived from the isocyanate group of the starting material had completely disappeared, and instead, an absorption peak derived from the urethane bond had been generated, yielding a silane coupling agent (K1-2) whose main component is represented by the following chemical formula (20). As a minor component, the mixture contains 2-10 condensates of chemical formula (20) (compounds where n in general formula (11) is 2-10).

[0411] [ka]

[0412] <Manufacturing of leveling agent (N)> (Leveling agent (N1-1)) In a nitrogen-purged reaction vessel, 67.6 parts of the compound represented by chemical formula (20) and 200 parts of methyl ethyl ketone were charged, and the mixture was heated to 50°C while stirring under a nitrogen stream. Next, 4.2 parts of 2,2'-bipyridyl and 1.5 parts of cuprous chloride were charged, and the mixture was stirred at 50°C for 30 minutes. Subsequently, 2.7 parts of ethyl 2-bromoisobutyrate were added, and the mixture was reacted under a nitrogen stream at 50°C for 3 hours to synthesize the A block portion, which is a polymer of the compound represented by chemical formula (21). Next, 32.4 parts of 1-adamantyl methacrylate were added to the reaction system containing block A, which is a polymer of the compound represented by chemical formula (21), and the reaction was carried out at 50°C for 18 hours to synthesize block B, which is a polymer of 1-adamantyl methacrylate. Then, 30 parts of activated alumina were added and the mixture was stirred. After filtration, the mixture was distilled under reduced pressure to obtain a leveling agent (N1-1) having monomer units represented by general formula (12) and monomer units represented by general formula (13) in a block structure. Subsequently, PGMAc was added so that the non-volatile content was 1% by mass.

[0413] [ka]

[0414] (Leveling agent (N1-2)) In a nitrogen-purged reaction vessel, 15.0 parts of 3-methacryloyloxypropyltris(trimethylsiloxy)silane and 79.0 parts of methyl ethyl ketone were charged, and the mixture was heated to 50°C while stirring under a nitrogen stream. Next, 4.2 parts of 2,2'-bipyridyl and 1.5 parts of cuprous chloride were charged, and the mixture was stirred at 50°C for 30 minutes. Subsequently, 2.7 parts of ethyl 2-bromoisobutyrate were added, and the mixture was reacted under a nitrogen stream at 50°C for 3 hours to synthesize the A block portion, which is a polymer of 3-methacryloyloxypropyltris(trimethylsiloxy)silane. Next, 35.0 parts of poly-1,2-butylene glycol monomethacrylate (average number of repeats of 1,2-butylene glycol: 6) were added to the reaction system containing block A, which is a polymer of 3-methacryloyloxypropyltris(trimethylsiloxy)silane, and the reaction was carried out at 50°C for 18 hours to synthesize block B, which is a polymer of poly-1,2-butylene glycol monomethacrylate (average number of repeats of 1,2-butylene glycol: 6). Subsequently, 30 parts of activated alumina were added and the mixture was stirred. After filtration, vacuum distillation was performed to obtain a leveling agent (N1-2) having monomer units represented by general formula (12) and monomer units represented by general formula (14) of the block structure. Then, PGMAc was added so that the non-volatile content was 1% by mass.

[0415] <Dispersion manufacturing> (Dispersion 1) After uniformly stirring and mixing the following raw materials, the mixture was dispersed for 3 hours using an Eiger mill (Eiger Japan's "Mini Model M-250 MKII") with a 0.5 mm diameter zirconia bead, and then filtered through a 1.0 μm pore size filter to prepare dispersion 1. The non-volatile content was 21.0% by mass. Coloring agent (D-1): 15.0 parts Dispersed resin (G1-1) solution: 20.0 parts Organic solvent (P-1): 65.0 parts

[0416] (Dispersion 2~12) Dispersions 2-12 were prepared in the same manner as dispersion 1, except that the components and quantities listed in Table 2 were changed.

[0417] [Table 2]

[0418] The symbols in the table are as follows: [Coloring agent (D)] D-1: CI Pigment Green 58 D-2: CI Pigment Green 59 D-3: CI Pigment Green 63 D-4: CI Pigment Yellow 138 D-5: CI Pigment Yellow 139 D-6: CI Pigment Yellow 150 D-7: CI Pigment Red 254 D-8: CI Pigment Red 177 D-9: CI Pigment Blue 15:6 D-10: CI Pigment Violet 23 D-11: Compound with the following chemical formula (22)

[0419] [ka]

[0420] The colorants (D-1) to (D-10) were all micronized by salt milling, thoroughly washed with deionized water to ensure the photosensitive composition contained the specified amount of metal as described above, and then dried before use.

[0421] [Dye derivative (F)] [ka]

[0422] [Organic solvent (P)] P-1: Propylene glycol monomethyl ether acetate

[0423] <Manufacturing of photosensitive compositions> [Example 1] (Photosensitive composition 1) The following raw materials were mixed and stirred, and filtered through a 1.0 μm pore size filter to prepare photosensitive composition 1. The non-volatile content was 17.0% by mass. Dispersion 1: 23.0 parts Dispersion 4: 12.0 parts Dispersion 9: 1.0 part Alkali-soluble resin (A1-1) solution: 5.0 parts Alkali-soluble resin (A2-3) solution: 5.0 parts Polymerizable compound (B1-1): 2.0 parts Polymerizable compound (B1-3): 1.0 part Polymerizable compound (B2-1): 1.0 part Polymerization initiator (C1-1): 0.5 parts Polymerization initiator (C2-1): 0.2 parts Thermal crosslinkable compound (I-1): 0.7 part Thermal crosslinkable compound (I-2): 1.2 parts Silane coupling agent (K1-1): 0.2 parts Leveling agent (N1-1): 1.0 part Leveling agent (N1-2): 1.0 part Organic solvent (P): 45.2 parts

[0424] [Examples 2-64, and Comparative Examples 1 and 2] (Photosensitive composition 2-66) Photosensitive compositions 2 to 66 were prepared in the same manner as in Example 1, except that the raw materials and quantities of photosensitive composition 1 in Example 1 were changed to those listed in Tables 3-1 to 3-7.

[0425] [Table 3-1]

[0426] [Table 3-2]

[0427] [Table 3-3]

[0428] [Table 3-4]

[0429] [Table 3-5]

[0430] [Table 3-6]

[0431] [Table 3-7]

[0432] The ingredients listed in Tables 3-1 to 3-7 are as follows:

[0433] [Polymerizable compound (B)] (Polymerizable compound (B1)) B1-1: Aronics M-306 (manufactured by Toagosei Co., Ltd., a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, containing 65-70% pentaerythritol triacrylate) B1-2: Aronics M-403 (manufactured by Toagosei Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, containing 50-60% dipentaerythritol pentaacrylate) B1-3: Arronix M-510 (manufactured by Toagosei Co., Ltd., a trifunctional acrylate with acidic groups) B1-5: Arronix M-350 (manufactured by Toagosei Co., Ltd., trimethylolpropaneethylene oxide modified triacrylate) B1-6: KAYARAD DPEA-12 (manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol ethylene oxide modified hexaacrylate)

[0434] (Polymerizable compound (B2)) B2-1: CN9906NS (Arkema, a polyfunctional acrylate with amine structure and urethane linkage) B2-5: Arronix MT-3041 (manufactured by Toagosei Co., Ltd., a polyfunctional acrylate with an amine structure) B2-7: Arronix M-309 (manufactured by Toagosei Co., Ltd., trimethylolpropane triacrylate)

[0435] [Polymerization initiator (C)] (Polymerization initiator (C1)) C1-1: Compound (C1-1) as described above C1-2: Compounds of the above (C1-2) C1-3: Compounds of the above (C1-3) C1-4: Compounds of the above (C1-4) C1-5: Compounds of the above (C1-5)

[0436] (Polymerization initiator (C2)) C2-1: ADEKA Arcules NCI-831E (a compound containing one oxime ester group, manufactured by ADEKA Corporation) C2-2: Compound with the following chemical formula (23) C2-3: TRONLY TR-PBG-3057 (manufactured by Changzhou Strong New Materials Co., Ltd., a compound containing one oxime ester group) C2-4: Compounds with the following chemical formula (24)

[0437] [ka]

[0438] [Thermal crosslinkable compound (I)] I-1: EHPE-3150 (manufactured by Daicel Corporation, a compound containing an epoxy group) I-2: Duranate MF-K60B (manufactured by Asahi Kasei Corporation, a compound having a blocked isocyanate group, non-volatile content 60% by mass) I-3:BI7982 (manufactured by Baxenden Chemical, a compound containing a blocked isocyanate group, 70% by mass of nonvolatile content) I-4:BI7984 (manufactured by Baxenden Chemical, a compound containing a blocked isocyanate group, 75% by mass of nonvolatile content) I-5:BI7951 (manufactured by Baxenden Chemical, a compound containing a blocked isocyanate group, 75% by mass of nonvolatile content)

[0439] [Silane coupling agent (K)] (Silane coupling agent (K2)) K2-1: KBE-503 (manufactured by Shin-Etsu Chemical Co., Ltd., 3-methacryloxypropyltriethoxysilane)

[0440] [Leveling agent (N)] (Leveling agent (N2)) N2-1: 1% PGMac solution of BYK-333 (Vic Chemie, polyether-modified dimethylsiloxane)

[0441] [Organic solvent (P)] P-1:PGMAc P-2: Propylene glycol monomethyl ether P-3:3-Methoxy-1-Butanol P-4:3-Ethyl ethoxypropionate The above mixture of P-1, P-2, P-3, and P-4 in a mass ratio of 80:10:5:5 was used as the organic solvent (P).

[0442] <Evaluation of photosensitive compositions> The following evaluations were performed on the obtained photosensitive compositions 1 to 66. The evaluation results are shown in Table 4.

[0443] [Evaluation of developability] The obtained photosensitive composition was coated onto a 100 mm x 100 mm, 0.7 mm thick glass substrate (Corning Eagle 2000) using a spin coater to a dry film thickness of 2.0 μm, and then dried on a hot plate at 90°C for 2 minutes. After the substrate cooled to room temperature, it was illuminated with an ultra-high pressure mercury lamp at an illuminance of 30 mW / cm² through a photomask with a 100 μm wide stripe pattern. 2 , 100 mJ / cm 2 The substrate was exposed to light. After cooling the substrate to room temperature, it was spray-developed using an aqueous developer containing 0.12% by mass of a nonionic surfactant and 0.04% by mass of potassium hydroxide at 23°C, washed with deionized water, and air-dried. The substrate was observed under an optical microscope to check for the presence or absence of residue in unexposed areas. The evaluation criteria are as follows, with a score of 3 or higher considered practical. 5: No residue was found in the unexposed areas during development for the shortest possible time required to form a pattern. 4: With development 5 seconds longer than the shortest time required for pattern formation, there was no residue in the unexposed areas. 3: With development 10 seconds longer than the shortest time required for pattern formation, there was no residue in the unexposed areas. 2: With development 15 seconds longer than the shortest time required for pattern formation, there was no residue in the unexposed areas. 1: Even with development 20 seconds longer than the shortest time required for pattern formation, residue remained in the unexposed areas.

[0444] [Evaluation of low-temperature heat resistance] The obtained photosensitive composition was coated onto a 100 mm x 100 mm, 0.7 mm thick glass substrate (Corning Eagle 2000) using a spin coater to achieve a dry film thickness of 2.0 μm, and then dried on a hot plate at 90°C for 2 minutes. After the substrate cooled to room temperature, it was illuminated with an ultra-high pressure mercury lamp at an illuminance of 30 mW / cm² through a photomask with a 100 μm wide stripe pattern. 2 , 100 mJ / cm 2 The substrate was exposed to light. After cooling the substrate to room temperature, it was spray-developed using an aqueous developer containing 0.12% by mass of a nonionic surfactant and 0.04% by mass of potassium hydroxide at 23°C, washed with deionized water, and air-dried. The resulting substrate was heated in a clean oven at 90°C for 30 minutes to obtain an evaluation substrate. The obtained evaluation substrates were immersed in PGMAc at 25°C for 15 minutes, washed with deionized water, air-dried, and observed using an optical microscope on the 100 μm wide stripe pattern area. The evaluation criteria are as follows, with a score of 3 or higher considered practical. 5: There is no change in appearance or color. 4: Slight wrinkles may appear, but there is no change in color. 3: Some wrinkles may appear, but there is no change in color. 2: Wrinkles and other marks may appear throughout, and the color may fade slightly. 1: Peeling and fading may occur.

[0445] [High-temperature heat resistance evaluation] The obtained photosensitive composition was coated onto a 100 mm x 100 mm, 0.7 mm thick glass substrate (Corning Eagle 2000) using a spin coater to a dry film thickness of 0.6 μm, and then dried on a hot plate at 90°C for 2 minutes. After the substrate cooled to room temperature, it was illuminated using an ultra-high pressure mercury lamp at an illuminance of 30 mW / cm². 2 , 100 mJ / cm 2 The film was exposed to light and heated in a clean oven at 90°C for 30 minutes. Next, an inorganic film was formed on the surface of the obtained film by sputtering SiO2 to a thickness of 200 nm. The film with this inorganic film formed on its surface was heated in a nitrogen atmosphere at 300°C for 3 hours. The surface of the inorganic film after heating was observed with an optical microscope and measured at 1 cm 2 The number of cracks found was counted. The evaluation criteria are as follows, with a score of 3 or higher considered usable. 5:1cm 2 The number of cracks found is 5 or less. 4:1cm 2 The number of cracks you find must be between 5 and 20. 3:1cm 2 The number of cracks found is between 21 and 50. 2:1cm 2 The number of cracks found is between 51 and 100. 1:1cm 2 The number of successful cracks is 101 or more.

[0446] [Table 4] [Explanation of symbols]

[0447] 100 Infrared Sensors 110 Solid-state image sensor 111 Infrared Cut Filter 112 Color Filters 113 Infrared transmission filter 114 Resin film 115 Microlenses 116 Flat membrane

Claims

1. A photosensitive composition comprising an alkali-soluble resin (A), a polymerizable compound (B), and a polymerization initiator (C), A photosensitive composition wherein the alkali-soluble resin (A) comprises an alkali-soluble resin (A1) having a phenolic hydroxyl group-containing monomer unit (a1), and an alkali-soluble resin (A2) having a hydroxyl group-containing monomer unit (a2) other than the phenolic hydroxyl group-containing monomer unit (a1) (excluding the alkali-soluble resin (A1)).

2. The photosensitive composition according to claim 1, wherein the content of the alkali-soluble resin (A1) is 10 to 90% by mass of 100% by mass of the alkali-soluble resin (A).

3. The photosensitive composition according to claim 1, wherein the content of the phenolic hydroxyl group-containing monomer unit (a1) is 1 to 50 mol% of the total constituent units of the alkali-soluble resin (A1).

4. The photosensitive composition according to claim 1, wherein the content of the hydroxyl group-containing monomer unit (a2) is 1 to 60 mol% of the total constituent units of the alkali-soluble resin (A2).

5. The photosensitive composition according to claim 1, wherein the alkali-soluble resin (A2) has at least one selected from the group consisting of monomer units represented by the following general formula (3) and monomer units represented by the following general formula (4). 【Chemistry 1】 (In general formula (3), R ４ , and R ５ Each of these independently represents either a hydrogen atom or a methyl group. L ３ This represents a trivalent hydrocarbon group. L ４ This represents a divalent hydrocarbon group. In general formula (4), R ６ represents a hydrogen atom or a methyl group. R ７ , and R ８ Each of these independently represents an alkyl group having 1 to 10 carbon atoms. L ５ , L ７ , and L ８ each independently represents a single bond or a divalent organic group. L ６ (This represents a single bond or an oxygen atom.)

6. The photosensitive composition according to claim 1, wherein the polymerizable compound (B) comprises a polymerizable compound (B1) having at least one selected from the group consisting of a hydroxyl group, an acidic group, and an alkylene oxide group.

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

8. An optical filter having the film described in claim 7.

9. A solid-state image sensor having the optical filter described in claim 8.

10. An image display device having the optical filter described in claim 8.

11. An infrared sensor having the optical filter described in claim 8.

Images