Curable composition, film using same, optical filter, solid-state imaging element, image display device, and infrared sensor

Abstract

The purpose of the present invention is to provide: a curable composition having excellent adhesion and film resistance, and also having excellent developability and line width stability even after storage; and a film, an optical filter, a solid-state imaging element, an image display device, and an infrared sensor using the curable composition. The problem can be solved by a curable composition comprising an alkali-soluble resin (A), a polymerizable compound (B), a polymerization initiator (C), and a thermally crosslinkable compound (D), the polymerizable compound (B) contains a polyfunctional urethane (meth) acrylate (B1) having a secondary amine structure or a tertiary amine structure, and the thermally crosslinkable compound (D) contains a compound (D1) having a block isocyanate group.

Description

Technical Field

[0001] The present invention relates to a curable composition and its applications in films, filters, solid-state imaging devices, image display devices, and infrared sensors. Background Art

[0002] A color filter, which is one type of filter used in an image display device or a solid-state imaging device, etc., can be produced, for example, through the following steps. A pattern of a first color is obtained through the steps of coating a curable composition on a substrate such as glass (hereinafter referred to as the coating step), removing a solvent from the coating film through drying (hereinafter referred to as the drying step), irradiating the coating film with ultraviolet rays through a photomask having a desired pattern shape and curing it (hereinafter referred to as the exposure step), then cleaning and removing the unexposed portion of the coating film using a developer (hereinafter referred to as the development step), and thereafter, performing a heat treatment to fully cure the film (hereinafter referred to as the post-baking step). Then, depending on the need, a curable composition of a different color is used and the same operations are performed, whereby patterns of colors after the second color are sequentially formed to produce a color filter.

[0003] In recent years, due to the miniaturization and high pixelization of image display devices or solid-state imaging devices, patterns have become finer, and the difficulty of formation has increased. In addition, in order to improve the productivity of color filters, it is required to reduce the cumulative exposure amount required for pattern formation and to lower the heating temperature in order to reduce the environmental load. Therefore, the adhesion of patterns or the tolerance of films has become a problem. Furthermore, when storing the curable composition, there is also a problem that the development time or the width of the pattern changes compared to before storage.

[0004] In order to solve the above problems, for example, in Patent Document 1, as a photosensitive colored resin composition that can suppress the generation of development residues even under low-temperature heat treatment and can form a colored layer with a good pattern shape, the following photosensitive colored resin composition is disclosed. It contains a coloring material, an alkali-soluble resin, a non-reactive resin, a photopolymerizable compound, a photoinitiator, and a solvent. The acid value of the alkali-soluble resin exceeds 50 mgKOH / g, the acid value of the non-reactive resin is 7 mgKOH / g to 50 mgKOH / g, the content of the structural unit derived from methyl methacrylate is 50% by mass to 99% by mass in all structural units, and the weight average molecular weight is 5000 to 50000. In addition, in Patent Document 2, as a photosensitive resin composition that can achieve a photosetting pattern with excellent substrate adhesion, residual film rate, and high sensitivity, the following photosensitive resin composition is disclosed. It contains an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a solvent. The photopolymerization initiator contains a compound with a specific structure. In addition, in Patent Document 3, as a curable resin composition that can provide a cured product with sufficient surface hardness and excellent electrical properties, the following curable resin composition is disclosed. It contains an alkali-soluble resin, a polyfunctional compound having two or more functional groups, and a compound having at least one reactive functional group selected from the group consisting of an epoxy group, an oxetanyl group, and a blocked isocyanate group. The alkali-soluble resin is a polymer having a ring structure in the main chain.

[0005] [Prior Art Documents]

[0006] [Patent Documents]

[0007] [Patent Document 1] International Publication No. 2022 / 270358

[0008] [Patent Document 2] Japanese Patent Laid-Open No. 2019-200226

[0009] [Patent Document 3] Japanese Patent Laid-Open No. 2015-67699 Summary of the Invention

[0010] [Problems to be Solved by the Invention]

[0011] However, the adhesiveness and film tolerance of the compositions described in Patent Documents 1 to 3 are insufficient. In addition, the developability or pattern width after storing the composition is not considered.

[0012] An object of the present invention is to provide a curable composition having excellent adhesiveness and film tolerance, and excellent developability and line width stability even after storage.

[0013] [Means for Solving the Problems]

[0014] The present invention relates to a curable composition comprising: an alkali-soluble resin (A), a polymerizable compound (B), a polymerization initiator (C), and a thermally crosslinkable compound (D). In the curable composition,

[0015] the polymerizable compound (B) includes a polyfunctional urethane (meth)acrylate (B1) having a secondary amine structure or a tertiary amine structure.

[0016] the thermally crosslinkable compound (D) includes a compound (D1) having a blocked isocyanate group.

[0017] [Effects of the Invention]

[0018] According to the present invention, a curable composition having excellent adhesion, film tolerance, developability, and line width stability even after storage can be provided. In addition, the present invention can provide a film, a filter, a solid-state imaging device, an image display device, and an infrared sensor using the same. In addition, the so-called film tolerance is solvent tolerance. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 A schematic cross-sectional view of an infrared sensor having a filter of the present invention is shown.

[0020] [Description of Reference Numerals]

[0021] 100: Infrared sensor

[0022] 110: Solid-state imaging device

[0023] 111: Infrared cut-off filter

[0024] 112: Color filter

[0025] 113: Infrared transmission filter

[0026] 114: Resin film

[0027] 115: Microlens

[0028] 116: Flat film

[0029] h: Incident light DETAILED DESCRIPTION OF THE INVENTION

[0030] Hereinafter, the form of the curable composition for implementing the present invention will be described in detail. In addition, the present invention is not limited to the following embodiments and can be implemented with modifications within the scope capable of solving the problems.

[0031] In this specification, the terms “(meth)acryloyl”, “(meth)acrylic group”, “(meth)acrylic acid”, “(meth)acrylate” or “(meth)acrylamide” respectively mean “acryloyl and / or methacryloyl”, “acrylic group and / or methacrylic group”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, or “acrylamide and / or methacrylamide” unless otherwise specified.

[0032] In addition, “C.I.” means the Colour Index (C.I.; published by The Society of Dyers and Colourists).

[0033] In this specification, the polymerizable unsaturated group is an ethylenic unsaturated double bond.

[0034] In this specification, a monomer is a compound that forms a resin by polymerization. The monomer is in an unreacted state, and the monomer unit is in a state formed after the monomer is polymerized to form a resin.

[0035] In this specification, for a low-molecular compound with a determinable molecular weight, the value calculated by calculation (molecular weight) or the molecular weight measured by electrospray ionization-mass spectrometry (ESI-MS) is used. For a compound with a molecular weight distribution, the polystyrene-converted weight-average molecular weight measured by gel permeation chromatography using tetrahydrofuran as a solvent is used.

[0036] In this specification, the numerical range represented by “~” means the range including the numerical values described before and after “~” as the lower limit value and the upper limit value.

[0037] <Hardenable Composition>

[0038] The hardenable composition as one embodiment of the present invention contains: an alkali-soluble resin (A), a polymerizable compound (B), a polymerization initiator (C), and a thermally crosslinkable compound (D). The hardenable composition is characterized in that

[0039] the polymerizable compound (B) contains a polyfunctional urethane (meth)acrylate (B1) having a secondary amine structure or a tertiary amine structure,

[0040] the thermally crosslinkable compound (D) contains a compound (D1) having a blocked isocyanate group.

[0041] The mechanism by which the hardenable composition having the above structure can solve the problems of the present invention is not yet clear, but it is presumed as follows.

[0042] The curable composition decomposes a polymerization initiator by light or heat to generate active species. The active species add to the polymerizable compound to newly generate active species, and the reaction proceeds in a chain to cause polymerization. However, if the active species are inactivated due to external factors, the polymerization reaction stops. In the case where the active species are free radicals, oxygen hinders the polymerization (also referred to as oxygen inhibition). Since oxygen is in a triplet state in the ground state, it has high reactivity with free radicals and easily reacts with free radical active species to form peroxy radicals. The peroxy radicals have poor reactivity with the polymerizable compound, and thus hinder the progress of the polymerization reaction. Therefore, in the case where the cumulative exposure amount is small, the adhesion or film tolerance is likely to deteriorate.

[0043] Generally, since filters such as color filters are manufactured in an atmospheric environment, polymerization hindrance caused by oxygen occurs in the exposure process, and polymerization cannot be sufficiently carried out. However, polymerization is promoted by heat treatment at a high temperature thereafter. Therefore, in the case of heat treatment at a low temperature, the film tolerance is likely to deteriorate due to insufficient hardening.

[0044] The polyfunctional carbamate (meth)acrylate (B1) having a secondary amine structure or a tertiary amine structure has a secondary amine structure or a tertiary amine structure in the molecule, and thus it is presumed that hydrogen is easily extracted to generate a carbon radical. Therefore, the generated peroxy radicals extract hydrogen from the polyfunctional carbamate (meth)acrylate (B1) having a secondary amine structure or a tertiary amine structure, and the newly generated carbon radicals start polymerization. In addition, since the generated carbon radicals can capture oxygen, there is also an effect of reducing the oxygen concentration during polymerization. Based on these mechanisms, it is presumed that the polymerization hindrance caused by oxygen is suppressed and polymerization proceeds sufficiently, and thus the adhesion and film tolerance are improved. Furthermore, the polyfunctional carbamate (meth)acrylate (B1) having a secondary amine structure or a tertiary amine structure forms a chemical crosslinked structure based on polymerization and a physical crosslinked structure based on intermolecular hydrogen bonds between urethane bonds or between functional groups of the substrate. The intermolecular hydrogen bond of the urethane bond portion has a larger molecular cohesive energy than other organic structures such as ether bonds. Therefore, it is presumed that the film becomes firm due to the interaction between urethane bonds, and thus the adhesion and film tolerance are improved. Moreover, the isocyanate group of the compound (D1) having a blocked isocyanate group used in combination is protected by a blocking agent, and thus it is difficult to react with other components during storage, and even when used after a lapse of time, changes in developability and line width are suppressed. Furthermore, it is presumed that the film tolerance is further improved by the reaction of the isocyanate group after the blocking agent is removed by heating during post-baking or by transesterification with other components without the blocking agent being removed.

[0045] Hereinafter, the components that are included or may be included in the curable composition according to one embodiment will be described in detail.

[0046] [Alkali-soluble resin (A)]

[0047] The curable composition of the present invention contains an alkali-soluble resin (A).

[0048] The alkali-soluble resin (A) only needs to be soluble in the alkali developer described below, and there is no particular limitation, and known resins can be used. Examples of the resin type of the alkali-soluble resin (A) include: (meth)acrylic resin, styrene resin, styrene / (meth)acrylic resin, epoxy resin, urethane resin, polycarbonate resin, polyester resin, polyether resin, polyimide resin, polyamideimide resin, cyclic olefin resin, polysiloxane resin, etc.

[0049] The alkali-soluble resin (A) preferably has an alkali-soluble group. Examples of the alkali-soluble group include acidic groups such as carboxyl group, phosphoric acid group, and sulfonic acid group. Among these, from the viewpoint of developability, a carboxyl group is more preferable.

[0050] Examples of the structure of the alkali-soluble resin (A) include: chain random structure, chain block structure, graft structure, comb structure, and star structure, etc. Among these, from the viewpoint of film tolerance, a chain random structure is preferable.

[0051] The weight average molecular weight of the alkali-soluble resin (A) is preferably 3,000 to 50,000, and more preferably 4,000 to 40,000.

[0052] The acid value of the alkali-soluble resin (A) is preferably 30 mgKOH / g to 200 mgKOH / g, and more preferably 40 mgKOH / g to 180 mgKOH / g.

[0053] The alkali-soluble resin (A) can be used alone or in combination of two or more.

[0054] In 100% by mass of the non-volatile components of the curable composition, the alkali-soluble resin (A) is preferably 1% by mass to 95% by mass, and more preferably 3% by mass to 80% by mass.

[0055] (Alkali-soluble resin (A1) having a monomer unit (a1) containing a hydroxyl group)

[0056] From the viewpoint of film tolerance, the alkali-soluble resin (A) is preferably an alkali-soluble resin (A1) containing a monomer unit (a1) containing a hydroxyl group (hereinafter, also simply referred to as alkali-soluble resin (A1)). It is presumed that the hydroxyl group of the alkali-soluble resin (A1) reacts with the compound (D1) having a blocked isocyanate group in the post-baking process, so the film tolerance is improved.

[0057] The alkali-soluble resin (A1) is not particularly limited as long as it is an alkali-soluble resin having a hydroxyl group, and it can be produced by known methods. For example, it can be produced by the methods (i) to (iii) described below. In addition, the present invention is not limited to these.

[0058] <Method (i)>

[0059] Method (i) is to copolymerize a hydroxyl group-containing monomer that forms a hydroxyl group-containing monomer unit (a1) and a monomer that can be copolymerized with it arbitrarily.

[0060] [[Hydroxyl group-containing monomer unit (a1)]]

[0061] 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, 2-acryloyloxyethyl-2-hydroxyethyl phthalate, etc. These monomers can be used alone or in combination of two or more.

[0062] Examples of the monomer that can be copolymerized with the hydroxyl group-containing monomer include the monomers that form the following monomer units (a2) to monomer units (a8).

[0063] <Method (ii)>

[0064] Method (ii) is to introduce a hydroxyl group by adding a compound having a carboxyl group (modifying compound) to the epoxy group contained in the resin (precursor).

[0065] <Method (iii)>

[0066] Method (iii) is to introduce a hydroxyl group by adding a compound having an epoxy group (modifying compound) to the carboxyl group contained in the resin (precursor).

[0067] From the viewpoints of film tolerance, developability after storage, and line width stability after storage, in all the structural units of the alkali-soluble resin (A1), the content of the hydroxyl group-containing monomer unit (a1) is preferably 1 mol% to 60 mol%, more preferably 5 mol% to 50 mol%.

[0068] The alkali-soluble resin (A1) may contain monomer units other than the hydroxyl group-containing monomer unit (a1). The monomer units other than the hydroxyl group-containing monomer unit (a1) are not particularly limited, and examples thereof include monomer units (a2) containing a polycyclic alicyclic hydrocarbon group, monomer units (a3) containing an acidic group, monomer units (a4) containing an epoxy group, monomer units (a5) containing a polymerizable unsaturated group, monomer units (a6) containing an aromatic ring, monomer units (a7) containing a blocked isocyanate group, and other monomer units (a8). Among these, from the viewpoint of film tolerance, the alkali-soluble resin (A1) preferably has a monomer unit (a2) containing a polycyclic alicyclic hydrocarbon group, and from the viewpoint of developability, the alkali-soluble resin (A1) preferably has a monomer unit (a3) containing an acidic group.

[0069] [Monomer unit (a2) containing a polycyclic alicyclic hydrocarbon group]

[0070] Examples of the monomer that forms the monomer unit (a2) containing a polycyclic alicyclic hydrocarbon group include isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyl oxyethyl (meth)acrylate, adamantyl (meth)acrylate, etc. Among these, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentanyloxyethyl (meth)acrylate are preferred. These monomers can be used alone or in combination of two or more.

[0071] In all the structural units of the alkali-soluble resin (A1), the content of the monomer unit (a2) containing a polycyclic alicyclic hydrocarbon group is preferably 1 mol% to 60 mol%, more preferably 3 mol% to 40 mol%.

[0072] [Monomer unit (a3) containing an acidic group]

[0073] Examples of the monomer containing an acidic group include (meth)acrylic acid, crotonic acid, propargylic 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 hexyl hydrogen phthalic acid, styrene sulfonic acid, vinyl sulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid, tert-butylacrylamide sulfonic acid, 2-(meth)acryloyloxyethyl acid phosphate, etc. These monomers can be used alone or in combination of two or more.

[0074] From the viewpoint of developability, in all the structural units of the alkali-soluble resin (A1), the content of the monomer unit (a3) containing an acidic group is preferably 1 mol% to 60 mol%, more preferably 5 mol% to 50 mol%.

[0075] Regarding the method of introducing the monomer unit (a3) containing an acidic group into the alkali-soluble resin (A1), in addition to the method of copolymerizing a monomer containing a hydroxyl group and a monomer containing an acidic group, a method of adding an acid anhydride (modifying compound) to the hydroxyl group of the alkali-soluble resin (A1) can also be used. Examples of the acid anhydride include succinic anhydride, phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, etc.

[0076] 〔Monomer unit (a4) containing an epoxy group〕

[0077] Examples of the monomer containing an epoxy group include: (meth)acrylic acid oxiranyl ester, (meth)acrylic acid glycidyl ester, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, 2-oxiranylethyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate, 2-(3,4-epoxycyclohexylmethyloxy)ethyl (meth)acrylate, 3-(3,4-epoxycyclohexylmethyloxy)propyl (meth)acrylate, etc. These monomers can be used alone or in combination of two or more.

[0078] 〔Monomer unit (a5) containing a polymerizable unsaturated group〕

[0079] The method of containing the monomer unit (a5) containing a polymerizable unsaturated group in the alkali-soluble resin (A1) has, for example, the methods (iv) to (vi) shown below, etc.

[0080] <Method (iv)>

[0081] Method (iv) first synthesizes a precursor having a monomer unit (a4) containing an epoxy group, and then adds a monomer (modifying compound) having a carboxyl group in the monomer containing an acidic group to the epoxy group of the precursor.

[0082] <Method (v)>

[0083] Method (v) first synthesizes a precursor having a monomer unit (a3) containing an acidic group with a carboxyl group as the acidic group, and then adds the monomer containing an epoxy group (modifying compound) to the carboxyl group of the precursor.

[0084] Furthermore, the acid anhydride (modified compound) may further react with the hydroxyl groups generated by the reactions of method (iv) and method (v) to contain acidic groups.

[0085] Examples of the acid anhydride include: 1,2,3,6-tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, and the like.

[0086] <Method (vi)>

[0087] In method (vi), for example, a precursor having a monomer unit (a1) containing a hydroxyl group is first synthesized. Subsequently, the isocyanate group of the monomer (modified compound) containing an isocyanate group reacts with the hydroxyl group of the precursor.

[0088] Examples of the monomer containing an isocyanate group include: 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, 1,1-bis[methacryloyloxy]ethyl isocyanate, and the like. These monomers can be used alone or in combination of two or more.

[0089] [Monomer unit (a6) containing an aromatic ring]

[0090] Examples of the monomer containing an aromatic ring include: styrene, α-methylstyrene, vinylnaphthalene, (meth)acrylic acid phenyl ester, (meth)acrylic acid benzyl ester, (meth)acrylic acid phenoxyethyl ester, p-cumylphenol ethylene oxide (EO) modified (meth)acrylate or p-cumylphenol propylene oxide (PO) modified (meth)acrylate, phenol EO modified (meth)acrylate or phenol PO modified (meth)acrylate, nonylphenol EO modified (meth)acrylate or nonylphenol PO modified (meth)acrylate, N-phenylmaleimide, N-benzylmaleimide, and the like. These monomers can be used alone or in combination of two or more.

[0091] [Monomer unit (a7) containing a blocked isocyanate group]

[0092] The monomer containing a blocked isocyanate group is a monomer in which the isocyanate group of the monomer containing an isocyanate group is protected by a compound that dissociates by heat (hereinafter, also referred to as a blocking agent). The dissociation temperature of the blocking agent is preferably 60°C to 160°C.

[0093] Examples of the monomer containing an isocyanate group include: 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, methacryloyl isocyanate, etc. In addition, an equimolar reaction product of a 2-hydroxyalkyl (meth)acrylate and a diisocyanate compound can also be used.

[0094] Examples of the blocking agent include: oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, thiol compounds, imidazole compounds, imide compounds, urea compounds, imine compounds, and bisulfite compounds, etc.

[0095] Examples of the oxime compound include: formaldehyde oxime, acetaldehyde oxime, acetyl oxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, cyclohexanone oxime, benzophenone oxime, etc. Among these, methyl ethyl ketoxime is preferred.

[0096] Examples of the lactam compound include: ε-caprolactam, δ-valerolactam, γ-butyrolactam, β-propiolactam, etc.

[0097] Examples of the phenol compound include: phenol, cresol, 2,6-xylenol, 3,5-xylenol, ethylphenol, p-tert-butylphenol, nonylphenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, p-naphthol, p-nitrophenol, etc. Among these, 3,5-xylenol, methyl 2-hydroxybenzoate, and methyl 4-hydroxybenzoate are preferred.

[0098] Examples of the alcohol compound include: methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl alcohol.

[0099] Examples of the amine compound include: diphenylamine, phenylnaphthylamine, aniline, carbazole, etc.

[0100] Examples of the active methylene compound include: diethyl malate, dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-tert-butyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone, etc. Diethyl malonate is preferred.

[0101] Examples of the pyrazole compound include: pyrazole, methylpyrazole, 3,5-dimethylpyrazole, etc. 3,5-dimethylpyrazole is preferred.

[0102] Examples of the thiol compound include: butyl mercaptan, thiophenol, tert-dodecyl mercaptan, etc.

[0103] Examples of the imidazole compound include imidazole, 2-methylimidazole, 2-ethylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, and the like.

[0104] Examples of the imide compound include succinimide, maleimide, maleic imide, phthalimide, and the like.

[0105] Examples of the urea compound include urea, thiourea, ethylene urea, and the like.

[0106] Examples of the imine compound include ethyleneimine, polyethyleneimine, and the like.

[0107] Examples of the bisulfite compound include sodium bisulfite, potassium bisulfite, and the like.

[0108] The blocking agent can be used alone or in combination of two or more.

[0109] 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, thiol compounds, imidazole compounds, and imide compounds, and more preferably at least one selected from the group consisting of oxime compounds, phenol compounds, active methylene compounds, and pyrazole compounds from the viewpoints of the protection reaction and the deprotection reaction.

[0110] Examples of the monomer containing a blocked isocyanate group include the following compounds. In addition, the present invention is not limited to these.

[0111] [Chemical Formula 1]

[0112]

[0113] Commercially available products of the monomer containing a blocked isocyanate group include, for example, Karenz MOI-DEM (blocking agent dissociation temperature: 85°C to 95°C), MOI-BP (blocking agent dissociation temperature: 105°C to 115°C), MOI-BM (blocking agent dissociation temperature: 125°C to 135°C), etc. manufactured by Resonac. These monomers can be used alone or in combination of two or more.

[0114] In the case where the polymerization initiator (C) described below contains only the photopolymerization initiator (C1), from the viewpoint of film tolerance, the alkali-soluble resin (A1) preferably has a monomer unit (a7) containing a blocked isocyanate group. The isocyanate group after the blocking agent is removed by heat treatment reacts with the hydroxyl group or other components of the alkali-soluble resin (A1). Alternatively, the blocking agent does not dissociate and reacts with the hydroxyl group of the alkali-soluble resin (A1) by transesterification. Thus, it is speculated that the film tolerance is improved.

[0115] From the viewpoint of film tolerance, in all the structural units of the alkali-soluble resin (A1), the content of the monomer unit (a7) containing a blocked isocyanate group is preferably 1 mol% to 50 mol%, more preferably 3 mol% to 40 mol%.

[0116] 〔Other monomer units (a8)〕

[0117] Examples of other monomers include: acrylate esters such as ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, and diethylaminoethyl (meth)acrylate;

[0118] (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;

[0119] Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether;

[0120] Fatty acid vinyl esters such as vinyl acetate or vinyl propionate;

[0121] N-substituted maleimides such as methyl maleimide, ethyl maleimide, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 3-maleimidopropionic acid, and 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin;

[0122] Dimethyl-2,2'-[oxybis(methylene)]bis-2-acrylate, diethyl-2,2'-[oxybis(methylene)]bis-2-acrylate, di(n-propyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, di(isopropyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, di(2-ethylhexyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, etc. These monomers can be used alone or in combination of two or more.

[0123] The weight-average molecular weight of the alkali-soluble resin (A1) is preferably 3,000 to 50,000, more preferably 4,000 to 40,000.

[0124] The molecular weight distribution (weight-average molecular weight / number-average molecular weight) of the alkali-soluble resin (A1) is preferably 1.2 to 3.0, more preferably 1.3 to 2.8.

[0125] The acid value of the alkali-soluble resin (A1) is preferably 20 mgKOH / g to 200 mgKOH / g, more preferably 30 mgKOH / g to 180 mgKOH / g.

[0126] The alkali-soluble resin (A1) can be used alone or in combination of two or more.

[0127] In 100% by mass of the alkali-soluble resin (A), the content of the alkali-soluble resin (A1) is preferably 10% by mass to 100% by mass, more preferably 20% by mass to 100% by mass.

[0128] (Alkali-soluble resin (A2) other than the alkali-soluble resin (A1))

[0129] The alkali-soluble resin (A) may contain an alkali-soluble resin (A2) other than the alkali-soluble resin (A1) (hereinafter, also simply referred to as other alkali-soluble resin (A2)).

[0130] [Polymerizable compound (B)]

[0131] The curable composition of the present invention contains a polymerizable compound (B).

[0132] The polymerizable compound (B) is not particularly limited as long as it can polymerize, and known polymerizable compounds can be used. For example, monomers, oligomers, etc. having a polymerizable unsaturated group can be cited. Examples of the polymerizable unsaturated group include vinyl, (meth)allyl, (meth)acryloyl, (meth)acryloyloxy, styryl, etc.

[0133] The polymerizable compound (B) can be used alone or in combination of two or more.

[0134] In 100% by mass of the non-volatile components of the curable composition, the content of the polymerizable compound (B) is preferably 1% to 80% by mass, more preferably 5% to 70% by mass.

[0135] (Polyfunctional urethane (meth)acrylate (B1) having a secondary amine structure or a tertiary amine structure)

[0136] The polymerizable compound (B) contains polyfunctional urethane (meth)acrylate (B1) having a secondary amine structure or a tertiary amine structure.

[0137] In addition, the amine structure of the polyfunctional urethane (meth)acrylate (B1) having a secondary amine structure or a tertiary amine structure does not include an amide structure, an imide structure, a urethane structure, and a cyclic amine structure in which a carbonyl group is directly bonded to a nitrogen atom.

[0138] The polyfunctional urethane (meth)acrylate (B1) having a secondary amine structure or a tertiary amine structure is a compound containing two or more (meth)acryloyl groups. The number of (meth)acryloyl groups of the polyfunctional urethane (meth)acrylate (B1) having a secondary amine structure or a tertiary amine structure is preferably 2 to 60. In addition, the polyfunctional urethane (meth)acrylate (B1) having a secondary amine structure or a tertiary amine structure contains at least one urethane structure and may contain two or more urethane structures.

[0139] The weight average molecular weight of the polyfunctional urethane (meth)acrylate (B1) having a secondary amine structure or a tertiary amine structure is preferably 500 to 50,000, more preferably 1,000 to 30,000.

[0140] The molecular weight distribution (weight average molecular weight / number average molecular weight) of the polyfunctional urethane (meth)acrylate (B1) having a secondary amine structure or a tertiary amine structure is preferably 1.5 to 5.0.

[0141] The acid value of the polyfunctional urethane (meth)acrylate (B1) having a secondary amine structure or a tertiary amine structure is preferably 10 mgKOH / g or less.

[0142] The polyfunctional urethane (meth)acrylate (B1) having a secondary amine structure or a tertiary amine structure can be used alone or in combination of two or more.

[0143] In 100% by mass of the polymerizable compound (B), the content of the polyfunctional urethane (meth)acrylate (B1) having a secondary amine structure or a tertiary amine structure is preferably 0.1% to 80% by mass, more preferably 0.5% to 60% by mass.

[0144] The polyfunctional carbamate (meth)acrylate (B1) having a secondary amine structure or a tertiary amine structure can be synthesized as described below. For example, it can be synthesized by a urethane reaction of a Michael addition reaction product (precursor) of a (meth)acrylate compound (X) and an amine compound (Y) having a hydroxyl group, and a polyisocyanate compound (Z).

[0145] Examples of the (meth)acrylate compound (X) include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexylene glycol di(meth)acrylate, glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, diglycerol tri(meth)acrylate, diglycerol tetra(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate or trimethylolpropane PO-modified tri(meth)acrylate, di-trimethylolpropane EO-modified tetra(meth)acrylate or di-trimethylolpropane PO-modified tetra(meth)acrylate, pentaerythritol EO-modified tetra(meth)acrylate or pentaerythritol PO-modified tetra(meth)acrylate, dipentaerythritol EO-modified hexa(meth)acrylate or dipentaerythritol PO-modified hexa(meth)acrylate, etc.

[0146] The (meth)acrylate compound (X) can be used alone or in combination of two or more.

[0147] Examples of the amine compound (Y) having a hydroxyl group include ethanolamine, butanolamine, diethylene glycolamine, o-aminophenol, m-aminophenol, p-aminophenol, 2-aminobenzyl alcohol, N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-isopropylethanolamine, N-butylethanolamine, N-isobutylethanolamine, N-methylbutanolamine, N-ethylbutanolamine, N-butyl-4-hydroxybutylamine, etc.

[0148] The amine compound (Y) having a hydroxyl group can be used alone or in combination of two or more.

[0149] The method of the Michael addition reaction of the (meth)acrylate compound (X) and the amine compound (Y) having a hydroxyl group is not particularly limited, and known methods can be used. For example, the methods described in International Publication No. 2006 / 075754, Japanese Patent Application Laid-Open No. 2008-545859, Japanese Patent Application Laid-Open No. 2017-066347, Japanese Patent Application Laid-Open No. 2018-517797, etc. can be cited.

[0150] Examples of the polyisocyanate compound (Z) include polyisocyanate compounds having an aliphatic structure such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylidene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, etc.;

[0151] polyisocyanate compounds having an alicyclic structure such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dimethylcyclohexyl diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, bis(isocyanatomethyl)cyclohexane, etc.;

[0152] polyisocyanate compounds having an aromatic structure such as 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylylene diisocyanate, mesitylene tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, toluene diisocyanate, dichloromethyldiphenylmethane diisocyanate, 2,6-diisocyanate-benzyl chloride, bis(isocyanatomethyl)benzene, etc.

[0153] In addition, examples include biuret bodies, isocyanurate bodies, adducts, urethane-formate bodies, etc. of these.

[0154] The polyisocyanate compound (Z) can be used alone or in combination of two or more.

[0155] The method for the urethane reaction of the precursor with the polyisocyanate compound (Z) is not particularly limited, and known methods can be used. For example, the methods described in Japanese Patent Publication No. 2018-517797 can be cited.

[0156] From the viewpoint of adhesion, the polyfunctional urethane (meth)acrylate (B1) having a secondary amine structure or a tertiary amine structure is more preferably at least one selected from the group consisting of an aliphatic polyfunctional urethane (meth)acrylate having a secondary amine structure or a tertiary amine structure and an alicyclic polyfunctional urethane (meth)acrylate having a secondary amine structure or a tertiary amine structure.

[0157] The aliphatic polyfunctional urethane (meth)acrylate having a secondary amine structure or a tertiary amine structure is obtained by using the polyisocyanate compound having the aliphatic structure as the polyisocyanate compound (Z).

[0158] The alicyclic polyfunctional carbamate (meth)acrylate having a secondary amine structure or a tertiary amine structure is obtained by using a polyisocyanate compound having the alicyclic structure as the polyisocyanate compound (Z).

[0159] Commercially available products of the polyfunctional carbamate (meth)acrylate (B1) having a secondary amine structure or a tertiary amine structure include, for example, CN9906NS, an aliphatic polyfunctional carbamate acrylate having a tertiary amine structure, manufactured by Arkema.

[0160] ((Meth)acrylate (B2) other than the polyfunctional carbamate (meth)acrylate (B1) having a secondary amine structure or a tertiary amine structure)

[0161] From the viewpoints of film tolerance, developability after storage, and line width stability after storage, the polymerizable compound (B) is preferably a (meth)acrylate (B2) (hereinafter, also simply referred to as other (meth)acrylate (B2)) other than the polyfunctional carbamate (meth)acrylate (B1) having a secondary amine structure or a tertiary amine structure.

[0162] Other (meth)acrylates (B2) can be used alone or in combination of two or more.

[0163] In 100% by mass of the polymerizable compound (B), the content of the other (meth)acrylate (B2) is preferably 20% by mass to 99.9% by mass.

[0164] From the viewpoints of film tolerance, developability after storage, and line width stability after storage, the other (meth)acrylate (B2) is preferably one or more selected from the group consisting of difunctional (meth)acrylate and trifunctional (meth)acrylate.

[0165] 〔Difunctional (meth)acrylate〕

[0166] Examples of bifunctional (meth)acrylates include: dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol (200) di(meth)acrylate, polyethylene glycol (400) di(meth)acrylate, polyethylene glycol (600) di(meth)acrylate, polypropylene glycol (400) di(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl glycol PO-modified diacrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, 2-hydroxy-3-methacryloylpropyl acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,6-hexanediol EO-modified di(meth)acrylate, 1,6-hexanediol PO-modified di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,11-undecanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, 1,13-tridecanediol di(meth)acrylate, 1,14-tetradecanediol di(meth)acrylate, 1,15-pentadecanediol di(meth)acrylate, 1,16-hexadecanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, dicyclopentenyl di(meth)acrylate, dicyclopentanyl di(meth)acrylate, 1,3-adamantanediol di(meth)acrylate, 5,7-dimethyl-1,3-adamantanediol di(meth)acrylate, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, 9,9-bis[4-(2-methacryloyloxyethoxy)phenyl]fluorene, 9,9-bis[4-(2-methacryloyloxyethoxy)-3-methylphenyl]fluorene, hydrogenated bisphenol A di(meth)acrylate, EO-modified hydrogenated bisphenol A di(meth)acrylate, bisphenol A EO-modified di(meth)acrylate, bisphenol F EO-modified di(meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate, glycerol di(meth)acrylate, etc.

[0167] Commercially available products of difunctional (meth)acrylates include, for example: Aronix M-208, M-211B, M-215, M-220, M-225, M-270, M-240, M-920 manufactured by Toagosei Co., Ltd.; NK Ester A-HD-N, A-NOD-N, A-DOD-N, A-NPG, 701A, A-200, A-400, A-600, APG-200, APG-400, APG-700, A-DCP, ABE-300, A-BPE-4, A-BPE-10, A-BPE-20, HD-N, NOD-N, DOD-N, NPG, 701, DCP, BPE-80N, BPE-100, BPE-200 manufactured by Shin-Nakamura Chemical Co., Ltd.; Miramer M202, M204, M210, M216, M220, M222, M232, N262, M270, HR6060, HR6100, HR6200 manufactured by Miwon Specialty Chemical Co., Ltd.; OGSOL EA-0200, EA-0300, GA-5060P, GA-2800 manufactured by Osaka Gas Chemical Co., Ltd.; New Frontier HPN, HBPE-4 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.; Light acrylate HPPA, MPD-A, Epoxy Ester 40EM, 70PA, 200PA, 80MFA, 3002M(N), 3000MK, 3000A of Kyoeisha Chemical Co., Ltd.; KAYARAD R-167, HX-220, HX-620, R-604 manufactured by Nippon Kayaku Co., Ltd., etc.

[0168] From the viewpoint of line width stability in the formed pattern after storage, the difunctional (meth)acrylate is preferably a compound represented by the following general formula (1).

[0169] General formula (1)

[0170] [Chemical formula 2]

[0171]

[0172] In general formula (1), R1 and R2 each independently represent a hydrogen atom or a methyl group, A1 and A2 each independently represent an alkylene group, l and m each independently represent an integer of 0 to 10, and n represents an integer of 6 to 20.

[0173] From the viewpoint of reactivity, R1 and R2 are preferably hydrogen atoms.

[0174] The number of carbon atoms of the alkylene group represented by A1 and A2 is preferably from 1 to 5, more preferably from 1 to 4, and particularly preferably 2 or 3. The alkylene group may be either straight-chain or branched. Specific examples of the alkylene group include ethylene, linear or branched propylene, and the like.

[0175] From the viewpoint of the line width stability after storage, l and m are preferably from 0 to 5, more preferably from 0 to 3.

[0176] From the viewpoint of the line width stability after storage, n is preferably from 6 to 12, more preferably from 6 to 10.

[0177] The difunctional (meth)acrylate can be used alone or in combination of two or more.

[0178] In 100% by mass of the other (meth)acrylate (B2), the content of the difunctional (meth)acrylate is preferably from 0.1% by mass to 20% by mass, more preferably from 0.1% by mass to 10% by mass.

[0179] [Trifunctional (meth)acrylate]

[0180] Examples of the trifunctional (meth)acrylate include trimethylolpropane tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerol tri(meth)acrylate, glycerol PO-modified tri(meth)acrylate, and caprolactone-modified trimethylolpropane tri(meth)acrylate.

[0181] Examples of commercially available trifunctional (meth)acrylates include Aronix M-309, M-310, M-321, M-350, M-360, M-315, M-305, M-306, M-510 manufactured by Toagosei Co., Ltd.; KAYARAD GPO-303, TMPTA, PET-30 manufactured by Nippon Kayaku Co., Ltd.; NK Ester A-TMPT, A-TMPT-9EO, AT-20E, A-GLY-3E, A-GLY-9E, A-9300, A-TMM-3, A-TMM-3L, A-TMM-3LM-N manufactured by Shin-Nakamura Chemical Co., Ltd.; Sarbox SB520E35, SB510E35 manufactured by Sartomer Company, Inc.

[0182] In terms of film tolerance, the trifunctional (meth)acrylate is preferably a trifunctional (meth)acrylate containing a hydroxyl group. Further, in terms of developability after storage, the trifunctional (meth)acrylate is preferably a trifunctional (meth)acrylate containing an acidic group.

[0183] The trifunctional (meth)acrylate may be used alone or in combination of two or more.

[0184] In 100% by mass of the other (meth)acrylate (B2), the content of the trifunctional (meth)acrylate is preferably 5% to 99% by mass, more preferably 10% to 99% by mass.

[0185] Other (meth)acrylates (B2) may include difunctional (meth)acrylates and (meth)acrylates other than trifunctional (meth)acrylates. Examples thereof may include: methyl (meth)acrylate, ethyl (meth)acrylate, cyclohexyl (meth)acrylate, lauryl (meth)acrylate, phenol EO-modified (meth)acrylate, 2-ethylhexyl EO-modified (meth)acrylate, N-acryloyloxyethyl hexahydrophthalimide, dicyclopentenyl (meth)acrylate, dicyclopentenyl oxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalate, 2,3-dihydroxypropyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, 4-hydroxyphenyl (meth)acrylate, 2-sulfoethyl (meth)acrylate, 2-(meth)acryloyloxyethyl acid phosphate, 3-(meth)acryloyloxypropionic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxypropyl tetrahydrophthalic acid, ω-carboxy-polycaprolactone-monoacrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol EO-modified tetra(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol EO-modified penta(meth)acrylate, dipentaerythritol PO-modified penta(meth)acrylate, caprolactone-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol EO-modified hexa(meth)acrylate, dipentaerythritol PO-modified hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, etc.

[0186] Examples of commercially available products include: Light Ester HOA(N), HOP-A(N), HOB(N), Light acrylate HOB-A, Epoxy Ester M-600A, HOA-MPE(N), UA-306H, UA-306T, UA-306I, UA-510H manufactured by Kyoeisha Chemical Co., Ltd.; Blemmer GLM, GLM-EX, GLM-R, G-FA80, PE-90, PE-200, PP-500, 50PEP-300 manufactured by NOF Corporation; Aronix M101A, M102, M-111, M-113, M-120, M-140, M-5400, M-5700, M-408, M-400, M-402, M-403, M-404, M-405, M-406, M-471, M-460, M-520, M-521 manufactured by Toagosei Co., Ltd.; KAYARAD T-1420(T), RP-1040, DPHA, DPEA-12, D-310, DPCA-20, DPCA-30, DPCA-60, DPCA-120 manufactured by Nippon Kayaku Co., Ltd.; UA-1100H, U-6LPA, UA-33H, U-10HA, U-15HA manufactured by Shin-Nakamura Chemical Co., Ltd.; Viscoat #150, 150D, 155, 196, 200, MEDOL-10, OXE-10, OXE-30, 1000LT manufactured by Osaka Organic Chemical Industry Co., Ltd.; Miramer SP-1106, SP-1108 manufactured by Miwon Specialty Chemical Co., Ltd.; CN2301, CN2302, CN2303, CN2304 manufactured by Sartomer Company; Etercure 6361-100, 6362-100, 6363, DR-E522, etc. manufactured by Eternal Materials Co., Ltd.

[0187] [Polymerization initiator (C)]

[0188] The curable composition of the present invention contains a polymerization initiator (C).

[0189] The polymerization initiator (C) is not particularly limited, and known polymerization initiators can be used. For example, compounds that generate free radicals by the action of light or heat to initiate or promote radical polymerization reactions can be cited.

[0190] The polymerization initiator (C1) that generates free radicals through light (hereinafter also simply referred to as the photoinitiator (C1)) is preferably a compound that generates free radicals with respect to light from ultraviolet rays to the visible region.

[0191] The polymerization initiator (C2) that generates free radicals through heat (hereinafter also simply referred to as the thermal initiator (C2)) can also be a compound that generates free radicals by the action of heat and light.

[0192] (Photoinitiator (C1))

[0193] Examples of the photoinitiator (C1) include α-hydroxy ketone compounds such as 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methylacetophenone, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone;

[0194] α-amino ketone compounds such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, 2-dimethylamino-2-(4-methylbenzyl)-1-[4-(morpholinophenyl)]-butan-1-one;

[0195] Acylphosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, diphenyl-2,4,6-trimethylbenzoylphosphine oxide;

[0196] Oxime compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime), acetophenone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime);

[0197] Triazine compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphthalen-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthalen-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine;

[0198] Quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, etc.

[0199] Among commercially available products, examples of α-hydroxy ketone compounds include Omnirad 127, 184, 1173, and 2959 manufactured by IGM Resins; examples of α-amino ketone compounds include Omnirad 907, 369E, and 379EG manufactured by IGM Resins; examples of acylphosphine compounds include Omnirad 819 and TPO manufactured by IGM Resins; examples of oxime compounds include IRGACURE OXE-01, 02, 03, 04, and 05 manufactured by BASF Japan, Adeka arkls N-1919T, NCI-730, 831E, and 930 manufactured by ADEKA, TRONLY TR-PBG-301, 304, 305, 309, 314, 345, 358, 380, 365, 610, 3054, and 3057 manufactured by Changzhou Qiangli New Materials Co., Ltd., Omnirad 1312, 1314, and 1316 manufactured by IGM Resins, SPI-02, 03, 04, 05, 06, and 07 manufactured by Samyang Corporation, DFI-020, 306, and EOX-01 manufactured by DaitoChemix, etc.

[0200] In addition, examples also include 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, JP-T-2019-507108, JP-T-2019-528331, WO 2021 / 175855, JP-T-2022-5115524, etc.

[0201] From the viewpoints of adhesion and film tolerance, the photopolymerization initiator (C1) preferably contains an oxime compound. From the viewpoints of adhesion and film tolerance, the oxime compound is more preferably an oxime compound having an extinction coefficient of 5.0×10 3 L / mol·cm or more for light at a wavelength of 365 nm in propylene glycol monomethyl ether acetate.

[0202] (Thermal polymerization initiator (C2))

[0203] Examples of the thermal polymerization initiator (C2) include: pinacol compounds such as benzoin, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-diphenoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetrakis(4-methylphenyl)ethane, 1,2-diphenoxy-1,1,2,2-tetrakis(4-methoxyphenyl)ethane, 1,2-bis(trimethylsilyloxy)-1,1,2,2-tetraphenylethane, 1,2-bis(triethylsilyloxy)-1,1,2,2-tetraphenylethane, 1,2-bis(tert-butyldimethylsilyloxy)-1,1,2,2-tetraphenylethane, 1-hydroxy-2-trimethylsilyloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-triethylsilyloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-tert-butyldimethylsilyloxy-1,1,2,2-tetraphenylethane; azo compounds such as 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide], 1-[(1-cyano-1-methylethyl)azo]formamide, 2,2'-azobis(N-butyl-2-methylpropionamide), 2,2'-azobis(N-cyclohexyl-2-methylpropionamide); organic peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,2-bis(tert-butylperoxy)butane, succinic peroxide, benzoyl peroxide, etc.

[0204] In addition, oxime sulfonate compounds described in International Publication No. 2012 / 101245, International Publication No. 2016 / 030790, etc. can be cited.

[0205] In terms of film tolerance, developability after storage, and line width stability after storage, the 10-hour half-life temperature of the thermal polymerization initiator (C2) is preferably 70°C to 130°C, more preferably 80°C to 120°C. Specifically, examples include: 1,1-bis(tert-hexylperoxy)cyclohexane (87.1°C), 1,1-bis(tert-butylperoxy)cyclohexane (90.7°C), 2,2-bis(4,4-di-tert-butylperoxycyclohexyl)propane (94.7°C), tert-hexyl peroxyisopropyl monocarbonate (95°C), tert-butyl peroxy-2-ethylhexyl monocarbonate (99°C), tert-butyl peroxyacetate (101.9°C), butyl 4,4-bis[(tert-butyl)peroxy]valerate (104.5°C), di-tert-hexyl peroxide (116.4°C), di(2-tert-butylperoxyisopropyl)benzene (119.2°C), etc. In addition, the values in parentheses are the 10-hour half-life temperatures.

[0206] The polymerization initiator (C) can be used alone or in combination of two or more.

[0207] In 100% by mass of the non-volatile components of the curable composition, the content of the polymerization initiator (C) is preferably 0.1% by mass to 20% by mass, more preferably 0.5% by mass to 10% by mass.

[0208] In terms of film tolerance, the polymerization initiator (C) is preferably used in combination of a photopolymerization initiator (C1) and a thermal polymerization initiator (C2). By carrying out a radical polymerization reaction in both the exposure step and the post-baking step, the film tolerance is further improved.

[0209] The mass ratio of the photopolymerization initiator (C1) to the thermal polymerization initiator (C2) is preferably 90:10 to 10:90, more preferably 80:20 to 20:80.

[0210] [Thermal crosslinking compound (D)]

[0211] The curable composition of the present invention contains a thermal crosslinking compound (D). In addition, the thermal crosslinking compound (D) does not have an alkali-soluble group.

[0212] The thermal crosslinking compound (D) is not particularly limited as long as it is a compound having a thermal crosslinking group, and known compounds can be used. For example, examples include: compounds having an epoxy group, compounds having a blocked isocyanate group, compounds having an oxetanyl group, compounds having a hydroxymethyl group, compounds having a phenolic group, etc.

[0213] The thermal crosslinking compound (D) can be used alone or in combination of two or more.

[0214] In 100% by mass of the nonvolatile components of the curable composition, the content of the thermally crosslinkable compound (D) is preferably 0.5% to 50% by mass, more preferably 1% to 40% by mass.

[0215] (Compound (D1) having a blocked isocyanate group)

[0216] The thermally crosslinkable compound (D) contains a compound (D1) having a blocked isocyanate group.

[0217] The compound (D1) having a blocked isocyanate group is a compound in which the isocyanate group of a compound having an isocyanate group is protected by a blocking agent. The dissociation temperature of the blocking agent for the blocked isocyanate group is preferably 60°C to 160°C, more preferably 70°C to 130°C or lower.

[0218] The compound (D1) having a blocked isocyanate group is synthesized by reacting a compound having an isocyanate group with a blocking agent by a known method. Examples thereof include the methods described in JP-A-52-116420, JP-A-60-149572, JP-A-7-31953, JP-A-10-306136, JP-A-2012-012567, and the like.

[0219] Examples of the blocking agent include the above compounds. Among these, at least one selected from the group consisting of an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, a pyrazole compound, a thiol compound, an imidazole compound, and an imide compound is preferred, at least one selected from the group consisting of an oxime compound, a phenol compound, an active methylene compound, and a pyrazole compound is more preferred, and an active methylene compound, a pyrazole compound, or an oxime compound is further preferred. From the viewpoints of film tolerance, developability after storage, and line width stability after storage, an active methylene compound is particularly preferred. Since the dissociation temperature or the transesterification reaction temperature of the active methylene compound is 80°C to 110°C, no reaction occurs during storage, and the developability and line width stability after storage can be maintained. Thus, by carrying out the reaction in the post-baking step, the film tolerance is improved.

[0220] Examples of the compound having an isocyanate group include: compounds having an aliphatic structure such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylidene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate; compounds having an alicyclic structure such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dimethylcyclohexyl diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, bis(isocyanatomethyl)cyclohexane; compounds having an aromatic structure such as 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylylene diisocyanate, mesitylene tetramethyl xylylene diisocyanate, 4,4-diphenylmethane diisocyanate, toluene diisocyanate, dichloromethyldiphenylmethane diisocyanate, 2,6-diisocyanate-benzyl chloride, bis(isocyanatomethyl)benzene. In addition, examples include: biuret bodies, isocyanurate bodies, adducts, urethane-formate bodies of these compounds, and reaction products of these compounds with polyols, etc.

[0221] From the viewpoint of adhesion, the compound having an isocyanate group is preferably a compound having an aliphatic structure, or a biuret body, isocyanurate body, adduct, urethane-formate body of a compound having an alicyclic structure.

[0222] Examples of the compound (D1) having a blocked isocyanate group include the following compounds. In the following structural formulas, X represents a blocked isocyanate group. In addition, the present invention is not limited to these.

[0223] [Chemical formula 3]

[0224]

[0225] Examples of the X (blocked isocyanate group) of the compound include the structures represented by the following (X-1) to (X-7). In the following structures, * represents a bonding part. In addition, the present invention is not limited to these.

[0226] [Chemical formula 4]

[0227]

[0228] Among commercially available products of the compound (D1) having a blocked isocyanate group, examples of the compound having an aliphatic structure include: Duranate SBN-70D, SBB-70P, SBF-70E, TPA-B80E, 17B-60P, MF-B60B, E402-B80B, MF-K60B, WM44-L70G manufactured by Asahi Kasei Corporation; Takenate B-882 manufactured by Mitsui Chemicals, Inc.; BI7960, BI7961, BI7982, BI7991, BI7992 manufactured by Baxenden Chemical Company, etc.; examples of the compound having an alicyclic structure include: Takenate B-846N manufactured by Mitsui Chemicals, Inc.; Coronate BI-301, 2507, 2554 manufactured by Tosoh Corporation; BI7950, BI7951, BI7990 manufactured by Baxenden Chemical Company, etc.; examples of the compound having an aromatic structure include Takenate B-830, B-815N manufactured by Mitsui Chemicals, Inc.

[0229] The number of blocked isocyanate groups of the compound (D1) having a blocked isocyanate group is preferably 1 to 20, more preferably 2 to 15.

[0230] The weight average molecular weight of the compound (D1) having a blocked isocyanate group is preferably 300 to 5,000, more preferably 500 to 3,000.

[0231] The acid value of the compound (D1) having a blocked isocyanate group is preferably 10 mgKOH / g or less.

[0232] The compound (D1) having a blocked isocyanate group can be used alone or in combination of two or more.

[0233] In 100% by mass of the non-volatile components of the curable composition, the content of the compound (D1) having a blocked isocyanate group is preferably 0.5% by mass to 50% by mass, more preferably 1% by mass to 40% by mass.

[0234] (Compound (D2) having an epoxy group)

[0235] From the viewpoint of film tolerance, the thermally crosslinkable compound (D) preferably further contains a compound (D2) having an epoxy group.

[0236] The so-called epoxy group refers to a group having a three-membered ring cyclic ether structure and also includes an alicyclic epoxy group.

[0237] Examples of the compound (D2) having an epoxy group include: polyglycidyl ether compounds of bisphenols such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and hydrogenated bisphenol F diglycidyl ether; polyglycidyl ether compounds of polyhydric alcohols such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether; polyglycidyl ether compounds of polyether polyols formed by adding an alkylene oxide to polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerol; compounds having two or more 3,4-epoxycyclohexyl groups in the molecule such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane, bis(3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexanecarboxylate, methylene bis(3,4-epoxycyclohexane), ethylene bis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, and tetrakis(3,4-epoxycyclohexylmethyl) modification of ε-caprolactone of butanetetracarboxylic acid; 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, etc.

[0238] Commercially available products of the compound (D2) having an epoxy group include, for example: Epicoat 807, 815, 825, 827, 828, 190P, 191P manufactured by Yuka Shell Epoxy Co., Ltd.; Techmore VG3101L manufactured by Mitsui Chemicals, Inc.; EPPN-201, 501H, 502H, EOCN-102S, 103S, 104S, 1020 manufactured by Nippon Kayaku Co., Ltd.; Epicoat 1004, 1256, JER1032H60, 157S65, 157S70, 152, 154 manufactured by Nippon Epoxy Resin Co., Ltd.; Celloxide 2021, EHPE-3150, Epolead GT401 manufactured by Daicel Chemical Industries, Ltd.; Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721 manufactured by Nagase ChemteX Corporation; Tepic-L, H, S manufactured by Nissan Chemical Industries, Ltd.; Epiclon 830, 840, 850, 860, 1050, 3050, 4050, N-660, N-670, N-740, N-770, N865, HP-7200, HP-4700, HP-4770, HP-5000, HP-6000, HP-9500, etc. manufactured by DIC Corporation.

[0239] The compound (D2) having an epoxy group is preferably a compound having 2 to 50 epoxy groups in the molecule.

[0240] The epoxy equivalent of the compound (D2) having an epoxy group is preferably 50 g / eq to 400 g / eq, more preferably 100 g / eq to 200 g / eq. In addition, the epoxy equivalent is defined as the mass of the epoxy compound containing 1 equivalent of epoxy groups.

[0241] From the viewpoint of film tolerance, the compound (D2) having an epoxy group is preferably a compound represented by the following general formula (2).

[0242] General formula (2)

[0243] [Chemical formula 5]

[0244]

[0245] In the general formula (2), R represents a group obtained by removing m hydroxyl groups from an m-valent alcohol, m represents an integer of 1 to 6, and n represents an integer of 1 to 30.

[0246] R represents a group obtained by removing m hydroxyl groups from an m-valent alcohol.

[0247] The group obtained by removing m hydroxyl groups from an m-valent alcohol is preferably an alkyl group having 2 to 20 carbon atoms, which may be linear, branched, or cyclic, or a group formed by bonding them. Examples of the alkyl group having 2 to 20 carbon atoms include: methyl, ethyl, propyl, isopropyl, 2,2-dimethylpropyl, butyl, isobutyl, tert-butyl, 3,3-dimethylbutyl, pentyl, isopentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, hexadecyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, cyclohexylmethyl, etc. Among these, a branched alkyl group having 3 to 12 carbon atoms is more preferable.

[0248] m represents an integer of 1 to 6, and n represents an integer of 1 to 30. When m is 2 or more, the n in each group within the parentheses in the general formula (2) may be the same or different.

[0249] Examples of the compound represented by the general formula (2) include the 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol. Commercially available products include EHPE-3150, EHPE-3150CE, etc. manufactured by Daicel Corporation.

[0250] The acid value of the compound (D2) having an epoxy group is preferably 10 mgKOH / g or less.

[0251] The compound (D2) having an epoxy group can be used alone or in combination of two or more.

[0252] In 100% by mass of the non-volatile components of the curable composition, the content of the compound (D2) having an epoxy group is preferably 0.5% by mass to 50% by mass, more preferably 1% by mass to 40% by mass.

[0253] The mass ratio of the compound (D1) having a blocked isocyanate group to the compound (D2) having an epoxy group is preferably 99:1 to 1:99, more preferably 95:5 to 5:95.

[0254] [Silane Coupling Agent (E)]

[0255] From the viewpoint of film tolerance, the curable composition of the present invention preferably further contains a silane coupling agent (E).

[0256] The silane coupling agent (E) is a compound having a hydrolyzable group. The hydrolyzable group is a group that is directly bonded to a silicon atom and forms a siloxane bond through at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include: a halogen atom, an alkoxy group, an acyloxy group, etc.

[0257] Among these, from the viewpoint of film tolerance, an alkoxy group is preferred. Examples of the alkoxy group include a methoxy group, an ethoxy group, a butoxy group, etc. From the viewpoints of film tolerance, developability after storage, and line width stability after storage, an ethoxy group is preferred.

[0258] The silane coupling agent (E) may have a reactive functional group other than the hydrolyzable group. Examples of the reactive functional group include an epoxy group, an amino group, a vinyl group, a (meth)acryloyl group, an isocyanate group, an isocyanurate group, a mercapto group, an oxetanyl group, a styryl group, a ureido group, etc. Among these, from the viewpoint of film tolerance, an epoxy group is preferred.

[0259] The silane coupling agent (E) is not particularly limited, and known compounds can be used. Examples of the silane coupling agent (E) include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, p-styryltrimethoxysilane, 3-ureidopropyltrialkoxysilane, N,N-bis[3-(trimethoxysilyl)propyl]ethylenediamine, bis[3-(triethoxysilyl)propyl]tetrasulfide, 1,6-bis(trimethoxysilyl)hexane, 1,8-bis(trimethoxysilyl)octane, tris(trimethoxysilylpropyl)isocyanurate, etc.

[0260] Among these, from the viewpoints of film tolerance, developability after storage, and line width stability after storage, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane are preferred.

[0261] Examples of commercially available products of the silane coupling agent (E) include: KBM-302, KBM-402, KBM-403, KBE-402, KBE-403, KBM-4803, KBM-602, KBM-603, KBM-903, KBE-9103P, KBM-573, KBM-6803, KBM-1003, KBE-1003, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5803, X-12-1048, X-12-1050, KBE-9007N, KBM-9659, KBM-802, KBM-803, KBM-1043, KBM-3086, KBE-585A, X-12-50, X-12-5263HP, etc., manufactured by Shin-Etsu Chemical Co., Ltd.

[0262] In addition, the silane coupling agent (E) may also be of the polymer type. Examples of the polymer type include the polysiloxane type and the organic polymer type.

[0263] The polysiloxane type is a compound in which a hydrolyzable group is bonded to a polymer having a polysiloxane backbone in the main chain. Examples of commercially available products of the polysiloxane type include KR-513, KR-516, KR-517, X-41-1805, X-41-1810, etc., manufactured by Shin-Etsu Chemical Co., Ltd.

[0264] The organic polymer type is a silane coupling agent (E) in which a hydrolyzable group is bonded to an organic polymer having an organic structure in the main chain. Examples of commercially available products of the organic polymer type include X-12-9815, X-12-9845, X-12-1154, X-12-972F, X-12-1159L, etc., manufactured by Shin-Etsu Chemical Co., Ltd.

[0265] The silane coupling agent (E) can be used alone or in combination of two or more.

[0266] In 100% by mass of the non-volatile components of the curable composition, the content of the silane coupling agent (E) is preferably 0.1% to 10% by mass, more preferably 0.2% to 5% by mass.

[0267] The curable composition of the present invention preferably contains one or more of a pigment (F) and a dye (G). Thereby, the transmittance in each wavelength region of the filter can be controlled.

[0268] [Pigment (F)]

[0269] From the viewpoint of film tolerance, the curable composition of the present invention more preferably contains a pigment (F).

[0270] The pigment (F) is not particularly limited, and examples thereof include colored pigments, achromatic pigments, near-infrared absorbing pigments, transparent pigments, and fluorescent pigments. The pigment (F) can be either an inorganic pigment or an organic pigment, or an inorganic pigment and an organic pigment can be used in combination. In addition, the pigment (F) can also be an organic-inorganic composite.

[0271] When the curable composition of the present invention is used for a color filter, the pigment (F) is preferably a colored pigment. The colored pigment can be used alone or in combination of two or more. When the curable composition of the present invention is used for a near-infrared cut-off filter, as the pigment (F), a near-infrared absorbing pigment is preferably used. The near-infrared absorbing pigment can be used alone or in combination of two or more. When used for a near-infrared transmitting filter, the pigment (F) is preferably a combination of two or more achromatic pigments (black) or colored pigments used as black. Furthermore, a near-infrared absorbing pigment can also be used in combination.

[0272] (Colored pigment)

[0273] The colored pigment is not particularly limited, and known colored pigments can be used. For example, compounds classified as pigments in the Color Index can be cited.

[0274] Examples of colored pigments include: C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 295, 296, pigments described in Japanese Patent Laid-Open No. 2014-134712, pigments described in Japanese Patent No. 6368844, and other red pigments.

[0275] Examples include: C.I. Pigment Orange 36, 38, 43, 64, 71, 73, and other orange pigments.

[0276] Examples include: 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, and the yellow pigments described in Japanese Patent Laid-Open No. 2012-226110.

[0277] In addition, examples of the yellow pigment include the following metal azo pigments, which contain: one or more anions selected from the group consisting of monoanions, dianions, trianions, and tetraanions of azo compounds represented by the following general formula (3) and their tautomeric structures, at least two metal ions selected from Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn, and a compound represented by the following general formula (4).

[0278] General formula (3)

[0279] [Chemical formula 6]

[0280]

[0281] In general formula (3), two R1s each independently represent -OH, -NH2, -NH-CN, acylamino, alkylamino, or arylamino, and two R2s each independently represent -OH or -NH2.

[0282] General formula (4)

[0283] [Chemical formula 7]

[0284]

[0285] In general formula (4), three R3s each independently represent a hydrogen atom or an alkyl group.

[0286] Examples of the metal azo pigments include those described in Japanese Patent Application Laid-Open No. 2014-12838, Japanese Patent Application Laid-Open No. 2017-171912, Japanese Patent Application Laid-Open No. 2017-171913, Japanese Patent Application Laid-Open No. 2017-171914, Japanese Patent Application Laid-Open No. 2017-171915, Japanese Patent Application Laid-Open No. 2022-61494, etc.

[0287] Examples include green pigments such as C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63, 64, 65, 66.

[0288] Examples include blue pigments such as C.I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, 80, 87, 88.

[0289] Examples include purple pigments such as C.I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50.

[0290] The colored pigments can be used alone or in combination of two or more. For example, in the case of black, in addition to using the achromatic pigments described below, two or more colored pigments selected from the group consisting of red pigments, yellow pigments, green pigments, blue pigments, and purple pigments can be used (combined) to obtain it. Examples of the combination include the following aspects.

[0291] (1) Containing a yellow pigment and a purple pigment.

[0292] (2) Containing a red pigment, a yellow pigment, and a purple pigment.

[0293] (3) Containing a red pigment, a yellow pigment, and a blue pigment.

[0294] (4) Containing a red pigment, a yellow pigment, and a green pigment.

[0295] (5) Containing a yellow pigment, a blue pigment, and a purple pigment.

[0296] (6) contains red pigment, yellow pigment, blue pigment, and purple pigment.

[0297] (7) contains yellow pigment, blue pigment, green pigment, and purple pigment.

[0298] Examples of the aspect of (1) may be listed as follows: The yellow pigment contains one or more selected from C.I. Pigment Yellow 139, 185, 231, 233, and the purple pigment contains C.I. Pigment Violet 23.

[0299] Examples of the aspect of (2) may be listed as follows: The red pigment contains one or more selected from C.I. Pigment Red 177, 254, 291, 295, 296, the yellow pigment contains one or more selected from C.I. Pigment Yellow 139, 185, 231, 233, and the purple pigment contains C.I. Pigment Violet 23.

[0300] Examples of the aspect of (3) may be listed as follows: The red pigment contains one or more selected from C.I. Pigment Red 177, 254, 291, 295, 296, the yellow pigment contains one or more selected from C.I. Pigment Yellow 139, 185, 231, 233, and the blue pigment contains one or more selected from C.I. Pigment Blue 15:3, 15:4, 15:6.

[0301] Examples of the aspect of (4) may be listed as follows: The red pigment contains one or more selected from C.I. Pigment Red 177, 254, 291, 295, 296, the yellow pigment contains one or more selected from C.I. Pigment Yellow 139, 185, 231, 233, and the green pigment contains one or more selected from C.I. Pigment Green 7, 36, 58, 59, 63.

[0302] Examples of the aspect of (5) may be listed as follows: The yellow pigment contains one or more selected from C.I. Pigment Yellow 139, 185, 231, 233, the blue pigment contains one or more selected from C.I. Pigment Blue 15:3, 15:4, 15:6, and the purple pigment contains C.I. Pigment Violet 23.

[0303] Examples of the aspect of (6) may be listed as follows: The red pigment contains one or more selected from C.I. Pigment Red 177, 254, 291, 295, 296, the yellow pigment contains one or more selected from C.I. Pigment Yellow 139, 185, 231, 233, the blue pigment contains one or more selected from C.I. Pigment Blue 15:3, 15:4, 15:6, and the purple pigment contains C.I. Pigment Violet 23.

[0304] Examples of the aspect of (7) may be listed as follows: the yellow pigment contains one or more selected from C.I. Pigment Yellow 139, 185, 231, 233; the blue pigment contains one or more selected from C.I. Pigment Blue 15:3, 15:4, 15:6; the green pigment contains one or more selected from C.I. Pigment Green 7, 36, 58, 59, 63; the purple pigment contains C.I. Pigment Violet 23.

[0305] Table 1 shows the preferred mass ratios (mass %) of the respective color pigments for each aspect.

[0306] [Table 1]

[0307] Table 1 Red pigment Yellow pigment Green pigment Blue pigment Purple pigment Aspect of (1) 20～80 20～80 Aspect of (2) 10～60 10～60 10～60 Aspect of (3) 20～70 10～40 10～60 Aspect of (4) 20～50 20～50 20～50 Aspect of (5) 20～40 20～40 20～40 Aspect of (6) 10～60 10～40 10～60 1～30 Aspect of (7) 20～40 1～10 20～40 20～40

[0308] The combination of the color pigments of (1) to (7) is preferred when the curable composition of the present invention is used for a near-infrared cut filter.

[0309] (achromatic pigment)

[0310] The achromatic pigment is not limited, and known achromatic pigments can be used. Examples of the achromatic pigment may include: C.I. Pigment White 1, 2, 3, 4, 5, 6, 6:1, 7, 8, 10, 11, 12, 13, 14, 15, 16, 17, 18, 18:1, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 30, 32, 33, C.I. Pigment Black 1, 6, 7, 12, 20, 31, titanium oxide, magnesium oxide, zirconium oxide, aluminum oxide, antimony oxide, barium sulfate, calcium carbonate, silicon dioxide, zinc oxide, mica, talc, kaolin, clay, strontium titanate, barium tungstate, zinc phosphate, aluminum hydroxide, aluminum silicate, hollow resin particles, carbon black, titanium black, acetylene black, lamp black, graphite, aniline black, cyanine black, perylene black, compounds described in Japanese Patent Laid-Open No. 2011-075786, International Publication No. 2013 / 061621, Japanese Patent Laid-Open No. 2015-047520, Japanese Patent Laid-Open No. 2015-164881, Japanese Patent Laid-Open No. 1-170601, Japanese Patent Laid-Open No. 2-34664, Japanese Patent Laid-Open No. 2007-302836, Japanese Patent Publication No. 2010-534726, Japanese Patent Publication No. 2012-515233, etc.

[0311] (near-infrared absorbing pigment)

[0312] The near-infrared absorbing pigment is a compound having a maximum absorption in the wavelength range of 700 nm to 2,000 nm, and can be either an organic pigment (also referred to as a near-infrared absorbing organic pigment) or an inorganic pigment (also referred to as a near-infrared absorbing inorganic pigment). In addition, a near-infrared absorbing organic pigment and a near-infrared absorbing inorganic pigment can be used in combination.

[0313] The near-infrared absorbing organic pigment is not particularly limited, and known near-infrared absorbing organic pigments can be used. For example, cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, indigo compounds, iminium compounds, anthraquinone compounds, pyrrolopyrrole compounds, squaraine compounds, croconium compounds, porphyrin compounds, etc. can be cited. Among these, from the viewpoints of near-infrared absorbability and heat resistance, naphthalocyanine compounds, pyrrolopyrrole compounds, squaraine compounds, and indigo compounds are preferred, and naphthalocyanine compounds, squaraine compounds, and indigo compounds are more preferred.

[0314] The near-infrared absorbing inorganic pigment is not particularly limited, and known near-infrared absorbing inorganic pigments can be used. For example, indium tin oxide, antimony tin oxide, zinc oxide, aluminum-doped zinc oxide, fluorine-doped tin dioxide, niobium-doped titanium dioxide, cesium tungsten oxide, lanthanum boride, metal oxide particles or metal particles such as copper, nickel, silver, and gold can be cited.

[0315] The pigment (F) can be used alone or in combination of two or more.

[0316] In 100% by mass of the non-volatile components of the curable composition, the content of the pigment (F) is preferably 0.5% by mass to 60% by mass, and more preferably 1% by mass to 50% by mass.

[0317] The pigment (F) is preferably used after being micronized. The micronization method is not particularly limited, and for example, any of wet grinding, dry grinding, and dissolution precipitation methods can be used. Among these, salt milling treatment using a kneader method, which is a kind of wet grinding, is preferred. The average primary particle diameter of the micronized pigment determined by a transmission electron microscope (TEM) is preferably 5 nm to 90 nm. In addition, from the viewpoint of dispersibility, the average primary particle diameter is more preferably 10 nm to 70 nm.

[0318] In the salt grinding treatment, a resin may be added as needed. By adding the resin, the pigment (F) is coated with the resin, and the stability, light resistance, etc. are improved. The type of the resin is not particularly limited, and examples thereof include natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, etc. Among these, those that are solid at room temperature and water-insoluble are preferred, and those that are partially soluble in organic solvents are also preferred. The addition amount of the resin is preferably 2 to 200 parts by mass with respect to 100 parts by mass of the pigment (F).

[0319] [Dye (G)]

[0320] The dye (G) is not particularly limited, and known dyes can be used. For example, acidic dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, etc. can be cited. In addition, derivatives thereof, or lake pigments obtained by lake-forming the dyes can also be cited.

[0321] The acidic dye preferably has an acidic group such as a sulfonic acid group or a carboxylic acid group. In addition, a salt-forming compound which is a salt of an acidic dye and a nitrogen-containing compound such as a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound or a primary amine compound is preferred. In addition, a salt-forming compound which is a salt of a resin component having these functional groups and an acidic dye is also preferred. In addition, the salt-forming compound is modified to a sulfonamide compound by sulfonamidation, so that a curable composition excellent in tolerance (light resistance, solvent resistance) can be easily obtained.

[0322] In addition, a salt-forming compound of an acidic dye and a compound having an onium salt group is also preferred because of its excellent tolerance (light resistance, solvent resistance). In addition, the compound having an onium salt group is preferably a resin having a cationic group.

[0323] The basic dye can be used directly, but a salt-forming compound formed with an organic acid, perchloric acid or a metal salt thereof is preferred. The salt-forming compound of the basic dye is preferred because of its excellent tolerance (light resistance, solvent resistance) or affinity with the pigment. In addition, in the salt-forming compound of the basic dye, the anionic component acting as a counter ion is preferably an organic sulfonic acid, organic sulfuric acid, fluorine-containing phosphorus anion compound, fluorine-containing boron anion compound, cyanide-containing nitrogen anion compound, anionic compound containing a conjugate base of an organic acid having a halogenated hydrocarbon group, or a salt-forming compound obtained by forming a salt with an acidic dye. In addition, if the salt-forming compound contains a polymerizable unsaturated group in the molecule, the tolerance is further improved.

[0324] In terms of color characteristics such as hue, color separation property, and color non-uniformity, the chemical structure of the dye (G) is preferably a pigment structure derived from a pigment selected from azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, naphthalocyanine dyes, and subphthalocyanine dyes, and more preferably a pigment structure derived from a pigment selected from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes.

[0325] The dye (G) can be used alone or in combination of two or more.

[0326] In 100% by mass of the non-volatile components of the curable composition, the content of the dye (G) is preferably 0.5% by mass to 60% by mass, and more preferably 1% by mass to 50% by mass.

[0327] [Pigment derivative (H)]

[0328] The curable composition of the present invention may contain a pigment derivative (H). When the pigment derivative (H) is used, the pigment (F) can be stably dispersed.

[0329] The pigment derivative (H) is not particularly limited, and known pigment derivatives can be used. For example, compounds having a structure in which a part of the pigment is substituted with an acidic group, a basic group, a neutral group, etc. can be cited. Specifically, compounds having acidic substituents such as sulfo group, carboxyl group, and phosphoric acid group; amine salts thereof and compounds having basic substituents such as sulfonamide group or having a tertiary amino group at the end; and compounds having neutral substituents such as phenyl group or phthalimidoalkyl group can be cited.

[0330] Examples of the pigment include diketopyrrolopyrrole compounds, phthalocyanine compounds, anthraquinone compounds, quinacridone compounds, dioxazine compounds, perinone compounds, perylene compounds, thiazine indigo compounds, triazine compounds, benzimidazolone compounds, benzisoindole compounds, isoindoline compounds, isoindolinone compounds, quinophthalone compounds, naphthol compounds, squarylium compounds, vat compounds, naphthalocyanine compounds, etc. In addition, pigment derivatives are sometimes referred to as pigment derivatives, dispersants, dispersion aids, pigment dispersants, or simply compounds, etc., but have the same meaning.

[0331] The pigment derivative (H) is preferably added during the micronization of the pigment (F) or during the dispersion treatment of the pigment (F) described below. The average primary particle diameter of the pigment derivative (H) is preferably 5 nm to 200 nm.

[0332] The pigment derivative (H) can be used alone or in combination of two or more.

[0333] With respect to 100 parts by mass of the pigment (F), the content of the pigment derivative (H) is preferably from 1 part by mass to 50 parts by mass, more preferably from 2 parts by mass to 40 parts by mass.

[0334] [Dispersion resin (I)]

[0335] The curable composition of the present invention may contain a dispersion resin (I). The dispersion resin (I) can stably disperse the pigment (F) which is a component of the curable composition.

[0336] The dispersion resin (I) is preferably a resin having an adsorption group with high affinity for the pigment (F). The adsorption group preferably has one or more of a basic group and an acidic group.

[0337] Examples of the basic group include groups containing a nitrogen atom such as a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium salt group, and a nitrogen-containing heterocyclic group.

[0338] Examples of the acidic group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group.

[0339] Examples of the resin type of the dispersion resin (I) include: urethane resin; polycarboxylic acid esters such as polyacrylate, unsaturated polyamide, polycarboxylic acid, (partial) amine salts of polycarboxylic acid, ammonium salts of polycarboxylic acid, alkylamine salts of polycarboxylic acid, polysiloxane, long-chain polyaminoamide phosphate, hydroxy-containing polycarboxylic acid ester, or modified products thereof; amides or salts thereof formed by the reaction of poly(lower alkyleneimine) and a polyester having a free carboxyl group; water-soluble resins or water-soluble high molecular compounds such as (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone; polyester-based, modified polyacrylate-based, ethylene oxide / propylene oxide adduct, phosphate-based, etc.

[0340] Examples of the structure of the dispersion resin (I) include: chain-like random structure, chain-like block structure, graft structure, comb structure, and star structure. Among these, from the viewpoint of dispersion stability, a chain-like block structure, a graft structure, and a comb structure are preferred.

[0341] From the viewpoint of film tolerance, the dispersion resin (I) preferably has a thermally crosslinkable group and / or a polymerizable unsaturated group. Examples of the thermally crosslinkable group include: a hydroxyl group, an epoxy group, an oxetanyl group, a tert-butyl group, a blocked isocyanate group, etc.

[0342] Examples of the dispersion resin (I) include resins described in paragraph numbers 0122 to 0155 of International Publication No. 2013 / 175978, resins described in paragraph numbers 0317 to 0321 of Japanese Patent Application Laid-Open No. 2019-78878, resins described in paragraph number 0083 of International Publication No. 2018 / 139534, resins described in paragraph numbers 0167 to 0191 of International Publication No. 2019 / 163505, resins described in paragraph numbers 0299 to 0310 of International Publication No. 2021 / 131927, resins described in paragraph numbers 0080 to 0085 of International Publication No. 2022 / 102367, resins described in paragraph numbers 0099 to 0109 of International Publication No. 2022 / 172607, and the like.

[0343] Commercially available products of the dispersion resin (I) include, for example: Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164, or Anti-Terra-U203, 204, or BYK-P104, P104S, 220S, or Lactimon, Lactimon-WS or Bykumen, etc., manufactured by BYK-Chemie Japan Co., Ltd.; SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc., manufactured by Lubrizol Japan Co., Ltd.; EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., manufactured by BASF Japan Co., Ltd.; Ajisper PA111, PB711, PB821, PB822, PB824, etc., manufactured by Ajinomoto Fine-Techno Co., Ltd.Resins described in Japanese Patent Laid-Open No. 2008-029901, Japanese Patent Laid-Open No. 2009-155406, Japanese Patent Laid-Open No. 2010-185934, Japanese Patent Laid-Open No. 2011-157416, International Publication No. 2008 / 007776, Japanese Patent Laid-Open No. 2009-251481, Japanese Patent Laid-Open No. 2007-23195, Japanese Patent Laid-Open No. 1996-143651, etc.

[0344] The dispersion resin (I) can be used alone or in combination of two or more.

[0345] Regarding the content of the dispersion resin (I), from the viewpoint of dispersion stability, it is preferably 3 to 200 parts by mass, more preferably 5 to 150 parts by mass, relative to 100 parts by mass of the pigment (F).

[0346] [Sensitizer (J)]

[0347] The curable composition of the present invention may contain a sensitizer (J).

[0348] The sensitizer (J) is not particularly limited, and known sensitizers can be used. The sensitizer is preferably, for example, a thioxanthone-based compound or a benzophenone-based compound.

[0349] The sensitizer (J) can be used alone or in combination of two or more.

[0350] The content of the sensitizer (J) is preferably 10 to 400 parts by mass, more preferably 20 to 300 parts by mass, relative to 100 parts by mass of the polymerization initiator (C).

[0351] [Hardener (hardening accelerator)]

[0352] In order to assist the curing of the thermally crosslinkable compound (D), the curable composition of the present invention may be used in combination with a hardener (hardening accelerator). Examples of the hardener include amine-based compounds, acid anhydrides, active esters, carboxylic acid-based compounds, sulfonic acid-based compounds, etc.

[0353] The hardener can be used alone or in combination of two or more.

[0354] The content of the hardener is preferably 0.01 to 15 parts by mass relative to 100 parts by mass of the thermally crosslinkable compound (D).

[0355] [Thiol-based chain transfer agent (K)]

[0356] The curable composition of the present invention may contain a thiol-based chain transfer agent (K).

[0357] The thiol-based chain transfer agent (K) is not limited, and examples thereof include: thiophenol, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-benzimidazole, butanethiol, octanethiol, 1-dodecanethiol, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate and other monofunctional thiol compounds; 2-mercaptoethanol, 1-thioglycerol, thioglycolic acid, 2-mercaptobenzoic acid, 3-mercaptobenzoic acid, 4-mercapto-nicotinic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 4-mercaptobutyric acid, octyl thioglycolate, mercaptosuccinic acid, 11-mercaptoundecanoic acid, 2-mercaptoethanesulfonic acid and other monofunctional thiol compounds having a hydroxyl group or an acidic group; hexanedithiol, decanedithiol, 1,4-butanediol bis(thioglycolate), 1,4-butanediol bis(thiopropionate), ethylene glycol bis(thioglycolate), ethylene glycol bis(thiopropionate), trimethylolpropane tris(thioglycolate), trimethylolpropane tris(thiopropionate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(thioglycolate), pentaerythritol tetrakis(3-mercaptopropionate), tris(2-hydroxyethyl) isocyanurate tris(3-mercaptopropionate), 1,4-dimethylthiobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine and other polyfunctional thiol compounds.

[0358] The thiol-based chain transfer agent (K) can be used alone or in combination of two or more.

[0359] In 100% by mass of the non-volatile components of the curable composition, the content of the thiol-based chain transfer agent (K) is preferably 0.1% by mass to 10% by mass.

[0360] [Polymerization inhibitor (L)]

[0361] From the viewpoints of the developability after storage and the line width stability after storage, the curable composition of the present invention preferably contains a polymerization inhibitor (L).

[0362] The polymerization inhibitor (L) is not particularly limited, and known polymerization inhibitors can be used. For example, there can be mentioned: phenol compounds, hydroquinone compounds, benzoquinone compounds, phenothiazine compounds, catechol compounds, nitrobenzene compounds, nitroso compounds, amine compounds, hindered amine compounds, phosphorus compounds, etc. Among these, from the viewpoints of the developability after storage and the line width stability after storage, it is preferable to contain a hydroquinone compound.

[0363] Examples of phenol compounds include: p-methoxyphenol, 2,5-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-methylphenol, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, etc.

[0364] Examples of hydroquinone compounds include: hydroquinone, methylhydroquinone, ethylhydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, 2,6-di-tert-butylhydroquinone, 2,3,5-trimethylhydroquinone, 2,5-dichlorohydroquinone, etc.

[0365] Examples of benzoquinone compounds include: p-benzoquinone, methyl-p-benzoquinone, 2-tert-butyl-1,4-benzoquinone, 2,5-diphenyl-p-benzoquinone, chlorobenzoquinone, 2,5-dichlorobenzoquinone, 2,6-dichlorobenzoquinone, tetrachlorobenzoquinone, tetrabromobenzoquinone, etc.

[0366] Examples of phenothiazine compounds include: phenothiazine, 3,7-dioctylphenothiazine, 3,7-dicumylphenothiazine, 10-methylphenothiazine, 2-methoxyphenothiazine, etc.

[0367] Examples of catechol compounds include: 4-methylcatechol, 4-tert-butylcatechol, 3,5-di-tert-butylcatechol, etc.

[0368] Examples of nitrobenzene compounds include: nitrobenzene, o-dinitrobenzene, m-dinitrobenzene, p-dinitrobenzene, 2,4-dinitrotoluene, dinitromesitylene, 2,2-diphenyl-1-picrylhydrazyl, etc.

[0369] Examples of nitroso compounds include: nitroso benzene, 2-nitrosotoluene, 1,2,4,5-tetramethyl-3-nitroso benzene, 4-nitrosophenol, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 4-nitroso-diphenylamine, etc.

[0370] Examples of amine compounds include: N,N-diphenylamine, 4,4'-di-tert-butyl-diphenylamine, 4,4'-dioctyldiphenylamine, 4-aminodiphenylamine, p-nitrosodiphenylamine, N-nitrosodinaphthylamine, N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, N-nitrosophenylhydroxylamine, N,N'-dialkyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-1,4-phenylenediamine, N,N'-di-2-naphthyl-p-phenylenediamine, N,N-diethylhydroxylamine, 1,4-phenylenediamine, N-(1,4-dimethylpentyl)-N'-phenyl-1,4-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-1,4-phenylenediamine, etc.

[0371] Examples of hindered amine compounds include: 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethyl-1-hydroxypiperidine, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-oxo-2,2,6,6-tetramethyl-1-oxypiperidine, etc.

[0372] Examples of phosphorus compounds include: triphenylphosphine, triphenyl phosphite, triethyl phosphite, tris(isodecyl) phosphite, tris(tridecyl) phosphite, phenyl diisooctyl phosphite, phenyl diisodecyl phosphite, phenyl bis(tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl tridecyl phosphite, phosphonic acid [1,1-diphenyl-4,4'-diyl-bis-tetra-2,4-bis(1,1-dimethylethyl)phenyl] ester, tris(nonylphenyl) phosphite, 4,4'-isopropylidenediphenol alkylene phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(biphenyl) phosphite, distearyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphate, bis(nonylphenyl) pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, tetra(tridecyl)-4,4'-butylidenebis(3-methyl-6-tert-butylphenol) diphosphite, hexa(tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane triphosphite, 3,5-di-tert-butyl-4-hydroxybenzyl phosphate diethyl ester, etc.

[0373] The polymerization inhibitor (L) can be used alone or in combination of two or more.

[0374] In 100% by mass of the non-volatile components of the curable composition, the content of the polymerization inhibitor (L) is preferably 0.01% to 0.5% by mass.

[0375] [Antioxidant (M)]

[0376] The curable composition of the present invention may contain an antioxidant (M).

[0377] The antioxidant (M) is not particularly limited, and known antioxidants can be used. For example, phenolic compounds, hindered amine compounds, phosphorus compounds, sulfur compounds, hydroxylamine compounds, etc. can be cited. Among these, phenolic compounds, hindered amine compounds, phosphorus compounds, and sulfur compounds are preferred.

[0378] Commercially available products of phenolic compounds can be cited, for example: Adekastab AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, AO-330 manufactured by ADEKA Corporation; KEMINOX 101, 179, 76, 9425 manufactured by Chemipro Kasei Co., Ltd.; IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565 manufactured by BASF Japan Co., Ltd.; CYANOX CY-1790, CY-2777 manufactured by Sun Chemical Corporation, etc.

[0379] Commercially available products of hindered amine compounds can be cited, for example: Adekastab LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402F, LA-502XP manufactured by ADEKA Corporation; KAMISTAB 29, 62, 77, 94 manufactured by Chemipro Kasei Co., Ltd.; Tinuvin 111FDL, 123, 144, 249, 292, 5100 manufactured by BASF Japan Co., Ltd.; CYASORB UV-3346, UV-3529, UV-3853 manufactured by Sun Chemical Corporation, etc.

[0380] Examples of commercially available phosphorus compounds include Adekastab PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, and TPP manufactured by ADEKA Corporation; IRGAFOS 168 manufactured by BASF Japan Co., Ltd.; and Hostanox P-EPQ manufactured by Clariant chemicals, etc.

[0381] Examples of commercially available sulfur compounds include Adekastab AO-412S and AO-503 manufactured by ADEKA Corporation; and KEMINOX PLS manufactured by Chemipro Kasei Co., Ltd.

[0382] The antioxidant (M) can be used alone or in combination of two or more.

[0383] In 100% by mass of the non-volatile components of the curable composition, the content of the antioxidant (M) is preferably 0.5% to 5.0% by mass.

[0384] [Leveling agent (N)]

[0385] The curable composition of the present invention may contain a leveling agent (N).

[0386] The leveling agent (N) is not particularly limited, and known leveling agents can be used. For example, silicone-based leveling agents, fluorine-based leveling agents, acrylic-based leveling agents, acetylene glycol-based leveling agents, etc. can be cited.

[0387] Examples of commercially available silicone leveling agents include: BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, 3570 manufactured by BYK-Chemie; FZ-7002, 2110, 2122, 2123, 2191, 5609 manufactured by Toray Dow Corning; X-22-4952, X-22-4272, X-22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, KP-341 manufactured by Shin-Etsu Chemical Co., Ltd.; TegoGlide 432, 440, 450, TegoWet 250, 260, 265, 270, 280 manufactured by Evonik; MEGAFACE EFS-131, EFS-321, EFS-521, EFS-801 manufactured by DIC, etc.

[0388] Examples of commercially available fluorine leveling agents include: Surflon S-242, 243, 420, 611, 651, 386 manufactured by AGC Seimi Chemical; MEGAFACE F-253, 477, 551, 552, 554, 555, 556, 558, 559, 560, 561, 570, 575, 576, R-01, R-40, R-40-LM, R-41, RS-72-K manufactured by DIC; FC-4430, 4432 manufactured by Sumitomo 3M; EF-PP31N09, EF-PP33G1, EF-PP32C1 manufactured by Mitsubishi Materials Electronic Chemicals; Ftergent 602A manufactured by NEOS, etc.

[0389] Examples of commercially available acrylic leveling agents include: BYK-350, 352, 354, 355, 358, 380, 381, 392, 394 manufactured by BYK-Chemie; Polyflow 57, 77, 95 manufactured by Kyoeisha Chemical Co., Ltd.

[0390] Examples of commercially available acetylene diol-based leveling agents include Surfynol 420, 440, 465, 485, SE, DF110D, DE85, Olfine E1004, 1010, etc. manufactured by Nissin Chemical Industry Co., Ltd.

[0391] The leveling agent (N) can be used alone or in combination of two or more.

[0392] In 100% by mass of the non-volatile components of the curable composition, the content of the leveling agent (N) is preferably 0.001% to 2.0% by mass, more preferably 0.005% to 1.0% by mass.

[0393] [Storage stabilizer (O)]

[0394] The curable composition of the present invention may contain a storage stabilizer (O).

[0395] The storage stabilizer (O) is not particularly limited, and known compounds can be used. For example, quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxylamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as tert-butylcatechol, tetraethylphosphine, and tetraphenylphosphine, and phosphites can be cited.

[0396] In 100% by mass of the non-volatile components of the curable composition, the content of the storage stabilizer (O) is preferably 0.05% to 5% by mass.

[0397] [Ultraviolet absorber (P)]

[0398] The curable composition of the present invention may contain an ultraviolet absorber (P).

[0399] The ultraviolet absorber (P) is not particularly limited, and known ultraviolet absorbers can be used. For example, benzotriazole-based compounds, triazine-based compounds, benzophenone-based compounds, salicylate-based compounds, cyanoacrylate-based compounds, etc. can be cited.

[0400] Examples of commercially available benzotriazole-based compounds include TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, 1130 manufactured by BASF Japan, Adekastab LA-29, LA-31RG, LA-32, LA-36 manufactured by ADEKA, KEMISORB 71, 73, 74, 79, 279 manufactured by Chemipro Kasei, and RUVA-93 manufactured by Otsuka Chemical Co., Ltd.

[0401] Examples of commercially available triazine-based compounds include: KEMISORB 102 manufactured by Chemipro Kasei Co., Ltd.; TINUVIN 400, 405, 460, 477, 479, 1577ED manufactured by BASF Japan Co., Ltd.; Adekastab LA-46, LA-F70 manufactured by ADEKA Corporation; CYASORB UV-1164 manufactured by Sun Chemical Corporation, etc.

[0402] Examples of commercially available benzophenone-based compounds include: KEMISORB 10, 11, 11S, 12, 111 manufactured by Chemipro Kasei Co., Ltd.; SEESORB 101, 107 manufactured by Shipro Kasei Co., Ltd.; Adekastab 1413 manufactured by ADEKA Corporation; CYASORB UV-12 manufactured by Sun Chemical Corporation, etc.

[0403] Examples of salicylate-based compounds include phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenyl salicylate, etc.

[0404] In 100% by mass of the non-volatile components of the curable composition, the content of the ultraviolet absorber (P) is preferably 0.1% by mass to 5.0% by mass.

[0405] [Organic solvent (Q)]

[0406] The curable composition of the present invention may contain an organic solvent (Q).

[0407] The organic solvent (Q) is not limited and known compounds can be used. Examples of the organic solvent (Q) include: 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butanediol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxy-1-butanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, toluene, o-chlorotoluene, benzene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotert-butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid esters, etc.

[0408] From the viewpoint of the environment, the curable composition of the present invention preferably substantially does not contain an organic solvent which is an aromatic hydrocarbon (such as toluene, xylene, benzene, chlorobenzene, etc.). The so-called substantially does not contain means 50 mass ppm or less, preferably 30 mass ppm or less, more preferably 10 mass ppm or less in the curable composition.

[0409] The organic solvent (Q) can be used alone or in combination of two or more.

[0410] The content of the organic solvent (Q) is preferably an amount such that the nonvolatile components of the curable composition are 5% by mass to 60% by mass.

[0411] [Other Components]

[0412] The curable composition of the present invention may contain components other than those described above (hereinafter, also simply referred to as other components). Examples of other components include surfactants, acid generators, base generators, curing catalysts, matting agents, semiconductor nanocrystals, semiconductor materials, organic electroluminescent materials, insulating materials, and the like. The content of other components can be appropriately set within a range that does not impair the effects of the present invention.

[0413] [Content of Specific Metal Elements]

[0414] In the curable composition of the present invention, the total content of Li, Na, K, Mg, Ca, Fe, and Cr (hereinafter, also referred to as specific metal elements) contained in the curable composition is preferably 500 mass ppm or less.

[0415] Even after storage over time, the curable composition with the total amount of specific metal elements within the above range is excellent in dispersion stability and sensitivity. The content of specific metal elements can be measured by inductively coupled plasma optical emission spectrometry (Inductively Coupled Plasma, ICP).

[0416] [Content of Water]

[0417] In the curable composition of the present invention, the content of water contained in the curable composition is preferably 2.0% by mass or less.

[0418] Even after storage over time, the curable composition with the water content within the above range is excellent in dispersion stability and sensitivity. The water content can be measured by known methods such as the Karl Fischer method.

[0419] [Method for Producing Curable Composition]

[0420] The curable composition of the present invention can be prepared by mixing the above components. During preparation, the components can be formulated together, or they can be formulated sequentially after dissolving or dispersing each component in the polymerizable compound (B) or the organic solvent (Q). When using components with low solubility, such as the pigment (F), etc., it is preferable to perform a dispersion treatment.

[0421] For example, a dispersion is produced by adding a pigment (F), a dispersion resin (I), an organic solvent (Q), etc. and performing a dispersion treatment. Thereafter, it can be produced by formulating and mixing an alkali-soluble resin (A), a polymerizable compound (B), a polymerization initiator (C), and a thermosetting compound (D) in the dispersion. In addition, the timing of formulating each material is arbitrary. Also, multiple dispersion steps can be carried out.

[0422] Examples of the disperser for performing the dispersion treatment include a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or a grinder, etc.

[0423] The average dispersed particle diameter (secondary particle diameter) of the particles in the dispersion is preferably 30 nm to 200 nm, more preferably 40 nm to 200 nm. If it has a suitable particle diameter, it is easy to obtain a curable composition with high dispersion stability.

[0424] As a method for measuring the average dispersed particle diameter (secondary particle diameter), for example, Microtrack UPA-EX150 of Nikkiso Co., Ltd. using the dynamic light scattering method (fast Fourier transform (FFT) power spectrum method) is used. The particle permeability is set to the absorption mode, the particle shape is set to non-spherical, and the D50 particle diameter is set to the average diameter. The dilution solvent for measurement uses the organic solvent used in the dispersion respectively. When measuring the sample treated with ultrasonic waves immediately after sample adjustment, it is easy to obtain results with small deviations and is preferred.

[0425] Regarding the curable composition, it is preferred to remove coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more and the mixed dust by means such as centrifugal separation, filtration using a sintered filter or a membrane filter. The curable composition of the present invention preferably substantially does not contain particles of 0.5 μm or more, and more preferably does not contain particles of 0.3 μm or less.

[0426] The curable composition of the present invention is preferably used for pattern formation by photolithography. In addition, the present invention is not limited thereto.

[0427] <Film>

[0428] The film of the present invention is a film formed from the curable composition. The film is preferably a patterned film, but it can also be used as a flat film without forming a pattern.

[0429] [Method for manufacturing a film]

[0430] The method for manufacturing the film is not particularly limited, and known methods can be used. For example, it can be manufactured through a process of coating the curable composition of the present invention on a substrate and a process of drying.

[0431] 〔Coating process〕

[0432] Examples of the substrate include substrates made of materials such as glass, resin, and silicone. The glass can be colorless and transparent, or colored glass such as blue glass can be used according to the application. Examples of the resin include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, polycarbonate resins, and epoxy resins. The thickness of the substrate is preferably 0.01 mm to 10 mm.

[0433] An organic light-emitting layer can be formed on these substrates. In addition, imaging elements such as a charge-coupled device (CCD) and a complementary metal oxide semiconductor (CMOS) can be formed on the substrate. In addition, on the substrate, a bottom coating may be provided as needed to improve the adhesion to the upper layer, prevent the diffusion of substances, and achieve surface flattening.

[0434] The coating method is not particularly limited, and known methods can be used. For example, dropwise addition method, slit coating method, spraying method, roll coating method, spin coating method, casting coating method, inkjet method, flexographic printing, screen printing, gravure printing, offset printing, etc. can be cited.

[0435] The thickness of the film can be appropriately adjusted according to the purpose. The thickness of the film is preferably 0.05 μm to 20.0 μm, more preferably 0.3 μm to 10.0 μm.

[0436] 〔Drying process〕

[0437] The drying of the film coated on the substrate is not particularly limited, and known methods can be used. For example, vacuum drying method using a vacuum drying device, heating drying method using a hot plate, an infrared (IR) oven, a convection oven, etc., and a method combining them can be cited.

[0438] The drying temperature and time can be appropriately adjusted. The drying temperature is preferably about 50°C to 130°C, and the drying time is preferably about 5 seconds to 5 minutes.

[0439] Next, a pattern is formed. Examples of the method for forming a pattern include photolithography or dry etching. Among these, photolithography is preferred. In addition, in the case of using it as a flat film, the process of forming a pattern may not be performed.

[0440] 〔Exposure process〕

[0441] In the exposure process, an exposure apparatus such as a stepper is used to expose a specific pattern on a layer formed by coating and drying through a mask. Thereby, the exposed portion can be hardened. Examples of the actinic ray used in the exposure include ultraviolet rays such as g-ray (wavelength 436 nm), h-ray (wavelength 405 nm), and i-ray (wavelength 365 nm). In addition, light with a wavelength of 300 nm or less can also be used. Examples of the light with a wavelength of 300 nm or less include KrF ray (wavelength 248 nm), ArF ray (wavelength 193 nm), etc. When light of a specific wavelength is irradiated and used, a filter can also be utilized.

[0442] In addition, during exposure, light can be continuously irradiated for exposure, or light irradiation and stoppage can be repeatedly performed in a short period (for example, at the millisecond level or below) in cycles (pulse exposure) for exposure.

[0443] In addition, multiple actinic rays can be used in combination, or exposure can be performed in multiple times.

[0444] 〔Development process〕

[0445] Next, through an alkali development process, the unexposed portion of the layer is dissolved into the alkali developer, and only the hardened portion remains, thereby obtaining a patterned film.

[0446] Examples of the alkali developer include aqueous solutions containing alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]undec-7-ene, etc. Two or more of these alkaline compounds can be used in combination.

[0447] In addition to containing an alkaline compound and water, the alkali developer can also contain a surfactant or an organic solvent.

[0448] The concentration of the alkali developer is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 1% by mass. The pH of the alkali developer is preferably 11 to 13, more preferably 11.5 to 12.5. If used at an appropriate pH, roughness or peeling of the pattern is suppressed, and the residual film rate after development is increased.

[0449] Examples of the development method include dipping method, spraying method, puddle method, etc. The development temperature is preferably 15°C to 40°C. In addition, after alkali development, it is preferably washed with pure water.

[0450] 〔Post-baking process〕

[0451] After development, a heat treatment (post-baking) is performed. By post-baking, the film tolerance is improved. The temperature is preferably from 70°C to 300°C, more preferably from 80°C to 240°C. The time is preferably about 2 minutes to 2 hours.

[0452] In the case of using a raw material with low heat resistance in the substrate, in the case of using a substrate having an organic electroluminescent element as a light-emitting layer, or from the viewpoint of reducing the environmental load, it is preferably 180°C or lower, more preferably 150°C or lower, and particularly preferably 130°C or lower.

[0453] The curable composition of the present invention is preferably used at a post-baking temperature of 180°C or lower, more preferably at 150°C or lower, and particularly preferably at 130°C or lower.

[0454] <Filter>

[0455] The filter of the present invention has the film. Filters are used, for example, in color filters, black matrices, light-shielding filters, antireflection filters, infrared cut-off filters, infrared transmission filters, microlenses, etc. Regarding the manufacture of the filter of the present invention, it can be manufactured, for example, by the same method as the film.

[0456] <Solid-state imaging device>

[0457] The solid-state imaging device of the present invention has the filter.

[0458] The solid-state imaging device is not particularly limited as long as it includes the filter of the present invention and functions as a solid-state imaging device. For example, the following structures can be cited.

[0459] It has the following structure: on a substrate, there are a plurality of photodiodes constituting the light-receiving region of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) and a transfer electrode including polysilicon, etc. On the photodiodes and the transfer electrode, there is a light-shielding film that is only open to the light-receiving portion of the photodiodes. On the light-shielding film, there is a device protection film including silicon nitride, etc., formed so as to cover the entire surface of the light-shielding film and the light-receiving portion of the photodiodes. On the device protection film, there is the filter (color filter) of the present invention. Furthermore, it can also be a structure having a condensing member (for example, a microlens, etc. The same applies hereinafter) on the device protection film and below the filter (on the side closer to the substrate), or a structure having a condensing member on the filter. In addition, the filter can also have a structure in which a cured film forming each colored pixel is buried in a space partitioned by partition walls into, for example, a lattice shape. In this case, the partition walls are preferably of a low refractive index with respect to each colored pixel.

[0460] The imaging device including the solid-state imaging device of the present invention can be used for various applications such as digital cameras, electronic devices with imaging functions (mobile phones, smartphones, etc.), in-vehicle cameras, surveillance cameras, and the like.

[0461] <Image Display Device>

[0462] The image display device of the present invention has the filter. Examples of the image display device include a liquid crystal display, an organic electroluminescence (EL) display, and the like.

[0463] The form for the image display device is not particularly limited as long as it functions as an image display device. For example, the structure of a liquid crystal display as follows can be cited.

[0464] The liquid crystal display includes: a color filter, a counter substrate having a thin film transistor (TFT) array substrate, etc., and a liquid crystal layer formed between the color filter and the counter substrate. Examples of the driving method of the liquid crystal display include: the twisted nematic (TN) method, the in-plane switching (IPS) method, the optically compensatory bend (OCB) method, and the multi-domain vertically alignment (MVA) method, etc. The counter substrate can be appropriately selected and used according to the driving method. The liquid crystal layer can use various liquid crystals with different dielectric anisotropies and their mixtures according to the driving method.

[0465] Specifically, it is described in "Next-generation Liquid Crystal Display Technology (written by Tatsuo Uchida, Industrial Research Institute, Inc., published in 1994)", "Electronic Display Devices (written by Akio Sasaki, Industrial Research Institute, Inc., published in 1990)", "Display Devices (written by Junsho Ibuki, Sangyo Tosho Co., Ltd., published in 1989)", and the like.

[0466] <Infrared Sensor>

[0467] The infrared sensor of the present invention has the filter.

[0468] The form for the infrared sensor is not particularly limited as long as it includes the filter of the present invention and functions as an infrared sensor. For example, the structure as follows can be cited.

[0469] On a substrate, there are provided a plurality of photodiodes constituting a light-receiving region of a solid-state imaging device (such as a CCD image sensor, a CMOS image sensor, etc.) and transfer electrodes including polysilicon or the like. On these photodiodes and transfer electrodes, there is a light-shielding film that is open only to the light-receiving portion of the photodiodes. On the light-shielding film, there is a device protection film, and further on the device protection film, there is the filter of the present invention. Further, it may also be a structure in which a condensing member (for example, a microlens or the like. The same applies hereinafter) is provided on the device protection film and below the filter (the side closer to the substrate), or a structure in which a condensing member is provided on the filter.

[0470] Figure 1 It is a schematic cross-sectional view showing a structural example of an infrared sensor including the filter of the present invention.

[0471] Figure 1 The infrared sensor 100 shown includes a solid-state imaging device 110.

[0472] The imaging region provided on the solid-state imaging device 110 is constituted by combining an infrared cut-off filter 111 and a color filter 112.

[0473] The infrared cut-off filter 111 transmits light in the visible light region (for example, light having a wavelength of 400 nm to 700 nm) and blocks light in the infrared region (for example, light having a wavelength of 800 nm to 1,300 nm).

[0474] The color filter 112 is a color filter in which pixels that transmit and absorb light of specific wavelengths in the visible light region are formed. For example, a color filter in which pixels of red (R), green (G), and blue (B) are formed is used.

[0475] A resin film 114 is disposed between the infrared transmission filter 113 and the solid-state imaging device 110, and the resin film 114 can transmit light having a wavelength that passes through the infrared transmission filter 113.

[0476] The infrared transmission filter 113 is a filter having visible light shielding properties and transmitting infrared light of a specific wavelength. The infrared transmission filter 113 preferably blocks light having a wavelength of 400 nm to 830 nm and transmits light having a wavelength of 900 nm to 1,300 nm, for example.

[0477] A microlens 115 is disposed on the incident light h side of the color filter 112 and the infrared transmission filter 113. A flat film 116 is formed so as to cover the microlens 115.

[0478] In Figure 1 In the form shown, the resin film 114 is disposed, but an infrared transmission filter 113 may be formed instead of the resin film 114.

[0479] By means of the infrared sensor, image information is taken in simultaneously, so that motion sensing for detecting a moving object can be performed. In addition, distance information can be obtained according to the infrared sensor, so that photography of an image including three-dimensional (3D) information can also be performed. Furthermore, the infrared sensor can also be used as a biometric authentication sensor.

[0480] [Examples of Embodiments]

[0481] Examples of embodiments of the present invention are listed below. The present invention is not limited thereto.

[0482] <1> The curable composition of the present invention is a curable composition comprising: an alkali-soluble resin (A), a polymerizable compound (B), a polymerization initiator (C), and a thermally crosslinkable compound (D).

[0483] The polymerizable compound (B) includes a polyfunctional urethane (meth)acrylate (B1) having a secondary amine structure or a tertiary amine structure.

[0484] The thermally crosslinkable compound (D) includes a compound (D1) having a blocked isocyanate group.

[0485] <2> According to the curable composition of <1>, wherein the polyfunctional urethane (meth)acrylate (B1) having a secondary amine structure or a tertiary amine structure includes one or more selected from the group consisting of an aliphatic polyfunctional urethane (meth)acrylate having a secondary amine structure or a tertiary amine structure, and an alicyclic polyfunctional urethane (meth)acrylate having a secondary amine structure or a tertiary amine structure.

[0486] <3> According to the curable composition of <1> or <2>, wherein the polymerizable compound (B) further includes a (meth)acrylate (B2) other than the polyfunctional urethane (meth)acrylate (B1) having a secondary amine structure or a tertiary amine structure.

[0487] <4> According to the curable composition of any one of <1> to <3>, wherein the blocked isocyanate group of the compound (D1) having a blocked isocyanate group is a structure protected by an active methylene compound, a pyrazole compound, or an oxime compound.

[0488] <5> According to the curable composition of any one of <1> to <4>, wherein the alkali-soluble resin (A) includes an alkali-soluble resin (A1) having a monomer unit (a1) containing a hydroxyl group.

[0489] <6> The curable composition according to any one of <1> to <5> further includes a silane coupling agent (E).

[0490] <7> A film formed from the curable composition according to any one of <1> to <6>.

[0491] <8> A filter having the film according to <7>.

[0492] <9> A solid-state imaging device having the filter according to <8>.

[0493] <10> An image display device having the filter according to <8>.

[0494] <11> An infrared sensor having the filter according to <8>.

[0495] [Examples]

[0496] Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited to the examples. In addition, "parts" means "parts by mass", and "%" means "% by mass".

[0497] In addition, in the present invention, the non-volatile component or the non-volatile component concentration refers to the mass residue component after standing in an oven at 110 °C for 3 hours.

[0498] Before the examples, each measurement method will be described.

[0499] The measurement of the weight-average molecular weight (Mw), number-average molecular weight (Mn), acid value (mgKOH / g), amine value (mgKOH / g), and extinction coefficient (L / mol·cm) of the resin is as described below.

[0500] (Molecular weight)

[0501] The number-average molecular weight (Mn) and weight-average molecular weight (Mw) are measured using a gel permeation chromatograph (GPC) equipped with a refractive index (RI) detector. HLC-8220GPC (manufactured by Tosoh Corporation) is used as the device, and two separation columns are connected in series. Two "TSK gel super HZM-N (TSK-GEL SUPER HZM-N)" are used as the fillers in both. The measurement is carried out at an oven temperature of 40 °C, using a tetrahydrofuran (THF) solution as the eluent, and a flow rate of 0.35 ml / min. The sample is dissolved in a solvent containing 1 mass% of the eluent and 20 μl is injected. The molecular weight is a polystyrene conversion value.

[0502] (Acid value of the resin)

[0503] 80 ml of acetone and 10 ml of water were added to 0.5 g to 1 g of the resin solution and stirred to dissolve it uniformly. A 0.1 mol / L aqueous solution of potassium hydroxide (KOH) was used as the titrant, and titration was performed using an automatic titrator (“COM-555” manufactured by Hiranuma Sangyo Co., Ltd.) to measure the acid value (mgKOH / g). Moreover, the acid value per unit nonvolatile component of the resin was calculated from the acid value of the resin solution and the concentration of the nonvolatile component of the resin solution.

[0504] (Amine value of resin)

[0505] The amine value of the resin is the value obtained by converting the measured total amine value (mgKOH / g) to nonvolatile components according to the method of American Society for Testing Materials (ASTM) D2074.

[0506] (Absorption coefficient)

[0507] 0.001 g of a polymerization initiator was dissolved in 0.01 L of propylene glycol monomethyl ether acetate to prepare a 0.1 mass% measurement solution. Further, the obtained 0.1 mass% measurement solution was diluted with propylene glycol monomethyl ether acetate to prepare 0.01 mass% and 0.001 mass% measurement solutions. Using a spectrophotometer (“U-3010” manufactured by Hitachi High-Technologies Corporation), the absorbance at a wavelength of 365 nm of the measurement solutions at each concentration was measured, and the absorption coefficient (L / mol·cm) was calculated from the slope when the horizontal axis was set to molar concentration and the vertical axis was set to absorbance.

[0508] <Manufacture of alkali-soluble resin (A)>

[0509] (Solution of alkali-soluble resin (A1-1) having a monomer unit (a1) containing a hydroxyl group)

[0510] In a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen inlet tube, a dropping tube, and a stirring device, 100.0 parts of propylene glycol monomethyl ether acetate (hereinafter also referred to as PGMAc) was placed. While injecting nitrogen into the reaction vessel, it was heated to 120 °C. At this temperature, a mixture of 56.86 parts (0.40 mol) of glycidyl methacrylate, 66.09 parts (0.30 mol) of dicyclopentanyl methacrylate, and 31.25 parts (0.30 mol) of styrene and a substance obtained by dissolving 5.0 parts of azobisisobutyronitrile as a polymerization initiator in PGMAc were dropped from the dropping tube over 2.5 hours to carry out a polymerization reaction. After the dropping was completed, it was further stirred at 120 °C for 2 hours to obtain a precursor. Then, the inside of the reaction vessel was purged with air. 0.30 part of tri-dimethylaminomethylphenol and 0.30 part of hydroquinone were added to 28.82 parts (0.40 mol) of acrylic acid as a modifying compound, and the reaction was carried out at 120 °C for 5 hours. Thus, the epoxy group of glycidyl methacrylate reacted with the carboxyl group of acrylic acid, and a hydroxyl group was generated by the cleavage of the epoxy group of glycidyl methacrylate, and at the same time, a polymerizable unsaturated group was introduced.

[0511] Subsequently, 48.68 parts (0.32 mol) of tetrahydrophthalic anhydride and 0.5 part of triethylamine as modifying compounds were added, and the reaction was carried out at 120 °C for 4 hours. Thus, a part of the hydroxyl group generated by the cleavage of the epoxy group of glycidyl methacrylate reacted with tetrahydrophthalic anhydride to introduce a carboxyl group. Thereafter, PGMAc was added so that the non-volatile content became 40% by mass, thereby preparing a solution of an alkali-soluble resin (A1-1) having a monomer unit (a1) containing a hydroxyl group. The weight average molecular weight (Mw) was 10,000, and the acid value was 77 mgKOH / g.

[0512] (Solution of alkali-soluble resin (A1-2) to alkali-soluble resin (A1-6) having a monomer unit (a1) containing a hydroxyl group)

[0513] Except that the formulation of the alkali-soluble resin (A1-1) was changed as described in Table 2, the same procedure as for the alkali-soluble resin (A1-1) was carried out to separately synthesize alkali-soluble resins (A1-2) to (A1-6) having a monomer unit (a1) containing a hydroxyl group. In addition, PGMAc was added separately so that the non-volatile content was 40% by mass. The weight average molecular weight of the resin was adjusted by appropriately changing the amount of the polymerization initiator used. The blending amounts in Table 2 are in mol%.

[0514]

[0515] Aronix M-110 described in Table 2 is a cumylphenol ethylene oxide-modified acrylate manufactured by Toagosei Co., Ltd., and Karenz MOI-DEM is 2-[[[[[2-methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl malonate manufactured by Resonac Co., Ltd.

[0516] (Other alkali-soluble resin (A2-1) solution)

[0517] In a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen inlet tube, a dropping tube, and a stirring device, 160 parts of PGMAc was placed, and while injecting nitrogen into the reaction vessel, it was heated to 120 °C. At this temperature, 109.25 parts (0.62 mol) of benzyl methacrylate, 24.1 parts (0.28 mol) of methacrylic acid, 22.03 parts (0.1 mol) of dicyclopentanyl methacrylate, 1.0 part of azobisisobutyronitrile as a polymerization initiator, and a mixture of PGMAc were added dropwise from the dropping tube over 2.5 hours and allowed to react.

[0518] After the addition was completed, stirring was continued at 120 °C for 2 hours to continue the reaction. Thereafter, PGMAc was added so that the non-volatile content became 40% by mass to prepare an other alkali-soluble resin (A2-1) solution. The weight average molecular weight was 17,500 and the acid value was 98 mgKOH / g.

[0519] [Polymerizable compound (B)]

[0520] (Polyfunctional carbamate (meth)acrylate (B1-1) having a secondary amine structure or a tertiary amine structure)

[0521] In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and an air inlet tube, 634.7 parts of trimethylolpropane triacrylate, 2.0 parts of 4-methoxyphenol, 2.0 parts of triphenyl phosphite, and 2.0 parts of phenothiazine were placed, and the temperature was raised to 50 °C while stirring. Then, while slowly dropping 160.8 parts of N-methylethanolamine into the flask from the dropping funnel, the reaction was carried out. After the addition was completed, stirring was continued at 50 °C for 2 hours to continue the reaction.

[0522] Next, the temperature was raised to 100 °C, and while slowly dropping 198.3 parts of isophorone diisocyanate into the flask from the dropping funnel, the reaction was carried out. After the addition was completed, the reaction was carried out while stirring at 100 °C for 4 hours to obtain an alicyclic polyfunctional carbamate acrylate having a tertiary amine structure.

[0523] (Polyfunctional carbamate (meth)acrylate (B1-2) having a secondary amine structure or a tertiary amine structure)

[0524] In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and an air inlet tube, 998.4 parts of di-trimethylolpropane tetraacrylate, 2.0 parts of 4-methoxyphenol, 2.0 parts of triphenyl phosphite, and 2.0 parts of phenothiazine were placed, and the temperature was raised to 50 °C while stirring. Then, while slowly dropping 160.8 parts of N-methylethanolamine into the flask from the dropping funnel, the reaction was carried out. After the dropping was completed, the mixture was stirred at 50 °C for 2 hours and the reaction was continued.

[0525] Then, the temperature was raised to 100 °C, and while slowly dropping 198.3 parts of isophorone diisocyanate into the flask from the dropping funnel, the reaction was carried out. After the dropping was completed, the reaction was carried out while stirring at 100 °C for 4 hours to obtain an alicyclic polyfunctional carbamate acrylate having a tertiary amine structure.

[0526] (Polyfunctional carbamate (meth)acrylate (B1-3) having a secondary amine structure or a tertiary amine structure)

[0527] In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and an air inlet tube, 754.0 parts of pentaerythritol tetraacrylate, 2.0 parts of 4-methoxyphenol, 2.0 parts of triphenyl phosphite, and 2.0 parts of phenothiazine were placed, and the temperature was raised to 50 °C while stirring. Then, while slowly dropping 160.8 parts of N-methylethanolamine into the flask from the dropping funnel, the reaction was carried out. After the dropping was completed, the mixture was stirred at 50 °C for 2 hours and the reaction was continued.

[0528] Then, the temperature was raised to 100 °C, and while slowly dropping 198.3 parts of isophorone diisocyanate into the flask from the dropping funnel, the reaction was carried out. After the dropping was completed, the reaction was carried out while stirring at 100 °C for 4 hours to obtain an alicyclic polyfunctional carbamate acrylate having a tertiary amine structure.

[0529] (Polyfunctional carbamate (meth)acrylate (B1-4) having a secondary amine structure or a tertiary amine structure)

[0530] In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and an air inlet tube, 754.0 parts of pentaerythritol tetraacrylate, 2.0 parts of 4-methoxyphenol, 2.0 parts of triphenyl phosphite, and 2.0 parts of phenothiazine were placed, and the temperature was raised to 50 °C while stirring. Then, while slowly dropping 160.8 parts of N-methylethanolamine into the flask from the dropping funnel, the reaction was carried out. After the dropping was completed, the mixture was stirred at 50 °C for 2 hours and the reaction was continued.

[0531] Next, the temperature was raised to 100 °C, and while slowly dropping 149.7 parts of hexamethylene diisocyanate into the flask from the dropping funnel, the reaction was carried out. After the dropping was completed, the reaction was carried out while stirring at 100 °C for 4 hours to obtain an aliphatic polyfunctional urethane acrylate having a tertiary amine structure.

[0532] (Polyfunctional urethane (meth)acrylate (B1-5) having a secondary amine structure or a tertiary amine structure)

[0533] In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and an air inlet tube, 754.0 parts of pentaerythritol tetraacrylate, 2.0 parts of 4-methoxyphenol, 2.0 parts of triphenyl phosphite, and 2.0 parts of phenothiazine were placed, and the temperature was raised to 50 °C while stirring. Next, while slowly dropping 160.8 parts of N-methylethanolamine into the flask from the dropping funnel, the reaction was carried out. After the dropping was completed, the mixture was stirred at 50 °C for 2 hours and the reaction was continued.

[0534] Next, the temperature was raised to 100 °C, and while slowly dropping 155.0 parts of 2,4-toluene diisocyanate into the flask from the dropping funnel, the reaction was carried out. After the dropping was completed, the reaction was carried out while stirring at 100 °C for 4 hours to obtain an aromatic polyfunctional urethane acrylate having a tertiary amine structure.

[0535] <Manufacture of heat-crosslinkable compound (D)>

[0536] (Solution of heat-crosslinkable compound (D1-1))

[0537] The flask including a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube was purged with nitrogen, charged with 200 parts of hexamethylene diisocyanate and 6.6 parts of trimethylolpropane, and the temperature was raised to 80 °C while stirring, and the reaction was carried out while stirring for 2 hours. Thereafter, it was cooled to 60 °C, tetrabutylammonium acetate was added, and phosphoric acid was added to stop the reaction at the time when the yield reached 45%. After filtering the reaction solution, the unreacted hexamethylene diisocyanate was removed using a thin-film evaporation device to obtain an adduct of hexamethylene diisocyanate and trimethylolpropane.

[0538] Next, a flask equipped with a stirrer, a thermometer, a reflux condenser tube, and a nitrogen inlet tube was purged with nitrogen, charged with 100 parts of an adduct of hexamethylene diisocyanate and trimethylolpropane, 39 parts of n-butyl acetate, and while stirring, a mixture of 78 parts of diethyl malonate and 0.7 part of a 28% sodium methoxide solution was slowly added. After the addition was completed, the temperature was raised to 60°C and the reaction was carried out while stirring for 6 hours. Thereafter, butanol was added so that the non-volatile content became 60% by mass, and a compound obtained by block-copolymerizing an active methylene compound with an adduct of hexamethylene diisocyanate having a weight average molecular weight of 1,200 was obtained.

[0539] (Thermally crosslinkable compound (D1-2) solution)

[0540] A flask equipped with a stirrer, a thermometer, a reflux condenser tube, and a nitrogen inlet tube was purged with nitrogen, charged with 1,000 parts of hexamethylene diisocyanate, and while stirring, the temperature was raised to 60°C, and 0.1 part of trimethylbenzylammonium hydroxide was added. After 4 hours, 0.2 g of phosphoric acid was added at the time when the conversion reached 38% to stop the reaction. After filtering the reaction solution, the unreacted hexamethylene diisocyanate was removed using a thin-film evaporation apparatus to obtain an isocyanurate of hexamethylene diisocyanate.

[0541] Next, a flask equipped with a stirrer, a thermometer, a reflux condenser tube, and a nitrogen inlet tube was purged with nitrogen, charged with 100 parts of an isocyanurate of hexamethylene diisocyanate, 39 parts of n-butyl acetate, and while stirring, a mixture of 92 parts of diethyl malonate and 0.8 part of a 28% sodium methoxide solution was slowly added. After the addition was completed, the temperature was raised to 60°C and the reaction was carried out while stirring for 6 hours. Thereafter, butanol was added so that the non-volatile content became 60% by mass, and a compound obtained by block-copolymerizing an active methylene compound with an isocyanurate of hexamethylene diisocyanate having a weight average molecular weight of 985 was obtained.

[0542] <Manufacture of pigment (F)>

[0543] (Near-infrared absorbing pigment (F-11))

[0544] 400 parts of toluene was mixed with 40.0 parts of 1,8-diaminonaphthalene, 32.2 parts of 3,5-dimethylcyclohexanone, and 0.087 part of p-toluenesulfonic acid monohydrate, and heated with stirring in a nitrogen atmosphere, and reacted while refluxing for 3 hours. The water generated during the reaction was removed from the reaction system by azeotropic distillation. After the reaction was completed, the dark brown solid obtained by distilling toluene extracted with acetone was recrystallized from a mixed solvent of acetone and ethanol to be purified. The obtained brown solid was dissolved in a mixed solvent of 240 parts of toluene and 160 parts of n-butanol, 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione was added, and heated with stirring in a nitrogen atmosphere and refluxed for 8 hours. The water generated during the reaction was removed from the reaction system by azeotropic distillation.

[0545] After the reaction was completed, the solvent was distilled off, and 200 parts of hexane was added while stirring the obtained reaction mixture. After the obtained dark brown precipitate was separated by filtration, it was washed successively with hexane, ethanol, and acetone, and dried under reduced pressure to obtain the near-infrared absorbing pigment (F-11) represented by the following chemical formula (5). 50 parts of the obtained near-infrared absorbing pigment (F-11), 500 parts of sodium chloride, and 60 parts of diethylene glycol were charged into a stainless steel gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60 °C for 12 hours. Then, the kneaded mixture was put into warm water, heated to about 80 °C while stirring for 1 hour to form a slurry, and after repeated filtration and washing with ion-exchanged water, it was dried at 80 °C for a whole day and night and pulverized to obtain the micronized near-infrared absorbing pigment (F-11).

[0546] Chemical formula (5)

[0547] [Chemical formula 8]

[0548]

[0549] (Near-infrared absorbing pigment (F-12))

[0550] In a reaction vessel, 26 parts of phthalonitrile, 143 parts of 2,3-dicyanonaphthalene, 890 parts of n-pentanol, 137 parts of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and 34 parts of aluminum trichloride were mixed and stirred. After heating, the mixture was refluxed at 136 °C for 5 hours. While maintaining stirring, the reaction solution cooled to 30 °C was injected into a mixed solvent containing 5,000 parts of methanol and 10,000 parts of ion-exchanged water to obtain a blue slurry. The slurry was filtered, washed, and dried using a mixed solvent containing 2,000 parts of methanol and 4,000 parts of ion-exchanged water to obtain Compound a.

[0551] Subsequently, in a reaction vessel, 140 parts of Compound a were added to 1,500 parts of concentrated sulfuric acid under an ice bath and stirred for 1 hour. Subsequently, the sulfuric acid solution was injected into 1,000 parts of cold water at 3 °C, and the resulting precipitate was treated in the order of filtration, washing with water, washing with a 2.5% aqueous sodium hydroxide solution, and washing with water, and then dried to obtain Compound b.

[0552] 5 parts of diphenylphosphoric acid were added to 200 parts of N-methylpyrrolidone, and after thorough stirring and mixing, the mixture was heated to 50 °C. After adding 10 parts of Compound b drop by drop to the solution, the mixture was stirred at 90 °C for 120 minutes. For confirmation of the reaction end point, for example, the reaction solution was dropped onto a filter paper, and the end point was when the exudation disappeared. Subsequently, the reaction solution was injected into 2,000 parts of ion-exchanged water, and the resulting precipitate was repeatedly filtered and washed with ion-exchanged water and then dried to obtain a mixture of the compound represented by the following Chemical Formula (6) (mass ratio of n1:n2:n3:n4 = 7:19:59:15), namely, a near-infrared absorbing pigment (F-12). Subsequently, it was micronized in the same manner as the near-infrared absorbing pigment (F-11).

[0553] Chemical Formula (6)

[0554] [Chemical Formula 9]

[0555]

[0556] (Near-infrared absorbing pigment (F-13))

[0557] According to the description in International Publication No. 2019 / 058882, the near-infrared absorbing pigment (F-13) represented by the following Chemical Formula (7) was obtained. Subsequently, it was micronized in the same manner as the near-infrared absorbing pigment (F-11).

[0558] Chemical Formula (7)

[0559] [Chemical formula 10]

[0560]

[0561] (Near-infrared absorbing pigment (F-14))

[0562] In a reaction vessel, 10.7 parts of aniline, 120 parts of bromobenzene, and 25.7 parts of diazabicyclooctane were added and stirred. Thereafter, 95.2 parts of a 1 mol / L toluene solution of titanium tetrachloride were added dropwise. After the addition, 10.0 parts of indigo were added and refluxed for 10 hours. After the reaction was completed, methanol was added and filtration was carried out to obtain a green powder. Liquid separation was performed using dichloromethane and water, and the organic layer was concentrated to obtain 14.6 parts of compound c.

[0563] In a reaction vessel, 13.5 parts of compound c, 9.0 parts of zinc(II) bis(2,4-pentanedionate), and 120 parts of tetrahydrofuran were mixed and stirred. After heating, the mixture was stirred at 40 °C for 5 hours. While maintaining stirring, the reaction solution cooled to 30 °C was poured into 500 parts of methanol while stirring to obtain a blue slurry. The slurry was filtered, washed with 500 parts of methanol, washed multiple times with 500 parts of ion-exchanged water, and dried to obtain a mixture of the compound represented by the following chemical formula (8) (mass ratio of dimer: trimer: tetramer = 81:17:2), that is, near-infrared absorbing pigment (F-14). Subsequently, it was micronized in the same manner as near-infrared absorbing pigment (F-11).

[0564] Chemical formula (8)

[0565] [Chemical formula 11]

[0566]

[0567] <Manufacture of dispersion resin (I)>

[0568] (Dispersion resin (I-1) solution)

[0569] In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 108 parts of 1-thioglycerol, 174 parts of pyromellitic dianhydride, 650 parts of PGMAc, and 0.2 part of monobutyltin oxide as a catalyst were charged. After purging with nitrogen, the reaction was carried out at 120 °C for 5 hours (the first step). By measuring the acid value, it was confirmed that more than 95% of the acid anhydride was semi-esterified. Subsequently, 160 parts of the compound obtained in the first step in terms of non-volatile components, 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 inside of the reaction vessel was heated to 80 °C, 1.2 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, and the reaction was carried out for 12 hours (the second step). By measuring the non-volatile components, it was confirmed that 95% of the reaction occurred. Finally, 500 parts of a 50% PGMAc solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate, and 0.1 part of hydroquinone were charged, and the reaction was carried out until the peak at 2,270 cm -1 based on the isocyanate group disappeared as confirmed by IR (the third step). After cooling, PGMAc was added so that the non-volatile components became 30% by mass, and a solution of a comb-shaped dispersant resin (I-1) having a polymerizable unsaturated group was obtained. The acid value was 68 mgKOH / g, and the weight-average molecular weight was 13,000.

[0570] (Dispersant resin (I-2) solution)

[0571] In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of isobutyl methacrylate, 20 parts of benzyl methacrylate, and 50 parts of PGMAc were charged and purged with nitrogen. The inside of the reaction vessel was heated and stirred to 50 °C, and 12 parts of 3-mercapto-1,2-propanediol were added. The temperature was raised to 90 °C, and a solution prepared by adding 0.1 part of 2,2'-azobisisobutyronitrile to 90 parts of PGMAc was added while reacting for 7 hours. By measuring the non-volatile components, it was confirmed that 95% of the reaction occurred. 19 parts of pyromellitic dianhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 part of 1,8-diazabicyclo[5.4.0]undec-7-ene as a catalyst were added, and the reaction was carried out at 100 °C for 7 hours. In the measurement of the acid value, it was confirmed that more than 98% of the acid anhydride was semi-esterified, and the reaction was terminated. After cooling, PGMAc was added so that the non-volatile components became 30% by mass, and a solution of a comb-shaped dispersant resin (I-2) was obtained. The acid value was 70 mgKOH / g, and the weight-average molecular weight was 8,500.

[0572] (Dispersed resin (I-3) solution)

[0573] In a reaction apparatus equipped with a gas inlet tube, a condenser, stirring blades, and a thermometer, 40 parts of methyl methacrylate, 10 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine as a catalyst were charged. While flowing nitrogen, it was stirred at 50 °C for 1 hour to displace the nitrogen in the system. Then, 9.3 parts of ethyl 2-bromoisobutyrate as an initiator, 5.6 parts of cuprous chloride as a catalyst, and 100 parts of PGMAc were charged, and it was heated to 110 °C under a nitrogen stream to initiate the polymerization of the first block (B block). After polymerizing for 4 hours, a sample of the polymerization solution was taken to measure the non-volatile content, and based on the conversion of the non-volatile content, it was confirmed that the polymerization conversion rate was 98% or more. Then, 50 parts of PGMAc, 40 parts of dimethylaminoethyl methacrylate as the monomer of the second block (A block), and 10 parts of methacryloyloxyethyl benzyldimethylammonium chloride were added to the reaction apparatus, and it was stirred while maintaining the state at 110 °C and in a nitrogen environment to continue the reaction. Two hours after the addition, a sample of the polymerization solution was taken to measure the non-volatile content, and based on the conversion of the non-volatile content, it was confirmed that the polymerization conversion rate of the second block (A block) was 98% or more. After cooling, PGMAc was added so that the non-volatile content became 30% by mass to prepare a dispersed resin (I-3) solution having a chain block structure. The amine value was 169.8 mgKOH / g.

[0574] (Dispersed resin (I-4) solution)

[0575] According to Example A3 of International Publication No. 2022 / 172607, a dispersed resin (I-4) having a polymerizable unsaturated group was synthesized, and PGMAc was added so that the non-volatile content became 30% by mass. The amine value was 67 mgKOH / g, and the weight average molecular weight was 5,600.

[0576] <Manufacture of dispersion>

[0577] (Dispersion 1)

[0578] After stirring and mixing the following raw materials to make them uniform, zirconia beads with a diameter of 0.5 mm were used and dispersed for 3 hours using an Eiger mill (manufactured by "mini model M-250MKII" of Eiger Japan Co., Ltd.), and then filtered through a filter with a pore size of 1.0 μm to produce Dispersion 1. The non-volatile content was 22.5% by mass.

[0579] Pigment (F-1): 15.00 parts

[0580] Dispersed resin (I-1) solution: 10.00 parts

[0581] Dispersed resin (I-3) solution: 15.00 parts

[0582] Organic solvent (Q-1): 60.00 parts

[0583] (Dispersions 2 to 14)

[0584] Except for changing the raw materials and amounts described in Tables 3-1 and 3-2, Dispersions 2 to 14 were prepared in the same manner as Dispersion 1.

[0585]

[0586] [Table 3-2]

[0587]

[0588] Each component described in Tables 3-1 and 3-2 is as follows.

[0589] [Pigment (F)]

[0590] F-1: C.I. Pigment Green 63

[0591] F-2: C.I. Pigment Green 58

[0592] F-3: C.I. Pigment Blue 15:3

[0593] F-4: C.I. Pigment Blue 15:6

[0594] F-5: C.I. Pigment Yellow 139

[0595] F-6: C.I. Pigment Yellow 150

[0596] F-7: C.I. Pigment Yellow 231

[0597] F-8: C.I. Pigment Red 177

[0598] F-9: C.I. Pigment Red 254

[0599] F-10: C.I. Pigment Violet 23

[0600] Pigments (F-1) to (F-10) were each micronized by salt milling, washed thoroughly with ion-exchanged water so that the curable composition had the specified amount of the specific metal, dried, and then used.

[0601] [Pigment derivative (H)]

[0602] [Chemical formula 12]

[0603]

[0604] [Organic solvent (Q)]

[0605] Q-1: Propylene glycol monomethyl ether acetate

[0606] <Manufacture of the curable composition>

[0607] [Example 1]

[0608] (Curable composition 1)

[0609] The following raw materials were mixed and stirred, and then filtered through a filter with a pore size of 1.0 μm to obtain curable composition 1. The nonvolatile content was 15.00% by mass.

[0610] Dispersion 1: 12.10 parts

[0611] Dispersion 3: 4.10 parts

[0612] Dispersion 5: 6.70 parts

[0613] Dispersion 7: 4.10 parts

[0614] Solution of alkali-soluble resin (A1-1) having a hydroxyl group-containing monomer unit (a1): 2.00 parts

[0615] Polyfunctional urethane (meth)acrylate (B1-1) having a secondary amine structure or a tertiary amine structure: 0.50 part

[0616] Other (meth)acrylate (B2-1): 0.10 part

[0617] Other (meth)acrylate (B2-4): 1.00 part

[0618] Other (meth)acrylate (B2-5): 1.00 part

[0619] Other (meth)acrylate (B2-7): 0.40 part

[0620] Photopolymerization initiator (C1-1): 0.15 part

[0621] Photopolymerization initiator (C1-2): 0.15 part

[0622] Thermal polymerization initiator (C2-1): 0.45 part

[0623] Compound (D1-3) having a blocked isocyanate group: 5.00 parts

[0624] Compound (D2-1) having an epoxy group: 0.30 part

[0625] Silane Coupling Agent (E-1): 0.75 parts

[0626] Polymerization Inhibitor (L-1): 0.75 parts

[0627] Leveling Agent (N): 0.02 parts

[0628] Ultraviolet Absorbent (P): 0.15 parts

[0629] Organic Solvent (Q): 60.28 parts

[0630] [Examples 2 to 59, and Comparative Example 1]

[0631] (Hardenable Compositions 2 to 60)

[0632] Except for changing the hardenable composition 1 of Example 1 to the raw materials and amounts described in Tables 4-1 to 4-6, the hardenable compositions 2 to 60 were produced in the same manner as in Example 1.

[0633] [Table 4-1]

[0634]

[0635]

[0636]

[0637]

[0638]

[0639]

[0640] Each of the raw materials described in Tables 4-1 to 4-6 is as follows.

[0641] [Polymerizable Compound (B)]

[0642] (Polyfunctional Carbamate (Meth)acrylate having a secondary amine structure or a tertiary amine structure)

[0643] B1-6: CN9906NS (manufactured by Arkema, aliphatic polyfunctional carbamate acrylate having a tertiary amine structure)

[0644] (Other (Meth)acrylate (B2))

[0645] B2-1: 1,6-Hexanediol Diacrylate (in the general formula (1), a compound in which R1 and R2 are hydrogen atoms, l and m are 0, and n is 6)

[0646] B2-2: 1,9-Nonanediol diacrylate (in the general formula (1), the compound where R1 and R2 are hydrogen atoms, l and m are 0, and n is 9)

[0647] B2-3: Tricyclodecane dimethanol diacrylate

[0648] B2-4: Aronix M-306 (manufactured by Toagosei Co., Ltd., a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, with pentaerythritol triacrylate being 65% - 70%)

[0649] B2-5: Aronix M-510 (manufactured by Toagosei Co., Ltd., a trifunctional acrylate containing an acidic group)

[0650] B2-6: Aronix M-350 (manufactured by Toagosei Co., Ltd., trihydroxymethylpropane EO-modified triacrylate)

[0651] B2-7: Aronix M-402 (manufactured by Toagosei Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, with dipentaerythritol pentaacrylate being 30% - 40%)

[0652] [Polymerization initiator (C)]

[0653] (Photoinitiator (C1))

[0654] C1-1: Adeka arkls NCI-831E (manufactured by ADEKA Corporation, an oxime compound with an extinction coefficient of 13,410 L / mol·cm for light at a wavelength of 365 nm)

[0655] C1-2: Irgacure OXE04 (manufactured by BASF Japan Ltd., an oxime compound with an extinction coefficient of 7,051 L / mol·cm for light at a wavelength of 365 nm)

[0656] C1-3: Irgacure OXE02 (manufactured by BASF Japan Ltd., an oxime compound with an extinction coefficient of 2,401 L / mol·cm for light at a wavelength of 365 nm)

[0657] (Thermal initiator (C2))

[0658] C2-1: 1,1-Bis(tert-hexylperoxy)cyclohexane (10-hour half-life temperature is 87.1 °C)

[0659] C2-2: 2,2-bis(4,4-di-tert-butylperoxycyclohexyl)propane (10-hour half-life temperature: 94.7 °C)

[0660] C2-3: di-tert-hexyl peroxide (10-hour half-life temperature: 116.4 °C)

[0661] C2-4: dilauroyl peroxide (10-hour half-life temperature: 61.6 °C)

[0662] C2-5: cumene hydroperoxide (10-hour half-life temperature: 145 °C)

[0663] [Thermal crosslinking compound (D)]

[0664] (Compound (D1) having a blocked isocyanate group)

[0665] D1-3: Duranate MF-K60B (manufactured by Asahi Kasei Corporation, isocyanurate of hexamethylene diisocyanate blocked with an active methylene compound, non-volatile content: 60% by mass)

[0666] D1-4: BI7982 (manufactured by Baxenden Chemical Company, isocyanurate of hexamethylene diisocyanate blocked with a pyrazole compound, non-volatile content: 70% by mass)

[0667] D1-5: BI7984 (manufactured by Baxenden Chemical Company, isocyanurate of hexamethylene diisocyanate blocked with an oxime compound, non-volatile content: 75% by mass)

[0668] D1-6: BI7951 (manufactured by Baxenden Chemical Company, isocyanurate of isophorone diisocyanate blocked with a pyrazole compound, non-volatile content: 75% by mass)

[0669] D1-7: Takenate B-830 (manufactured by Mitsui Chemicals, adduct of toluene diisocyanate blocked with an oxime compound, non-volatile content: 55.5% by mass)

[0670] (Compound (D2) having an epoxy group)

[0671] D2-1: EHPE-3150 (manufactured by Daicel Corporation, compound represented by the general formula (2), average number of epoxy groups: 15, epoxy equivalent: 170 g / eq to 190 g / eq)

[0672] D2-2: DENACOL EX-611 (manufactured by Nagase ChemteX Corporation, average number of epoxy groups is 4, epoxy equivalent is 155 g / eq to 175 g / eq)

[0673] [Silane Coupling Agent (E)]

[0674] E-1: KBE-403 (manufactured by Shin-Etsu Chemical Co., Ltd., 3-glycidoxypropyltriethoxysilane)

[0675] E-2: KBE-402 (manufactured by Shin-Etsu Chemical Co., Ltd., 3-glycidoxypropylmethyldiethoxysilane)

[0676] E-3: KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd., 3-glycidoxypropyltrimethoxysilane)

[0677] E-4: KBE-503 (manufactured by Shin-Etsu Chemical Co., Ltd., 3-methacryloxypropyltriethoxysilane)

[0678] [Polymerization Inhibitor (L)]

[0679] L-1: 1% solution of methylhydroquinone in propylene glycol monomethyl ether acetate

[0680] L-2: 1% solution of p-methoxyphenol in propylene glycol monomethyl ether acetate

[0681] [Leveling Agent (N)]

[0682] N-1: BYK-330 (manufactured by BYK-Chemie GmbH, polyether-modified dimethylsiloxane)

[0683] N-2: Block copolymer with the following structure (n:m = 50:50 (mol%))

[0684] Above, N-1 and N-2 are mixed at a mass ratio of 8:2 to prepare the leveling agent (N).

[0685] [Chemical Formula 13]

[0686]

[0687] [Ultraviolet Absorbent (P)]

[0688] P-1: Tinuvin 460 (manufactured by BASF Japan Ltd., hydroxyphenyltriazine-based compound)

[0689] P-2: Tinuvin 326 (manufactured by BASF Japan, benzotriazole-based compound)

[0690] As described above, P-1 and P-2 are mixed at a mass ratio of 5:5 to prepare the ultraviolet absorber (P).

[0691] [Organic solvent (Q)]

[0692] Q-1: PGMAc

[0693] Q-2: Propylene glycol monomethyl ether

[0694] Q-3: 3-Methoxy-1-butanol

[0695] Q-4: Ethyl 3-ethoxypropionate

[0696] As described above, Q-1, Q-2, Q-3, and Q-4 are mixed at a mass ratio of 80:10:5:5 to prepare the organic solvent (Q).

[0697] <Evaluation of the curable composition>

[0698] The following evaluations were performed on the obtained curable compositions 1 to 60. The evaluation results are shown in Table 5.

[0699] [Adhesion evaluation]

[0700] Using a spin coater, the obtained curable composition was coated on a glass substrate (Eagle 2000 manufactured by Corning) with a length of 100 mm × width of 100 mm and a thickness of 0.7 mm so that the dried film thickness became 2.0 μm, and dried on a hot plate at 90°C for 2 minutes. Subsequently, after cooling the substrate to room temperature, using an ultra-high pressure mercury lamp, through a photomask with stripe patterns of widths 5 μm, 10 μm, 15 μm, 20 μm, and 25 μm, exposure was performed at an illuminance of 30 mW / cm 2 and an exposure dose of 100 mJ / cm 2 . After that, the substrate was spray-developed using an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23°C, then washed with ion-exchanged water, air-dried, and baked in a clean oven at 110°C for 30 minutes. The spray development was performed for each film of the curable composition within the shortest time capable of forming a pattern without development residue, and this was taken as the appropriate development time.

[0701] The patterns with widths of 5 μm to 25 μm on the evaluation substrate were observed using an optical microscope, and remaining patterns were confirmed. The evaluation criteria are as described below, and a value of 3 or more was regarded as practical.

[0702] 5: There remains a pattern with a size of 10 μm or less.

[0703] 4: There remains a pattern with a size of 15 μm or more. There is no remaining pattern with a size of 10 μm or less.

[0704] 3: There remains a pattern with a size of 20 μm or more. There is no remaining pattern with a size of 15 μm or less.

[0705] 2: There remains a pattern with a size of 25 μm. There is no remaining pattern with a size of 20 μm or less.

[0706] 1: There is no remaining pattern.

[0707] [Film tolerance evaluation]

[0708] The obtained curable composition was applied using a spin coater onto a glass substrate (Eagle 2000 manufactured by Corning) having a length of 100 mm, a width of 100 mm, and a thickness of 0.7 mm such that the film thickness after drying was 2.0 μm, and dried on a hot plate at 90°C for 2 minutes. Subsequently, after cooling the substrate to room temperature, using an ultra-high pressure mercury lamp, through a photomask with stripe patterns having a width of 100 μm, exposure was performed at an illuminance of 30 mW / cm 2 and an exposure dose of 100 mJ / cm 2 . After that, the substrate was spray-developed using an aqueous developer at 23°C containing 0.12 mass% of a nonionic surfactant and 0.04 mass% of potassium hydroxide, then washed with ion-exchanged water, air-dried, and baked in a clean oven at 110°C for 30 minutes. The spray development was performed for each film of the curable composition for the shortest time capable of forming a pattern without development residue.

[0709] The obtained evaluation substrate was immersed in propylene glycol monomethyl ether acetate at room temperature for 15 minutes, then washed with ion-exchanged water, air-dried, and the stripe pattern portion with a width of 100 μm was observed using an optical microscope. The evaluation criteria are as described below, and a value of 3 or more is considered practical.

[0710] 5: No change in appearance and color.

[0711] 4: Slight wrinkles or the like are generated, but there is no change in color.

[0712] 3: Wrinkles or the like are generated in part, but there is no change in color.

[0713] 2: Wrinkles or the like are generated on the entire surface, and there is slight fading.

[0714] 1: Peeling or fading occurs.

[0715] [Developability evaluation]

[0716] Using a spin coater, the obtained curable composition was applied onto a glass substrate (Eagle 2000 manufactured by Corning Inc.) with a length of 100 mm, a width of 100 mm, and a thickness of 0.7 mm so that the dry film thickness became 2.0 μm, and dried on a hot plate at 90 °C for 2 minutes. Subsequently, after cooling the substrate to room temperature, using an ultra-high pressure mercury lamp, through a photomask with a stripe pattern having a width of 100 μm, with an illuminance of 30 mW / cm 2 , and an exposure dose of 100 mJ / cm 2 exposure was carried out. Thereafter, the substrate was spray-developed using an aqueous developer at 23 °C containing 0.12 mass% of a nonionic surfactant and 0.04 mass% of potassium hydroxide, and then washed and air-dried with ion-exchanged water. The spray development was carried out for each film of the curable composition within the shortest time capable of forming a pattern without development residue, and this was taken as the initial development time.

[0717] The curable composition was placed in a sealed container and stored at 40 °C for 1 week, and developed under the same conditions as the initial evaluation. The evaluation criteria are as described below, and a value of 3 or more was considered practical.

[0718] 5: The development time after storage was in the range of 90% or more and 110% or less of the initial development time

[0719] 4: The development time after storage was in the range of 80% or more and less than 90%, or more than 110% and 120% or less of the initial development time

[0720] 3: The development time after storage was in the range of 70% or more and less than 80%, or more than 120% and 130% or less of the initial development time

[0721] 2: The development time after storage was in the range of 60% or more and less than 70%, or more than 130% and 140% or less of the initial development time

[0722] 1: The development time after storage was less than 60% of the initial development time, or more than 140%

[0723] [Line Width Stability Evaluation]

[0724] Using the spin coating method, the obtained curable composition was applied onto a glass substrate (Eagle 2000 manufactured by Corning Inc.) with a length of 100 mm, a width of 100 mm, and a thickness of 0.7 mm so that the dry film thickness after drying became 2.0 μm, and dried on a hot plate at 90 °C for 2 minutes. Subsequently, after cooling the substrate to room temperature, using an ultra-high pressure mercury lamp, through a photomask with a stripe pattern having a width of 100 μm, with an illuminance of 30 mW / cm2 , Exposure dose: 100 mJ / cm 2 Exposure was performed. Thereafter, the substrate was spray-developed using an aqueous developer containing 0.12% by mass of a nonionic surfactant and 0.04% by mass of potassium hydroxide at 23°C, and then washed and dried with ion-exchanged water. The obtained substrate was post-baked in a clean oven at 110°C for 30 minutes to obtain an initial evaluation substrate. The line width of the obtained initial evaluation substrate was measured using an ECLIPSE LV100POL model optical microscope manufactured by Nikon Corporation, and this was taken as the initial line width (CD1).

[0725] The curable composition was placed in a sealed container and stored at 40°C for 1 week. A pattern was fabricated and the line width was measured under the same conditions as the initial evaluation, and this was taken as the line width after storage (CD2). The evaluation criteria are as described below, and a value of 3 or more is regarded as being practical.

[0726] Formula (1): ΔCD = |CD2 - CD1|

[0727] 5: ΔCD < 2 μm

[0728] 4: 2 μm ≤ ΔCD < 3 μm

[0729] 3: 3 μm ≤ ΔCD < 5 μm

[0730] 2: 5 μm ≤ ΔCD < 6 μm

[0731] 1: ΔCD ≥ 6 μm

[0732]

Claims

1. A curable composition comprising: an alkali-soluble resin (A), a polymerizable compound (B), a polymerization initiator (C), and a thermally crosslinkable compound (D), wherein: The polymerizable compound (B) comprises a polyfunctional urethane (meth)acrylate (B1) having a secondary amine structure or a tertiary amine structure, The thermally crosslinkable compound (D) includes a compound (D1) having a blocked isocyanate group.

2. The curable composition according to claim 1, wherein The polyfunctional urethane (meth)acrylate (B1) having a secondary amine structure or a tertiary amine structure includes at least one selected from the group consisting of an aliphatic polyfunctional urethane (meth)acrylate having a secondary amine structure or a tertiary amine structure, and an alicyclic polyfunctional urethane (meth)acrylate having a secondary amine structure or a tertiary amine structure.

3. The curable composition according to claim 1, wherein The polymerizable compound (B) further includes a (meth)acrylate (B2) other than the polyfunctional urethane (meth)acrylate (B1) having a secondary amine structure or a tertiary amine structure.

4. The curable composition according to claim 1, wherein The blocked isocyanate group of the compound (D1) having a blocked isocyanate group is a structure protected by an active methylene compound, a pyrazole compound or an oxime compound.

5. The curable composition according to claim 1, wherein The alkali-soluble resin (A) includes an alkali-soluble resin (A1) having a hydroxyl-containing monomer unit (a1). The curable composition according to claim 1 , further comprising a silane coupling agent (E). 7 . A film formed from the curable composition according to claim 1 .

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

9. A solid-state imaging element comprising the optical filter according to claim 8.

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

11. An infrared sensor comprising the optical filter according to claim 8.

Images