JP7722164B2 - Photosensitive composition, optical filter, image display device and solid-state imaging device - Google Patents

Description

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

Organic EL (Electro-Luminescence) display devices using OLEDs (Organic Light-Emitting Diodes) and other elements do not require backlighting, making them lighter, thinner, and more energy-efficient than LCDs and other displays. They are also foldable, and are used in a variety of applications, including smartphones, tablet devices, and televisions.

Because the heat resistance of the organic light-emitting layers used in organic EL display devices is generally low, it is preferable to cure the photosensitive composition used to form the optical filters used in organic EL display devices at low temperatures, for example, 150°C or below. However, when curing is performed at low temperatures, the curing does not proceed sufficiently, resulting in a decrease in hardness of the cured film, and problems such as reduced adhesion and changes in film thickness at high temperatures and high humidity can occur.

Organic EL display devices also feature a circular polarizer as an anti-reflection filter to prevent reduced visibility due to reflection of external light. However, circular polarizers are generally thick and have low flexibility, so photosensitive compositions that can be used to form optical filters in place of circular polarizers are being investigated. However, because such photosensitive compositions have a low colorant concentration, when optical filters are formed using photolithography, they tend to transmit ultraviolet light, which creates a problem of increased line width in the pattern.

To solve the above problems, for example, Patent Document 1 discloses a coloring composition that contains a colorant containing a red colorant, a resin having a repeating unit containing a blocked isocyanate group, a polymerizable compound, and a photopolymerization initiator, and that specifies the ratio of the maximum and minimum absorbance values at a specific wavelength. Furthermore, Patent Document 2 discloses a coloring composition that contains a colorant, a polymer, and a polymerizable compound, and at least one selected from the group consisting of the colorant, polymer, and polymerizable compound has a specific partial structure and a hydroxyl group.

International Publication No. 2021/054248 Japanese Patent Application Laid-Open No. 2021-102759

However, the compositions described in Patent Documents 1 and 2 were unable to satisfy all of the following requirements at a certain level: pattern line width stability, hardness of the cured film when cured at low temperature, and high-temperature/high-humidity resistance (adhesion and film thickness stability).

The present invention aims to provide a photosensitive composition that can form a cured film that has excellent pattern line width stability, excellent hardness even when cured at low temperatures, and high-temperature and high-humidity resistance (adhesion and film thickness stability).

The present invention provides a photosensitive composition comprising an alkali-soluble resin (A), a polymerizable compound (B), a photopolymerization initiator (C), a thermosetting compound (D), and an imidazole compound (E),
The present invention relates to a photosensitive composition in which the imidazole compound (E) contains a compound (E1) represented by the following general formula (1):
General formula (1)

(In general formula (1), X ₁ to X ₃ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms.)

The present invention provides a photosensitive composition that can form a cured film that has excellent pattern line width stability, excellent hardness even when cured at low temperatures, and high-temperature, high-humidity resistance (adhesion and film thickness stability). The present invention also provides optical filters, image display devices, and solid-state imaging devices.

The following describes in detail embodiments of the photosensitive composition of the present invention. Note that the present invention is not limited to the following embodiments, and can be modified within the scope of the problems that can be solved.

In this specification, unless otherwise specified, "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" means "acryloyl and/or methacryloyl", "acrylic and/or methacrylic", "acrylic acid and/or methacrylic acid", "acrylate and/or methacrylate", or "acrylamide and/or methacrylamide", respectively. In addition, "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 a compound in the present invention, for a low molecular weight compound whose molecular weight can be specified, the molecular weight is a calculated value (formula weight) or a molecular weight measured by ESI-MS (electrospray ionization mass spectrometry), and for a compound having a molecular weight distribution, the molecular weight is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran as a solvent.
A monomer is a compound that polymerizes to form a resin. A monomer is in an unreacted state, and a monomer unit is a monomer that forms a resin after polymerization.

<Photosensitive composition>
A photosensitive composition according to one embodiment of the present invention is a photosensitive composition comprising an alkali-soluble resin (A), a polymerizable compound (B), a photopolymerization initiator (C), a thermosetting compound (D), and an imidazole compound (E),
The imidazole compound (E) contains a compound (E1) represented by the following general formula (1):
General formula (1)

(In general formula (1), X ₁ to X ₃ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms.)

The mechanism by which the photosensitive composition having the above configuration can solve the problems of the present invention is unclear, but is speculated as follows.

The imidazole compound (E) reacts with the thermosetting compound (D) to promote the initiation of a crosslinking reaction between the thermosetting compounds (D). It is presumed that the compound (E1) represented by general formula (1) in which the nitrogen at position 1 is substituted with a benzyl group reacts with the thermosetting compound (D) at a lower temperature than an imidazole compound in which the nitrogen at position 1 is not substituted with a benzyl group, and then the crosslinking reaction between the thermosetting compounds (D) proceeds. Therefore, a cured film having excellent hardness and high-temperature and high-humidity resistance can be formed even at low temperature curing.
It is speculated that this mechanism involves the fact that when the nitrogen at position 1 is not substituted with a benzyl group, the 1-position is a secondary amine and the 3-position is a tertiary amine, but in reality, the hydrogen bonded to the nitrogen at position 1 forms a resonance structure with the nitrogen at position 3, making them equivalent, inhibiting the reaction between the thermosetting compound (D) and the tertiary amine, making the reaction rate-determining and causing the reaction to occur only at high temperatures. In contrast, when the 1-position is substituted with a benzyl group, the resonance disappears, resulting in a structure with two tertiary amines, which allows the thermosetting compound (D) to react with the tertiary amine even at lower temperatures, initiating a crosslinking reaction between the curable compounds (D).

The components that are or can be included in one embodiment of the photosensitive composition are described in detail below.

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

The alkali-soluble resin (A) may be any resin that dissolves in an alkaline developer, and known resins can be used. Examples include (meth)acrylic resins, styrene resins, styrene-(meth)acrylic resins, urethane resins, polycarbonate resins, polyester resins, polyether resins, polyimide resins, polyamide-imide resins, and cyclic olefin resins.

From the viewpoint of developability, the weight-average molecular weight (Mw) of the alkali-soluble resin (A) is preferably 4,000 to 40,000, and more preferably 4,000 to 35,000. Furthermore, the Mw/Mn value is preferably 10 or less. An appropriate weight-average molecular weight (Mw) improves adhesion to the substrate and solubility in development.

The acid value of the alkali-soluble resin (A) is preferably 30 to 200 mgKOH/g, more preferably 40 to 180 mgKOH/g. A moderate acid value improves adhesion to the substrate and solubility in development.

The content of alkali-soluble resin (A) is preferably 1 to 80% by mass, more preferably 5 to 60% by mass, and particularly preferably 10 to 50% by mass, based on 100% by mass of the non-volatile content of the photosensitive composition.

The alkali-soluble resin (A) can be used alone or in combination of two or more types.

(Alkali-soluble resin having blocked isocyanate group-containing monomer unit (a1) and hydroxyl group-containing monomer unit (a2))
From the viewpoint of low-temperature curing, the photosensitive composition of the present invention preferably contains an alkali-soluble resin (A) having a blocked isocyanate group-containing monomer unit (a1) and a hydroxyl group-containing monomer unit (a2), which crosslinks between or within the alkali-soluble resin (A) upon heating, improving the durability of the cured film.

[Blocked isocyanate group-containing monomer unit (a1)]
The blocked isocyanate group-containing monomer is a monomer in which the isocyanate group of an isocyanate group-containing monomer is protected with a compound that is eliminated by heat (hereinafter also referred to as a blocking agent). The elimination temperature of the blocking agent is preferably 60 to 160°C, more preferably 80 to 140°C.

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

Blocking agents include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, imide compounds, urea compounds, imine compounds, and bisulfite compounds.

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

The blocking agent is preferably at least one selected from the group consisting of oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds, and from the viewpoint of protection reactions and deprotection reactions, at least one selected from the group consisting of oxime compounds, phenol compounds, active methylene compounds, and pyrazole compounds is more preferred.

Examples of blocked isocyanate group-containing monomers include the following compounds. However, the present invention is not limited to these.

Commercially available blocked isocyanate group-containing monomers include, for example, Karenz MOI-DEM (blocking agent desorption temperature: 85-95°C), MOI-BP (blocking agent desorption temperature: 105-115°C), and MOI-BM (blocking agent desorption temperature: 125-135°C) manufactured by Showa Denko K.K.

From the viewpoint of low-temperature curing, the content of the blocked isocyanate group-containing monomer unit (a1) is preferably 1 to 50 mol %, and more preferably 5 to 40 mol %, of all structural units of the alkali-soluble resin.

[Hydroxyl group-containing monomer unit (a2)]
Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-acryloyloxyethyl-2-hydroxyethyl phthalate.

From the viewpoint of low-temperature curing, the content of the hydroxyl group-containing monomer unit (a2) is preferably 5 to 50 mol %, and more preferably 10 to 40 mol %, of all structural units of the alkali-soluble resin.

From the viewpoint of low-temperature curing, the molar ratio of the blocked isocyanate group-containing monomer unit (a1) to the hydroxyl group-containing monomer unit (a2) is preferably 10:90 to 50:50, and more preferably 15:85 to 45:55.

The alkali-soluble resin having a blocked isocyanate group-containing monomer unit (a1) and a hydroxyl group-containing monomer unit (a2) may contain a monomer unit other than the blocked isocyanate group-containing monomer unit (a1) and the hydroxyl group-containing monomer unit (a2). Examples of such a monomer unit include an alicyclic hydrocarbon-containing monomer unit (a3), an acidic group-containing monomer unit (a4), an epoxy group-containing monomer unit (a5), a polymerizable unsaturated group-containing monomer unit (a6), and other monomer units (a7). Among these, from the viewpoints of the hardness of the cured film and resistance to high temperatures and high humidity, it is preferable to contain an alicyclic hydrocarbon-containing monomer unit (a3).

[Alicyclic hydrocarbon-containing monomer unit (a3)]
Examples of the alicyclic hydrocarbon-containing monomer include isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, adamantyl (meth)acrylate, etc. Among these, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentanyloxyethyl (meth)acrylate are preferred.

From the viewpoints of hardness of the cured film and resistance to high temperatures and humidity, the content of the alicyclic hydrocarbon-containing monomer unit (a3) is preferably 1 to 40 mol %, and more preferably 5 to 30 mol %, of all structural units of the alkali-soluble resin.

[Acidic group-containing monomer unit (a4)]
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, and 2-(meth)acryloyloxyethyl acid phosphate.

From the viewpoint of developability, the content of the acidic group-containing monomer unit (a4) is preferably 1 to 40 mol %, and more preferably 5 to 30 mol %, of all structural units of the alkali-soluble resin.

[Epoxy group-containing monomer unit (a5)]
Examples of epoxy group-containing monomers include oxiranyl (meth)acrylate, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, 2-oxiranylethyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate, 2-(3,4-epoxycyclohexylmethyloxy)ethyl (meth)acrylate, and 3-(3,4-epoxycyclohexylmethyloxy)propyl (meth)acrylate.

[Polymerizable unsaturated group-containing monomer unit (a6)]
Examples of the polymerizable unsaturated group-containing monomer unit (a6) include units introduced by the following methods (i) to (iii).

<Method (i)>
There is also mentioned a method (i) in which the above-mentioned epoxy group-containing monomer is added to the acidic group of a resin having an acidic group-containing monomer unit (a4).

<Method (ii)>
There is also mentioned a method (ii) in which the above-mentioned acidic group-containing monomer is added to the epoxy group of a resin having an epoxy group-containing monomer unit (a5).

In addition, units obtained by further reacting an acid anhydride with the hydroxyl group generated by the reaction of methods (i) and (ii) are also preferred as polymerizable unsaturated group-containing monomer units (a6).

Examples of acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride.

<Method (iii)>
A method (iii) in which the hydroxyl group of a resin having the hydroxyl group-containing monomer unit (a2) is reacted with the isocyanate group of an isocyanate group-containing monomer is exemplified.

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

[Other monomer units (a7)]
Other monomers include, for example, acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of nonylphenol, EO- or PO-modified (meth)acrylate of paracumylphenol, dimethylaminoethyl (meth)acrylate, and diethylaminoethyl (meth)acrylate;
aromatic vinyl compounds such as styrene, α-methylstyrene, p-vinyltoluene, p-chlorostyrene, and vinylnaphthalene;
(meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or acryloylmorpholine;
vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether;
vinyl fatty acid vinyl compounds such as vinyl acetate or vinyl propionate;
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-substituted maleimides such as N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, and 9-maleimidoacridine;
Examples include dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, diethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, di(n-propyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(isopropyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(2-ethylhexyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, etc. These monomers can be used alone or in combination of two or more.

Alkali-soluble resins having blocked isocyanate group-containing monomer units (a1) and hydroxyl group-containing monomer units (a2) can be used alone or in combination of two or more types.

From the viewpoint of low-temperature curing, the content of the alkali-soluble resin having the blocked isocyanate group-containing monomer unit (a1) and the hydroxyl group-containing monomer unit (a2) is preferably 30% by mass or more, and more preferably 50 to 100% by mass, based on 100% by mass of the alkali-soluble resin (A).

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

The polymerizable compound (B) may be a monomer or oligomer having a polymerizable unsaturated group. Examples of the polymerizable unsaturated group include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, and a (meth)acryloyloxy group. Examples of the polymerizable compound (B) include a lactone-modified polymerizable compound, a polymerizable compound having an acidic group, a polymerizable compound having a urethane bond, a polymerizable compound having a tertiary amine structure, a polymerizable compound having a dendrimer structure or a hyperbranched structure, and other polymerizable compounds. The polymerizable compound (B) is a compound that contributes to film formation. The number of polymerizable unsaturated groups in the polymerizable compound (B) is 1 or more, preferably 2 or more.

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

Commercially available lactone-modified polymerizable compounds include, for example, KAYARAD DPCA-20, DPCA-30, and DPCA-60 manufactured by Nippon Kayaku Co., Ltd.

(Polymerizable Compound Having an Acidic Group)
Examples of the polymerizable compound having an acidic group include esters of dicarboxylic acids and free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohols and (meth)acrylic acid, and esters of polycarboxylic acids and monohydroxyalkyl(meth)acrylates. The polymerizable compound having an acidic group does not have a urethane bond.

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

Examples of the dicarboxylic acids include malonic acid, succinic acid, maleic acid, glutaric acid, phthalic acid, itaconic acid, etc.

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

Commercially available polymerizable compounds having an acidic group include Viscoat #2500P manufactured by Osaka Organic Chemical Industry Co., Ltd., Aronix M-5300, M-5400, M-5700, M-510, M-520, and M-521 manufactured by Toagosei Co., Ltd., and β-CEA manufactured by Daicel Allnex Corporation.

(Polymerizable compound having a urethane bond)
Examples of the polymerizable compound having a urethane bond include urethane (meth)acrylates obtained by reacting a hydroxyl group-containing (meth)acrylate with a polyfunctional isocyanate, and urethane (meth)acrylates obtained by reacting a polyhydric alcohol with a polyfunctional isocyanate and then reacting the resulting mixture with a hydroxyl group-containing (meth)acrylate.

Examples of the hydroxyl group-containing (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide (EO)-modified penta(meth)acrylate, dipentaerythritol propylene oxide (PO)-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, reaction products of epoxy group-containing compounds and carboxy(meth)acrylates, and hydroxyl group-containing polyol polyacrylates.

Examples of the polyfunctional isocyanate include aromatic diisocyanates such as tolylene diisocyanate, diphenylmethylene diisocyanate, and xylene diisocyanate; aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate; alicyclic diisocyanates such as isophorone diisocyanate; and their biuret derivatives, isocyanate nurate derivatives, and trimethylolpropane adducts.

From the viewpoint of developability, the polymerizable compound having a urethane bond may further have an acidic group. Examples of the acidic group include a sulfonic acid group, a carboxyl group, and a phosphate group. Of these, a carboxyl group is preferred.

To introduce acidic groups into a polymerizable compound having a urethane bond, for example, first react the above-mentioned hydroxyl group-containing (meth)acrylate with the above-mentioned polyfunctional isocyanate. Then, a mercapto compound having a carboxyl group is added to the product.

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

Commercially available polymerizable compounds having a urethane bond include, for example, AH-600, UA-306H, UA-306T, UA-306I, UA-510H, and UF-8001G manufactured by Kyoeisha Chemical Co., Ltd., UA-1100H, U-6LPA, UA-33H, U-10HA, and U-15HA manufactured by Shin-Nakamura Chemical Co., Ltd., and EBECRYL1290 and KRM8452 manufactured by Daicel-Allnex Corporation.

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

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

The (meth)acrylate compound (X) can be used alone or in combination of two or more types.

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

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

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. Examples include the methods described in International Publication No. 2006/075754, JP-A No. 2008-545859, and JP-A No. 2017-066347.

The polymerizable compound having a tertiary amine structure may have an acidic group and/or a hydroxyl group. Methods for introducing the acidic group and/or the hydroxyl group include, for example, using a compound having an acidic group and/or a hydroxyl group in the (meth)acrylate compound (X) or the amine compound (Y), or adding an acid anhydride after a Michael addition reaction.

Commercially available polymerizable compounds having a tertiary amine structure include, for example, Aronix MT-3041 and 3042 manufactured by Toagosei Co., Ltd.

(Polymerizable Compound Having Dendrimer Structure or Hyperbranched Structure)
A polymerizable compound having a dendrimer structure has a chemical structure in which branches are regularly repeated outward from a chemical structure constituting a core (hereinafter also referred to as the core portion), and polymerizable unsaturated groups are bonded to the ends of the branches, and has a spherical, highly controlled chemical structure and molecular weight. The hyperbranched structure has a chemical structure similar to that of a dendrimer structure.

Commercially available polymerizable compounds having a dendrimer structure or a hyperbranched structure include, for example, Viscoat #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) and Miramer SP-1108 (dendrimer structure, average number of acryloyl groups: 13) manufactured by Miwon Specialty Chemical Co., Ltd., and CN2301 (hyperbranched structure, average number of acryloyl groups: 9), CN2302 (hyperbranched structure, average number of acryloyl groups: 16), CN2303 (hyperbranched structure, average number of acryloyl groups: 6), and CN2304 (hyperbranched structure, average number of acryloyl groups: 18) manufactured by SARTOMER. Examples include Etercure 6361-100 (hyperbranched structure, average number of acryloyl groups: 8), Etercure 6362-100 (hyperbranched structure, average number of acryloyl groups: 12), Etercure 6363 (hyperbranched structure, average number of acryloyl groups: 16), and Etercure DR-E522 (hyperbranched structure, average number of acryloyl groups: 15), all manufactured by Materials.

(Other polymerizable compounds)
Other polymerizable compounds include, 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 di(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, and 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, tricyclodecanyl (meth)acrylate, (meth)acrylic acid ester of methylolated melamine, various acrylic acid esters and methacrylic acid esters such as epoxy (meth)acrylate, 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.

Other commercially available polymerizable compounds include, for example, 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, and D-330 manufactured by Nippon Kayaku Co., Ltd., and Aronix M-303, M-305, M-306, M-309, M-310, M-321, M-325, and M manufactured by Toagosei Co., Ltd. -350, 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-211B, M-101A, Viscoat #310HP, #335HP, #700, #295, #330, #360, #GPT, #400, #405 manufactured by Osaka Organic Chemical Industry Ltd., OGSOL EA-0200, EA-0300, GA-5060P, GA-2800 manufactured by Osaka Gas Chemicals Co., Ltd., and Miwon Specialty Chemical Co., Ltd. Examples include Miramer HR6060, 6100, and 6200 manufactured by Daicel Chemical Industries, Ltd.; NK Ester ABE-300, A-DOG, A-DCP, A-BPE-4, and A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd.; and EBECRYL 40, 130, 140, and 145 manufactured by Daicel Allnex Corporation.

The polymerizable compound (B) can be used alone or in combination of two or more types.

The content of polymerizable compound (B) is preferably 30 to 90% by mass, and more preferably 40 to 80% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[Photopolymerization initiator (C)]
The photosensitive composition of the present invention contains a photopolymerization initiator (C), which allows the photosensitive composition to be cured by irradiation with active energy rays.

Examples of the photopolymerization initiator (C) include acetophenone-based compounds such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone;
triazine-based compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine;
Oxime compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], or ethanol, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime);
acylphosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide;
Examples include quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; and carbazole compounds.

Commercially available products include acetophenone compounds such as Omnirad 907, 369E, 379EG, 184, and 2959 manufactured by IGM Resins, acylphosphine compounds such as Omnirad 819 and TPO manufactured by IGM Resins, oxime compounds such as IRGACURE OXE-01, 02, 03, and 04 manufactured by BASF Japan, N-1919, NCI-730, 831, and 930 manufactured by ADEKA, TRONLY TR-PBG-301, 304, 305, 309, 314, 345, 358, 380, 365, 610, 3054, and 3057 manufactured by Changzhou Strong New Materials Co., Ltd., and IGM Examples of suitable adhesives include Omnirad 1312, 1314, and 1316 manufactured by Resins Co., Ltd., SPI-02, 03, 04, 05, 06, and 07 manufactured by Samyang Corporation, and DFI-020, 306, and EOX-01 manufactured by Daito Chemix Co., Ltd.
Further, oxime compounds described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-037223, JP-A-2010-215575, JP-A-2011-020998, WO 2015/036910, WO 2021/175855, etc. are also included.

The photopolymerization initiator (C) can be used alone or in combination of two or more types.

The content of the photopolymerization initiator (C) is preferably 0.5 to 20% by mass, and more preferably 1 to 10% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

(Compound represented by general formula (2))
The photosensitive composition of the present invention preferably contains a compound represented by the following general formula (2) as the photopolymerization initiator (C) from the viewpoints of pattern line width stability, hardness upon low-temperature curing, and high-temperature and high-humidity resistance.

General formula (2)

(In general formula (2), R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ₃ represents a hydrogen atom or a monovalent substituent.)

R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
The alkyl group having 1 to 8 carbon atoms may be linear, branched, or cyclic, or may be a combination of these, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a cyclopentyl group, a cyclopentylmethyl group, a cyclohexyl group, a cyclohexylmethyl group, a cyclohexylmethyl group, etc. Of these, from the viewpoint of the pattern shape, a linear alkyl group having 3 to 8 carbon atoms is preferred, and a linear alkyl group having 4 to 6 carbon atoms is more preferred.

_R3 represents a hydrogen atom or any monovalent substituent.
Examples of the monovalent substituent include alkyl groups having 1 to 20 carbon atoms, such as methyl and ethyl groups; alkoxy groups having 1 to 20 carbon atoms, such as methoxy and ethoxy groups; halogen atoms such as F, Cl, Br, and I; acyl groups having 1 to 20 carbon atoms; alkyl ester groups having 1 to 20 carbon atoms; alkoxycarbonyl groups having 1 to 20 carbon atoms; halogenated alkyl groups having 1 to 20 carbon atoms, aromatic ring groups having 4 to 20 carbon atoms; amino groups; aminoalkyl groups having 1 to 20 carbon atoms; hydroxyl groups; nitro groups; cyano groups; optionally substituted benzoyl groups; and optionally substituted thenoyl groups. Examples of the substituents that the benzoyl group or thenoyl group may have include alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and alkoxycarbonyl groups having 1 to 10 carbon atoms. Among these, from the viewpoint of radical generation efficiency, a hydrogen atom and a nitro group are preferred, and a hydrogen atom is more preferred.

Methods for producing the compound represented by general formula (2) include those described in, for example, JP-T-2019-507108 and JP-T-2019-528331.

Specific examples of compounds represented by general formula (2) are shown below. Note that the present invention is not limited to these.

Among the compounds of chemical formulas (4) to (7), the compound of chemical formula (4) is preferred from the viewpoints of pattern line width stability, hardness at low temperature curing, and resistance to high temperatures and humidity.

The compound represented by general formula (2) can be used alone or in combination of two or more types.

The content of the compound represented by general formula (2) is preferably 90 to 100% by mass, and more preferably 95 to 100% by mass, based on 100% by mass of the photopolymerization initiator (C).

[Thermosetting compound (D)]
The photosensitive composition of the present invention contains a thermosetting compound (D), which crosslinks upon heating, improving the hardness and high-temperature, high-humidity resistance of the cured film.

The thermosetting compound (D) may be a low molecular weight compound or a high molecular weight compound such as a resin. Examples of the thermosetting compound (D) include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. Among these, from the viewpoint of low-temperature curing, epoxy compounds, oxetane compounds, and melamine compounds are preferred, and epoxy compounds are more preferred.

(epoxy compound)
The epoxy compound is preferably a compound having an aromatic ring and/or an aliphatic ring, and is more preferable than a compound having an aliphatic ring from the viewpoints of hardness at low temperature curing and resistance to high temperatures and high humidity. The epoxy group is preferably bonded to the aromatic ring and/or the aliphatic ring via a single bond or a linking group. Examples of the linking group include an alkyl group, an arylene group, -O-, -NR- (wherein R represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group), -SO ₂ -, -CO-, -O-, and -S-. In the case of a structure having an aliphatic ring, it is more preferable that the epoxy group be bonded to the aliphatic ring via a single bond.

From the standpoint of hardness when cured at low temperatures and resistance to high temperatures and humidity, epoxy compounds having two or more epoxy groups in the molecule are preferred, compounds having 5 to 50 epoxy groups are more preferred, and compounds having 10 to 30 epoxy groups are particularly preferred.

The epoxy equivalent of the epoxy compound is preferably 50 to 400 g/eg, and more preferably 100 to 200 g/eg. The epoxy equivalent is defined as the mass of the epoxy compound containing one equivalent of epoxy groups.

Epoxy compounds include, for example, polycondensates of bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) with various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), polycondensates of phenols with various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, Examples of epoxy resins include polymers of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), polycondensates of phenols and aromatic dimethanols (benzenedimethanol, α,α,α',α'-benzenedimethanol, biphenyldimethanol, α,α,α',α'-biphenyldimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes, glycidyl ether epoxy resins obtained by glycidylating alcohols, alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidylamine epoxy resins, and glycidyl ester epoxy resins.

Commercially available products include, for example, Epicoat 807, 815, 825, 827, 828, 190P, and 191P manufactured by Yuka Shell Epoxy Co., Ltd.; TECHMORE VG3101L manufactured by Mitsui Chemicals, Inc.; EPPN-201, 501H, 502H, EOCN-102S, 103S, 104S, and 1020 manufactured by Nippon Kayaku Co., Ltd.; Epicoat 1004, 1256, JER1032H60, 157S65, 157S70, 152, and 154 manufactured by Japan Epoxy Resins Co., Ltd.; and Celoxide 2021 and E manufactured by Daicel Chemical Industries, Ltd. Examples include HPE-3150, Epolead GT401, Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, and 721 manufactured by Nagase ChemteX Corporation, TEPIC-L, H, and S manufactured by Nissan Chemical Industries, Ltd., and EPICLON 830, 840, 850, 860, 1050, 3050, 4050, N-660, N-670, N-740, N-770, N865, HP-7200, HP-4700, HP-4770, HP-5000, HP-6000, and HP-9500 manufactured by DIC Corporation.

From the viewpoints of hardness upon low-temperature curing and resistance to high temperatures and humidity, the content of the epoxy compound is preferably 1 to 20% by mass, and more preferably 5 to 15% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

(Oxetane compounds)
The oxetane compound is a known compound having an oxetane group, and examples of the oxetane compound include monofunctional oxetane compounds, bifunctional oxetane compounds, and trifunctional or higher functional oxetane compounds.

Examples of monofunctional oxetane compounds include (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, and 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane.

Commercially available products include, for example, OXE-10 and 30 manufactured by Osaka Organic Chemical Industry Co., Ltd., and OXT-101 and 212 manufactured by Toagosei Co., Ltd.

Examples of bifunctional oxetane compounds include 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether, di[1-ethyl(3-oxetanyl)]methyl ether 3-ethyl-3-hydroxymethyloxetane, 3- Ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenyl bis(3-ethyl- 1,4-bis(3-ethyl-3-oxetanylmethyl)ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, ethylene oxide (EO) modified bis(3-ethyl-3-oxetanylmethyl)ether Examples include bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO)-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, and EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether.

Commercially available products include OXBP and OXTP manufactured by Ube Industries, Ltd., and OXT-121 and 221 manufactured by Toagosei Co., Ltd.

Examples of trifunctional or higher oxetane compounds include pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, and caprolactone-modified dipentaerythritol. Examples include erythritol hexa(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl) ether, resins containing oxetane groups (such as the oxetane-modified phenol novolac resin described in Japanese Patent No. 3783462), and polymers obtained by radical polymerization of (meth)acrylic monomers such as the aforementioned OXE-30.

From the viewpoints of hardness during low-temperature curing and resistance to high temperatures and humidity, the content of the oxetane compound is preferably 1 to 20% by mass, and more preferably 5 to 15% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

(Melamine compounds)
The melamine compound is a compound having a melamine ring structure, and is preferably a compound having a methylol group.

Commercially available products include Nikalac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS-001, MX-002, MX-730, MX-750, MX-708, MX-706, MX-042, MX-45, MX-500, MX-520, MX-43, MX-417, and MX-410 manufactured by Sanwa Chemical Co., Ltd., and Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, and 370 manufactured by Nippon Cytec Industries Co., Ltd.

From the viewpoints of hardness during low-temperature curing and resistance to high temperatures and humidity, the content of the melamine compound is preferably 0.01 to 10% by mass, and more preferably 0.1 to 5% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

Thermosetting compounds (D) can be used alone or in combination of two or more types.

[Imidazole compound (E)]
(Compound (E1) represented by general formula (1))
The photosensitive composition of the present invention contains a compound (E1) represented by general formula (1) as the imidazole compound (E).

General formula (1)

(In general formula (1), X ₁ to X ₃ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms.)

The alkyl group having 1 to 20 carbon atoms may be linear, branched, or cyclic, or may be a combination of any of these, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group, a 2-ethylhexyl group, a nonyl group, an isononyl group, a decyl group, an isodecyl group, an undecyl group, a dodecyl group, a hexadecyl group, a cyclopentyl group, a cyclopentylmethyl group, a cyclohexyl group, a cyclohexylmethyl group, and a cyclohexylmethyl group.
Examples of the aryl group having 6 to 30 carbon atoms include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group, and an anthryl group.
Examples of the arylalkyl group having 7 to 30 carbon atoms include a benzyl group, an α-methylbenzyl group, an α,α-dimethylbenzyl group, and a phenylethyl group.

From the viewpoint of hardness and resistance to high temperatures and humidity, _X1 is preferably one selected from the group consisting of a methyl group, an ethyl group, and a phenyl group.

From the viewpoint of reactivity, _X2 and _X3 are preferably one selected from the group consisting of a hydrogen atom, a methyl group, and an ethyl group.

Examples of the compound (E1) represented by general formula (1) include 1-benzylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-4-methylimidazole, 1-benzyl-2-ethylimidazole, 1-benzyl-2-propylimidazole, 1-benzyl-2-isopropylimidazole, 1-benzyl-2-phenylimidazole, and 1-benzyl-2-phenyl-4-(4-methylphenyl)imidazole. Among these, 1-benzyl-2-methylimidazole and 1-benzyl-2-phenylimidazole are preferred from the viewpoints of hardness at low temperatures and resistance to high temperatures and humidity.

Compound (E1) represented by general formula (1) can be used alone or in combination of two or more types.

The content of compound (E1) represented by general formula (1) is preferably 50% by mass or more, and more preferably 70% by mass or more, based on 100% by mass of imidazole compound (E).

(Compound (E2) represented by general formula (3))
From the viewpoints of hardness at low temperature curing and resistance to high temperatures and high humidity, the photosensitive composition of the present invention preferably further contains a compound (E2) represented by the following general formula (3) as the imidazole compound (E). The compound (E2) represented by general formula (3) initiates a reaction with the thermosetting compound (D) at a higher temperature than the compound (E1) represented by general formula (1). However, the reaction mechanism is different, and once the reaction occurs, the subsequent reaction rate with the thermosetting compound (D) is presumably fast. Therefore, a cured film having high hardness and resistance to high temperatures and high humidity can be obtained.

General formula (3)

(In general formula (3), X ₄ to X ₆ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms.)

The alkyl group having 1 to 20 carbon atoms may be linear, branched, or cyclic, or may be a combination of any of these, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group, a 2-ethylhexyl group, a nonyl group, an isononyl group, a decyl group, an isodecyl group, an undecyl group, a dodecyl group, a hexadecyl group, a cyclopentyl group, a cyclopentylmethyl group, a cyclohexyl group, a cyclohexylmethyl group, and a cyclohexylmethyl group.
Examples of the aryl group having 6 to 30 carbon atoms include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group, and an anthryl group.
Examples of the arylalkyl group having 7 to 30 carbon atoms include a benzyl group, an α-methylbenzyl group, an α,α-dimethylbenzyl group, and a phenylethyl group.

From the viewpoint of hardness and resistance to high temperatures and humidity, _X4 is preferably one selected from the group consisting of a methyl group, an ethyl group, and a phenyl group.

From the viewpoint of reactivity, _X5 and _X6 are preferably one selected from the group consisting of a hydrogen atom, a methyl group, and an ethyl group.

Examples of compound (E2) represented by general formula (3) include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-butylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2-phenylimidazole, 4-phenylimidazole, 4-methyl-2-phenylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, and 2,4-diphenylimidazole. Of these, 2-methylimidazole and 2-phenylimidazole are preferred.

Compound (E2) represented by general formula (3) can be used alone or in combination of two or more types.

The total content of the compound (E1) represented by general formula (1) and the compound (E2) represented by general formula (3) is preferably 60% by mass or more, and more preferably 80% by mass or more, based on 100% by mass of the imidazole compound (E).
The content of the compound (E1) represented by the general formula (1) is preferably 50% by mass or more, and more preferably 80% by mass or more, relative to 100% by mass of the total content of the compound (E1) represented by the general formula (1) and the compound (E2) represented by the general formula (3).

(Other imidazole compounds (E3))
The photosensitive composition of the present invention may contain, as the imidazole compound (E), an imidazole compound other than the compound (E1) represented by general formula (1) and the compound (E2) represented by general formula (3) (hereinafter, also simply referred to as other imidazole compound (E3)).

Other imidazole compounds (E3) include 1-methylimidazole, 1-ethylimidazole, 1-propylimidazole, 1-isopropylimidazole, 1-phenylimidazole, 1,2-dimethylimidazole, 1-cyanomethyl-2-methylimidazole, and 1-cyanoethyl-2-ethyl-4-methylimidazole.

The content of the imidazole compound (E) is preferably 1 to 20 parts by mass, and more preferably 1.5 to 15 parts by mass, per 100 parts by mass of the thermosetting compound (D).

[Colorant (F)]
The photosensitive composition of the present invention may contain a colorant (F), which makes it possible to control the transmittance of each wavelength region of the optical filter and improves color separation.

The colorant (F) may be a pigment or a dye, with pigments being preferred from the standpoints of light resistance, heat resistance, and solvent resistance.

(Pigment)
The pigment is preferably a compound classified as a pigment in the Color Index.
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, 1 84, 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, pigments described in JP-A-2014-134712, and pigments described in Japanese Patent No. 6368844. Among these, from the viewpoints of heat resistance, light fastness, and transmittance, C.I. Pigment Red 48: 1,122,177,224,242,269,254,291,295,296, pigments described in JP-A-2014-134712, and pigments described in Japanese Patent No. 6368844 are preferred, C.I. Pigment Red 177,254,291,295,296, pigments described in JP-A-2014-134712, and pigments described in Japanese Patent No. 6368844 are more preferred.

Examples of orange pigments include C.I. Pigment Orange 36, 38, 43, 64, 71, and 73.

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, JP 2012-226110 A, JP 2017-171912 A, JP 2017-171913 A, JP 2017-171914 A, JP 2017-171915 A, and the like. Among these, C.I. Pigment Yellow 138, 139, 150, 185, 231, 233 and the pigments described in JP-A 2012-226110 are preferred.

Examples of green pigments include 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, and 63. Of these, C.I. Pigment Green 36, 58, 59, 62, and 63 are preferred.

Examples of blue pigments 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, and 79. Of these, C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, and 15:6 are preferred.

Examples of purple pigments 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, and 50. Of these, C.I. Pigment Violet 19 and 23 are preferred.

Specific examples of black pigments include C.I. Pigment Black 1, 6, 7, 12, 20, 31, and 32. Other examples include compounds described in JP-A-2010-534726, JP-A-2012-515233, JP-A-2012-515234, JP-A-1-170601, and JP-A-2-34664.

When the photosensitive composition of the present invention is used in an anti-reflection filter, it preferably contains, as a colorant (F), one or more pigments selected from the group consisting of red pigments, yellow pigments, blue pigments, green pigments, purple pigments, and black pigments.

Suitable combinations for use in anti-reflection filters include, for example, the following embodiments.
(1) Contains green pigment and purple pigment.
(2) Contains yellow pigment, blue pigment, and purple pigment.
(3) Contains yellow pigment, green pigment, and purple pigment.
(4) Contains a red pigment, a yellow pigment, and a blue pigment.
(5) Contains a yellow pigment, a green pigment, a blue pigment, and a purple pigment.
(6) Contains a red pigment, a yellow pigment, a blue pigment, and a purple pigment.
(7) Contains a red pigment, a green pigment, a blue pigment, and a purple pigment.
(8) Contains a yellow pigment, a blue pigment, a purple pigment, and a black pigment.

An example of the above embodiment (1) is an embodiment in which the green pigment contains at least one selected from C.I. Pigment Green 7, 36, 58, 59, and 63, and the purple pigment contains C.I. Pigment Violet 23.
An example of the above embodiment (2) is an embodiment in which the yellow pigment contains at least one selected from C.I. Pigment Yellow 139, 185, 231, and 233, the blue pigment contains at least one selected from C.I. Pigment Blue 15:3, 15:4, and 15:6, and the purple pigment contains C.I. Pigment Violet 23.
An example of the above embodiment (3) is an embodiment in which the yellow pigment contains at least one selected from C.I. Pigment Yellow 139, 185, 231, and 233, the green pigment contains at least one selected from C.I. Pigment Green 7, 36, 58, 59, and 63, and the purple pigment contains C.I. Pigment Violet 23.
An example of the above embodiment (4) is an embodiment in which the red pigment contains at least one selected from C.I. Pigment Red 177, 254, 291, 295, and 296, the yellow pigment contains at least one selected from C.I. Pigment Yellow 139, 185, 231, and 233, and the blue pigment contains at least one selected from C.I. Pigment Blue 15:3, 15:4, and 15:6.
The above embodiment (5) is, for example, an embodiment in which the yellow pigment is at least one selected from C.I. Pigment Yellow 139, 185, 231, and 233, the green pigment is at least one selected from C.I. Pigment Green 7, 36, 58, 59, and 63, the blue pigment is at least one selected from C.I. Pigment Blue 15:3, 15:4, and 15:6, and the purple pigment is C.I. Pigment Violet 23.
The above embodiment (6) is, for example, an embodiment in which the red pigment is at least one selected from C.I. Pigment Red 177, 254, 291, 295, and 296, the yellow pigment is at least one selected from C.I. Pigment Yellow 139, 185, 231, and 233, the blue pigment is at least one selected from C.I. Pigment Blue 15:3, 15:4, and 15:6, and the purple pigment is C.I. Pigment Violet 23.
The above embodiment (7) is, for example, an embodiment in which the red pigment is at least one selected from C.I. Pigment Red 177, 254, 291, 295, and 296, the green pigment is at least one selected from C.I. Pigment Green 7, 36, 58, 59, and 63, the blue pigment is at least one selected from C.I. Pigment Blue 15:3, 15:4, and 15:6, and the purple pigment is C.I. Pigment Violet 23.
The above embodiment (8) is, for example, an embodiment in which the yellow pigment contains at least one selected from C.I. Pigment Yellow 139, 185, 231, and 233, the blue pigment contains at least one selected from C.I. Pigment Blue 15:3, 15:4, and 15:6, the purple pigment contains C.I. Pigment Violet 23, and the black pigment contains at least one selected from C.I. Pigment Black 7 and 32.

Table 1 shows the preferred mass ratio (mass%) of each pigment for each embodiment.

In addition, inorganic pigments such as titanium oxide, barium sulfate, zinc oxide, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, umber, and synthetic iron black can also be used as the colorant (F).

(dye)
Examples of dyes include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, etc. Also included are derivatives of these dyes and lake pigments obtained by converting dyes into lakes.

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

While basic dyes can be used as is, salt-forming compounds that form salts with organic acids, perchloric acid, or their metal salts are preferred. Salt-forming compounds of basic dyes are preferred due to their excellent resistance (lightfastness and solvent resistance) and affinity with pigments. Furthermore, in salt-forming compounds of basic dyes, the anion component that acts as a counterion is preferably an organic sulfonic acid, organic sulfuric acid, a fluorine-containing phosphorus anion compound, a fluorine-containing boron anion compound, a cyano-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid with a halogenated hydrocarbon group, or a salt-forming compound formed with an acid dye. Furthermore, salt-forming compounds that contain polymerizable unsaturated groups in the molecule further improve resistance.

The chemical structure of dyes can be, for example, azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azido dyes, Examples of dye structures include dyes derived from dyes selected from the group consisting of quinone dyes, polymethine dyes (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 metal complex dyes thereof.

Among these, from the viewpoint of color properties such as hue, color separation, and color unevenness, dye structures derived from dyes selected from azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes are preferred, and dye structures derived from dyes selected from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes are more preferred.

The colorant (F) can be used alone or in combination of two or more types.

When used in an anti-reflection filter, the content of colorant (F) is preferably 5% by mass or less, and more preferably 0.5 to 3% by mass, based on 100% by mass of the non-volatile content of the photosensitive composition.

(Fine Pigment)
The pigment is preferably micronized before use. The micronization method is not particularly limited, and for example, wet milling, dry milling, or solution precipitation can be used. Among these, salt milling treatment using a kneader method, which is a type of wet milling, is preferred. The average primary particle size of the micronized pigment determined by TEM (transmission electron microscope) is preferably 5 to 90 nm. From the viewpoints of dispersibility and contrast ratio, the average primary particle size is more preferably 10 to 70 nm.

Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt, and water-soluble organic solvent is mechanically kneaded while heated using a kneader, two-roll mill, three-roll mill, ball mill, attritor, sand mill, or other kneading machine, and then the water-soluble inorganic salt and water-soluble organic solvent are removed by rinsing with water. The water-soluble inorganic salt acts as a crushing aid, and the high hardness of the inorganic salt is used to crush the pigment during salt milling. By optimizing the conditions for salt milling pigment, it is possible to obtain pigments with extremely fine primary particle diameters and a narrow, sharp particle size distribution.

Examples of water-soluble inorganic salts include sodium chloride, potassium chloride, and sodium sulfate, with sodium chloride (table salt) being preferred from the standpoint of cost. From the perspectives of both processing efficiency and production efficiency, the amount of water-soluble inorganic salt used is preferably 50 to 2,000 parts by weight, and more preferably 300 to 1,000 parts by weight, per 100 parts by weight of pigment.

The water-soluble organic solvent functions to moisten the pigment and water-soluble inorganic salt. It is not particularly limited as long as it is soluble (miscible) in water and does not substantially dissolve the inorganic salt used. However, because the temperature rises during salt milling and the solvent becomes more likely to evaporate, high-boiling solvents with a boiling point of 120°C or higher are preferred for safety reasons. Examples of water-soluble organic solvents that can be used include 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, and liquid polypropylene glycol. The amount of water-soluble organic solvent used is preferably 5 to 1,000 parts by weight, and more preferably 50 to 500 parts by weight, per 100 parts by weight of the pigment.

If necessary, a resin may be added to the salt milling treatment. There are no particular limitations on the type of resin, and examples include natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. Of these, resins that are solid at room temperature, insoluble in water, and partially soluble in the organic solvents listed above are preferred. The amount of resin added is preferably 2 to 200 parts by weight per 100 parts by weight of the pigment.

[Dispersion resin (G)]
The photosensitive composition of the present invention may contain a dispersing resin (G). The dispersing resin (G) is used for the purpose of dispersing the colorant (F), which is a raw material of the photosensitive composition, when producing a dispersion of the colorant (F), and is distinguished from the alkali-soluble resin (A).

The dispersing resin (G) is preferably a resin having an adsorption group that has a high affinity for the colorant (F). The adsorption group preferably has one or more basic groups and acidic groups.

Examples of basic groups include primary amino groups, secondary amino groups, tertiary amino groups, quaternary ammonium bases, and groups containing nitrogen atoms such as nitrogen-containing heterocycles.

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

Examples of resin types for the dispersing resin (G) include urethane resins, polycarboxylates and other polycarboxylate esters, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylate ammonium salts, polycarboxylate alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylate esters and their modified products, amides and salts formed by the reaction of poly(lower alkylene imines) with polyesters having free carboxyl groups, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohols, polyvinylpyrrolidone, and other water-soluble resins and water-soluble polymers, polyesters, modified polyacrylates, ethylene oxide/propylene oxide adducts, and phosphate esters.

The structure of the dispersing resin (G) may be, for example, a random structure, a block structure, a graft structure, a comb structure, or a star structure. Of these, from the viewpoint of dispersion stability, the block structure and the comb structure are preferred.

Commercially available dispersion resins (G) include, for example, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, and 2095 manufactured by BYK Japan. , 2150, 2155, 2163, 2164, or Anti-Terra-U203, 204, or BYK-P104, P104S, 220S, or Lactimon, Lactimon-WS, or Bykumen, etc.; SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26 manufactured by Lubrizol Japan Co., Ltd. 000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, etc. manufactured by BASF Japan Co., Ltd. 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., and Ajisuper PA111, PB711, PB821, PB822, PB824 manufactured by Ajinomoto Fine-Techno Co., Ltd.

From the viewpoints of hardness upon low-temperature curing and resistance to high temperatures and high humidity, the dispersing resin (G) preferably has a polymerizable unsaturated group. Examples of dispersing resins having a polymerizable unsaturated group include the resins described in paragraphs [0317] to [0321] of JP 2019-78878 A, the resins described in paragraph [0083] of WO 2018/139534 A, the resins described in paragraphs [0167] to [0191] of WO 2019/163505 A, and the resins described in paragraphs [0299] to [0310] of WO 2021/131927 A.

Dispersion resin (G) can be used alone or in combination of two or more types.

From the viewpoint of dispersion stability, the content of the dispersing resin (G) is preferably 3 to 200 parts by mass, and more preferably 5 to 100 parts by mass, per 100 parts by mass of the colorant (F).

[Thiol-based chain transfer agent (H)]
The photosensitive composition of the present invention preferably contains a thiol-based chain transfer agent (H) from the viewpoints of hardness upon low-temperature curing and resistance to high temperatures and high humidity. When the thiol-based chain transfer agent (H) is used in combination with the photopolymerization initiator (C), it generates thiyl radicals that are resistant to polymerization inhibition by oxygen during radical polymerization after light irradiation, thereby improving the photosensitivity of the photosensitive composition. As a result, hardness and resistance to high temperatures and high humidity are improved.

The thiol chain transfer agent (H) is preferably a multifunctional thiol having two or more thiol groups (SH groups), and more preferably a multifunctional thiol having four or more thiol groups. Increasing the number of functional groups makes it easier for the film to be photocured from the surface to the deepest part.

Examples of polyfunctional thiols include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthioglycolate, Examples include erythritol tetrakisthiopropionate, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, and 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine. Preferred examples include ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

The thiol chain transfer agent (H) can be used alone or in combination of two or more types.

From the viewpoints of line width stability, hardness upon low-temperature curing, and resistance to high temperatures and humidity, the content of the thiol chain transfer agent (H) is preferably 0.1 to 2.0% by mass, and more preferably 0.2 to 1.5% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[Leveling agent (I)]
The photosensitive composition of the present invention may contain a leveling agent (I). This further improves the wettability and drying properties of the composition to a substrate during application. Examples of the leveling agent (I) include silicone surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.

Examples of silicone surfactants include linear polymers consisting of siloxane bonds and modified siloxane polymers in which organic groups have been introduced into the side chains or terminals.

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, and 3570 manufactured by BYK-Chemie, and FZ-7002 and 211 manufactured by Dow Corning Toray. Examples include 0, 2122, 2123, 2191, 5609, and Shin-Etsu Chemical Co., Ltd.'s X-22-4952, X-22-4272, X-22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, and KP-341.

Examples of fluorosurfactants include surfactants or leveling agents with fluorocarbon chains.

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

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, polyoxyphenylenedistyrenated phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, and sorbitan tristearate. acrylate, 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 sorbitan tetraoleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkyl alkanolamide, alkyl imidazoline, etc.

Commercially available products include 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, and LS- manufactured by Kao Corporation. 106, LS-110, LS-114, MS-110, A-60, A-90, B-66, PP-290, LATEMURU PD-420, PD-430, PD-430S, PD-450, Rheodor 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, C Examples include H-60(K), Amit 102, 105, 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, ADEKA Corporation's Adeka Pluronic (registered trademark) L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R, and Kyoeisha Chemical Co., Ltd.'s (meth)acrylic acid (co)polymer Polyflow No. 75, No. 90, No. 95.

Examples of cationic surfactants include alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, and their ethylene oxide adducts.

Commercially available products include, for example, Acetamine 24, Cortamine 24P, 60W, and 86P Concentrate, manufactured by Kao Corporation.

Examples of anionic surfactants include polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine styrene-acrylic acid copolymers, and polyoxyethylene alkyl ether phosphate esters.

Commercially available products include, for example, Futergent 100 and 150 manufactured by Neos Corporation, and Adeka Hope YES-25, Adekacol TS-230E, PS-440E, and EC-8600 manufactured by ADEKA Corporation.

Examples of amphoteric surfactants include alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, and alkyl dimethylaminoacetic acid betaine, and alkyl amine oxides such as lauryl dimethylamine oxide.

Commercially available products include Kao Corporation's Anhithol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, and 20N.

Leveling agents (I) can be used alone or in combination of two or more types.

The content of leveling agent (I) is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition. When an appropriate amount is included, the balance between the coatability and adhesion of the photosensitive composition is further improved.

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

There are no particular restrictions on the organic solvent (J), so long as it satisfies the solubility and coatability of each component of the photosensitive composition of the present invention, and any known compound can be used.

Examples of organic solvents (J) include 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, and 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 mono Hexyl 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. Among these, from the viewpoint of resin solubility and coatability, glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate, alcohols such as diacetone alcohol, and ketones such as cyclohexanone are preferred.

From an environmental perspective, the photosensitive composition of the present invention preferably contains substantially no organic solvents that are aromatic hydrocarbons (toluene, xylene, benzene, chlorobenzene, etc.). "Substantially no" means that the content of such organic solvents in the photosensitive composition is 50 ppm by mass or less, preferably 30 ppm by mass or less, and more preferably 10 ppm by mass or less.

The organic solvent (J) can be used alone or in combination of two or more types.

The content of organic solvent (J) is preferably an amount such that the nonvolatile content of the photosensitive composition is 5 to 50% by mass.

[Other ingredients]
The photosensitive composition of the present invention may contain other components in addition to those described above. Examples of the other components include dye derivatives, sensitizers, polymerization inhibitors, ultraviolet absorbers, antioxidants, storage stabilizers, adhesion improvers, and near-infrared absorbers. The content of the other components can be appropriately set within a range that does not impair the effects of the present invention.

[Method for producing photosensitive composition]
The photosensitive composition of the present invention can be produced by, for example, adding a colorant (F), a dispersing resin (G), an organic solvent (J), and the like and performing a dispersion process to produce a dispersion. The dispersion can then be blended and mixed with an alkali-soluble resin (A), a polymerizable compound (B), a photopolymerization initiator (C), a thermosetting compound (D), and a compound (E1) represented by general formula (1). The timing of blending each material is arbitrary. The dispersion process can also be performed multiple times.

Dispersing machines used for the dispersion process include, for example, two-roll mills, three-roll mills, ball mills, horizontal sand mills, vertical sand mills, annular bead mills, and attritors.

The average dispersed particle size (secondary particle size) of the colorant (F) in the dispersion is preferably 30 to 200 nm, and more preferably 40 to 200 nm. Having an appropriate particle size makes it easier to obtain a photosensitive composition with high dispersion stability.

The average dispersed particle size (secondary particle size) is measured, for example, using Nikkiso's Microtrac UPA-EX150, which employs dynamic light scattering (FFT power spectrum) with particle permeability set to absorption mode, particle shape set to non-spherical, and the D50 particle size taken as the average diameter. The organic solvent used for dispersion should be used as the dilution solvent for measurement, and it is preferable to measure samples treated with ultrasound immediately after sample preparation, as this tends to yield results with little variation.

The photosensitive composition is preferably subjected to centrifugation, filtration using a sintered filter or membrane filter, or other means to remove coarse particles of 5 μm or larger, preferably coarse particles of 1 μm or larger, and even more preferably coarse particles of 0.5 μm or larger, as well as any contaminated dust. The photosensitive composition of the present invention preferably contains substantially no particles of 0.5 μm or larger, and more preferably contains no particles of 0.3 μm or smaller.

<Optical filter>
The optical filter of the present invention comprises a substrate and a cured film of a photosensitive composition, the cured film being preferably a film patterned by photolithography.

[Method of manufacturing optical filters]
The method for producing an optical filter is not particularly limited, and the optical filter can be produced, for example, by carrying out the following steps: (1) applying a photosensitive composition onto a substrate to form a composition layer; (2) exposing the layer to light through a mask in a pattern; (3) developing the unexposed portions with an alkali to form a patterned cured film; and (4) heat-treating (post-baking) the pattern. In the present invention, the optical filter is produced at a temperature of 150° C. or less throughout all steps, and more preferably at a temperature of 130° C. or less.

The manufacturing method for optical filters is explained in detail below.

(Step (1))
In the step (1) of forming a composition layer, the photosensitive composition is applied onto a substrate by a method such as spin coating, roll coating, slit coating, cast coating, or inkjet coating, and then dried (prebaked) at a temperature of 50 to 100°C for 10 to 120 seconds using an oven, a hot plate, or the like, as 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 upper layers, prevent diffusion of substances, and flatten the substrate surface.
The coating is preferably carried out so that the layer has a thickness of 0.05 to 10.0 μm after drying, and more preferably 0.3 to 5.0 μm.

(Step (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.
Examples of radiation used for exposure include ultraviolet rays such as g-line (wavelength 436 nm), h-line (wavelength 405 nm), and i-line (wavelength 365 nm). Light with a wavelength of 300 nm or less can also be used. Examples of light with a wavelength of 300 nm or less include KrF line (wavelength 248 nm) and ArF (wavelength 193 nm).
Furthermore, the exposure may be performed by continuous irradiation with light, or by repeating irradiation and pauses of light in short cycles (for example, milliseconds or less) (pulse exposure).

(Step (3))
The cured film obtained in step (2) is subjected to an alkali development treatment, whereby the composition layer in the unexposed areas is eluted in an alkaline aqueous solution, leaving only the cured areas, thereby obtaining 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, and 1,8-diazabicyclo-[5.4.0]-7-undecene.
The concentration of the alkaline developer is preferably from 0.001 to 10% by mass, more preferably from 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, roughening and peeling of the pattern is suppressed, and the remaining film rate after development is improved.

Developing methods include, for example, the dipping method, spraying method, and puddling method. The development temperature is preferably 15 to 40°C. After alkaline development, it is preferable to wash with pure water.

(Step (4))
In the heat treatment (post-baking), the patterned cured film obtained in step (3) is sufficiently cured by heating. The heating temperature for post-baking is preferably 150°C or lower, more preferably 130°C or lower. There is no particular lower limit to the heating temperature as long as curing can be promoted, but a temperature of 50°C or higher is preferred. The heating time is preferably 5 minutes to 1 hour.

The optical filter of the present invention can be used for a variety of purposes. For example, it can be used as an anti-reflection filter, color filter, black matrix, infrared transmission filter, light-shielding filter, microlens, etc. Because it can be cured at low temperatures, it is preferably used as an anti-reflection filter for organic EL display devices.

<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 and an organic EL display.
The configuration used for the image display device is not particularly limited as long as it functions as an image display device. For example, the configuration described in "Next Generation Liquid Crystal Display Technology" (by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd. in 1994) can be mentioned.
The definition of image display devices and details of each image display device are described, for example, in "Electronic Display Devices" (written by Akio Sasaki, published by Kogyo Chosakai Co., Ltd. in 1990) and "Display Devices" (written by Nobuaki Ibuki, published by Sangyo Tosho Co., Ltd. in 1989).

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

The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these examples. In addition, "parts" means "parts by mass" and "%" means "% by mass".
In the present invention, the nonvolatile content or nonvolatile content concentration refers to the mass remaining after leaving the sample to stand in an oven at 230° C. for 30 minutes.

Before going into the examples, we will explain each measurement method.

The resin's weight average molecular weight (Mw), number average molecular weight (Mn), acid value (mg KOH/g), and amine value (mg KOH/g) were measured as follows:

(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. An HLC-8220GPC (manufactured by Tosoh Corporation) was used as the instrument, with two separation columns connected in series. Both columns were packed with "TSK-GEL SUPER HZM-N" in series. The oven temperature was 40°C, a tetrahydrofuran (THF) solution was used as the eluent, and the measurement was performed at a flow rate of 0.35 ml/min. The sample was dissolved in a solvent consisting of 1% by mass of the above eluent, and 20 μl was injected. The molecular weight is a polystyrene equivalent value.

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

(Amine value of resin)
The amine value of the resin is the total amine value (mg KOH/g) measured in accordance with the method of ASTM D 2074 and converted into nonvolatile content.

<Production of alkali-soluble resin (A)>
(Alkali-soluble resin (A-1) solution)
100 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAc) was placed in a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, and the mixture was stirred while replacing the atmosphere with nitrogen and heated to 78°C. Next, a mixture of 25.2 parts of Karenz MOI-DEM (malonic acid-2-[[[[(2-methyl-1-oxo-2-propenyl)oxy]ethyl]amino]carbonyl]-1,3-diethyl ester, a blocked isocyanate group-containing monomer manufactured by Showa Denko K.K.), 31.2 parts of 2-hydroxyethyl methacrylate, a hydroxyl group-containing monomer, 37.5 parts of dicyclopentanyl methacrylate, an alicyclic hydrocarbon-containing monomer, 20.7 parts of methacrylic acid, an acidic group-containing monomer, and 27.0 parts of methyl methacrylate, an other monomer unit, and a solution of 12.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) dissolved in 50 parts of PGMAc were each added dropwise from the dropping funnel to 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, thereby preparing an alkali-soluble resin (A-1) solution. The alkali-soluble resin (A-1) had an acid value of 74 mg KOH/g and a weight-average molecular weight of 8,000.

(Alkali-soluble resin (A-2) solution)
An alkali-soluble resin (A-2) was synthesized so as to have the molar ratios of the constituent components shown in Table 2, and PGMAc was added to adjust the nonvolatile content to 40% by mass.

<Production of Colorant (F)>
(Finely divided blue pigment (F-1))
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 stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 12 hours at 50° C. This kneaded mixture was added to 3,000 parts of warm water, and while heating to about 70° C., it was stirred in a high-speed mixer for about 1 hour to form a slurry, and after repeated filtration and washing with water to remove the sodium chloride and diethylene glycol, it was dried at 80° C. for 24 hours and pulverized to obtain a finely divided blue pigment (F-1).

(Finely divided purple pigment (F-2))
100 parts of C.I. Pigment Violet 23, 1,000 parts of sodium chloride, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 12 hours at 70° C. This kneaded mixture was added to 3,000 parts of warm water, and while heating to about 70° C., it was stirred for about 1 hour using a high-speed mixer to form a slurry, which was then repeatedly filtered and washed with water to remove the sodium chloride and diethylene glycol. Thereafter, the slurry was dried at 80° C. for 24 hours and pulverized to obtain a finely divided purple pigment (F-2).

(Finely divided red pigment (F-3))
100 parts of C.I. Pigment Red 177, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 6 hours at 60° C. Next, this kneaded product was added to 3,000 parts of warm water, and while heating to about 80° C., it was stirred for 1 hour with a high-speed mixer to form a slurry, which was then filtered and washed with water to remove the sodium chloride and diethylene glycol, and then dried at 80° C. for 24 hours and pulverized to obtain a finely divided red pigment (F-3).

(Finely divided yellow pigment (F-4))
100 parts of C.I. Pigment Yellow 139, 800 parts of sodium chloride, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 12 hours at 70° C. This kneaded product was added to 3,000 parts of warm water, and while heated to about 70° C., it was stirred in a high-speed mixer for about 1 hour to form a slurry, which was then repeatedly filtered and washed with water to remove the sodium chloride and diethylene glycol, and then dried at 80° C. for 24 hours and pulverized to obtain a finely divided yellow pigment (F-4).

(Finely divided green pigment (F-5))
100 parts of C.I. Pigment Green 58, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 6 hours at 70 ° C. This kneaded mixture was added to 3,000 parts of warm water, and stirred for 1 hour with a high-speed mixer while heating to 70 ° C. to form a slurry, which was then repeatedly filtered and washed with water to remove the sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours and pulverized to obtain a finely divided green pigment (F-5).

(Finely divided green pigment (F-6))
100 parts of C.I. Pigment Green 36, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 6 hours at 70 ° C. This kneaded mixture was added to 3,000 parts of warm water, and stirred for 1 hour with a high-speed mixer while heating to 70 ° C. to form a slurry, which was then repeatedly filtered and washed with water to remove the sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours and pulverized to obtain a finely divided green pigment (F-6).

(Finely divided black pigment (F-7))
100 parts of C.I. Pigment Black 1, 800 parts of sodium chloride, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 12 hours at 70 ° C. This kneaded product was added to 3,000 parts of hot water, and while heated to about 70 ° C, it was stirred with a high-speed mixer for about 1 hour to form a slurry, and after repeated filtration and washing with water to remove the sodium chloride and diethylene glycol, it was dried at 80 ° C. for 24 hours and pulverized to obtain a finely divided black pigment (F-7).

(Finely divided black pigment (F-8))
100 parts of C.I. Pigment Black 32, 800 parts of sodium chloride, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 12 hours at 70 ° C. This kneaded product was added to 3,000 parts of hot water, and while heated to about 70 ° C, it was stirred in a high-speed mixer for about 1 hour to form a slurry, and after repeated filtration and washing with water to remove the sodium chloride and diethylene glycol, it was dried at 80 ° C. for 24 hours and pulverized to obtain a finely divided black pigment (F-8).

<Production of Dispersion Resin (G)>
(Dispersion resin (G-1) solution)
A reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer was charged with 108 parts of 1-thioglycerol, 174 parts of pyromellitic anhydride, 650 parts of PGMAc, and 0.2 parts of monobutyltin oxide as a catalyst. The atmosphere was then replaced with nitrogen gas, and the mixture was allowed to react for 5 hours at 120 ° C. (step 1). It was confirmed that 95% or more of the acid anhydride was half-esterified by measuring the acid value. Next, 160 parts of the compound obtained in step 1, calculated on a nonvolatile basis, 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of tert-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, 200 parts of methyl acrylate, 50 parts of methacrylic acid, and 663 parts of PGMAc were charged. The reaction vessel was heated to 80 ° C., and 1.2 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) were added, followed by a 12-hour reaction (step 2). Measurement of the nonvolatile content confirmed 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 parts of hydroquinone were charged, and the reaction was carried out until the disappearance of the peak at 2270 cm ⁻¹ due to the isocyanate group was confirmed by IR (third step). After confirming the disappearance of the peak, the reaction solution was cooled, and the nonvolatile content was adjusted with PGMAc to obtain a dispersion resin (G-1) solution having a polymerizable unsaturated group with a nonvolatile content of 30% by mass. The dispersion resin (G-1) had an acid value of 68 mg KOH/g and a weight average molecular weight of 13,000.

(Dispersion resin (G-2) solution)
A reaction vessel equipped with a gas inlet tube, thermostat, condenser, and stirrer was charged with 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, and the atmosphere was replaced with nitrogen gas. The reaction vessel was heated to 50 ° C and stirred, and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90 ° C, and a solution of 0.1 parts of 2,2'-azobisisobutyronitrile and 90 parts of PGMAc was added, and the reaction was carried out for 7 hours. Measurement of the nonvolatile content confirmed that 95% had reacted. 19 parts of pyromellitic anhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 parts 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. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value, and the mixture was diluted with PGMAc to a nonvolatile content of 30% by mass to obtain a dispersion resin (G-2) solution. Dispersion resin (G-2) had an acid value of 70 mgKOH/g and a weight-average molecular weight of 8,500.

(Dispersion resin (G-3) solution)
A reactor equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer was charged with 30 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, 20 parts of hydroxyethyl methacrylate, and 13.2 parts of tetramethylethylenediamine, and the mixture was stirred at 50°C for 1 hour while flowing nitrogen, thereby replacing the atmosphere in the system 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 polymerization of the first block (B block). After 4 hours of polymerization, a sample was taken from the polymerization solution and the nonvolatile content was measured. It was confirmed that the polymerization conversion rate was 98% or higher, calculated from the nonvolatile content.
Next, 61 parts of PGMAc and 20 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate (Fancryl FA-711MM, manufactured by Hitachi Chemical Co., Ltd.) as a second block (A block) monomer were added to this reactor, and the reaction was continued by stirring while maintaining the temperature at 110°C under a nitrogen atmosphere. Two hours after the addition of 1,2,2,6,6-pentamethylpiperidyl methacrylate, a sample of the polymerization solution was taken and the nonvolatile content was measured. It was confirmed that the polymerization conversion rate of the second block (A block) was 98% or higher, calculated from the nonvolatile content. The reaction solution was then cooled to room temperature to terminate the polymerization. The solution was diluted with PGMAc to a nonvolatile content of 30% by mass, yielding a dispersion resin (G-3) solution. The dispersion resin (G-3) had an amine value of 57 mgKOH/g and a number average molecular weight of 4,500.

<Preparation of Dispersion>
(Dispersion 1)
The following raw materials were mixed and stirred to a uniform consistency, then dispersed in an Eiger mill (Eiger Japan Co., Ltd., "Mini Model M-250 MKII") using zirconia beads with a diameter of 0.5 mm for 3 hours, and then filtered through a filter with a pore size of 1.0 μm to prepare Dispersion 1. The organic solvent (J-1) was PGMAc.
Finely divided blue pigment (F-1): 10.0 parts Dispersion resin (G-1) solution: 10.0 parts Dispersion resin (G-2) solution: 5.0 parts Organic solvent (J-1): 75.0 parts

(Dispersion 2 to 10)
Dispersions 2 to 10 were prepared in the same manner as Dispersion 1, except that the raw materials and amounts shown in Table 3 were changed.

<Production of Photosensitive Composition>
[Example 1]
(Photosensitive composition 1)
The following raw materials were mixed and stirred, and then filtered through a filter having a pore size of 1.0 μm to obtain a photosensitive composition 1.
Dispersion 2: 1.6 parts Dispersion 5: 1.6 parts Alkali-soluble resin (A-1) solution: 10.0 parts Polymerizable compound (B-1): 12.5 parts Photopolymerization initiator (C-1): 1.0 parts Thermosetting compound (D-1): 2.0 parts Compound (E1-1) represented by general formula (1): 0.6 parts Compound (E2-1) represented by general formula (3): 0.02 parts Thiol-based chain transfer agent (H-1): 0.2 parts Leveling agent (I): 1.0 parts Organic solvent (J): 69.48 parts

[Examples 2 to 34, Comparative Examples 1 and 2]
(Photosensitive compositions 2 to 36)
Photosensitive compositions 2 to 36 were prepared in the same manner as in Example 1, except that the photosensitive composition 1 in Example 1 was changed to the raw materials and amounts shown in Tables 4-1 to 4-4.

The details of each ingredient listed in Tables 4-1 to 4-4 are as follows:

[Polymerizable compound (B)]
B-1: Aronix M-450 (manufactured by Toagosei Co., Ltd.)

[Photopolymerization initiator (C)]
C-1: Compound of the above-mentioned chemical formula (4) C-2: Omnirad 907 (manufactured by IGM Resins)
C-2: Irgacure OXE-02 (manufactured by BASF)

[Thermosetting compound (D)]
D-1: EHPE-3150 (manufactured by Daicel Corporation, a 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol having approximately 15 epoxy groups)
D-2: Nikalac MX-706 (manufactured by Sanwa Chemical Co., Ltd., a methylated melamine compound having an imino group and a methylol group)

[Imidazole compound (E)]
(Compound (E1) represented by general formula (1))
E1-1: 10% PGMAc solution of 1-benzyl-2-methylimidazole E1-2: 10% PGMAc solution of 1-benzyl-2-phenylimidazole E1-3: 10% PGMAc solution of 1-benzylimidazole

(Compound (E2) represented by general formula (3))
E2-1: 10% PGMAc solution of 2-methylimidazole E2-2: 10% PGMAc solution of 2-phenylimidazole E2-3: 10% PGMAc solution of imidazole

(Other imidazole compounds (E3))
E3-1: 10% PGMAc solution of 1,2-dimethylimidazole

[Thiol-based chain transfer agent (H)]
H-1: Pentaerythritol tetrakis(3-mercaptopropionate)
H-2: Pentaerythritol tetrakis(3-mercaptobutyrate)

[Leveling agent (I)]
I-1: BYK-330 (manufactured by BYK-Chemie)
I-2: Megafac F-554 (DIC Corporation)
One part each of (I-1) and (I-2) was mixed and dissolved in 98 parts of PGMAc to prepare a mixed solution, which was used as a leveling agent (I).

[Organic solvent (J)]
J-1: Propylene glycol monomethyl ether acetate 30 parts J-2: Cyclohexanone 30 parts J-3: Ethyl 3-ethoxypropionate 10 parts J-4: Propylene glycol monomethyl ether 10 parts J-5: Cyclohexanol acetate 10 parts J-6: Dipropylene glycol methyl ether acetate 10 parts The above (J-1) to (J-6) were mixed in the above parts by mass to obtain organic solvent (J).

<Evaluation of Photosensitive Composition>
The obtained photosensitive compositions 1 to 36 (Examples 1 to 34 and Comparative Examples 1 and 2) were evaluated as follows. The evaluation results are shown in Table 5.

[Line width stability evaluation]
The resulting photosensitive composition was applied by spin coating to a 100 mm x 100 mm, 0.7 mm thick glass substrate (Corning Eagle 2000) so that the dried film thickness was 2.0 μm, and then dried on a hot plate at 70 °C for 1 minute. The substrate was then cooled to room temperature and exposed to light using a high-pressure mercury lamp at an illuminance of 30 mW/cm ² and two exposure levels of 50 mJ/cm ² and 100 mJ/cm ² through a 100 μm wide stripe pattern photomask. The substrate was then spray-developed using an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23 °C, then washed with ion-exchanged water, and air-dried. The resulting substrate was post-baked in a clean oven at 100 °C for 60 minutes to obtain an evaluation substrate.
The resulting evaluation substrate was measured for line width at an exposure dose of 50 mJ/ ^cm2 ( _CD50 ) and 100 mJ/ ^cm2 ( _CD100 ) using a Nikon ECLIPSE LV100POL Model optical microscope, and the difference in line width (ΔCD) due to differences in exposure dose was calculated using the following formula. The evaluation criteria were as follows, with a score of 3 or higher being considered practical.
Formula: ΔCD = CD ₁₀₀ - CD ₅₀
5: ΔCD is less than 2 μm 4: ΔCD is 2 μm or more and less than 3 μm 3: ΔCD is 3 μm or more and less than 5 μm 2: ΔCD is 5 μm or more and less than 6 μm 1: ΔCD is 6 μm or more

[Hardness evaluation]
The obtained photosensitive composition was applied by spin coating to a 100 mm x 100 mm, 0.7 mm thick glass substrate (Corning Eagle 2000) so that the dried film thickness was 2.0 μm, and then dried on a hot plate at 70°C for 1 minute. The substrate was then cooled to room temperature and exposed to light at an illuminance of 30 mW/ ^cm2 and 50 mJ/ ^cm2 using a high-pressure mercury lamp. After cooling to room temperature, the substrate was spray-developed using an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23°C, washed with ion-exchanged water, and air-dried. The obtained substrate was then post-baked in a clean oven at 100°C for 60 minutes to obtain an evaluation substrate.
The pencil hardness of the resulting cured film was measured in accordance with JIS K5400-1999, using the following evaluation criteria, with a score of 3 or higher being considered practical.
5: Pencil hardness is 5H or more 4: Pencil hardness is 4H
3: Pencil hardness is 3H
2: Pencil hardness is 2H
1: Pencil hardness is H or less

[Evaluation of high temperature and humidity resistance (1): Adhesion]
The obtained photosensitive composition was applied by spin coating to a 100 mm x 100 mm, 0.7 mm thick glass substrate (Corning Eagle 2000) so that the dried film thickness was 2.0 μm, and then dried on a hot plate at 70°C for 1 minute. The substrate was then cooled to room temperature and exposed to light at an illuminance of 30 mW/ ^cm2 and 50 mJ/ ^cm2 using a high-pressure mercury lamp. After cooling to room temperature, the substrate was spray-developed using an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23°C, washed with ion-exchanged water, and air-dried. The obtained substrate was then post-baked in a clean oven at 100°C for 60 minutes to obtain an evaluation substrate.
The resulting cured film was cut with a cutter knife into a 1 mm square grid pattern (100 squares) and stored for 2 hours under conditions of a temperature of 120°C and humidity of 100%. After storage, a transparent adhesive tape (CT-24 manufactured by Nichiban Co., Ltd.) was firmly pressed onto the film and peeled off in a direction of approximately 180°C. The state of the grid patterns was observed, and the number of peeled grid patterns was counted. The evaluation criteria are as follows, with a score of 3 or higher being considered practical.
5: Less than 2 4: 2 or more but less than 5 3: 5 or more but less than 10 2: 10 or more but less than 15 1: 15 or more

[Evaluation of High Temperature and Humidity Resistance (2): Film Thickness Stability]
The resulting photosensitive composition was applied to a 100 mm x 100 mm x 0.7 mm thick glass substrate (Corning Eagle 2000) using a spin coater to a dry film thickness of 2.0 μm, and then dried on a hot plate at 70°C for 1 minute. Next, using an ultra-high pressure mercury lamp, the composition was exposed to ultraviolet light at an illuminance of 30 mW/ ^cm2 and 50 mJ/ ^cm2 through a photomask with a 100 μm wide stripe pattern. After cooling to room temperature, the substrate was spray-developed using an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23°C, washed with ion-exchanged water, and air-dried. The resulting substrate was post-baked in a clean oven at 100°C for 60 minutes, and the film thickness of the pattern was measured. This film thickness was taken as the post-baked film thickness.
The obtained substrate was stored for 200 hours under conditions of a temperature of 85°C and a humidity of 85%. After storage, the film thickness was measured at the same location where the film thickness after post-baking was measured. This film thickness was taken as the film thickness after storage. The film thickness change rate was calculated from the two film thicknesses using the following formula. The evaluation criteria were as follows, with a score of 3 or higher being practical. The film thickness was measured using a Dektak 3030 (manufactured by Japan Vacuum Engineering Co., Ltd.).
Formula: Change rate (%) = |film thickness after post-baking - film thickness after storage| / film thickness after post-baking × 100
5: The rate of change is less than 3%. 4: The rate of change is 3% or more but less than 6%. 3: The rate of change is 6% or more but less than 10%. 2: The rate of change is 10% or more but less than 15%. 1: The rate of change is 15% or more.

Claims (8)

A photosensitive composition comprising an alkali-soluble resin (A), a polymerizable compound (B), a photopolymerization initiator (C), a thermosetting compound (D), and an imidazole compound (E),
the alkali-soluble resin (A) contains an alkali-soluble resin having a blocked isocyanate group-containing monomer unit (a1) and a hydroxyl group-containing monomer unit (a2);
The photosensitive composition, wherein the imidazole compound (E) comprises a compound (E1) represented by the following general formula (1):
General formula (1)

(In general formula (1), X ₁ to X ₃ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms.) The photosensitive composition according to claim 1 , wherein the photopolymerization initiator (C) comprises a compound represented by the following general formula (2):
General formula (2)

(In general formula (2), R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ₃ represents a hydrogen atom or a monovalent substituent.) 3. The photosensitive composition according to claim 1, wherein the imidazole compound (E) further comprises a compound (E2) represented by the following general formula (3):
General formula (3)

(In general formula (3), X ₄ to X ₆ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms.) The photosensitive composition according to claim 3, wherein the content of the compound (E1) represented by the general formula (1) is 50% by mass or more, based on a total of 100% by mass of the compound (E1) represented by the general formula (1) and the compound (E2) represented by the general formula (3). The photosensitive composition according to any one of claims 1 to 4, further comprising a colorant (F), the content of which is 5% by mass or less based on 100% by mass of the nonvolatile content of the photosensitive composition. An optical filter having a substrate and a cured film of the photosensitive composition described in any one of claims 1 to 5. An image display device having the optical filter described in claim 6. A solid-state imaging device having the optical filter described in claim 6.