Photosensitive composition, cured film using the same, optical filter, image display device, and solid-state imaging device

Abstract

To provide a photosensitive composition which is excellent in pattern formability and can form a cured film having excellent solvent resistance even when cured at a low temperature.SOLUTION: The photosensitive composition contains a resin (A), a polymerizable compound (B), a photopolymerization initiator (C), and an organic solvent (D). The polymerizable compound (B) contains a polymerizable compound (B1) having three or more (meth)acryloyl groups and an amine structure. The resin (A) contains a resin (A1) having a blocked isocyanate group-containing monomer unit (a1) using an active methylene compound as a blocking agent and an acidic group-containing monomer unit (a2).SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] A color filter, which is a type of optical filter, is used in image display devices, solid-state imaging devices, and the like. The manufacturing of a color filter involves the steps of applying a photosensitive composition onto a glass substrate and removing the solvent from this coating film by drying; irradiating and curing (hereinafter referred to as exposure) this coating film with radiation through a photomask having a desired pattern shape; then, washing and removing (hereinafter referred to as development) the unexposed portion of this coating film; and thereafter, performing a heat treatment (hereinafter referred to as post-bake) to sufficiently cure the cured film to obtain a pattern of the first color. Then, by performing the same operations, patterns of other colors are formed, and the color filter is completed.

[0003] Post-bake is usually performed at a temperature of 200 to 250°C for about 10 to 60 minutes to promote curing and enhance the resistance of the cured film. In recent years, the replacement of conventional glass substrates with flexible plastic substrates and the formation of color filters on organic semiconductor devices such as organic electroluminescence display elements (organic EL) have been studied. However, such members have low heat resistance, so it is required to form color filters at low temperatures. However, when post-bake is performed at a low temperature, the curing of the film becomes insufficient, and there is a problem that the solvent resistance of the cured film deteriorates.

[0004] Also, in the development process, if the adhesion of the film is insufficient, there is a problem that the pattern shape defects occur due to chipping or peeling of the exposed portion.

[0005] Regarding compositions that can be used for plastic substrates, organic ELs, etc., Patent Document 1 discloses a colored composition containing a polymerizable compound having an alkylene oxide structure. Further, Patent Document 2 discloses a colored resin composition containing C.I. Pigment Violet 19, a red pigment, a yellow pigment, a resin, a polymerizable compound, and a polymerization initiator. Also, Patent Document 3 discloses a colored composition containing a colorant, a polymer, and a polymerizable compound, wherein at least one selected from the group consisting of the colorant, the polymer, and the polymerizable compound has a specific partial structure and a hydroxyl group.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0007] However, the compositions described in Patent Documents 1 to 3 could not satisfy the pattern formability and the solvent resistance of the cured film in low-temperature heat treatment at a certain level or higher.

[0008] An object of the present invention is to provide a photosensitive composition capable of forming a cured film having excellent pattern formability and excellent solvent resistance even in low-temperature curing.

Means for Solving the Problems

[0009] The present invention is a photosensitive composition containing a resin (A), a polymerizable compound (B), a photopolymerization initiator (C), and an organic solvent (D), wherein the polymerizable compound (B) includes a polymerizable compound (B1) having three or more (meth)acryloyl groups and an amine structure, The photosensitive composition relates to a resin (A) containing a resin (A1) having a blocked isocyanate group-containing monomer unit (a1) and an acidic group-containing monomer unit (a2) using an active methylene compound as a blocking agent.

Advantages of the Invention

[0010] According to the present invention described above, it is possible to provide a photosensitive composition capable of forming a cured film that is excellent in pattern formability and has excellent solvent resistance even at low-temperature curing. Further, the present invention can provide a cured film, an optical filter, an image display device, and a solid-state imaging device.

Embodiments for Carrying Out the Invention

[0011] Hereinafter, embodiments for carrying out the photosensitive composition of the present invention will be described in detail. Note that the present invention is not limited to the following embodiments and can be implemented with modifications within the range capable of solving the problems.

[0012] In this specification, “(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, unless otherwise specified. Also, “C.I.” means Color Index (C.I.; published by The Society of Dyers and Colourists). The polymerizable unsaturated group is an ethylenically unsaturated double bond. Regarding the molecular weight of the compounds in the present invention, for low-molecular compounds whose molecular weight can be specified, it is the value calculated by calculation (formula weight) or the molecular weight measured by ESI-MS (electrospray ionization mass spectrometry), and for compounds having a molecular weight distribution, it is the polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography using tetrahydrofuran as a solvent. A monomer is a compound that forms a resin by polymerization. The monomer is in an unreacted state, and the monomer unit is the state in which the monomer forms a resin after polymerization.

[0013] <Photosensitive composition> A photosensitive composition according to an embodiment of the present invention is a photosensitive composition containing a resin (A), a polymerizable compound (B), a photopolymerization initiator (C), and an organic solvent (D), wherein the polymerizable compound (B) includes a polymerizable compound (B1) having three or more (meth)acryloyl groups and an amine structure. Also, the photosensitive composition of the present invention is preferably used for forming a cured film obtained by exposure and post-baking at a temperature of 130 °C or lower.

[0014] The mechanism by which the problems of the present invention can be solved with the photosensitive composition having the above configuration is not clear, but it is presumed as follows.

[0015] In the photosensitive composition, the photopolymerization initiator decomposes by light to generate active species. These active species add to the polymerizable compound to newly generate active species, which proceed chainwise to polymerize. However, if these active species are inactivated by external factors, the polymerization reaction stops. When the active species are radicals, oxygen inhibits the polymerization (also referred to as oxygen inhibition). Since oxygen is in the triplet state in the ground state, it has high reactivity with radicals and easily reacts with radical active species to form hydroxyperoxy radicals. These hydroxyperoxy radicals have poor reactivity with the polymerizable compound, so the progress of the polymerization reaction is inhibited. Normally, an optical filter such as a color filter is manufactured in an air atmosphere, so it is subject to polymerization inhibition by oxygen in the exposure process and the polymerization does not proceed sufficiently, but the polymerization is promoted by heat treatment at a high temperature thereafter. However, in the case of heat treatment at a low temperature, it is necessary to sufficiently proceed the polymerization in the exposure process in order to obtain sufficient resistance. Since the polymerizable compound (B1) having three or more (meth)acryloyl groups and an amine structure has a nitrogen atom in the molecule, hydrogen is easily abstracted to generate a carbon radical. Therefore, the generated hydroxyperoxy radical abstracts hydrogen from the polymerizable compound (B1) having three or more (meth)acryloyl groups and an amine structure, and the newly generated carbon radical initiates polymerization. In addition, since the generated carbon radical can also capture oxygen, it also has the effect of reducing the oxygen concentration. Due to these mechanisms, polymerization inhibition by oxygen is suppressed and polymerization proceeds sufficiently. Therefore, it is presumed that sufficient solvent resistance can be obtained even if the subsequent heat treatment is at a low temperature. In addition, since the amine structure has polarity, it is presumed that the adhesion to the substrate is improved.

[0016] [Resin (A)] The resin (A) is used, for example, for the purpose of dispersing particles such as pigments in the photosensitive composition and for the purpose of imparting resistance to the cured film. Note that the resin (A) mainly used for dispersing particles such as pigments is also referred to as a dispersion resin, and the resin (A) used for imparting resistance to the cured film is also referred to as a binder resin. However, such uses of the resin (A) are just examples, and it can also be used for other purposes.

[0017] The weight average molecular weight (Mw) of the resin (A) is preferably 4,000 to 40,000, more preferably 4,000 to 35,000.

[0018] The content of the resin (A) is preferably 5 to 70% by mass, more preferably 10 to 60% by mass in 100% by mass of the non-volatile content of the photosensitive composition.

[0019] The resin (A) can be used alone or in combination of two or more.

[0020] Examples of the resin (A) include a resin (A1), a resin (A2), a resin (A3), and a resin (A4).

[0021] (Resin (A1)) From the perspective of solvent resistance, the resin (A) preferably contains a resin (A1) (hereinafter also simply referred to as resin (A1)) having a blocked isocyanate group-containing monomer unit (a1) and an acidic group-containing monomer unit (a2) as a binder resin. Thereby, even at low temperatures, curing progresses more, and the solvent resistance of the cured film is further improved.

[0022] The production method of the resin (A1) is not particularly limited, and known methods can be used. For example, it can be obtained by copolymerizing a monomer that forms a blocked isocyanate group-containing monomer unit (a1), a monomer that forms an acidic group-containing monomer unit (a2), and optionally other monomers copolymerizable therewith.

[0023] [[Blocked Isocyanate Group-Containing Monomer Unit (a1)]] The blocked isocyanate group-containing monomer is a monomer in which the isocyanate group of the isocyanate group-containing monomer is protected with a compound that desorbs with heat (hereinafter also referred to as a blocking agent).

[0024] Examples of the isocyanate group-containing monomer 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, methacryloyl isocyanate, etc. Also, an equimolar reaction product of 2-hydroxyalkyl (meth)acrylate and a diisocyanate compound can be used. Among these, 2-isocyanatoethyl (meth)acrylate and 2-isocyanatopropyl (meth)acrylate are preferred. Examples of the blocking agent include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, imide compounds, urea compounds, imine compounds, and bisulfite compounds.

[0025]

[0026] Examples of the oxime compound include formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, cyclohexanone oxime, benzophenone oxime, etc., and methyl ethyl ketoxime is preferred. Examples of the lactam compound include ε-caprolactam, δ-valerolactam, γ-butyrolactam, β-propiolactam, etc. Examples of the phenol compound include phenol, cresol, 2,6-xylenol, 3,5-xylenol, ethylphenol, p-tert-butylphenol, nonylphenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, p-naphthol, p-nitrophenol, etc., and 3,5-xylenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate are preferred. Examples of the alcohol compound include methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl alcohol. Examples of the amine compound include diphenylamine, phenylnaphthylamine, aniline, carbazole, etc. Examples of the active methylene compound include dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone, etc., and diethyl malonate is preferred. Examples of the pyrazole compound include pyrazole, methylpyrazole, 3,5-dimethylpyrazole, etc., and 3,5-dimethylpyrazole is preferred. Examples of the mercaptan compound include butyl mercaptan, thiophenol, tert-dodecyl mercaptan, etc. Examples of the imidazole compound include imidazole, 2-methylimidazole, 2-ethylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, etc. Examples of the imide compound include succinimide, maleimide, maleic imide, phthalimide, and the like. Examples of the urea compound include urea, thiourea, ethylene urea, and the like. Examples of the imine compound include ethylene imine, polyethylene imine, and the like. Examples of the bisulfite compound include sodium bisulfite, potassium bisulfite, and the like. These blocking agents can be used alone or in combination of two or more.

[0027] The blocking agent is preferably at least one selected from the group consisting of an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, a pyrazole compound, a mercaptan compound, an imidazole compound, and an imide compound. From the viewpoints of the protection reaction and the deprotection reaction, more preferably at least one selected from the group consisting of an oxime compound, a phenol compound, an active methylene compound, and a pyrazole compound.

[0028] Examples of the blocked isocyanate group-containing monomer include the following compounds. However, the present invention is not limited thereto.

[0029]

Chemical formula

[0030] Commercially available products of the blocked isocyanate group-containing monomer include Karenz MOI-DEM (desorption temperature of the blocking agent: 85 to 95 °C), MOI-BP (desorption temperature of the blocking agent: 105 to 115 °C), MOI-BM (desorption temperature of the blocking agent: 125 to 135 °C) manufactured by Showa Denko KK, and the like.

[0031] From the viewpoint of solvent resistance, the content of the blocked isocyanate group-containing monomer unit (a1) is preferably 1 to 50 mol% in all the constituent units of the resin (A1), more preferably 5 to 40 mol%.

[0032] 〔Acidic group-containing monomer unit (a2)〕 Examples of the acidic group of the acidic group-containing monomer include a carboxyl group, a sulfonic acid group, a phosphoric acid group, etc. Among these, a carboxyl group is preferred.

[0033] Examples of the acidic group-containing monomer include (meth)acrylic acid, crotonic acid, propiolic acid, cinnamic acid, itaconic acid, itaconic anhydride, maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, maleic anhydride, fumaric acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl hexylhydrophthalic acid, p-styrenesulfonic acid, vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, 2-(meth)acryloyloxyethyl acid phosphate, etc.

[0034] From the viewpoint of developability, the content of the acidic group-containing monomer unit (a2) is preferably 1 to 50 mol%, more preferably 5 to 40 mol%, based on all the constitutional units of the resin (A1).

[0035] In addition to the blocked isocyanate group-containing monomer unit (a1) and the acidic group-containing monomer unit (a2), the resin (A1) can contain the following monomer units. For example, a hydroxyl group-containing monomer unit (a3), an epoxy group-containing monomer unit (a4), a polymerizable unsaturated group-containing monomer unit (a5), an alicyclic hydrocarbon-containing monomer unit (a6), a monomer unit (a7) represented by the general formula (1), and other monomer units (a8).

[0036] General formula (1)

Chemical formula

[0037] In the general formula (1), R1 represents a hydrogen atom or a methyl group. R2 represents an alkylene group having 2 or 3 carbon atoms. n represents an integer of 1 to 15. When n is 2 or more, a plurality of R2 may be the same or different from each other.

[0038] 〔Monomer unit (a3) containing a hydroxyl group〕 Examples of the monomer containing a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2,3-hydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxyethyl phthalate, and the like.

[0039] 〔Monomer unit (a4) containing an epoxy group〕 Examples of the monomer containing an epoxy group include oxiranyl (meth)acrylate, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, 2-oxiranylethyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate, 2-(3,4-epoxycyclohexylmethyloxy)ethyl (meth)acrylate, 3-(3,4-epoxycyclohexylmethyloxy)propyl (meth)acrylate, and the like.

[0040] 〔Monomer unit (a5) containing a polymerizable unsaturated group〕 Examples of the method for incorporating the monomer unit (a5) containing a polymerizable unsaturated group into the resin (A1) include the following methods (i) to (iii).

[0041] <Method (i)> There is a method (i) in which an acidic group of an acidic group-containing monomer is added to the epoxy group of the monomer unit (a4) containing an epoxy group contained in the resin (A1).

[0042] <Method (ii)> There is a method (ii) of adding an epoxy group of an epoxy group-containing monomer to the acidic group of the acidic group-containing monomer unit (a2) contained in the resin (A1).

[0043] In addition, a reaction product obtained by reacting an acid anhydride with the hydroxyl group generated by the reactions of methods (i) and (ii) is also useful as the polymerizable unsaturated group-containing monomer unit (a5).

[0044] Examples of the acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, and the like.

[0045] <Method (iii)> There is a method (iii) of reacting an isocyanate group of an isocyanate group-containing monomer with the hydroxyl group of the hydroxyl group-containing monomer unit (a3) contained in the resin (A1).

[0046] Examples of the isocyanate group-containing monomer include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, or 1,1-bis[methacryloyloxy]ethyl isocyanate, and the like.

[0047] [Alicyclic hydrocarbon-containing monomer unit (a6)] Examples of the alicyclic hydrocarbon-containing monomer include isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, adamantyl (meth)acrylate, and the like.

[0048] [Monomer unit (a7) represented by the general formula (1)] Examples of the monomer represented by the general formula (1) include ethylene oxide (EO) or propylene oxide (PO) modified (meth)acrylate of paracumylphenol, and the like.

[0049] ​Other monomer unit (a8) The monomers forming the other monomer unit (a8) are, for example, acrylic acid esters such as 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, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, EO or PO modified (meth)acrylate of phenol, EO or PO modified (meth)acrylate of nonylphenol, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate; Aromatic vinyl compounds such as styrene, α-methylstyrene, p-vinyltoluene, p-chlorostyrene, vinylnaphthalene; (Meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or acryloylmorpholine; Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether; Vinyl fatty acids such as vinyl acetate or vinyl propionate; N-substituted maleimides such as phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimidoacridine; Dimethyl 2,2'-[oxybis(methylene)]bis-2-propenoate, diethyl 2,2'-[oxybis(methylene)]bis-2-propenoate, di(n-propyl )-2,2'-[oxybis(methylene)]bis-2-propenoate, di(isopropyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(2-ethylhexyl)-2,2'-[oxybis(methylene)]bis-2-propenoate and the like. These monomers can be used alone or in combination of two or more.

[0050] Resin (A1) can be used alone or in combination of two or more.

[0051] From the viewpoint of solvent resistance, the weight average molecular weight (Mw) of resin (A1) is preferably 4,000 to 40,000, more preferably 4,000 to 35,000.

[0052] From the viewpoint of developability, the acid value of resin (A1) is preferably 30 to 200 mgKOH / g, more preferably 40 to 180 mgKOH / g.

[0053] From the viewpoint of solvent resistance, the content of the resin (A1) is preferably 5% by mass or more, more preferably 10 to 100% by mass, based on 100% by mass of the resin (A).

[0054] (Resin (A2)) The resin (A2) is a resin (A2) (hereinafter, also simply referred to as resin (A2)) that does not have the block isocyanate group-containing monomer unit (a1) described above as a binder resin, and has at least one monomer unit selected from an alicyclic hydrocarbon-containing monomer unit (a6) and a monomer unit (a7) represented by the general formula (1), and an acidic group-containing monomer unit (a2).

[0055] The resin (A2) can contain monomer units other than the above (a1), (a2), (a6), and (a7). For example, the monomer units of the above (a3) to (a5) and (a8) can be mentioned. Among these, from the viewpoint of solvent resistance, it is preferable to have a polymerizable unsaturated group-containing monomer unit (a5).

[0056] The resin (A2) can be used alone or in combination of two or more.

[0057] From the viewpoint of solvent resistance, the weight average molecular weight (Mw) of the resin (A2) is preferably 4,000 to 40,000, more preferably 4,000 to 35,000.

[0058] From the viewpoint of developability, the acid value of the resin (A2) is preferably 30 to 200 mgKOH / g, more preferably 40 to 180 mgKOH / g.

[0059] (Resin (A3)) The resin (A3) is a dispersion resin that disperses particles such as pigments.

[0060] The resin (A3) is preferably a resin having an adsorption group with high affinity for particles such as pigments. The adsorption group preferably has at least one of a basic group and an acidic group.

[0061] Examples of the basic group include groups containing a nitrogen atom such as a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, and a nitrogen-containing heterocyclic ring.

[0062] Examples of the acidic group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group.

[0063] Examples of the resin species of the resin (A3) include urethane resins, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, (partial) amine salts of polycarboxylic acids, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyamino amidine phosphates, hydroxyl group-containing polycarboxylic acid esters, and modified products thereof, amides and salts thereof formed by the reaction of poly(lower alkyleneimine) and a polyester having a free carboxyl group, water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylate copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and polyvinylpyrrolidone, polyester-based, modified polyacrylate-based, ethylene oxide / propylene oxide addition compounds, phosphate ester-based, and the like.

[0064] Examples of the structure of the resin (A3) include a random structure, a block structure, a graft structure, a comb structure, and a star structure. Among these, from the viewpoint of dispersion stability, a block structure or a comb structure is preferable.

[0065] From the viewpoint of solvent resistance, the resin (A3) is preferably a resin having a polymerizable unsaturated group.

[0066] The resin (A3) specifically includes 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-P104, P104S, 220S, or Lactimon, Lactimon-WS, or Bykumen, etc., 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, 76500, etc., manufactured by Lubrizol Japan; 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., manufactured by BASF Japan; Ajisuper PA111, PB711, PB821, PB822, manufactured by Ajinomoto Fine-Techno Co., Ltd.Examples of the resin include those described in PB824, JP-A-2008-029901, JP-A-2009-155406, JP-A-2010-185934, JP-A-2011-157416, WO2008 / 007776, JP-A-2008-029901, JP-A-2009-155406, JP-A-2010-185934, JP-A-2011-157416, JP-A-2012-255128, JP-A-2009-251481, JP-A-2007-23195, JP-A-1996-143651, JP-A-2017-206689, JP-A-2019-095548, etc.

[0067] The resin (A3) can be used alone or in combination of two or more.

[0068] (Resin (A4)) The resin (A4) is a resin other than the resins (A1) to (A3).

[0069] The resin (A4) is not particularly limited, and known resins can be used. For example, (meth)acrylic resins, styrene resins, styrene-(meth)acrylic resins, epoxy resins, urethane resins, polycarbonate resins, polyester resins, polyether resins, polyimide resins, polyamideimide resins, cyclic olefin resins, etc. can be mentioned, and they can be used alone or in combination of two or more. and used together.

[0070] [Polymerizable compound (B)] Examples of the polymerizable compound (B) include monomers and oligomers having a polymerizable unsaturated group. Examples of the polymerizable unsaturated group include vinyl groups of ethylenically unsaturated double bonds, (meth)allyl groups, (meth)acryloyl groups, etc.

[0071] (Polymerizable compound (B1) having three or more (meth)acryloyl groups and an amine structure) The amine structure in the polymerizable compound (B1) having three or more (meth)acryloyl groups and an amine structure (hereinafter also simply referred to as the polymerizable compound (B1)) includes a primary amine, a secondary amine, and a tertiary amine. Among them, a tertiary amine is preferred. Note that the amine structure of the polymerizable compound (B1) does not include an amide structure, an imide structure, and a urethane structure in which a carbonyl group is directly bonded to a nitrogen atom.

[0072] The number of (meth)acryloyl groups in the polymerizable compound (B1) is not particularly limited as long as it is three or more. However, from the viewpoint of pattern formability, the upper limit is preferably 16 or less.

[0073] The polymerizable compound (B1) can be used alone or in combination of two or more.

[0074] From the viewpoints of pattern formability and solvent resistance, the content of the polymerizable compound (B1) is preferably 1% by mass or more, more preferably 5 to 80% by mass, and particularly preferably 5 to 60% by mass in 100% by mass of the polymerizable compound (B).

[0075] Examples of the polymerizable compound (B1) include tris(acryloyloxyethyl)amine, tris(methacryloyloxyethyl)amine, tris(2-hydroxy-3-methacryloyloxypropyl)amine, and Michael addition reaction products of a (meth)acrylate compound (X) and an amine compound (Y).

[0076] (Meth)acrylate compound (X) includes, 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 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, dipentaerythritol alkylene oxide modified tetra, penta and hexa(meth)acrylate, etc. In the alkylene oxide modification, examples of the alkylene oxide unit include ethylene oxide, propylene oxide, and butylene oxide. Also, as the (meth)acrylate compound (X), (meth)acrylate compounds having an acidic group are also included.

[0077] (Meth)acrylate compound (X) can be used alone or in combination of two or more.

[0078] Amine compound (Y) includes, for example, primary amines such as n-propylamine, n-butylamine, n-hexylamine, benzylamine, aminocaproic acid, monoethanolamine, 2-(2-aminoethoxy)ethanol, o-aminophenol, m-aminophenol, p-aminophenol; Examples include dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, morpholine, piperidine, 1-methylpiperazine, proline, N-methylethanolamine, N-acetylethanolamine, diethanolamine, and the like.

[0079] The amine compound (Y) can be used alone or in combination of two or more.

[0080] The method for producing the Michael addition reaction product of the (meth)acrylate compound (X) and the amine compound (Y) is not particularly limited, and known methods can be used. For example, the methods described in International Publication No. 2006 / 075754, Japanese Patent Application Laid-Open No. 2008-545859, Japanese Patent Application Laid-Open No. 2017-066347, and the like can be mentioned.

[0081] The polymerizable compound (B1) having three or more (meth)acryloyl groups and an amine structure may have an acidic group or / and a hydroxyl group. Examples of the method for introducing an acidic group or / and a hydroxyl group include using a compound having an acidic group or / and a hydroxyl group in the (meth)acrylate compound (X) or the amine compound (Y), and adding an acid anhydride after the Michael addition reaction.

[0082] Commercially available products of the polymerizable compound (B1) include Aronix MT-3041, 3042, etc. manufactured by Toagosei Co., Ltd.

[0083] (Polymerizable compound (B2) other than the polymerizable compound (B1) having three or more (meth)acryloyl groups and an amine structure) From the viewpoint of solvent resistance, the photosensitive composition of the present invention preferably contains a polymerizable compound (B2) other than the polymerizable compound (B1) having three or more (meth)acryloyl groups and an amine structure (hereinafter, also simply referred to as the polymerizable compound (B2)) as the polymerizable compound (B).

[0084] The polymerizable compound (B2) is, for example, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol EO-modified penta(meth)acrylate, dipentaerythritol PO-modified penta(meth)acrylate, tricyclodecanyl (meth)acrylate, (meth)acrylate of methylolated melamine, epoxy (meth)acrylate and other various acrylic acid esters and methacrylic acid esters, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, acrylonitrile and the like can be mentioned. Among these, from the viewpoints of reactivity and solvent resistance, it is preferable to contain a polymerizable compound having 4 or more (meth)acryloyl groups.

[0085] In addition, the polymerizable compound (B2) may contain an acidic group. Examples of the acidic group include a sulfonic acid group, a carboxyl group, a phosphoric acid group, and the like.

[0086] Examples of the polymerizable compound containing an acidic group include esterified products of polyhydric alcohols and free hydroxyl group-containing poly(meth)acrylates with (meth)acrylic acid and dicarboxylic acids; esterified products of polyvalent carboxylic acids and monohydroxyalkyl (meth)acrylates, and the like. The polymerizable compound containing an acidic group is a free carboxyl group-containing monoesterified product of a monohydroxyoligoacrylate or monohydroxyoligomethacrylate such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, and dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, terephthalic acid; a free carboxyl group-containing oligoesterified product of tricarboxylic acids such as propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, and monohydroxymonoacrylate or monohydroxymonomethacrylate such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and the like.

[0087] In addition, the polymerizable compound (B2) may contain a urethane bond. Examples thereof include polyfunctional urethane acrylates obtained by reacting a polyfunctional isocyanate with a (meth)acrylate having a hydroxyl group, and polyfunctional urethane acrylates obtained by reacting a polyfunctional isocyanate with an alcohol and further reacting with a (meth)acrylate having a hydroxyl group.

[0088] Examples of (meth)acrylates having a salicylic acid group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, EO-modified di(meth)acrylate of isocyanuric acid, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, EO-modified dipentaerythritol penta(meth)acrylate, PO-modified dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol penta(meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, reaction product of an epoxy group-containing compound and carboxy(meth)acrylate, hydroxyl group-containing polyol polyacrylate, and the like. Examples of polyfunctional isocyanates include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, polyisocyanate, and the like.

[0089] Commercially available products of the polymerizable compound (B2) include KAYARAD R-128H, R526, PEG400DA, MAND, NPGDA, R-167, HX-220, R-551, R712, R-604, R-684, GPO-303, TMPTA, DPHA, DPEA-12, DPHA-2C, D-310, D-330, DPCA-20, DCPA-30, DCPA-60, DCPA-120 manufactured by Nippon Kayaku Co., Ltd., and Aronix M-303, M-305, M-306, M-309, M-310, M-321, M-325, M-3 manufactured by Toagosei Co., Ltd. 50, M-360, M-313, M-315, M-400, M-402, M-403, M-404, M-405, M-406, M-450, M-452, M-408, M-520, M-521, M-211B, M-101A, M-5300, M-5400, M-5700, Biscoat #310HP, #335HP, #700, #295, #330, #360, #GPT, #400, #405, #2500 manufactured by Osaka Organic Chemical Industry Co., Ltd., AH-600, AT-600, UA-306H, UA-306T, UA-306I, UF-8001G manufactured by Kyoeisha Chemical Co., Ltd., NK Ester A-9300, ABE-300, A-DOG, A-DCP, A-BPE-4, UA-160TM manufactured by Shin-Nakamura Chemical Co., Ltd., Miramer HR6060, 6100, 6200 manufactured by Miwon Specialty Chemical Co., Ltd., EBECRYL 40, 130, 140, 145 manufactured by Daicel Ornex Co., Ltd., OGSOL EA-0200, 0300, GA-5060, GA-2800, etc. manufactured by Osaka Gas Chemical Co., Ltd.

[0090] From the viewpoint of solvent resistance, the polymerizable compound (B2) more preferably contains a polymerizable compound having a dendrimer structure or a hyperbranched structure.

[0091] A polymerizable compound having a dendrimer structure has a chemical structure in which branching is regularly repeated from the chemical structure constituting the core (hereinafter also referred to as the core part) to the outside, and a polymerizable unsaturated group is bonded to its terminal, and has a spherical and highly controlled chemical structure and molecular weight. The hyperbranched structure has a chemical structure similar to the dendrimer structure. Therefore, compared with a general linear polymerizable compound, the distance between the polymerizable unsaturated groups in the molecule is close and the density is high, so it is less affected by oxygen inhibition, reacts sufficiently by exposure, and a cured film having excellent solvent resistance can be obtained even by low-temperature curing.

[0092] From the viewpoint of solvent resistance, the polymerizable compound having a dendrimer structure or a hyperbranched structure preferably has an average of 6 to 18 polymerizable unsaturated groups.

[0093] The polymerizable compound having a dendrimer structure or a hyperbranched structure preferably has at least one polymerizable unsaturated group selected from the group consisting of a vinyl group, a (meth)allyl group, and a (meth)acryloyl group from the viewpoint of solvent resistance, and a (meth)acryloyl group is more preferable.

[0094] The polymerizable compound having a dendrimer structure or a hyperbranched structure can be used alone or in combination of two or more.

[0095] From the viewpoint of solvent resistance, the content of the polymerizable compound having a dendrimer structure or a hyperbranched structure is preferably 10% by mass or more, more preferably 20 to 100% by mass in 100% by mass of the polymerizable compound (B2).

[0096] As the polymerizable compound having a dendrimer structure or a hyperbranched structure, those synthesized as appropriate may be used, or commercially available products may be used.

[0097] As a method for synthesizing a dendrimer structure, a divergent method in which synthesis proceeds from the core to the outside, a convergent method in which synthesis proceeds from the terminal polymerizable unsaturated group to the inside, and a combination of these two are known. For example, using the convergent method, in the first step, 2-(4-hydroxyphenoxyethyl)-acrylate and 5-hydroxyisophthalic acid are coupled, and in the second step, trimesic acid is coupled to obtain a polymerizable compound having a dendrimer structure. As a method for synthesizing a hyperbranched structure, it is obtained by self-condensation of an ABx type molecule having a total of three or more two types of substituents in one molecule. For example, using 3,5-dihydroxybenzoic acid as a raw material, a hyperbranched polyester can be obtained by polycondensation. In this case, a hydroxyl group is present at the terminal, and by reacting (meth)acrylic acid therewith, a polymerizable compound having a hyperbranched structure can be obtained.

[0098] Commercially available polymerizable compounds having a dendrimer structure or a hyperbranched structure include, for example, Biscoat #1000LT (dendrimer structure, average number of acryloyl groups: 14) manufactured by Osaka Organic Chemical Industry Co., Ltd., Miramer SP-1106 (dendrimer structure, average number of acryloyl groups: 18), Miramer SP-1108 (dendrimer structure, average number of acryloyl groups: 13) manufactured by Miwon Specialty Chemical Co., Ltd., CN2301 (hyperbranched structure, average number of acryloyl groups: 9), CN2302 (hyperbranched structure, average number of acryloyl groups: 16), CN2303 (hyperbranched structure, average number of acryloyl groups: 6), CN2304 (hyperbranched structure, average number of acryloyl groups: 18) manufactured by Sartomer Co., Inc., Etercure6361-100 (hyperbranched structure, average number of acryloyl groups: 8), Etercure6362-100 (hyperbranched structure, average number of acryloyl groups: 12), Etercure6363 (hyperbranched structure, average number of acryloyl groups: 16), EtercureDR-E522 (hyperbranched structure, average number of acryloyl groups: 15) manufactured by Eternal Materials Co., Ltd., and the like.

[0099] The content of the polymerizable compound (B) is preferably 1 to 60% by mass, more preferably 2 to 50% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0100] [Photoinitiator (C)] The photosensitive composition of the present invention contains a photoinitiator (C). Thereby, the photosensitive composition can be cured by irradiation with active energy rays.

[0101] The photoinitiator (C) is, for example, an acetophenone-based compound such as 4-phenoxydichloroacetophenone, 4-t-butyldichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; a triazine-based compound 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-(naphthalen-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthalen-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; an oxime-based compound such as 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime), or ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetoxyoxime); an acylphosphine-based compound such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; a quinone such as 9,10-phenanthrenequinone, camphorquinone, or ethylanthraquinone Examples include systems compounds, borate compounds, carbazole compounds, imidazole compounds, or metallocene compounds and the like.

[0102] In commercial products, as acetophenone compounds, Omnirad 907, 369E, 379EG manufactured by IGM Resins; as acylphosphine compounds, Omnirad 819, TPO manufactured by IGM Resins; as oxime compounds, IRGACURE OXE-01, 02, 03, 04 manufactured by BASF Japan, N-1919, NCI-730, 831, 930 manufactured by ADEKA, TRONLY TR-PBG-301, 304, 305, 309, 314, 345, 358, 380, 365, 610, 3054, 3057 manufactured by Changzhou Qiangli New Materials Co., Ltd., Omnirad 1312, 1314, 1316 manufactured by IGM Resins, SPI-02, 03, 04, 05, 06, 07 manufactured by Samyang Corporation, DFI-020, 306, EOX-01, etc. manufactured by Daito Chemicals can be mentioned. In addition, oxime compounds described in JP-A No. 2007-210991, JP-A No. 2009-179619, JP-A No. 2010-037223, JP-A No. 2010-215575, JP-A No. 2011-020998, International Publication No. 2015 / 036910, International Publication No. 2021 / 175855, etc. can also be mentioned.

[0103] When the photosensitive composition of the present invention contains a colorant (E) to be described later, it is more preferable to contain an oxime compound as the photopolymerization initiator (C).

[0104] Specific examples of the oxime compound include, for example, the following. Note that the present invention is not limited thereto.

[0105]

Chemical formula

Chemical formula

[0106] From the viewpoint of photocurability, the content of the photopolymerization initiator (C) is preferably 0.5 to 100 parts by mass, more preferably 1 to 50 parts by mass, and particularly preferably 2 to 25 parts by mass with respect to 100 parts by mass of the polymerizable compound (B).

[0107] [Organic solvent (D)] The photosensitive composition of the present invention contains an organic solvent (D).

[0108] The organic solvent (D) is not particularly limited as long as it satisfies the solubility of each component contained in the photosensitive composition of the present invention and the coatability, and known compounds can be used.

[0109] The organic solvent (D) is, for example, 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, toluene, o-chlorotoluene, benzene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether,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 and the like can be mentioned. Among these, from the viewpoints of solubility in resin and coatability, glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, alcohols such as diacetone alcohol, and ketones such as cyclohexanone are preferable.,

[0110] From the environmental aspect, it is preferable that the photosensitive composition of the present invention substantially does not contain organic solvents which are aromatic hydrocarbons (such as toluene, xylene, benzene, chlorobenzene). Substantially not containing means that it is 50 mass ppm or less in the photosensitive composition, preferably 30 mass ppm or less, and more preferably 10 mass ppm or less.

[0111] The organic solvent (D) can be used alone or in combination of two or more kinds.

[0112] The content of the organic solvent (D) is included to such an extent that the nonvolatile content of the photosensitive composition is 5 to 50% by mass. It is preferable to have.

[0113] [Colorant (E)] The photosensitive composition of the present invention can contain a colorant (E). Thereby, the transmittance of each wavelength region of the optical filter can be controlled, and the color separation property and the shielding property are improved.

[0114] The colorant (E) may be either a pigment or a dye and can be used in combination.

[0115] [Pigment] As the pigment, compounds classified as pigments in the Color Index are preferable. Red pigments include, for example, C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 295, 296, the pigments described in JP-A No. 2014-134712, the pigments described in Patent No. 6368844, etc. Among these, from the viewpoints of heat resistance, light resistance, and transmittance, C.I. Pigment Red 48:1, 122, 177, 224, 242, 269, 254, 291, 295, 296, the pigments described in JP-A No. 2014-134712, and the pigments described in Patent No. 6368844 are preferable, and C.I. Pigment Red 177, 254, 291, 295, 296, the pigments described in JP-A No. 2014-134712, and the pigments described in Patent No. 6368844 are more preferable.

[0116] Orange pigments include, for example, C.I. Pigment Orange 36, 38, 43, 64, 71, 73, etc.

[0117] Yellow pigments include, for example, C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233, pigments described in JP-A No. 2012-226110, JP-A No. 2017-171912, JP-A No. 2017-171913, JP-A No. 2017-171914, JP-A No. 2017-171915, etc. Among these, C.I. Pigment Yellow 138, 139, 150, 185, 231, 233, and the pigments described in JP-A No. 2012-226110 are preferred.

[0118] Green pigments include, for example, C.I. 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. Among these, C.I. Pigment Green 36, 58, 59, 62, 63 are preferred.

[0119] Examples of the cyan pigment include C.I. 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. Among these, C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6 are preferred.

[0120] Examples of the purple pigment include C.I. 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, 50, etc. Among these, C.I. Pigment Violet 19, 23 are preferred.

[0121] Specific examples of the black pigment include C.I. Pigment Black 1, 6, 7, 12, 20, 31, 32, etc. Compounds described in Japanese Patent Application Laid-Open Nos. 2010-534726, 2012-515233, 2012-515234, 1-170601, 2-34664, etc. are also included.

[0122] When the photosensitive composition of the present invention is used for an infrared transmission filter, the colorant (E) preferably contains two or more pigments selected from the group consisting of a red pigment, a yellow pigment, a cyan pigment, a green pigment, and a purple pigment and exhibits black.

[0123] Examples of the combination that exhibits black include the following embodiments. (1) Containing a yellow pigment and a purple pigment. (2) Containing a red pigment, a yellow pigment, and a purple pigment. (3) Containing a red pigment, a yellow pigment, and a cyan pigment. (4) Containing a red pigment, a yellow pigment, and a green pigment. (5) Containing a yellow pigment, a cyan pigment, and a purple pigment. It contains red pigment, yellow pigment, blue pigment, and purple pigment.

[0124] In addition, inorganic pigments such as titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, cobalt blue, chromium oxide green, cobalt green, amber, synthetic iron black, etc. can also be used.

[0125] (Dye) Examples of dyes include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, building dyes, sulfur dyes, etc. Derivatives thereof and lake pigments obtained by lake-forming dyes are also included.

[0126] Acid dyes preferably have acidic groups such as sulfonic acid and carboxylic acid. In addition, salt-forming compounds that are salts of acid dyes and nitrogen-containing compounds such as quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, or primary amine compounds are preferred. Salt-forming compounds that are salts of resin components having these functional groups and acid dyes are also preferred. Also, the salt-forming compound is easily sulfonamidated and modified into a sulfonic acid amide compound to obtain a photosensitive composition excellent in resistance (light resistance, solvent resistance). In addition, salt-forming compounds of acid dyes and compounds having an onium base are also preferred because of their excellent resistance (light resistance, solvent resistance). The compound having an onium base is preferably a resin having a cationic group.

[0127] Basic dyes can be used as they are, but salt-forming compounds that form salts with organic acids, perchloric acid, or their metal salts are preferred. The salt-forming compounds of basic dyes are preferred because they have excellent resistance (light resistance, solvent resistance) and affinity with pigments. In addition, among the salt-forming compounds of basic dyes, the anionic component that acts as a counterion is an organic sulfonic acid, organic sulfuric acid, fluorine group-containing phosphorus anion compound, fluorine group-containing boron anion compound, cyano group-containing nitrogen anion compound, anionic compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, or a salt-forming compound formed by salting with an acid dye. Note that the salt-forming compound has better resistance when it contains a polymerizable unsaturated group in the molecule.

[0128] The chemical structure of the dye is derived from a dye selected from, for example, azo dyes, disazo dyes, azomethine dyes (such as indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (such as benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (such as oxazine dyes, thiazine dyes, etc.), azine dyes, polymethine dyes (such as oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and their metal complex dyes.

[0129] Among these, from the viewpoint of color characteristics such as hue, color separation property, and color unevenness, a pigment structure derived from a pigment selected from azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes is preferable, and a pigment structure derived from a pigment selected from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes is more preferable.

[0130] The colorant (E) can be used alone or in combination of two or more.

[0131] The content of the colorant (E) is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, in 100% by mass of the non-volatile content of the photosensitive composition.

[0132] (Micronization of Pigment) The pigment is preferably used after being micronized. The micronization method is not particularly limited, and for example, any of wet grinding, dry grinding, and solvent precipitation methods can be used. Among these, salt milling treatment by the kneader method, which is a type of wet grinding, is preferable. The average primary particle diameter determined by TEM (transmission electron microscope) of the micronized pigment is preferably 5 to 90 nm. From the viewpoints of dispersibility and contrast ratio, the average primary particle diameter is more preferably 10 to 70 nm.

[0133] The salt milling treatment is a treatment in which a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is mechanically kneaded while heating using a kneading machine such as a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, or a sand mill, and then the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed by utilizing the high hardness of the inorganic salt during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, a pigment having a very fine primary particle diameter, a narrow distribution width, and a sharp particle size distribution can be obtained. ​

[0134] Examples of the water-soluble inorganic salts include sodium chloride, potassium chloride, sodium sulfate, etc., and sodium chloride (table salt) is preferred from the viewpoint of price. The amount of the water-soluble inorganic salt used is preferably 50 to 2,000 parts by mass, more preferably 300 to 1,000 parts by mass, based on 100 parts by mass of the pigment, from the viewpoints of both treatment efficiency and production efficiency.

[0135] The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it is soluble (miscible) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent is likely to evaporate, a high-boiling solvent having a boiling point of 120 °C or higher is preferred from the viewpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. are used. The amount of the water-soluble organic solvent used is preferably 5 to 1,000 parts by mass, more preferably 50 to 500 parts by mass, based on 100 parts by mass of the pigment.

[0136] A resin may be added to the salt milling treatment as necessary. The type of the resin is not particularly limited, and examples include natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, etc. Among these, it is preferably solid at room temperature, water-insoluble, and partially soluble in the above organic solvent. The addition amount of the resin is preferably 2 to 200 parts by mass, based on 100 parts by mass of the pigment.

[0137] [Sensitizer (F)] The photosensitive composition of the present invention can contain a sensitizer (F).

[0138] The sensitizer (F) is, for example, a chalcone compound, unsaturated ketones typified by dibenzalacetone, 1,2-diketone compounds typified by benzyl and camphorquinone, benzoin compounds, fluorene compounds, naphthoquinone compounds, anthraquinone compounds, xanthene compounds, thioxanthene compounds, xanthone compounds, thioxanthone compounds, coumarin compounds, ketocoumarin compounds, polymethine dyes such as cyanine compounds, merocyanine compounds, oxonol compounds, acridine compounds, azine compounds, thiazine compounds, oxazine compounds, indoline compounds, azulene compounds, azulenium compounds, squarylium compounds, porphyrin compounds, tetraphenylporphyrin compounds, triarylmethane compounds, tetrabenzoporphyrin compounds, tetrapyrazinoporphyrazine compounds, phthalocyanine compounds, tetraazaporphyrazine compounds, tetraquinoxalyloporphyrazine compounds, naphthalocyanine compounds, subphthalocyanine compounds, pyrylium compounds, thiopyrylium compounds, tetraphyllin compounds, annulene compounds, spiropyran compounds, spirooxazine compounds, thiospiropyran compounds, metal arene complexes, organoruthenium complexes, or benzophenone compounds, etc. Among these, from the viewpoints of developability and pattern formability, thioxanthone compounds and benzophenone compounds are preferred.

[0139] Examples of the thioxanthone compounds include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, etc. Among these, 2,4-diethylthioxanthone is preferred.

[0140] Examples of the benzophenone compounds include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 2-aminobenzophenone, etc. Among these, 4,4'-bis(diethylamino)benzophenone is preferred.

[0141] The sensitizer (F) can be used alone or in combination of two or more kinds.

[0142] From the viewpoint of pattern formation property, the content of the sensitizer (F) is preferably 10 to 400 parts by mass, more preferably 20 to 300 parts by mass with respect to 100 parts by mass of the photopolymerization initiator (C).

[0143] [Dye derivative (G)] The photosensitive composition of the present invention can contain a dye derivative (G).

[0144] Examples of the dye derivative (G) include compounds having a structure in which a part of the dye is substituted with an acidic group, a basic group, a neutral group, etc. Examples of the dye derivative (G) include compounds having an acidic substituent such as a sulfo group, a carboxy group, a phosphate group, and amine salts thereof, compounds having a basic substituent such as a sulfonamide group and a tertiary amino group at the terminal, and compounds having a neutral substituent such as a phenyl group and a phthalimidoalkyl group. Examples of the dye include diketopyrrolopyrrole compounds, phthalocyanine compounds, anthraquinone compounds, quinacridone compounds, dioxazine compounds, perinone compounds, perylene compounds, thiazine indigo compounds, triazine compounds, benzimidazolone compounds, benzisoindole compounds, isoindoline compounds, isoindolinone compounds, quinophthalone compounds, naphthol compounds, squarylium compounds, fluorene compounds, naphthalocyanine compounds, etc.

[0145] Specifically, as for the pyrrolopyrrole-based pigment derivatives, see JP-A-2001-220520, WO 2009 / 081930, WO 2011 / 052617, WO 2012 / 102399, JP-A-2017-156397, WO 2018 / 101189; as for the phthalocyanine-based pigment derivatives, see JP-A-2007-226161, WO 2016 / 163351, JP-A-2017-165820, Patent No. 5753266; as for the anthraquinone-based pigment derivatives, see JP-A-63-264674, JP-A-09-272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO 2009 / 025325; as for the quinacridone-based pigment derivatives, see JP-A-48-54128, JP-A-03-9961, JP-A-2000-273383; as for the dioxazine-based pigment derivatives, see JP-A-2011-162662; as for the thiazine indigo-based pigment derivatives, see JP-A-2007-314785; as for the triazine-based pigment derivatives, see JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, JP-A-2004-217842, JP-A-2007-314681; as for the benzisoindole-based pigment derivatives, see JP-A-2009-57478; as for the quinophthalone-based pigment derivatives, see JP-A-2003-167112, JP-A-2006-291194, JP-A-2008-31281, JP-A-2012-226110; as for the naphthol-based pigment derivatives, see JP-A-2012-208329, JP-A-2014-5439; as for the squarylium-based pigment derivatives, see WO 2020 / 054718; as for the azo-based pigment derivatives, see Special JP-A-2001-172520, JP-A-2012-172092; as the acidic substituent, JP-A-2004-307854; as the basic substituent, JP-A-2002-201377, JP-A-2003-171594, JP-A-2005-181383, JP-A-2005-213404, etc. Known dye derivatives described therein can be mentioned. Note that in these documents, they may be described as derivatives, pigment derivatives, dispersants, dispersion aids, pigment dispersants or simply compounds, etc., but they are synonymous with the dye derivative (G).

[0146] The dye derivative (G) can be used alone or in combination of two or more.

[0147] [Thermosetting compound (H)] The photosensitive composition of the present invention can contain a thermosetting compound (H). Thereby, the thermosetting compound (H) reacts in the heating step, and the crosslinking density increases, so that the heat resistance is improved.

[0148] The thermosetting compound (H) may be a low molecular compound or a high molecular weight compound such as a resin. Examples of the thermosetting compound (H) include an epoxy compound, an oxetane compound, a benzoguanamine compound, a rosin-modified maleic acid compound, a rosin-modified fumaric acid compound, a melamine compound, a urea compound, and a phenol compound. Among these, epoxy compounds and oxetane compounds are preferred.

[0149] The content of the epoxy compound (H1) is preferably 0.5 to 50% by mass, more preferably 1 to 40% by mass in 100% by mass of the nonvolatile content of the photosensitive composition.

[0150] The content of the oxetane compound (H2) is preferably 0.5 to 50% by mass, more preferably 1 to 40% by mass in 100% by mass of the nonvolatile content of the photosensitive composition.

[0151] The thermosetting compound (H) can be used alone or in combination of two or more.

[0152] [Curing agent (curing accelerator)] In order to assist the curing of the thermosetting compound (H), a curing agent (curing accelerator) can be used in combination with the photosensitive composition of the present invention. Examples of the curing agent include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds, and the like.

[0153] The curing agent can be used alone or in combination of two or more.

[0154] The content of the curing agent is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the thermosetting compound (H).

[0155] [Thiol-based chain transfer agent (I)] The photosensitive composition of the present invention can contain a thiol-based chain transfer agent (I). When the thiol-based chain transfer agent (I) is used in combination with the photopolymerization initiator (C), during radical polymerization after light irradiation, thiyl radicals that are less susceptible to polymerization inhibition by oxygen are generated, and the photosensitivity of the photosensitive composition is improved.

[0156] The thiol-based chain transfer agent (I) is preferably a polyfunctional thiol having two or more thiol groups (SH groups), and more preferably a polyfunctional thiol having four or more. As the number of functional groups increases, it becomes easier to photocure from the surface to the deepest part of the film.

[0157] Examples of the polyfunctional thiol include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhio Examples include pionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, tris(2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, etc. Preferably, examples include ethylene glycol bisthioglycolate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, etc.

[0158] The thiol-based chain transfer agent (I) can be used alone or in combination of two or more.

[0159] The content of the thiol-based chain transfer agent (I) is preferably 1 to 10 parts by mass, more preferably 2 to 8 parts by mass, based on 100 parts by mass of the non-volatile content of the photosensitive composition. When contained in an appropriate amount, the photosensitivity is improved and wrinkles are less likely to occur on the surface of the cured film.

[0160] [Polymerization inhibitor (J)] The photosensitive composition of the present invention can contain a polymerization inhibitor (J).

[0161] The polymerization inhibitor (J) is, for example, 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-t-butylcatechol, 3-t-butylcatechol, 4-t-butylcatechol, 3,5-di-t-butylcatechol and other alkylcatechol compounds, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-t-butylresorcinol, 4-t-butylresorcinol and other alkylresorcinol compounds, methylhydroquinone, ethylhydroquinone, propylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone and other alkylhydroquinone compounds, tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine and other phosphine compounds, trioctylphosphine oxide, triphenylphosphine oxide and other phosphine oxide compounds, triphenylphosphite, trisnonylphenylphosphite and other phosphite compounds, pyrogallol, phloroglucin and the like.

[0162] The content of the polymerization inhibitor (J) is preferably 0.01 to 0.4% by mass in 100% by mass of the nonvolatile content of the photosensitive composition.

[0163] [Ultraviolet absorber (K)] The photosensitive composition of the present invention can contain an ultraviolet absorber (K).

[0164] The ultraviolet absorber (K) is an organic compound having an ultraviolet absorption function, and examples thereof include benzotriazole-based organic compounds, triazine-based organic compounds, benzophenone-based organic compounds, salicylic acid ester-based organic compounds, cyanoacrylate-based organic compounds, and salicylate-based organic compounds.

[0165] The content of the ultraviolet absorber (K) is preferably 5 to 70% by mass in a total of 100% by mass of the photopolymerization initiator (C) and the ultraviolet absorber (K).

[0166] [Antioxidant (L)] The photosensitive composition of the present invention can contain an antioxidant (L). The antioxidant (L) prevents yellowing caused by oxidation of the photopolymerization initiator (C) and the thermosetting compound (H) in the photosensitive coloring composition during thermosetting or heat treatment during ITO annealing.

[0167] Examples of the antioxidant (L) include compounds such as hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. Among these, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.

[0168] The antioxidant (L) can be used alone or in combination of two or more.

[0169] The content of the antioxidant (L) is preferably 0.5 to 5.0% by mass in 100% by mass of the non-volatile content of the photosensitive composition. When contained in an appropriate amount, the transmittance, spectral characteristics, and sensitivity are improved.

[0170] [Leveling agent (M)] The photosensitive composition of the present invention can contain a leveling agent (M). Thereby, the wettability and drying property with respect to the substrate during coating are further improved. Examples of the leveling agent (M) include silicone-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.

[0171] Silicone surfactants include, for example, linear polymers composed of siloxane bonds and modified siloxane polymers with organic groups introduced into the side chains or terminals.

[0172] Commercially available products include, for example, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, 3570 manufactured by BYK Chemie GmbH; FZ-7002, 2110, 2122, 2123, 2191, 5609 manufactured by Toray Dow Corning Co., Ltd.; 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 manufactured by Shin-Etsu Chemical Co., Ltd.

[0173] Fluorine-based surfactants include, for example, surfactants or leveling agents having fluorocarbon chains.

[0174] Commercially available products include, for example, Surfron S-242, 243, 420, 611, 651, 386 manufactured by AGC Seimi Chemical Co., Ltd.; Megafac F-253, 477, 551, 552, 555, 558, 560, 570, 575, 576, R-40-LM, R-41, RS-72-K, DS-21 manufactured by DIC Corporation; FC-4430, 4432 manufactured by Sumitomo 3M Limited; EF-PP31N09, EF-PP33G1, EF-PP32C1 manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.; Phthalgent 602A manufactured by Neos Corporation.

[0175] Nonionic surfactants include, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristyl ether, polyoxyethylene octyldodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylene distyrylphenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol , polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbitol tetraoleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkylalkanolamide, alkylimidazoline, etc.

[0176] Commercially available products include, for example, Kao's Emulgen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430, 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS-106, LS-110, LS-114, MS-110, A-60, A-90, B-66, PP-290, Latemul PD-420, PD-430, PD-430S, PD-450, Leodol SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V, SP-O30V, Super SP-L10, AS-10V, AO-10V, AO-15V, TW-L120, TW-L106, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-IS399C, Super TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, Emanon 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-60(K), Amite 102, 105, 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, ADEKA's Adekapuronics (registered trademark) L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R, Kyoeisha Chemical's (meth)acrylic acid-based (co)polymers Polyflow - No.75, No.90, No.95, etc.

[0177] Examples of cationic surfactants include alkylamine salts and quaternary alkylammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, and ethylene oxide adducts thereof.

[0178] Commercially available products include, for example, Kao's Acetamine 24, Kotamine 24P, 60W, 86P Conc, etc.

[0179] Anionic surfactants include, for example, polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonate, sodium alkyl diphenyl ether disulfonate, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, stearic acid monoethanolamine, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate esters, and the like.

[0180] Commercially available products include, for example, Ftergent 100, 150 manufactured by Neos Co., Ltd., ADEKA HOPE YES-25, ADEKA COOL TS-230E, PS-440E, EC-8600 manufactured by ADEKA Corporation, and the like. Commercially available products include, for example, Amphitol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, 20N manufactured by Kao Corporation, and the like.

[0181] Amphoteric surfactants include, for example, alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocoamidopropyl betaine, stearyl betaine, alkyl dimethylaminoacetic acid betaine, and alkylamine oxides such as lauryldimethylamine oxide.

[0182] Commercially available products include, for example, Amphitol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, 20N manufactured by Kao Corporation, and the like.

[0183] The leveling agent (M) can be used alone or in combination of two or more.

[0184] The content of the leveling agent (M) is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass in 100% by mass of the non-volatile content of the photosensitive composition. When contained in an appropriate amount, the balance between the coating property and the adhesion of the photosensitive composition is further improved.

[0185] [Storage Stabilizer (N)] The photosensitive composition of the present invention can contain a storage stabilizer (N). Thereby, the viscosity of the photosensitive composition over time is stabilized. Examples of the storage stabilizer (N) include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine, and tetraphenyl, and phosphites.

[0186] The content of the storage stabilizer (N) is preferably 0.05 to 5% by mass in 100% by mass of the nonvolatile content of the photosensitive composition.

[0187] [Adhesion improver (O)] The photosensitive composition of the present invention can contain an adhesion improver (O). Thereby, the adhesion between the cured film and the substrate is improved. Also, it becomes easier to form a pattern with a narrow width by the photolithography method.

[0188] The adhesion promoter (O) includes, for example, silane coupling agents. Examples of silane coupling agents include vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane; (meth)acrylic silanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane; epoxy silanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane; amino silanes such as N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; mercapto silanes such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryl silanes such as p-styryltrimethoxysilane; ureido silanes such as 3-ureidopropyltriethoxysilane; sulfide silanes such as bis(triethoxysilylpropyl)tetrasulfide; and isocyanate silanes such as 3-isocyanatopropyltriethoxysilane, etc. Examples of the silane coupling agent include isocyanate silanes such as 3-isocyanatopropyltriethoxysilane.

[0189] The adhesion promoter (O) can be used alone or in combination of two or more.

[0190] The content of the adhesion promoter (O) is preferably 0.05 to 5% by mass in 100% by mass of the non-volatile content of the photosensitive composition.

[0191] [Method for manufacturing the photosensitive composition] When the photosensitive composition of the present invention uses a colorant (E), for example, a dispersion is produced by adding a resin (A), an organic solvent (D), a colorant (E), etc. and performing a dispersion treatment. Then, it can be produced by blending and mixing a resin (A), a polymerizable compound (B), a photopolymerization initiator (C), etc. into the dispersion. Note that the timing of blending each material is arbitrary. Also, the dispersion step can be performed multiple times.

[0192] Examples of the disperser for performing the dispersion treatment include a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor, etc.

[0193] The average dispersed particle diameter (secondary particle diameter) of the colorant (E) in the dispersion is preferably 30 to 200 nm, more preferably 40 to 200 nm. When it has an appropriate particle diameter, it is easy to obtain a photosensitive composition with high dispersion stability.

[0194] As a method for measuring the average dispersed particle diameter (secondary particle diameter), for example, using the Microtrac UPA-EX150 of Nikkiso Co., Ltd. that adopts the dynamic light scattering method (FFT power-spectrum method), the particle permeability is set to the absorption mode, the particle shape is set to non-spherical, and the D50 particle diameter is set as the average diameter. As the dilution solvent for measurement, the organic solvents used for dispersion are each used, and when measuring the sample treated with ultrasonic waves immediately after sample preparation, it is easy to obtain a result with less variation, which is preferable.

[0195] It is preferable to remove coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more, and mixed dust from the photosensitive composition by means such as centrifugation, filtration with a sintered filter or a membrane filter. The photosensitive composition of the present invention preferably does not substantially contain particles of 0.5 μm or more, and more preferably does not contain particles of 0.3 μm or less.

[0196] <Cured film> The cured film of the present invention is a cured product of the photosensitive composition. The cured film of the present invention can be used for an optical filter.

[0197] [Method of manufacturing the cured film] The method for producing the cured film is not particularly limited, and may include, for example, a method of carrying out the steps of (1) applying a photosensitive composition onto a substrate to form a layer of the composition, (2) exposing the layer to light through a mask in a pattern, (3) developing the unexposed parts with an alkali to form a patterned cured film, and (4) heat-treating (post-baking) the pattern. In the present invention, the preparation of the cured film is preferably carried out at a temperature of 130° C. or less throughout all steps, and more preferably at a temperature of 100° C. or less.

[0198] The method for producing the cured film will now be described in detail.

[0199] (Process (1)) The step (1) of forming a layer of the composition includes applying a photosensitive composition onto a substrate by, for example, spin coating or rotocoating. The coating is applied by a method such as roll coating, slit coating, casting coating, or inkjet coating, and dried (pre-baked) at a temperature of 50 to 100° C. for 10 to 120 seconds using an oven or a hot plate, if necessary. Examples of the substrate include a glass substrate, a resin substrate, and a silicon substrate. Examples of the resin substrate include a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamideimide substrate, and a polyimide substrate. An organic light-emitting layer may be formed on these substrates. For example, an imaging element such as a CCD or a CMOS may be formed on the surface of the silicon substrate. If necessary, an undercoat layer may be provided on the substrate to improve adhesion with the upper layer, prevent diffusion of substances, and flatten the substrate surface. The thickness of the layer is not particularly limited, but it is preferable to coat the layer so that the thickness after drying is 0.05 to 10.0 μm, and more preferably 0.3 to 5.0 μm.

[0200] (Process (2)) In the exposure step, the layer obtained in step (1) is exposed to light in a specific pattern through a mask using an exposure device such as a stepper, thereby obtaining a cured film. The radiation used for exposure includes, for example, ultraviolet rays such as g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), and i-rays (wavelength 365 nm). In addition, 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 lines (wavelength 248 nm), ArF (wavelength 193 nm), etc. Also, during exposure, the light may be continuously irradiated for exposure, or the exposure may be performed by repeating the irradiation and pause of the light in a short time cycle (for example, at the millisecond level or less) (pulse exposure).

[0201] (Step (3)) The cured film obtained in step (2) is subjected to an alkali development treatment, whereby the layer of the composition in the unexposed portion is eluted into the alkaline aqueous solution, and only the cured portion remains to obtain a patterned cured film. Examples of the developer include alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo-[5.4.0]-7-undecene, etc. The concentration of the alkaline developer is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. The pH of the alkaline developer is preferably 11 to 13, more preferably 11.5 to 12.5. When used at an appropriate pH, roughness and peeling of the pattern are suppressed, and the residual film rate after development is improved.

[0202] Examples of the development method include the dip method, the spray method, the paddle method, etc. The development temperature is preferably 15 to 40°C. In addition, after the alkali development, it is preferably washed with pure water.

[0203] (Step (4)) The heat treatment (post-bake) fully cures the patterned cured film obtained in step (3) by heating. The post-bake heating temperature is preferably 130°C or lower, more preferably 100°C or lower. The lower limit of the heating temperature is not particularly limited as long as curing can be promoted, but 50°C or higher is preferred. Also, the heating time is not particularly limited, but 5 minutes to 1 hour is preferred.

[0204] <Optical filter> The optical filter of the present invention has a cured film formed from the photosensitive composition of the present invention. The optical filter can be used for various applications. For example, it can be used for color filters, black matrices, infrared transmission filters, infrared cut filters, light-shielding filters, microlenses, etc. For example, by appropriately selecting the type of colorant (E) to be used, the color filter has the cured film of the present invention as red, green, and blue pixels. Similarly, it can also have magenta pixels, cyan pixels, yellow pixels, white pixels, gray pixels, and black pixels. Furthermore, it can also have clear pixels. The optical filter of the present invention can be manufactured in the same manner as the above-described cured film.

[0205] <Image display device> The image display device of the present invention includes the optical filter of the present invention. Examples of the image display device include a liquid crystal display, an organic EL display, etc. The form used in the image display device is not particularly limited as long as it functions as an image display device. For example, the configurations described in "Next-generation Liquid Crystal Display Technology" (written by Tatsuo Uchida, published by Kogyo Chosa Kai, 1994) can be mentioned. Regarding the definition of the image display device and the details of each image display device, they are described in, for example, "Electronic Display Devices" (written by Akio Sasaki, published by Kogyo Chosa Kai, 1990), "Display Devices" (written by Junsho Ibuki, published by Sangyo Tosho Co., Ltd., 1989), etc.

[0206] <Solid-state imaging device> The solid-state imaging device of the present invention includes the optical filter of the present invention. The form used for the solid-state imaging device is not particularly limited. For example, on a substrate, it has a plurality of photodiodes that constitute the light-receiving area of the solid-state imaging device (such as a CCD image sensor, a CMOS image sensor, etc.) and transfer electrodes made of polysilicon or the like. It has a light-shielding film with an opening only in the light-receiving part of the photodiode on the photodiode and the transfer electrodes, and has a device protection film made of silicon nitride or the like formed so as to cover the entire surface of the light-shielding film and the light-receiving part of the photodiode. On the device protection film, it has a configuration with a filter. Further, a configuration having condensing means (for example, a microlens, etc. The same applies hereinafter) on the device protection film and under the filter (the side closer to the substrate), or a configuration having condensing means on the filter may be used. Also, the filter may have a structure in which a cured film forming each colored pixel is embedded in a space partitioned, for example, in a lattice shape by partition walls. In this case, the partition walls preferably have a low refractive index with respect to each colored pixel. The imaging device provided with the solid-state imaging device of the present invention can be used for various applications such as, for example, a digital camera, an electronic device having an imaging function (such as a mobile phone, a smartphone, etc.), an in-vehicle camera, a surveillance camera, and an optical sensor.

Example

[0207] Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited thereto. Note that "part" means "part by mass" and "%" means "% by mass". In the present invention, the non-volatile content or the non-volatile content concentration refers to the mass residue after standing in an oven at 230 °C for 30 minutes.

[0208] Prior to the examples, each measurement method will be described.

[0209] The measurement of the weight average molecular weight (Mw), number average molecular weight (Mn), acid value (mgKOH / g), and amine value (mgKOH / g) of the resin is as follows.

[0210] (Average molecular weight of resin) The number average molecular weight (Mn) and weight average molecular weight (Mw) of the resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. Using HLC-8220GPC (manufactured by Tosoh Corporation) as the apparatus, two separation columns were connected in series, and for both packing materials, "TSK-GEL SUPER HZM-N" was connected in pairs and used. The oven temperature was 40°C, a tetrahydrofuran (THF) solution was used as the eluent, and the measurement was carried out at a flow rate of 0.35 ml / min. The sample was dissolved in a solvent consisting of 1 mass% of the above eluent and 20 μl was injected. The molecular weight is in terms of polystyrene conversion.

[0211] (Acid value of the resin) To 0.5 - 1 g of the resin solution, 80 ml of acetone and 10 ml of water were added and stirred until uniformly dissolved. Using a 0.1 mol / L aqueous KOH solution as the titrant, titration was carried out using an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.), and the acid value (mgKOH / g) was measured. Then, from the acid value of the resin solution and the non-volatile content concentration of the resin solution, the acid value per non-volatile content of the resin was calculated.

[0212] (Amine value of the resin) The amine value of the resin is the value obtained by converting the total amine value (mgKOH / g) measured in accordance with the method of ASTM D 2074 to non-volatile content.

[0213] (Production of resin (A)) (Resin (A1-1) solution) Into a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 257.3 g of propylene glycol monomethyl ether acetate (hereinafter, PGMAc) was placed. After that, while purging with nitrogen, the mixture was stirred and heated to 78°C. Next, 22.4 parts of dicyclopentanyl methacrylate, which is a monomer forming an alicyclic hydrocarbon-containing monomer unit (a6), 17.2 parts of methacrylic acid, which is a monomer forming an acidic group-containing monomer unit (a2), 49.8 parts of methyl methacrylate, which is a monomer forming other monomer units (a8), and 63.0 parts of Calenz MOI-DEM (2-[[[2-methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl ester of malonic acid, manufactured by Showa Denko K.K.), which is a monomer forming a blocked isocyanate group-containing monomer unit (a1), and 11.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) dissolved in 78.7 parts of PGMAc were added dropwise from the dropping funnel into the flask. After completion of the dropwise addition, the mixture was stirred at 78°C for 3 hours. Thereafter, PGMAc was added so that the nonvolatile content became 40% by mass to prepare a resin (A1-1) solution. The resin (A1-1) had an acid value of 111 mgKOH / g and a weight average molecular weight of 9,500.

[0214] (Resin (A1-2) to (A1-4) solutions) Resins (A1-2) to (A1-4) were synthesized so as to have the molar ratios of the respective components described in Table 1, and PGMAc was added to make the nonvolatile content 40% by mass.

[0215]

Table 1

[0216] (Resin (A2-1) solution) 196 parts of cyclohexanone was charged into a separable four-necked flask equipped with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping funnel, and a stirrer, and the temperature was raised to 80 °C. After replacing the inside of the reaction vessel with nitrogen, a mixture of 20.2 parts of methacrylic acid, which is a monomer forming a monomer unit (a2) containing an acidic group, 21.8 parts of 2-hydroxyethyl methacrylate, which is a monomer forming a monomer unit (a3) containing a hydroxyl group, 38.9 parts of Aronix M-110 (para-cumylphenol EO-modified acrylate manufactured by Toagosei Co., Ltd.), which is a monomer represented by the general formula (1), 39.0 parts of benzyl methacrylate, which is a monomer forming another monomer unit (b8), 35.8 parts of n-butyl methacrylate, and 1.0 part of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours from the dropping funnel. After completion of the dropping, the reaction was further continued for 3 hours. After cooling to room temperature, PGMAc was added so that the non-volatile content became 40% by mass to prepare a resin (A2-1) solution. The resin (A2-1) had an acid value of 81 mgKOH / g and a weight average molecular weight of 28,000.

[0217] (Resin (A2-2) and (A2-3) solutions) Resins (A2-2) and (A2-3) were synthesized so as to have a molar ratio with each of the constituent components described in Table 2, and PGMAc was added to make the non-volatile content 40% by mass.

[0218]

Table 2

[0219] GMA+AA described in Table 2 represents a polymerizable unsaturated group-containing monomer unit (b5) obtained by adding acrylic acid (hereinafter also referred to as AA) to the epoxy group of glycidyl methacrylate (hereinafter also referred to as GMA). GMA+AA+THPA represents a polymerizable unsaturated group-containing monomer unit (b5) obtained by reacting the hydroxyl group of GMA+AA with tetrahydrophthalic anhydride (hereinafter also referred to as THPA).

[0220] (Resin (A3-1) solution) Into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 108 parts of 1-thioglycerol, 174 parts of pyromellitic dianhydride, 650 parts of PGMAc, and 0.2 part of monobutyltin oxide as a catalyst were charged. After purging with nitrogen gas, the mixture was reacted at 120 °C for 5 hours ( First step). It was confirmed by acid value measurement that 95% or more of the acid anhydride was half-esterified. Next, 160 parts of the compound obtained in the first step in terms of non-volatile content, 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of t-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, 200 parts of methyl acrylate, 50 parts of methacrylic acid, and 663 parts of PGMAc were charged. The inside of the reaction vessel was heated to 80 °C, 1.2 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, and the mixture was reacted for 12 hours (second step). It was confirmed by non-volatile content measurement that 95% had reacted. Finally, 500 parts of a 50% PGMAc solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate (MOI), and 0.1 part of hydroquinone were charged, and the reaction was carried out until the disappearance of the peak at 2270 cm -1 based on the isocyanate group was confirmed by IR (third step). After confirming the disappearance of the peak, the reaction solution was cooled, and the non-volatile content was adjusted with PGMAc to obtain a resin (A3-1) solution having a non-volatile content of 30% by mass. Resin (A3-1) had an acid value of 68 mg KOH / g, an unsaturated double bond equivalent of 1,593, and a weight average molecular weight of 13,000.

[0221] (Resin (A3-2) solution) Into a reaction vessel equipped with a gas inlet tube, a temperature sensor, a condenser, and a stirrer, 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of i-butyl methacrylate, 20 parts of benzyl methacrylate, and 50 parts of PGMAc were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated and stirred at 50 °C, and 12 parts of 3-mercapto-1,2-propanediol were added. The temperature was raised to 90 °C, and a solution prepared by adding 0.1 part of 2,2'-azobisisobutyronitrile to 90 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAc) was added while reacting for 7 hours. It was confirmed by non-volatile content measurement that 95% of the reaction had occurred. 19 parts of pyromellitic dianhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 part of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was carried out at 100 °C for 7 hours. It was confirmed by acid value measurement that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. PGMAc was added and diluted to a non-volatile content of 30% by mass to obtain a resin (A3-2) solution. The resin (A3-2) had an acid value of 70 mgKOH / g and a weight average molecular weight of 8,500.

[0222] (Resin (A3-3) solution) Into a reaction apparatus equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, 30 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, 20 parts of hydroxyethyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged, stirred at 50 °C for 1 hour while flowing nitrogen, and the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and the temperature was raised to 110 °C under a nitrogen stream to initiate the polymerization of the first block (B block). After 4 hours of polymerization, the polymerization solution was sampled for non-volatile content measurement, and it was confirmed that the polymerization conversion rate was 98% or more in terms of non-volatile content. Next, 61 parts of PGMAc and 20 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate (Funacryl FA-711MM, manufactured by Hitachi Chemical Co., Ltd.) as the second block (A block) monomer were charged into this reactor, and the mixture was stirred while maintaining the temperature at 110°C under a nitrogen atmosphere to continue the reaction. Two hours after the addition of 1,2,2,6,6-pentamethylpiperidyl methacrylate, the polymerization solution was sampled for non-volatile content measurement. It was confirmed that the polymerization conversion rate of the second block (A block) was 98% or more in terms of non-volatile content, and the reaction solution was cooled to room temperature to stop the polymerization. PGMAc was added for dilution so that the non-volatile content became 30% by mass in the non-volatile content measurement to obtain a resin (A3-3) solution. The resin (A3-3) had an amine value of 57 mgKOH / g and a number average molecular weight of 4,500.

[0223] <Production of Polymerizable Compound (B)> (Polymerizable Compound (B1-3)) 250 parts of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate were added to a four-necked flask equipped with a thermometer, a stirrer, and a reflux tube. After adding 17.3 parts of di-n-butylamine at room temperature, the reaction was carried out at 50°C for 4 hours to obtain a polymerizable compound (B1-3). The reaction was carried out under a mixed atmosphere of air / nitrogen.

[0224] (Polymerizable Compound (B2-8)) 400 parts of dipentaerythritol pentaacrylate, 100 parts of PGMAc, and 0.5 part of N,N-dimethylbenzylamine were charged into a five-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping tube. The temperature was raised to 70°C, and a mixture of 66 parts of toluene diisocyanate and 66 parts of PGMAc was dropped from the dropping tube over 2 hours. After the dropping, the reaction was carried out at a temperature of 50 to 70°C for 8 hours, and the disappearance of the absorption of isocyanate at 2180 cm -1 was confirmed by IR. Then, 35 parts of mercaptoacetic acid and 0.6 part of 4-methoxyphenol were charged, and the reaction was carried out at a temperature of 50 to 60°C for 6 hours to obtain a polymerizable compound (B2-8) having an acidic group and a urethane bond. PGMAc was added so that the non-volatile content became 50% by mass.​

[0225] <Production of Colorant (E)> (Fine - grained Blue Pigment (E - 2)) 100 parts of C.I. Pigment Blue 15:6, 1,000 parts of sodium chloride, and 100 parts of diethylene glycol were charged into a 1 - gallon stainless - steel kneader (manufactured by Inoue Seisakusho), and kneaded at 50°C for 12 hours. This mixture was poured into 3,000 parts of warm water, stirred with a high - speed mixer for about 1 hour while heating to about 70°C to form a slurry, and then filtered and washed repeatedly to remove sodium chloride and diethylene glycol. After that, it was dried at 80°C for 24 hours and pulverized to obtain the fine - grained blue pigment (E - 2).

[0226] (Fine - grained Violet Pigment (E - 3)) 100 parts of C.I. Pigment Violet 23, 1,000 parts of sodium chloride, and 100 parts of diethylene glycol were charged into a 1 - gallon stainless - steel kneader (manufactured by Inoue Seisakusho), and kneaded at 70°C for 12 hours. This mixture was poured into 3,000 parts of warm water, stirred with a high - speed mixer for about 1 hour while heating to about 70°C to form a slurry, and then filtered and washed repeatedly to remove sodium chloride and diethylene glycol. After that, it was dried at 80°C for 24 hours and pulverized to obtain the fine - grained violet pigment (E - 3).

[0227] (Fine - grained Red Pigment (E - 4)) 100 parts of C.I. Pigment Red 254, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1 - gallon stainless - steel kneader (manufactured by Inoue Seisakusho), and kneaded at 60°C for 6 hours. Next, the kneaded mixture was poured into 3,000 parts of warm water, stirred with a high - speed mixer for 1 hour while heating to about 80°C to form a slurry, and then filtered and washed to remove sodium chloride and diethylene glycol. After that, it was dried at 80°C for 24 hours and pulverized to obtain the fine - grained red pigment (E - 4).

[0228] (Fine - grained Red Pigment (E - 5)) 100 parts of C.I. Pigment Red 177, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho), and kneaded at 60 °C for 6 hours. Next, this mixture was poured into 3,000 parts of warm water, stirred with a high-speed mixer for 1 hour while heating to about 80 °C to form a slurry, filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 °C for 24 hours and pulverized to obtain a refined red pigment (E-5).

[0229] (Refined yellow pigment (E-6)) 100 parts of C.I. Pigment Yellow 138, 1,000 parts of sodium chloride, and 100 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho). It was kneaded at 80 °C for 6 hours. This mixture was poured into 3,000 parts of warm water, stirred with a high-speed mixer for 1 hour while heating to 80 °C to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 °C for 24 hours and pulverized to obtain a refined yellow pigment (E-6).

[0230] (Refined yellow pigment (E-7)) 100 parts of C.I. Pigment Yellow 139, 800 parts of sodium chloride, and 100 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho), and kneaded at 70 °C for 12 hours. This mixture was poured into 3,000 parts of warm water, stirred with a high-speed mixer for about 1 hour while heating to about 70 °C to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 °C for 24 hours and pulverized to obtain a refined yellow pigment (E-7).

[0231] (Refined green pigment (E-8)) 100 parts of C.I. Pigment Green 58, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 70°C for 6 hours. This kneaded product was put into 3,000 parts of warm water and stirred with a high-speed mixer for 1 hour while heating to 70°C to form a slurry. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80°C for a whole day and night and pulverized to obtain a green pigment (E-8) that was micronized.

[0232] <Manufacture of Dispersion> (Dispersion 1) After stirring and mixing the following raw materials to make them uniform, they were dispersed using zirconia beads with a diameter of 0.5 mm in an Eiger mill (manufactured by Eiger Japan Co., Ltd., "Mini Model M-250 MKII") for 3 hours, and then filtered through a filter with a pore size of 1.0 μm to prepare Dispersion 1. The organic solvent (D-1) is PGMAc. Carbon black (manufactured by Mitsubishi Chemical Corporation #850): 15.0 parts Resin (A3-1) solution: 15.0 parts Resin (A3-2) solution: 5.0 parts Dye derivative (G-1): 0.5 part Organic solvent (D-1): 64.5 parts

[0233] Mitsubishi Chemical Corporation #850 is carbon black with an average primary particle diameter of 17 nm and a specific surface area of 220 m 2 / g.

[0234] Dye derivative (G-1): The following structure

Chemical formula

[0235] (Dispersions 2 to 11) Dispersions 2 to 8 were prepared in the same manner as Dispersion 1, except that the raw materials and amounts described in Table 3 were changed.

[0236]

Table 3

[0237] Dye derivative (G-2) in Table 3: The following structure [Chemical formula]

[0238] Dye derivative (G-3) in Table 3: The following structure [Chemical formula]

[0239] Dye derivative (G-4) in Table 3: The following structure [Chemical formula]

[0240] <Production of photosensitive composition> [Example 1] (Photosensitive composition 1) The following raw materials were mixed, stirred, and filtered through a filter with a pore size of 1.0 μm to obtain photosensitive composition 1. Dispersion 2: 32.0 parts Dispersion 3: 2.0 parts Resin (A1-2) solution: 5.0 parts Polymerizable compound (B1-1): 1.0 part Polymerizable compound (B2-1): 4.0 parts Photoinitiator (C-1): 0.4 part Sensitizer (F): 0.6 part Leveling agent (M): 1.0 part Organic solvent (D): 54.0 parts

[0241] [Examples 2 to 48, Comparative Example 1] (Photosensitive compositions 2 to 49) Photosensitive compositions 2 to 49 were prepared in the same manner as in Example 1, except that the raw materials and amounts described in Tables 4-1 to 4-5 were changed.

[0242]

Table 4-1

[0243]

Table 4-2

[0244]

Table 4-3

[0245]

Table 4-4

[0246]

Table 4-5

[0247] Regarding each of the raw materials described in Tables 4-1 to 4-5, it is as follows.

[0248] [Polymerizable compound (B)] (Polymerizable compound (B1)) B1-1: Aronix MT-3041 (manufactured by Toagosei Co., Ltd.) B1-2: Aronix MT-3042 (manufactured by Toagosei Co., Ltd.) B1-4: Tris(acryloyloxyethyl)amine

[0249] (Polymerizable compound (B2)) B2-1: Etercure 6361-100 (manufactured by Eternal Materials, a polymerizable compound having a hyperbranched structure with an average acryloyl group number of 8) B2-2: CN2303 (manufactured by Sartomer, a polymerizable compound having a hyperbranched structure with an average acryloyl group number of 6) B2-3: Etercure 6363 (a compound manufactured by Eternal Materials, having a hyperbranched structure with an average acryloyl group number of 16) B2-4: Miramer SP-1106 (a polymerizable compound manufactured by Miwon Specialty Chemical, having a dendrimer structure with an average acryloyl group number of 18) B2-5: Biscoat #1000LT (a polymerizable compound manufactured by Osaka Organic Chemical Industry Co., Ltd., having a dendrimer structure with an average acryloyl group number of 14) B2-6: Aronix M-402 (a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Toagosei Co., Ltd.) B2-7: Aronix M-520 (a penta-functional acrylate having an acidic group, manufactured by Toagosei Co., Ltd.) B2-9: Aronix M-309 (trimethylolpropane triacrylate, manufactured by Toagosei Co., Ltd.)

[0250] [Photoinitiator (C)] C-1: The photoinitiator of the above chemical formula (8) C-2: The photoinitiator of the above chemical formula (9) C-3: The photoinitiator of the above chemical formula (10) C-4: Omnirad 369E (manufactured by IGM Resins, an acetophenone-based compound)

[0251] [Organic solvent (D)] D-1: 30 parts of propylene glycol monomethyl ether acetate D-2: 30 parts of cyclohexanone D-3: 10 parts of ethyl 3-ethoxypropionate D-4: 10 parts of propylene glycol monomethyl ether D-5: 10 parts of cyclohexanol acetate D-6: 10 parts of dipropylene glycol methyl ether acetate Above, (D-1) to (D-6) were mixed in the above parts by mass respectively to obtain the organic solvent (D).

[0252] [Sensitizer (F)] F-1: Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd., thioxanthone-based compound) F-2: CHEMARK DEABP (manufactured by Chemark Chemical, benzophenone-based compound) As described above, (F-1) and (F-2) were each mixed in the same amount to obtain a sensitizer (F).

[0253] [Leveling agent (M)] M-1: BYK-330 (manufactured by BYK Chemie, silicone surfactant) M-2: Megafac F-551 (manufactured by DIC Corporation, fluorine-based surfactant) As described above, (M-1) and (M-2) were each mixed in 1 part and dissolved in 98 parts of PGMAc to obtain a mixed solution as the leveling agent (M). The resulting mixed solution was used as the leveling agent (M).

[0254] [Evaluation of photosensitive composition] For the obtained photosensitive compositions 1 to 49 (Examples 1 to 48, Comparative Example 1), the evaluation of pattern formability and solvent resistance was carried out by the following methods. The evaluation results are shown in Table 5.

[0255] [Pattern formability evaluation: Adhesion] The obtained photosensitive composition was spin-coated onto a glass substrate (Eagle 2000 manufactured by Corning) with a length of 100 mm, a width of 100 mm, and a thickness of 0.7 mm so that the film thickness after drying was 2.0 μm, and then dried on a hot plate at 70°C for 1 minute. Next, after cooling this substrate to room temperature, using a high-pressure mercury lamp, it was exposed through a photomask of stripe patterns with a width of 5 to 25 μm in 5-μm increments at an illuminance of 30 mW / cm 2 , 50 mJ / cm 2 . Then, this substrate was spray-developed using an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23°C, and then washed with ion-exchanged water and air-dried. The spray development was carried out at the shortest time capable of forming a pattern without any remaining development for the coating of each photosensitive composition. For the patterns on the obtained substrates with widths of 5, 10, 15, 20, and 25 μm, observation was carried out with an optical microscope, and the minimum line width of the remaining patterns was confirmed. The evaluation criteria are as follows, and a value of 3 or more is considered practical. 5: Fine lines of 10 μm or less remain. 4: Fine lines of 15 μm or more remain. 3: Fine lines of 20 μm or more remain. 2: Fine lines of 25 μm remain. 1: No fine lines remain.

[0256] [Solvent Resistance Evaluation (1): 130 °C Post-Bake] The obtained photosensitive composition was applied by the spin coating method onto a glass substrate (Eagle 2000 manufactured by Corning) with a length of 100 mm, a width of 100 mm, and a thickness of 0.7 mm so that the film thickness after drying would be 2.0 μm, and dried on a hot plate at 70 °C for 1 minute. Next, after cooling this substrate to room temperature, using a high-pressure mercury lamp, with an illuminance of 30 mW / cm 2 and 50 mJ / cm 2 , ultraviolet light was irradiated through a photomask with a 100-μm-wide stripe pattern. Further, after cooling this substrate to room temperature, spray development was carried out using an aqueous developer containing 0.12% of a non-ionic surfactant at 23 °C and 0.04% of potassium hydroxide, followed by washing with ion-exchanged water and air drying. Then, post-baking was carried out in a clean oven at 130 °C for 60 minutes to obtain a substrate for evaluation. The obtained substrate for evaluation was immersed in propylene glycol monomethyl ether acetate at room temperature for 15 minutes, then washed with ion-exchanged water and air dried, and the 100-μm-wide stripe pattern portion was observed using an optical microscope. The evaluation criteria are as follows, and a value of 3 or more is considered practical. 5: No change in appearance or color. 4: Slight wrinkles or the like occur, but there is no change in color. 3: Wrinkles or the like occur in part, but there is no change in color. 2: Wrinkles or the like occur over the entire surface, and there is a slight discoloration. 1: Peeling or discoloration occurs.

[0257] [Solvent Resistance Evaluation (2): 100 °C Post-Baking] The obtained photosensitive composition was applied by spin coating onto a glass substrate (Eagle 2000 manufactured by Corning Inc.) with a length of 100 mm, a width of 100 mm, and a thickness of 0.7 mm so that the film thickness after drying was 2.0 μm, and dried on a hot plate at 70 °C for 1 minute. Next, after cooling this substrate to room temperature, using a high-pressure mercury lamp, an illuminance of 30 mW / cm 2 , 50 mJ / cm 2 , and ultraviolet light was exposed through a photomask with a 100-μm-wide stripe pattern. Furthermore, after cooling this substrate to room temperature, it was spray-developed using an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 °C, then washed with ion-exchanged water and air-dried. Thereafter, it was post-baked in a clean oven at 100 °C for 60 minutes to obtain a substrate for evaluation. The obtained substrate for evaluation was immersed in propylene glycol monomethyl ether acetate at room temperature for 15 minutes, then washed with ion-exchanged water and air-dried, and the stripe pattern portion with a width of 100 μm was observed using an optical microscope. The evaluation criteria are as follows, and a score of 3 or more is considered practical. 5: No change in appearance or color. 4: Slight wrinkles or the like occur, but there is no change in color. 3: Wrinkles or the like occur in part, but there is no change in color. 2: Wrinkles or the like occur over the entire surface and fade slightly. 1: Peeling or fading occurs.

[0258]

Table 5

Claims

1. A photosensitive composition comprising a resin (A), a polymerizable compound (B), a photoinitiator (C), and an organic solvent (D), wherein the polymerizable compound (B) includes a polymerizable compound (B1) having three or more (meth)acryloyl groups and an amine structure, and a polymerizable compound (B2) other than the polymerizable compound (B1) having three or more (meth)acryloyl groups and an amine structure, and the polymerizable compound (B2) includes a polymerizable compound having a dendrimer structure or a hyperbranched structure; the resin (A) includes a resin (A1) having a blocked isocyanate group-containing monomer unit (a1) and an acidic group-containing monomer unit (a2) using an active methylene compound as a blocking agent, the photosensitive composition.

2. The photosensitive composition according to claim 1, wherein the polymerizable compound (B2) includes a polymerizable compound having four or more (meth)acryloyl groups.

3. The photosensitive composition according to claim 1 or 2, wherein the content of the polymerizable compound (B1) having three or more (meth)acryloyl groups and an amine structure is 5 to 80% by mass in 100% by mass of the polymerizable compound (B).

4. The photosensitive composition according to any one of claims 1 to 3, comprising a colorant (E).

5. A method for producing a cured film, comprising: a step (1) of applying a photosensitive composition on a substrate to form a layer of the composition; a step (2) of exposing the layer in a pattern through a mask; a step (3) of developing unexposed portions with an alkali to form a patterned cured film; and a step (4) of heat-treating the pattern at 130 ° C. or lower, wherein the photosensitive composition includes a resin (A), a polymerizable compound (B), a photoinitiator (C), and an organic solvent (D); the polymerizable compound (B) includes a polymerizable compound (B1) having three or more (meth)acryloyl groups and an amine structure, and a polymerizable compound (B2) other than the polymerizable compound (B1) having three or more (meth)acryloyl groups and an amine structure, and the polymerizable compound (B2) includes a polymerizable compound having a dendrimer structure or a hyperbranched structure; the resin (A) includes a resin (A1) having a blocked isocyanate group-containing monomer unit (a1) and an acidic group-containing monomer unit (a2) using an active methylene compound as a blocking agent, the method for producing a cured film.

6. A cured film which is a cured product of the photosensitive composition according to any one of claims 1 to 4.

7. An optical filter having the cured film according to claim 6. **Claim 8** An image display device having the optical filter according to claim 7. **Claim 9** A solid-state imaging device having the optical filter according to claim 7.

Images